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  • A TextBook of Inorganic Chemistry

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    The nineteenth century was an era Of great prosperity for scientific, inquiry. For numerous phenomena explanations have been found which possess a great degree Of probability. Still it cannot be denied that the present theories penetrate only a little into the real essence Of things, and the investigator Very soon stumbles upon questions whose explanation does not at present even seem to be a possibility. The chemical process that goes on when copper — to retain our former example — is heated in the air is well known. However, the deeper question, why the action takes place just SO and not otherwise, or why the resulting powder is black, still awaits a satisfactory answer.

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    The nineteenth century was an era Of great prosperity for scientific, inquiry. For numerous phenomena explanations have been found which possess a great degree Of probability. Still it cannot be denied that the present theories penetrate only a little into the real essence Of things, and the investigator Very soon stumbles upon questions whose explanation does not at present even seem to be a possibility. The chemical process that goes on when copper — to retain our former example — is heated in the air is well known. However, the deeper question, why the action takes place just SO and not otherwise, or why the resulting powder is black, still awaits a satisfactory answer.

    Авторское право:

    © All Rights Reserved
    Скачайте в формате PDF, TXT или читайте онлайн в Scribd
    Отметить как неприемлемый контент
    150 просмотров510 страниц

    A TextBook of Inorganic Chemistry

    Загружено:

    tili_secara127
    The nineteenth century was an era Of great prosperity for scientific, inquiry. For numerous phenomena explanations have been found which possess a great degree Of probability. Still it cannot be denied that the present theories penetrate only a little into the real essence Of things, and the investigator Very soon stumbles upon questions whose explanation does not at present even seem to be a possibility. The chemical process that goes on when copper — to retain our former example — is heated in the air is well known. However, the deeper question, why the action takes place just SO and not otherwise, or why the resulting powder is black, still awaits a satisfactory answer.

    Авторское право:

    © All Rights Reserved
    Скачайте в формате PDF, TXT или читайте онлайн в Scribd
    Отметить как неприемлемый контент
    из 510

    A TE X T B O O K -

    Q INO R GA NIC C HEMI STR Y .

    BY

    DR . A . F . D O LLE M A N ,
    Professor O rdin ar i u s in

    t h e Un iv er si t y O f A m st er da m ; E m er it us Professm
    O rd in ar ius in t h e Un iver s it y of G r on in ge n , N et h er l an ds . and

    Fel l ow of t h e R oya l A cade m y of Scien ces . A mst er dam .

    I SS UE D IN E NG L I S H IN C OO P E RA T I O N T
    WI H

    H ER M O N C H A R L E S C OO P ER .

    FO UR TH E N GL I SH E DI TI O N C O IM PL E TE L Y
    '

    TO TA L I SSU E , SI XT E E N T H OU S A N D .

    N EW Y O R K

    JO HN WI LEY SO N S,
    L O ND O N : C HA PM S N HA LL ,

    1913
    ?0 5 3 H

    C o p y r ig h t , 1 9 0 1 , 1 9 02 , 1 9 05 , 1 9 08 , 1 9 1 1 ,

    BY

    H ERMON C . C OO PE R .

    Firs t . Se c o n d , a nd T h i d E dit i
    r o n s e n t e re d at St at io n e r s

    H all .

    HQE s c m
    -
    mn c PR ES S
    R O G ERT DRUMM O N D AN D C O MPANY
    BR O O KLYN , N . Y.
    PR EFA C E TO THE FO UR TH E DI TI O N .

    T HE p resen t edition r e presents a thorough r evision O f t he w o rk


    b y the D utch autho r and the A merican collab orator It p ro t s .

    b y the author s exp erience with the frequent e d itions in o the r


    l anguages but is indep endent in com p osition .

    Very many of the descri p tive p ortions have b een rewr it t en ,

    notably those on the sulp hur oxides and acids rare gases nitroge n , ,

    o xi d es and acids sodium hydrox ide and carbonate radio activ e


    , ,

    elements and platinum as well as the sections on t herm o


    , ,

    chemistry colloids and the iron carbon system while t he sub


    ,
    -

    j ec t s of stability and the reality O f molecules and atoms furnish


    n e w material The chap ter on metal ammonia c om p ounds is
    .
    -

    r eprinted as app roved by Professor WE RN E R for the third edition .

    N otwithstanding the app earance O f di fferential formul ae in


    t he b ook i t is believed that a student who is unfamiliar wi t h
    ,

    t he calculus should have little di fc ulty in understanding t h e


    m eaning and use of such formul ae p rovided he 1 s w ill i ng t o tak e
    ,

    t h e author s word for the solutions O f the equations .

    Indep endent students m ay well be cautioned against regard


    in g any text book as infallible
    -
    Even in a book with a worl d
    .

    mar ket such as this o n e enj oys undergoing many revisions b y


    , ,

    the author and by collaborators in other nations and b eing ,

    frequently reviewed critically by the j our nals there will p robably , , ,

    always be some t extual errors and some p assages whose lucidity

    could be imp roved R eaders c an therefore r ender gre at se rvic e


    .

    by rep o rt n all unsatisfactory p assages t o l ish e rs .

    Thanks are herewith exp ressed to my c Professor H .

    M ONMO U T H S M I T H for c onstant ai


    ,

    R eferences in the text to O R G C H E M refe. .


    p anio n

    volume of this work H O LL E MAN S Text b ook


    ,
    O rgani c C hem
    -

    ist ry
    ,

    translated by WA L K E R an d M O TT .

    H . C . C O O PE R .

    SYRA C U S E UNI V ER S I T Y ,
    O c tob er, 1 9 1 1 .
    C O N TEN TS .

    Lig h t -
    fac e g ure s re fe r to p ag e s ; h e av y fa c e g u re s t o
    -
    p ar ag ra ph s .

    IN TR O DU C TI O N ( 1 5) -

    PHY S I C AL AND CHE M I C AL PHEN OM ENA ( 6 )


    CHE M I C A L O P ERATI O N S ( 7 )
    T H E E L E M EN TS ( 8)

    L aw O f HENRY , 1 1 ; O xidat ion ,


    1 2 ; An a lyt ic an d syn th etic meth ods ,

    13 .

    Hydr ogen ( I L 1 3 ) -

    O xyhydrog e n b lowp i pe , 1 5 ; D eton at in g g as , 1 5 ; R e duc t i on , 1 6 -


    .

    T H E C O N S ER V A T I O N O F M A TT ER
    W a ter ( 1 51 9
    )
    Phys ic a l prop ert i es , 2 0 ; N atura l w ater, 2 0 ; C omp os it i on O f w ater, 22 .

    C OM P O UND S AND M I X TURE S


    PHEN OM ENA A CCOM P ANYING THE FO R M ATI O N OR D E COM P OS I T I O N
    OF A C OM P O UND 2 7 , .

    EX P L ANATI O N O F T H E C O N S TANT C OM P OS I TI O N O F C OM P O UND S A T OM I C


    T HE O RY ( 2 1
    L aw O f c ons tant c ompos i tion 2 7 ; A to ms 2 8 ; M o le cule s 2 8 L aw , , ,

    O f mult i p le pro p ort i ons 2 9 ; T H E A T OM I C W EIGH T S O F T H E


    ,

    E L E M EN TS 2 9 ; C HE M I C A L SY M B O L S AND F O R M U L AE 3 0
    , ,
    .

    STO I C H I OM E T RI C A L CA L C U L A T I O N S
    C hl orin e ( 25
    C ataly t ic ct ion 3 4 ; Hyd ogen ch lorid 3 7 ; A cids b as
    a , r d s lts e, ,
    e s an a ,

    3 9 ; C omp o s it i on O f h ydro c h l or ic a ci d 4 1 ; L aw O f G A Y L U SS A C ,
    -

    4 3 ; A V O GADR O S h yp oth e is 4 4 ; M o le cul ar w eigh ts 4 5 ; R U L E S



    s , ,

    FO R D E TER M INI NG M O L E C U L AR AND A T OM I C W EIGH TS 47 ; ,

    K in etic th e o y 4 7 G eneral g as e qu t ion 4 8 ; T H E R EAL I TY O F


    r ,
    a ,

    M O L E C U L E S AND A T OMS AND T HEIR A B SO L U TE W EIGH T 4 9 ,


    .

    O zo ne ( 3 6 , 3 7 )
    Formul a O f, 52 ; All otrop i sm , 5 3 .

    Hydr ogen Per ox ide ( 3 8,


    Stat us n a s c e n di, 54 .

    M O L E C U L AR
    WEIGH T F R OM T H E M EA S URE M EN T O F T H E D E P RE SS I O N O F
    T HE F REE ZING P O INT AND E L E V A T I O N O F T H E B O I L ING P O INT ( 4 0
    - -

    Semi p erm e ab le memb r ane s O s mot ic pre ss ur e 58 ; PF E FF ER S


    -

    , ,

    exp erime n ts , 59 ; I so ton ic solutions , 62 ; mula


    For O f hydr ogen
    peroxi de 6 5 , .
    Vi C O N TEN TS .

    Br om in e ( 44 ,
    Hydr o en b r o g mide ,
    67 .

    I odine ( 464 8)
    Hy dr og en iodide ,
    71 .

    D I SSOC IATI O N ( 49
    Re v r ib le re ction s 7 3 ; Equilibrium 7 3 R e action ve lo city 7 5 ;
    e s a , , ,

    L aw O f c h mic al m as s a ct ion 7 5 Un imo l e cul ar an d b imol e cul ar


    e ,

    re c t io n s 7 6
    a ,
    .

    Fl uorin e ( 52, 5 3 )
    Hy dro en g uoride 8 1 ,
    .

    C omp ou n d O f t h e h aloge n s ( 54 s w ith e a ch oth er 83 ; w i th ,

    oxygen 83 ,
    .

    N OM EN C L A TURE 92 .

    Summ ry O f t h e h alogen group


    a 93 .

    E L E C TR O L Y TI C D I SSOC IAT I O N ( 65 66 ) ,

    I o ic quilib riu m 9 8 ; Str n gth O f a ci ds an d b as es 99 ; Hydr o lys i s


    n e ,
    e , ,

    1 01 .

    S u l p hu r ( 67 9 3 ) -

    A llotrop ic modic ation s


    B LE M E T A S T AB L E
    ,
    AND L 1 08 ; T H E PHA S E R U L E ,
    ,
    1 04 ;
    ABI LE
    T H E T RAN S I
    ,
    TI O N PO INT ,
    1 06 ; ST A

    O F G IBB S 1 09 ; Hydro gen s ulp h i de 1 1 5 ; So lub ili ty p rod u c t 1 1 9 ;


    , , ,

    Hydr oge n persulp h i de 1 20 C omp ounds O f s ulp h ur w i th t h e h al , ,

    1 2 1 ; V A L EN C E 1 22 ; C ompounds O f s ulph ur w it h o xy g en
    '

    o gen s , , ,

    1 2 4 O xy ge n a ci ds o f sulph ur 1 3 1 ; Vo lumetric analys is 1 4 6 , , .

    Sel eniu m and Tell u riu m (9 4 ,

    l ium 1 4 8 ; T el lurium 1 50
    Se en , , .

    Summ ary o f t h e oxy gen group , (9 6 ) 1 51 .

    T H ER MO C HE M I S TRY (9 71 04 )

    L aw Of HE SS , 1 53 : C HE M I C AL A FF INI TY , 1 56 ; T HE D I S P L A C E M ENT
    OF E Q UI L IBRIU M , 1 6 0 ; PA SS I V E R E S I S TAN C E S , 1 6 1 .

    N itr ogen ( 1 05
    m
    Th e at os ph e re , 1 6 5 ; A r gon h e lium n d compan ion e l ments 1 7 0 ; ,
    a e ,

    C ompou ds O f n itr g en n d h ydro gen 1 7 4 ; C omp o unds w i th t h e


    n o a ,

    h aloge 1 7 9 ; Hydroxy l ami n e 1 80 ; C omp o unds w i th oxy ge n


    ns, , ,

    1 8 1 ; O xy ge n aci ds 1 8 7 ; D erivat ives O f t h e n i troge n a ci d 1 95 ;


    , s,

    O th r n i tro g e comp oun ds 1 98


    e n ,
    .

    Phos phorus ( 1 3 1
    0

    Hydrogen compoun ds204 ; ,


    Hlog n compou
    a e n ds , 2 09 ; O y x gen com
    p oun ds ,
    2 1 1 A ci ds 2 1 2
    , ,
    .

    A rs enic ( 1 55
    Hy dr ogen r
    a se n ide ,
    22 3 ; H al o g e n c ompounds 226 ; ,
    O xygen c o m
    p o un ds 22 6 ; O xy a ci ds 2 28 ; Sulph ur c ompounds 2 2 9 ; Sulp h o
    -

    , , ,

    salts 2 3 0 ,
    .

    A n tim on y ( 1 65
    Hydro gen timon i de 23 2 ; H al o g e n compoun ds 23 3 ; O xygen com

    an , ,

    p ounds ,
    23 4 ; S ulphur compoun ds ,
    23 6 .
    C O N T E N TS . v ii

    Bis m u th ( 1 7 0 1 7 4 ) -

    S umm ry a O f t he n itrog en g ou p
    r 23 9 .

    C arbon
    A llotrop ic form s , 24 1 ; M ol e cul ar an d atomic w e igh t, 2 4 6 ; C o m
    po unds w i th h y dro gen , 24 8 ; C omp ou n ds w i th oxy g en , 24 9 ; O th e r
    c arb on compoun ds , 2 55 ; Th e am e , 2 56 .


    Silicon ( 1 90 1 96 )
    Hydro g en l ci de 2 62 ; Halogen comp ou d 263 ;
    Si i ,
    n s, O xy g e n c om
    p oun
    ds , 2 6 5 ; Silicic aci ds 2 66 ; C O LL O ID S 2 6 8 , ,
    .

    G erm an iu m ( 1 9 7 )
    Tin ( 1 98
    Stan n ou s c ompou n ds ,
    27 6 ; S tan n ic c omp ounds ,
    27 9 .

    L ead ( 203 206 ) -

    O xid s 2 83 ; Halog n comp oun d 285 ; O th er le d lt 2 86 ; S m


    e ,
    e s, a sa s, u

    m ry O f t h e c rb on group
    a 2 87
    a .

    M E T H O D S O F D E TER M INI NG T OM I C W EIGH T S (


    A 20 8 21 2)

    L w o f D U L O NG n d PE T I T 2 89 ; L aw f N EU M ANN 2 9 1 ; L aw o i
    a a ,
    o ,

    M I T SC H R L I C H 2 9 2 ; E X P ERI M EN T A L D E TER M INA TI O N O F E Q U V A


    E ,
    I

    L EN T W EIGH TS 2 9 3 ,
    .

    T HE PERI O DI C SY S TE M O F T H E E L E M EN TS ( 21 3 22 1 )

    C onstruc ti on f a ystem f t h e l em ent 3 03 ; A cer t am g atomic


    o s O e s, s in

    w e igh ts 3 05 ; Pre dic t ion f pro p e rt i


    ,
    f e l em ents 3 07 ; C orrec t O es O ,

    in g tomic w e ights 3 08 ; G rap h ic r epre entati on 3 08


    a ,
    s ,
    .

    Lithiu m a nd Sodiu m ( 222


    L ith ium 3 1 0 So dium 3 1 1
    , , ,

    O xi des an d hydroxid es O f, 3 1 2 , Sa lt s

    o f, 3 15, ( So da ,

    Potass iu m
    ( 22 7 23 1 )
    O xygen c ompounds 3 23 ; Sa ,
    lts , 3 24 .

    R u bidiu m a nd C ces iu m ( 23 2)
    S ummary O f t he group O f alk ali metals 330 .

    A m m on iu m S a l ts ( 23 4 )
    SA L SO L U I O N S 23 523 9
    T T ( )
    A C IDI M E
    TRY AND A LK A LI M E TRY ( 240, 241 )
    Indic ators 3 5 2 ,
    .

    24
    C opper ( 24 2 4)
    u
    C pro s o u c mpounds ,
    3 55 ; C pr u ic comp ounds ,
    3 58 .

    Sil ver ( 24 5 24 7 )

    C ompounds , 3 6 2

    Ph otogr aph y, 3 64 .

    G ol d ( 24 825 1 )
    T est in g O f gold n d Silver 3 69 ; A urou s comp ounds
    a , ,
    3 69 A ur ic com
    p ou n d 3 7 0 ; Summ ry O f t h e g ou p
    s, 371 a r .

    Beryl liu m M a gn esi um ( 253 255 )


    an d

    B ery llium , 3 7 2 ; M a gn e s ium , 3 7 4 ; M a gne s ium sa lt s, 3 75 .

    S tr on tiu m , 26 2
    C al ciu m , an d B ari u m ( 2 56 )
    Ca lcium , 3 76 ; O xi de s an d hydroxi de s O f, 3 7 7 ; Sa l ts O f, 3 79; G l as s ,
    I

    C O N TE N TS .

    PA G E

    3 84 ; Stront ium ,
    3 86 ; Bar ium ,
    3 87 ; S ummary O f t h e group Of t he
    lk lin e ea th 3 88
    a a r s, .

    SP E C T R OSCO P Y ( 263 265


    )
    T H E UNI TY O F M ATT ER ( 266 )
    .

    R adio -
    ac tive El em en ts ( 26 7 )
    Z in c ( 268 ,
    269 )
    C adm iu m ( 27 0)
    M er cu r y ( 2 7 1
    m lgam 4 1 2 ; M rcur u c ompoun d
    A a s, e o s s, 4 1 3 ; M er curic compoun ds ,

    4 1 4 ; Summ y f t h zi c gr oup ar O e n 417 .

    E L E C TR OC HE M I S T RY ( 2 7 6
    B or o n ( 2 82 ,

    Ha l o g e n c mp u n d
    o o s, 43 3 ; O xyg en c om pou n ds , 43 3 .

    A l u m in iu m ( 284
    m u
    C o p o n ds O f, 43 7 .

    G a lliu m , I n diu m , an d Tha ll iu m ( 28 7 ,


    44 1 .

    Summ ry o f t h g up
    a e ro 44 2 .

    The R a r e E ar ths ( 290)


    Ti tan iu m , Zircon iu m , ( 29 1 ) an d Thoriu m

    Van a diu m , N iobiu m an d Tan ta l u m ( 29 2 )


    ,


    G rou p ( 93 299 )
    C hr om iu m 2
    C hr o mium mou compou d 4 50 ;
    ,
    44 9 ; C hro s n s, mic comp ou n ds
    C hr o ,

    4 50 ; C h om at s 4 5 2 ; M o ly b d um 4 5 5 ;
    r e , en ,
    T ung t en 4 56 ; U a
    s , r

    n ium 4 5 7 ; Summ
    ,
    y f t h e g o u p 4 58 ar O r , .

    M an gan ese ( 3 00,


    M an gan ic a ci d an d pe rm an gan ic a ci d ,
    4 60 .


    I ron ( 0 3 08)
    3 2
    I ron -

    c b ar on sy s e t m ,
    466 ; Ferro u s c o mp o u n d s, 47 3 ; Ferr ic com
    po un d s, 47 4 .

    C oba l t an d N i ck e l 0 3 1 2
    ( 3 9 )
    C ob a
    47 7 ; N lt , e , 47 9 ick l .

    Pl atin u m M e tal s ( 3 1 3 3 1 6 )
    R uth n ium
    e ,
    4 82 ; mium
    Os ,
    4 83 ; R h od ium ,
    4 83 i ium
    Ir d ,
    4 84 ;
    P ll dium
    a a ,
    4 84 ; Pl tin um
    a ,
    485 .

    M et a l -
    amm o n ia C om pou n ds . W ERNER S
    EX TEN S I O N S OF THE N O TI O N
    OF VA L EN C E (3 1 7
    IN O R G A N IC C H E M I ST R Y .

    INTR O D UC TI O N .

    1 .C h em ist ry is a br anch of the natural science s t h e science s ,

    which deal with the things o n t h e ea rth and in the outside unive rse .

    The knowledge of these things is O btained by O bservatio n with


    our senses this being the only means we possess I t is well t o
    ,
    .

    under tand therefore that we know not the t hings themselves


    s
    , , ,

    but sim ply the im pressions which they make upo n our sense orga n s -
    .

    When we see an O bj ect we perceive in r eality o nly the e ffect o n


    , , ,

    o u r retina ; if we feel the obj ect it is not the body itself but t h e
    ,

    excitement O f the sens ory nerves O f touch in our ngers that we are
    made awar e of Hence it may be fairly asked whethe r the O bj ects
    .

    o f which we are cognizant are r eally j ust as we p erceive them or ,

    whether they even exist at all outside of our pe rso n The natural .


    S ciences leave this proble m o u t O f co nsideratio n its solution is t h e
    task of Speculative philoso phy In reality they are not co nce r ne d
    .

    with the O bj ects which in themselves we cannot know b ut with


    , ,

    the study O f the sens atio ns that we receive The se ns atio ns tak e
    .

    the place of t h e O bj ects and w e regard them as such


    , .

    2 .Th e Scie n t i c I v estigatio n of Thin g s


    n What is t o b e
    unde rstoo d b y t h e te rm ? I n the rst place a most accurat e ,

    descr iption O f t h e O bjects From a study of this it is foun d that


    .

    many O b jects resemble each other to a greater o r less degree and ,

    it is the refore possible to make a classicatio n i s an arrangement ,


    .

    O f lik e O bjects into grou ps and a se paratio n O f the various grou ps

    from each other By the descriptive method we are nally abl e


    .

    to divide the natural sciences into Zool ogy B otan y M in era l ogy , ,

    and A str on om y .

    3 . In the seco nd place , scientic i nvestigation includes t he


    stu dy O f t h e r elations which the O bj ects bear t o e ach o t her ; in
    o the r words the study O f phenom ena
    ,
    The heave nly bod ies mov e .

    towards each other ; water tur ns t o ice o n cooling ; W ood b ur ns


    when heated It is the task of the natur al sciences t o accur ately
    .

    O bserve and describe such phenomena i e to asce rtain in what ,


    . .

    way the heavenly bodies change their relative positions what ,

    conditio ns affect the freezing of water what becomes O f t h e b ur n ,

    ing wood un d er W hat conditions it can burn et c


    , ,
    .

    T h e descriptio n O f the phenomena leads to a d iffe re nt divis i o n


    o f t h e natural sciences than the descri ptio n of O bj ects V iz a divi ,
    .
    ,

    Sion int o Phys ics C hem is try and B iol ogy the latte r b eing t h e s tudy
    , ,

    O f Vital processes and including Physiology Path olo gy an d The ra


    , ,

    eu t ics
    p .

    4. The h u m an min d in p u r suing the,


    s cientic s tu d y O f natu r e ,

    does not feel contented with the accurate descriptio n O f O bj ect s


    an d phenomena ; it Seeks also for an explana tion of the latte r .

    Th e various attempt s at ex planations co nstitute the most im


    p o r tant part of S cience When fo r instance
    .
    ,
    we see that a r ay of ,

    light in passing through a piece of Iceland Spa r is Split u p into t w o


    o ther r ays O f different pro pe rties we strive t o account fo r t h e
    ,

    p henomeno n When co
    .
    pp er is heate d in the ai r it tu r ns into a ,

    black powder ; the question again arises why this thing is SO I n ,


    .

    searching fo r an explanation O f the phenome na we th u s end eavo r


    to penetrate dee pe r into the essence of thi ngs than is possible by
    direct O bse rvation Al though the phenomena themselves are
    .

    found to be unchangeable our explanation of them may be modi:


    ,

    e d as ou r knowledge increases The trans fo rmatio n O f co ppe r


    .

    into a black pow d er o n heating in the air was formerly explaine d


    b y the supposition that something left the metal ; subsequently ,

    "
    when the phenomenon was better unde rstood b y assuming that ,

    the co pper takes u p something from the ai r .

    Scientic investigation pu rsues in general then t h e foll o wing , ,

    cou rse : A phenomeno n is O bserved and studie d as careful ly as


    possible Thereupo n an ex planatio n O f it i s sought A h ypoth
    .
    .

    e s i s is set u p From this conclusions can b e forme d s ome of


    .
    ,

    which can b e tested by experiment If the latte r r eally leads t o .

    the ex pected result the hy pothesis gains in probabilit y I f it is


    , .

    s bsequently found t o ex plain and li nk tog ethe r a whol e seri O f


    u f m

    p henomena it becomes
    , a t h e o ry .
    PHYS I CA L A N D CHEM I CA L PHE N O M E N A .
    3

    Th e nineteenth century w as an era O f gr eat prospe rity fo r


    s cientific inquiry ,
    For nu me r ous phenomena explanatio ns have
    .

    b een found which possess a gr eat degree O f probab ility Still it .

    c a n not be de nied that t h e present theories p enetrate o nly a little

    int o the r eal essenc e O f things and the investigato r Very soo n ,

    s tum b les up o n questi o ns whos e ex planation does not at pres e n t

    e ven seem t o b e a p ossi bility Th e chemical process that goes o n


    .


    when co ppe r t o retain our forme r exampl e is heate d in t h e
    air is well kn own However the dee pe r questio n why t h e action
    .
    , ,

    takes plac e j us t SO and not othe rwise o r why t h e resul ting ,

    p owde r is black still awaits a satisfactory


    , ans we r .

    5 We O bse rve d in the preceding pa ragr aph that t h e natu r al


    .

    p henomena are foun d to be unchangea b l e T h e m o vement O f the.

    p lanets for
    ,
    exam p le still takes place in t h e,
    s ame manne r as in t h e

    times of the Ptolemies ; wheneve r wate r tur ns t o ice t h e same


    increase of volume is t o be O bserved ; the c rystal form O f comm o n
    s alt,
    whenever and whereve r examined is invariably the same ; ,

    from the bur n ing of wood the same products ar e always O btained ;
    the microsco pic st ructure O f t h e l eaves of o ne and t h e sam e plant
    is neve r found to vary This general principle nds its expression
    .

    in the phrase constancy of na tu ra l phenom ena Eve ry o ne is c o n


    , .

    V in ce d O f its t ruth and it is tacitly a cce pted as t h e b asis O f every


    ,

    n atural s cientic investigation If fo r example o ne h as measured


    .
    , ,

    the angles which t h e fac es O f a soda c rystal fo rm with each othe r ,

    he co nside rs it ce rtain that all soda c rystals m us t Sh ow the sam e


    angl e s at what e ve r t h e o r plac e they may b e m easure d
    ,
    If it h as .

    o nc e b ee n dete rmined that pur e alcohol boils at 7 8 unde r no rmal

    p r e ss u re it is fo,
    r thw ith assumed that th i s m u st b e t h e case with

    all alcohol n o matte r h ow it may b e O b tained or wh e n and W he re


    ,

    it m ay b e tested .

    P HY S I C A L A N D C H EMI C A L P H EN O MEN A .

    6 . It stated ab ove w as 3 ) that t h e des cription O f ph e nom e na


    l ead s t o a d iv ision O f t h e natural sciences into Physics C hemistry ,

    an d the study O f vital processes ( Bi ology ) In dening t h e province .

    of C hemist ry B iology may be left O u t O f co nsideration ; however ,

    it is desirable to com pare t h e eld O f C hemistry with that of


    ,

    Physics I n general it may be said that Physics deals with t h e


    .
    4 IN O R GA N I C C HE M I S TR Y . 6~

    tem p orary Ch emist ry with the lasting changes of matter By


    , ,
    .

    m a tter or s ubs ta nc e we und erstand the O bj ects without reference


    to their form I ron marble sand an d glass are kinds O f matter
    .
    , , ,

    or s u bstanc es inde pendent O f their external sha p e


    ,
    .

    A couple O f illustrations may make this conception of tem p orary


    and lasting changes clear .

    (a ) A platinum wire glows when held in a colorless gas flame -


    .

    O n removal it cools O ff and no change is visible This is a physical .

    p henomenon ; the c h ange the glowing is of a tem p,


    orary sort S O , .

    soon as the cause O f the change is removed the wire resumes ,

    its original condition When some magnesium wire is held in the


    .

    ame it burns with the emission of a brilliant light and turns into
    ,

    a W hite powder which is whol ly differe n t from t h e substance


    ,

    magnesium Here a lasting change has occurred ; we have to do


    .

    with a chemical phenomenon .

    ( b) A gain we may take two white crystallized substances n aph


    , ,

    t h al e n e a n d cane sugar and heat each separately in a reto rt with


    -

    receiver The naphthalene at rst m elts ; on continued heating it


    .

    begins to boil then distils over and condenses in the receiver The
    , .

    distilled naphthalene resembles the undistilled in every respect The .

    substance has as a result of heating undergone physical changes


    , ,

    melting change to va por and nally return t o the solid state Th e


    , , , .

    cane sugar behaves differently Here also a melting is O bserved at


    -

    rst but soon the sugar tur n s darker ; a brownish liquid distils
    ,

    over ; a peculiar O do r is noticeable and at last there remains in t h e


    retort a charred porous mass The cane sugar suffers a lasting
    , .
    -

    change o n being heated I n this case we have a chemical change


    .
    .

    ( c) A S a third and last exam ple we may consider the behavio r


    o f a metallic wire on the one hand and that of acidulated wate r

    on the other when an electric current passes through them Th e


    , .

    wire displays other pro perties SO l o ng as the current is o n I f .

    the latter ceases the wire returns to its original condition This
    , .

    is a physical action I n the acidulated water h owever the current


    .
    , ,

    induces an evolution O f gas and this gas arising from the wate r,

    has pro perties entirely diffe rent from those of the water A lasting .

    change in the substance has occurred ; a chemical action has t ake n


    p l ace .

    A sha rp distinction b etween physical and chemical henomen


    p a
    l
    is ften as wil be seen later very difficul t to make
    O
    .
    CHEM I CA L O PE R A TI O N S .

    C HE MI C A L O PER ATI O N S .

    .
    7 I n o rd e r t o avoi d r e p etitions it seems advisa b l e at this p oin t
    t o d escribe brie fly some O f the commo nest chemical o p erations .

    S uol tio n When sugar salt o r salt p etre for exam ple is pu t
    .
    , , ,

    into water the solid substance disappears and its taste is taken
    ,

    O n by the water The substance has dissolved in the wate r Ther e


    . .

    is a denite limit to the solubility of each of these fo r if t h e tem , ,

    e t r e is ke pt co nstant and more of the substance is graduall


    p r a u
    y
    added a p oint is nally reached when the water will take u p n o
    ,

    more The solution is then sa tu ra ted The solubility of most


    . .

    s O 1 i d s increases with the tem perature M oreover it is very differ


    .

    ent with different substances varying al l the way from solubility in


    ,

    all pro po rtions t o im p ercep tible solubility Thus cane sugar is dis .
    -

    solved in large quantity by water while sand is practically in sol u


    ,

    ble in it L i q u i d s can be either miscible in all pro portio ns


    .

    (water and alcohol ) or only partially soluble in each other When .


    ,

    for instance water is shaken with a sufcient quantity O f ether


    ,

    and allowed to stand two liquid layers are formed ; the water has
    ,

    dissolved some ether and the ether some water I n most cases .

    the solubility of liquids in each other also increases with the tem
    p er a t u r e
    . I n the case of g a s e S solubility decre ases with rising
    tem perature .

    Se par atio n O f a Soli d an d a L i qu i d



    This may be accom plishe d
    .

    b y ltr atio n A funnel is lined o n the interior with l t er pap er


    .
    -

    and the mixtur e poured u pon it The solid is retained o n t h e


    .

    p pa er while the liquid p asses through . D e c an t atio n is a less c o m "


    p l e t e method of se p aratio n ,
    since more liquid remains with t he
    solid by this method than by ltration However it is evident .
    ,

    that neithe r method a ffords a really com plete separatio n This .

    can only be accom plished by washing i e by re placing the por ,


    . .

    tion O f the liquid which remains between the solid particles by


    another liquid I f the liquid of the mixture be a salt solutio n
    .
    ,

    pure water is ve ry e ffective . I t is O bvious that by r e peating the


    washing several times the sal t solution can be w holly removed .

    Suppose that 1 salt solutio n remains between the particles of


    t h e solid and that 9 water is then added The solution is t hus .

    reduced t o o ne tenth O f its original concentration If 1


    -
    .

    o f this dilute solutio n a ain remai ns with the solid and anothe r
    g
    6 I N O R G A N I C C HE M I S TR Y . 7

    9 water is a d ded the concentratio n is then


    ,
    or o n e
    hundredt h O f the ori ginal concentration ; after s ix such O pera t ions
    it would b e only or o ne millionth O f the orig inal so that t h e ,

    separation is practically com plete .

    C ryst al l i z atio n I i a solution is saturate d in the warm and


    .

    l
    is then allowed to cool the dissolved substance frequently se parates
    ,

    o u t in the crystallized state A dvantage is O ften taken O f this


    .

    for purifying crystallizable substances .

    Di stil l atio n ( Fig This o eratio n is frequently made use


    .
    p
    of in working with liquids The liquid is placed in a ask or a
    .

    reto rt and heated t o boiling The esca ping v apo r is cooled to .

    FI G 1 D I S TI L L AT I O N
    . , .

    a liquid in a condens er The latter consists O f a su i cie nt l y wi de


    .

    tube encased in a j acket through whi ch water ows t o kee p t h e


    ,

    inner tube cold The condensed liquid is collected in the r ec eiv er


    .
    .

    I t is readily seen how volatile substances can be se parated from


    n o n volatile o nes by distillation e g water from salt
    -
    since t h e
    ,
    . .
    ,

    former distil over and the latter remain in the distilling ask -

    However liquids of di fferent volatility can also be se parated in


    ,

    t his manner . Take for exam ple a mixture O f alcohol and water
    , , .

    The more volatile constituent alcohol passes over for the most , ,

    p art in the early stage o f t h e o peratio n ; towards the end the le ss


    v olatile water
    , I f t h e t w o distillates are collected se parately an
    .

    approximate se paration r esul t s A fe w re petitions O f this SO call e d


    .
    -

    raction a l distillation b ring about a


    f practically com p le t e s e p arati o n
    in many cases .
    THE E L E M EN TS .

    Su bl im atio n C ertain
    solids e g cam phor when heated ( at
    . .
    ,
    .
    ,

    ordinary pressure ) turn to vap or without melting I f this va por


    , .

    comes in co ntact with a cold surface the substance is de posited in ,

    the solid crystallized state I t is evident that we have her e a nothe r


    ,
    .

    method O f se parating some substances .

    THE EL E MEN TS .

    8 . When a substance 6 ) is subj ected to various inuences ,

    such as heat electricity or light or is brought in co ntact with


    , , ,

    other substances it is very ofte n Split u p into two or more dis


    ,

    similar com po nents A s an exam ple let us take gunpowder


    . .

    Water is added and the whole is stirred well and gently warmed ;
    after a while it is ltered and that which remains on the lter is
    -
    ,

    found to be no lo nger gunpowder for it is un explosive O n e v apo ,


    .

    rating the ltrate a white crystalline substance salt petre remains , , .

    The undissolved part is dried and then shaken with another sol
    .

    vent carbo n disul phide A fter a time the mixture is ltered as


    ,
    .
    ,

    before and there is left o n the lter a black mass consisting of


    , ,

    c harcoal powder The carbon disulphide of the ltrate evaporates


    .

    a n d leaves yellow crystals of s ul phur Thus we see that by Su e .


    ,

    c e ss iv e treatment with water and carbo n disulphide gunpowder ,

    can be se parated into three sub stances viz carbon sulphur and ,
    .
    ,

    s alt petre The two former are inca pable even when subj ected
    .
    ,

    to all the agencies at our command O f division into different com ,

    p o n e n t s N.o t so with salt p etre for when the latter is heated


    ,

    s trongly a gas I S g i ven O ff in which a glowi ng wooden Splinter is

    at o nce ignited When the evolutio n O f gas ceases a substance


    .
    ,

    remains which gives O ff red fumes on treatment with sul phuric acid ,

    something that salt petre does not do Salt petre can evidently .

    be broken u p still farther by heating .

    If we subj ect all sorts O f substances to a successive treatment


    with reagents o f the most different kinds we nally discover cer ,

    tain o nes that cannot be resolved into sim pler substances by our
    p resent means Such .substances are called ele m e n t s A lthough .

    the number of substances according to 6 may be considered as , ,

    innitely great ex perience has taught that the number O f elements


    ,

    is Small There are about eight y


    . .

    A s our methods O f examinatio n im prove it may quite possi bly ,


    8 I N O R GA N I C C HE M I S TR Y .
    8

    b e found that the substances which the chem ist of t o day regards as -


    elements have no right to the name Therefore when we use the

    word element it is to be regarded as a relative term de pendent
    ,
    .
    ,

    o n the extent of our knowledge and the mean s at our command In .

    the history of che m istry so m e cases are to be found where sub


    s tances o nce believed to be elements were subsequently de co m
    , ,

    p osed .

    The exact nu mber O f elements cannot be de n it e l y st at e d b e ,

    cause on the one hand not all the substances that possibly exist
    , ,

    may be within our r e a ch f and o n the other hand it is doubtful


    <
    , ,

    whether certain substances now regarded as elements cannot be


    divided by means already known .

    O n the insid e O f the back c over will be found a list O f the


    elements now known .

    A s may be seen fro m this list the m etal s are incl uded in the ,

    ele ments Together with them we n d a number O f other sub


    .

    stances as oxygen sul phur phosp horus et c that are cl assed under
    , , , ,
    .
    ,

    the ter m n o n
    m etal s or m eta l l oids TO the l atter class bel ong .
    ,

    many very imp ortant substances e g oxygen an element that ,


    . .
    , ,

    combines with al most all others caus ing what is called combustion ,
    .

    O xyge n is present in a large amount in the air A nother no n .

    metal is carbon which is present in all organi z ed substances and


    , ,

    is therefore a constituent O f every animal and plant Sulphur .


    ,

    which burns with a b lue ame giving O ff a pungent O dor and , ,

    chlorine a greenish ye l low gas O f very disagreeable O dor whic h


    ,
    -

    combines readily with most metals are also non metals ,


    -
    .

    The elements occur i n very unequal pr oport io n s in the pa rt of

    the ea rth accessible to us O xygen which occurs in air in water


    .
    , , ,

    and in the solid part of the earth s crust is very preponderant , ,

    com posing approximately 5 0% O f these p ortio ns O f the earth whic h


    have been investigated The elements silicon alum inium iro n
    .
    , , ,

    calcium carbon magnesium sodium potassium and hydrogen


    , , , , , ,

    together with oxygen make u p 9 9 % of the earth s crust There
    , .

    remains therefore o nly 1 % fo r all the other elements Some of


    , ,
    .

    these are quite commo n e g lithium but they almost alway s ,


    . .
    , ,

    O f t he i te ri r
    n o earth o n ly a ve ry sm al l p art is kn ow n I f w e th i n k
    of t he .

    O f t h e e art h a s ab o ut t h e s iz e O f an o ran ge t h e de e pe st mi n e sha ft s w o ul d


    -

    n o t e ve n pen e trat e t h e th i n ye l l o w e xte i o r l aye r O f t h e ora n ge ski n r .


    51 0 I N O R GA N I C C H E M I S TR Y . 9

    Som e substan ces give O ff o xygen when heated t ogether with


    o thers as in the following cases
    ,

    ( 3 ) Potassium dichr omate or manganese dioxide when heate d ,

    with sulphuric acid ;


    (4 ) Zinc oxide when heated in a current O f chlorine
    ,
    .

    The atmospheric air consists principally of oxygen and nitrogen .

    The following met hod for separating these gases was employed by
    L A V O I S I ER in 1 7 7 4 He introduced some mercury into a retort A
    .

    ( Fig 3 ) with a long doubly bent neck that o pened under a bell
    .
    ,
    -

    j ar P l led with air and resting in a dish R O f mercur y He then .

    F IG 3. .
    A B SO R PT I O N OF O X YGEN BY M ER C URY .

    heated the reto rt steadily for several days kee ping the me r cur y ,

    almost boiling A s a result a part O f the air in P disa ppeared


    .
    , ,

    and the gas remaining was found t o possess other pro per t ies than

    air it was nitrogen At the same time the mercury had been
    .

    p a r tially tra nsformed into a red p owder mercuric oxide O n ,


    .

    heating the latter more strongly oxygen was O btained .

    O xygen in now pre p ared fro m liquid air (cf .

    The physical prop erties O f oxygen besides t hose alrea d y men


    ,
    ,

    t ion e d are as foll ows : Its s pecic gr avity assu ming the density
    , ,

    O f air t o be 1 is ,
    A liter O f oxygen at 0 and 7 60 mm
    .

    Hg pressure weighs g O xygen can be li queed ; the


    .

    di fficulties in O btaining it on a large scale in t he l iquid state


    have n o w been c ompletely overc ome A pparatuses for li que .

    fyin g oxygen have been c onstructe d by HAM PS O N an d by


    L I N D E a descri pti on O f which is t o be foun d in text b o oks
    ,
    -

    O f p hysics . The critical te mperat ur e O f oxygen is


    and its critical pressure 50 at mos pheres Li qui d oxygen .
    O X Y G EN . 11

    has a Specic gravity O f (based on water ) a n d a


    b o il i ng point O f
    - .

    at mm pressure Its co l or is . .

    light blue It can b e preserved for some time at ordinary pres


    .

    sure wit h the aid O f a SO called v a c u u m f l a S k ( Fig


    ,
    -

    The latter is a vessel enclosed in nan air tight j acket the s pace b e -

    ,
    ~

    t ween the walls being evacuated 1 00 1 water at 0 dissolves . .


    1 oxygen
    . The gas is also somewhat soluble in alcohol
    .

    and in molten silver When the silver solidies .


    ,

    the oxygen a volume about ten times that O f

    the metal suddenly esca pes from solution caus ,

    ing peculiar elevations on the surface O f the Silve r



    s pitting of silver) .

    We remarked above 7 ) that the solubility of


    gases in liquids dimi n ishes with increasing t e m
    p e r at u re A very remarkable
    . l aw ex p resses the
    relatio n that exists between the solubility of a gas
    '

    and its pressure namely the s ol u bil ity is propor , ,

    tion a l to the p ressu re This is the l aw of HENR Y . .

    F IG 4
    . . VA C UU M Thus when the pressure becomes a fold the solu
    -

    ,
    -

    FL A S K b ilit y also beco mes a fold As the mass of a gas


    ' -
    .

    which is present in a certain volume is like wise pro portional to the


    ressure the law of HENR Y can also be ex pressed thus : Th e vo l u m e
    p ,

    of a gas diss ol vin g in a c er tain qu a ntity of a l iqu id is in dep en dent

    of th e p r essu r e .

    This law is rigid when the solubility O f the gas is s m all ; whe n
    the solubility is large for instance 1 00 volumes in l of the liquid
    , ,

    its deviations are co nsiderable .

    S till another formulatio n of this law is O f value in understanding


    certain of its a pplications : The concen tra tion s of the dissol ved a n d
    u ndiss ol ved po rtion s of a ga s bear a co n s ta n t ra tio to ea ch oth er By

    concentratio n is meant the quantity O f the gas in grams per


    unit volume ( cubic centimeter ) .

    IO A .
    mong the c h em ic a l r
    p po er ties O f oxygen the most promi
    nent is its vigorous suppo rt O f combustion The following are .

    interesting exam ples :


    C harcoal glows in air only moderately and without much evolu a

    tio n of light I n oxygen however it burns with a bright glow


    . , , .

    ul
    S p hur which burns
    ,
    in air with o nly a small ame burns in ,

    oxygen with an intense blue light Phos phorus burns in oxygen .


    12 I N O R GA N I C C HE M IS TR Y .
    l 10

    with a blind ing white light steel wat ch Sp ring that has been . A -

    heated t o redness at one end and pu t into oxygen burns with ,

    scintillation Zinc also burns in it with a dazzling light I n all


    . .

    these and analogous cases the oxygen as well as the burning mate ,

    r ial disappears during the combustion while new substances are


    , ,

    formed A lasting change therefore takes pl ace and we have t o


    .

    do with a chemical process The product O f bur ning charcoal is .

    found to be a gas that makes lime water cloudy and is u nable t o -

    suppo rt combustion ; it is called carbonic acid gas Sul phur a lso .

    yields a gas ; it has a pungent O dor and is called S ul p hur dioxide .

    Phos phorus produces a white o c c u l e n t p owder phos phorus pent ,

    oxide When iron burns a black cindery powder is formed


    .
    , ,

    called hammer scale because it com poses the sparks that y
    -

    from the anvil .

    The question now arises as to what really o ccurs in the above


    cases I n the rst place it has been found that the weight of the
    .
    ,

    p roduct O f combustion is greater than that O f the substance burned .

    The i n c rease i n we i ght O f the substan c e d uring b urni ng can i n m any


    c ases be easily dem onstrated For instan c e a horseshoe m agnet that has
    .
    ,

    been d i pped i n i ron li ngs m ay be hung on the l ower si de O f a s c a le pan -

    and balanced by we i ghts pu t i n the other pan The iron lings m ay be .

    burned by passi ng a non lumi no u s am e Under the m a few t imes O n


    -
    .

    c oo ling the s c ale pan atta c hed to the m agnet Si nks I n a Similar way one
    ,
    -
    .

    m ay de m onstrate the i n c rease O f we i ght i n the b u rn i ng O f c o pper In .

    order to pro ve the i n c rease O f we i ght i n a c ase where only gaseo u s produc ts
    are form ed a c andle m ay be b urned and the co mb ust i on produ cts
    , ,

    c arbon d i o xi de and water v apor c o llected by lett i ng the m pass o ver ,

    uns la ked lim e with whic h both un ite


    ,
    .

    C loser investigation has revealed the fact that the increase d


    weight is due to the presence O f oxygen as well as the burned ,

    substance in all combustio n products The latter are com pou n ds


    ,
    .

    of these substances with oxygen The partici patio n O f oxygen i n .

    the burning of zinc ,for exam ple may be proved by heating the ,

    combustion product zinc white in a tube and leading over it


    , ,

    chlorine gas whereby oxygen is driven O ff The com pounds O f


    , .

    o xygen are called o xi de s , and the act O f this combinatio n is known

    as o x i datio n .

    When substances burn in the air it is only the oxygen which ,

    c ombines with them N eve rtheless the nitrogen O f the air is heated
    .
    ,
    H Y DR O GEN .

    and thus takes a p art of the h eat evolved in the combustion .

    Therefore th e tem perature O f a b urning O b j ect cannot rise so high


    as in pure oxygen and since the emissio n of light increases very
    , ,

    ra pidly as the tem perature rises c o mbustions in oxygen are fo r


    ,

    this reaso n much brighter than in air .

    There are two general methods of asce rtaining what elements


    e xist in a com p ound .A ccording to the one method the com pound
    is decom posed and the elements com posing it thereupon deter
    mined This is the a n a lytic method A ccording to the other
    . .
    ,

    the s yn thetic method the com position is found by combining


    ,

    di fferent elements to form new substances I n the above described .


    -

    experiment 8 ) O f L AV O I S I ER the com p osition of the red p owder


    is learned by decom posing it at high temperature whereup on it ,

    se parates into o nly mercury and oxygen I nversely it was possible .

    to O btain the red powder by heating pure oxygen and pure mercury
    together at a lower temp erature The forme r is an exam ple of
    .

    a nalysis the latter O f synthes is


    , .

    HYDR O G EN .

    I I Hydr o gen is a colorless an d o d orless gas that is rarely


    .

    found on the earth in the free state The gases O f some volcanoes
    .

    contain it and it can also result from processes of decay I n .

    com bination with other elements howe v e r hydro gen is very


    , ,

    widely dist ri buted and occu rs in very large amounts


    Hydrogen can b e pre pare d in v ari ous ways I n the rst place .
    ,

    hydro gen com pounds can be broken u p .

    ( 1 ) Wate r containin g some dissol v ed ele ctrolyte is decom posed


    by the electri c current with the e v oluti on o f hyd rogen at the
    negative pole ( cathode ) .

    The ordinary methods O f pre paring hydrogen de pend on the


    indirect dec om position O f hydro gen c om pounds i e their reaction ,
    . .
    ,

    with ot he r substances The follo wing are exam ples o f this so rt :


    .

    2
    ( ) T he acti on of zinc on dilute sul phuric acid This
    is the c omm onest method .

    For t h e preparation O f hydrogen in the laboratory the apparatus


    Shown i n Fig 5 i s O ften used
    . A c onta i ns granul ated zin c ( or i ron nail s )
    .

    and B dilute hydrochl ori c ac i d or sul phu ri c acid When t h e Coc k C is .

    o pened the ac i d ows th rough D to the m etal and the evo l ution O f hy
    dro gen commences at O nce The cock being c l osed a gain the gas stil l
    .
    ,
    14 I N O R G AN I C C HE M I S TR Y M 11

    c ontinue s t o com e off an d forces bac k t he ac id. Th is is fac ilit at e d by



    changing the relative level s of A and B .

    (3 ) Th e ac t i on of
    z in c o r aluminium l
    in gs o n caustic p otas h
    o r Slaked lim e .

    ( ) Th e action of
    4
    s o d ium o r p otassium

    o n wat e r or alcohol .

    ( 5) M a g n e s i u m
    p o w d e r,
    wh e n b oile d
    with water ,als o

    e volv e s hydrog e n ,

    espe ciall y wh e n som e


    F IG 5
    chloride O f magne

    sium is dissolved in th e wat e r because such a solution dissolves


    ,

    the magnesium oxide which forms on the surface of the metal .

    L ikewise re d h ot i ro n d ec o mpos es wat er with t he li b e r a t io n o f


    ,
    -

    hydroge n ( c om par e
    I I 2. Th e physica l prope rties o f hy d rog e n ar e thes e : I t is t h e
    lightes t of all known su b stances its s p ecic gravity ( air = 1 )
    ,

    O n e lite r o f hy d rogen at 0 an d

    a mounting to only

    7 6 0 mm Hg pressure weighs
    . . g Its lightness renders it
    .

    u seful fo r inating balloo ns It is very har d to liquefy becaus e


    .
    ,

    i t s cri t ical t e m perature lies o nl y 3 0 3 2 ab ov e t h e ab solute zer o


    O n t h e othe r hand t h e critical pressur e is only 1 5


    ,

    at mos phe r es . L iqui d hy d rogen is c olorless It b oils at .

    I t s s pecic g r avi t y w ith r eferenc e t o water is o nly


    ,
    at its ,

    b oilingpoint an d at its freezingp oint b ei n g therefore ,

    c o nsi d era b ly less than that o f all o ther known l iquids D E W AR .

    further suc c e ede d in b ringing hy d rogen t o t h e s oli d state b y


    allowing t e liqui d t o e va p orat e q uickly a t
    h 3
    0 4 0 mm pressu re . .

    Th e melt ing p oin t of soli d hydr ogen is ab out 1 6 ( ab so l ut e t e m


    -

    p e r a t u re ) .The heat o f e va p o r ation o f li qui d hyd r ogen is v e ry


    high b eing 2 00 cal ; for this r eason a ask c ontaining liq uid
    ,
    .

    hydrogen so on becomes c overe d with a lay er of li qu i d ai r w hich ,

    d r o ps down an d soon pa rtially soli d ies .

    Hydrogen Is Sligh t ly s olu b l e in wa t er 1 00 1 wa t er d iss olving , .

    o f t h e gas a t Al coh o l t ake s u p s o m e wha t m ore .

    1 3. C hem ica l Pr oper ties Hydrogen does not unite with as


    .
    H Y D R O G EN .
    15

    it dis plays a strong tendency t o unite with oxygen burni n g with ,

    an almost c olorless and a very hot ame to form water This .

    ro
    p p ert y serves for the identication of hydrogen gas
    .

    the hydrogen is ignited


    The high te mperature of t he hydrogen ame is made use Of in
    fusing platinum quart z et c , ,
    .

    Suc h a am e is known as an o xyhydr ogen am e A n apparatus .

    ( oxyhydrogen bl owpipe) like that re presented i n Fig 6 i s re quired for .

    prod uci ng i t The hydro gen enters at W a n d passes o ut at a where i t i s


    .

    lit O xygen is bl own i nto the a me at S Th us the gases do not mix


    .
    .

    t ill they reach the ame and the poss ib ili ty of an e x pl os i on i s av o i ded
    , .

    F IG . 6 .
    O X Y H YDR O GEN B L O W P I P E .

    A mixture of hydrogen and oxygen es pecially in the pro po r tio n ,

    o f 2 vols . H and 1 vol O (detona ting gas ) when ignited turns


    .
    -

    , ,

    instant aneously to steam ; in other words it explodes This ex ,


    .

    im n t can however be p erfor med harmlessly by using a wide


    p e r e , ,

    mouthed cylinder of not too great dimensions A loud report is .

    heard in this case because the steam at the moment of its form a
    ,

    tio n o ccupies a much larger vol um e at the high temperature of th e


    combustio n than the mixture O f the original gases and as a resul t ,

    the air is suddenly ej ected with violence When the explosion .

    occu rs in a closed vessel no sound is heard ( cf e g Fig 1 3 p


    ,
    . . . .
    , .

    The tem perature to which deto nating gas must be heated to -

    explode is found to be about A t a lower tem perature com


    binatio n between hydrogen and o x gye n also takes place but not ,

    instantaneously as in ex plosions ; the lower the tem perature the


    , ,

    Slower the process When therefore no change in cold detonating


    .
    , ,

    g as is O bs erved even in th e c ourse of several years we mu s t attribute ,

    the fact to the extraordinary slo wness of the p ro cess at ordinary


    t em p eratures A Simple calculatio n will make this plain
    . .

    B O D EN S T E I N O bserved that when detonating gas is heated at ,


    -


    509 for 50 minutes of the whole is changed to water N O W
    , .

    it is a general rule that when the tem perature Sinks ,


    a chemi
    0
    n
    16 I N O R G A N I C C H E M I S TR Y .
    l 13

    take 1 00 minutes till the p art of the gas had formed water .

    A t the or dinary tem p erature say at it would be,


    minutes ,

    that is about years The same can be said of all chemi


    .

    cal reactio ns When we see that wood sul phur etc burn quickly
    .
    , ,
    .
    ,

    at higher tem peratures we must admit that oxidatio n takes


    ,

    place also at ordinary tem p eratures though so slowly that we


    .

    cannot perceive it M O I SS AN however succeeded in provi ng


    .
    , ,

    that charcoal at 1 00 and sulphur at ordinary tem peratures are


    o xidized very Slowly in a current of oxygen .

    Hydrogen is not o nly able to unite with free oxygen but it al so ,

    has the power to withdraw oxygen from many of its comp ounds .

    The actio n of hydroge n o n a com pound is called in general , ,

    re du c tio n This actio n is ofte n a very useful means of determi ning


    .

    whether a com pound co ntains oxygen Since the latter if present , , ,

    will usually unite with the hydrogen to form water C o pper oxide .

    may serve as an exam ple of the a pplicatio n of this method A .

    little is placed in a tube hydroge n is led over it and heat is then


    , ,

    a pplied ; one soo n sees the black oxide change to red co pper and ,

    water de p ositing i n dro ps o n the colder parts of the tube M any .

    o ther oxides can be similarly reduced e g iro n oxide lead oxide ,


    . .
    , ,

    et c .

    THE C O N SE R VA TI O N O F M A TTER .

    4 The
    1 .quantitative relationshi p s in oxidizing and reducing
    ro cesses such as have been discussed in 1 3 i e the relatio ns
    p , ,
    . .

    o f the masses of the substances partici pating in the changes may ,

    be used to elucidate a very im portant law A de ni te amount of .

    C o pper p owder for exam ple may be placed in a tube and the
    , ,

    weight of the tube with the p owder ascertained O xygen is then .

    led over the co pper at a high tem perature The a pparatus should .

    be SO arranged that the volume of the oxyge n which combines with


    the co pper can be measured When the oxidatio n process has .

    p r oceeded for some time the tube containing ,


    the oxidized co pp e r
    is allowed t o cool an d then weighed The weight is found to have .

    increased and the increase is j us t equal to the weigh t of the volum e


    ,

    of oxyge n used u p Thereupo n hydrogen is passed through t h e


    .

    tube with the co pper oxide and heat a pplied Here also arrange .

    ments should be made for measur ing the volume of hydroge n co n


    sum ed in reductio n The reduction is allowed to go o n until all t h e
    .

    co pper oxide is trans formed back to co pper When the tube and .

    p owde r are subsequently weighed they will be found to have re


    ,
    I N O R G A N I C C HE M I S TR Y .

    gen and ai r or oxyge n explodes wate r is forme d Being h ow


    ,
    .
    ,

    e ver a supporter of an erro neous theory


    ,
    he failed to realiz e
    the im portance of his discovery L AV O I S I ER in 1 7 83 re peated this
    .

    ex periment and comprehended it as a Synthesis of water as w e still ,

    d o to day -

    With the aid of the a pparatus picture d in Fig 7 this synthesi s .


    ,

    can be easily dem o nstrated Th e hydr oge n is generated in t h e


    .

    F IG 7 COM BU S T I O N
    . . OF HYDR O GEN .

    two necked (WOU LFF) bottle from zin c and sul phu ri c acid
    -

    In .

    order to free the gas from water va por it is passed th ro ugh t h e ,

    horizontal tube which cont ains chloride o f calcium or bits of


    ,


    pumic e s to ne so aked in sul p huric acid The dry gas is ignited and
    .
    ,

    as it burns water is gradually d e p osited on the walls of the bell j ar


    ,
    -

    A mi xt u re of hydrogen an d o x ygen u n i tes to for m Water when ill u


    m in at e d w i th ul tra vi o l et li ght .

    I n addition t o this direct synthesis fro m its elements there are


    other ways of O btaining water For exam ple many c omp ounds .

    such as t h e b lue crystals O f co pper vitriol gi ve O ff wate r whe n ,

    heated .

    The formatio n of water by the actio n of hydrogen o n oxyge n


    com pounds was illustrated 1 3 ) i n the reductio n of co pper oxide .

    O n the other hand it is also produced by the actio n of oxyge n o n


    ,

    certain hydrogen compounds This is seen for exam ple in the


    .
    , ,

    burning of alcohol .

    Finally water can result from the reaction of a hydrogen com


    ,

    pound with o ne of oxygen This is the case when ammo nia gas
    .

    l 1 1 ) iS led over hot co pp er oxide


    _
    .
    Th e syn thetic metho ds of p rep aring water such as the above ,
    n amed and many others
    possess however m erely theoretical
    , , ,

    imp ortance E ven when water is wanted in a perfectly pu re


    .

    state natural water is resorted to This contains solids and gases


    , .

    in solution which must be eliminated I t s puricatio n is aecom


    , .

    p l is h e d b y distillatio n A n apparatus well suited t o this pur pos e


    .

    I S shown in Fig . 8 High pressure steam and electricity are


    .

    often used for h eating instead of the ame .

    Water is placed
    in the ret ort A ,

    wh ich rests over the


    re place and b oil ,

    e d The dissolved
    .

    g a ses are rst driven


    o ff ; the hot steam

    fol l ows , p assing


    t hrough the dome B
    into the condensin g
    c oil C ,

    which is c o oled by
    water in the vessel
    D . The c ondensed
    water no w p ure
    , ,

    ows do wn int o the


    bottle ; the s ol i d F m 8 PUR I FI C A T I O N O F WA TER BY D I S TI L L T
    . .
    A IO N .

    subs t a n ces that


    we re d iss olv ed in t h e w ate r r em a in In the ret o rt The co ole r
    .

    D is su pplie d with c o l d water through a tu b e entering near ,

    the bottom while the heat e d an d th e refo r e s pe cically lighter


    , , ,

    wate r ows out nea r the t o p The steam thus meets with cooling
    .

    water of a lower te m perature as it passes down the w or m an d is in this ,

    way very com pletely condensed (princi ple of the counter current ) -
    .

    A s i ngle d i st ill at i on i s u s u a lly i ns u fci ent for t h e c o m plete e limi nat i on


    of a ll gaseo u s and so li d c onst i t uents Fo r thi s purpose t h e O perat i on
    .

    mu st be repeated i n an apparat u s of plat inum (t in is less sat isfac tory)


    wi th a c ondensing c o il of t h e sam e m etal an d only the mi ddle fra c t i on
    ,

    c o lle cted .

    A n e xc e llent c ri ter i on for the pu r i ty of water i s to be fo und in the


    m eas urement of i ts ele c tr ic al res istan ce Very pure water c onduc ts the
    .

    e le c tric current s c ar c e ly at all K O H L RAU S C H fo und the c onduc t iv i ty at


    .
    20 IN O R GAN I C C H EM I S TR Y . 1 5_

    18
    of the purest water o bta ina ble to be expressed i n
    re ci proca l O hm s ; by th i s i s m ea n t the c ond uc t ivi ty O f a body a c o lum n

    of wh i ch 1 c m l ong and 1 cm s qu are i n c ross s e c t i on has a res i stan c e


    . .
    -

    of 1 O hm The m agn i tu de of the re s i stan c e of s uc h water i s better n u


    .

    der st o o d by c o m par in g i t wi th res i stan c e of c o pper 1 c u mm of th i s . . .

    water has at 0 the sam e res i stanc e as a c o pper w ire of the sam e c ross

    se c t i on and 25 milli on miles l ong ; it c o ul d be str u ng aro und the earth s

    e qu ator one tho u sand t im es The sli ghtest tra ces of sal ts or even c on .

    tact wi th the atm osphere cause a m ar ket i ncrease i n i ts c ond u ct i vi ty .

    PHYSICAL PR O PER TIES .

    1 6 . Wate r at
    rdinary tem peratures is an o do rless tasteles s
    o ,

    liquid showing no color in thin layers O n looking through a layer


    ,
    .

    2 6 meters thick S PR I N G observed a pure dark blue color


    ,
    Th e -
    .

    t h er m om e t er s c al e of C E L S I U S is xed according to the physical


    ~

    co nstants of water its freezing point being called 0 and its boiling
    ,
    -

    p oint at 7 6 0 mm p ressure These. two p oints are de p enden t


    o n the pressure A n increase of pressure lowers the freezing point
    .
    -


    5 pe r atmos phere ) This is the reaso n why ice melts unde r
    .

    high pressure Water p ossesses the very uncommo n pro perty of


    .

    having a maximum of density (minimum of volume ) at a denit e


    tem perature The volume of almost all other substances increase s
    .

    with rising tem perature b ut here it diminishes u p to ,


    above
    which tem perature water ex pands as heating continues During .

    the t ransformation O f water to ice t h e volume increases co nsiderably .

    O n e vol water at 0 yields . vol ice O f t h e same tem perature



    .
    .

    The s pecic heat of water is greater than that O f a vas t maj ority
    o f other substances I t s latent heat of fusio n is 7 9
    . its latent
    heat Of vaporizatio n 5 3 6 C al Water is extensively used as a sol .

    vent N um erous substances dissolve in it to a greater or less degree


    .
    .

    There are many liquid substances that mix with water in all pro
    portions and many also which do not
    , ( Se
    , e , .

    Th e re m ar k ab l e phys ic al pro pert i es of water pl ay a very im portant


    r Ol e i n nat u re ; th i s s ub j e c t i s e x tens iv e l y d i s cu s sed in hys ic s m eteor
    p ,

    o l ogy an d geo l ogy


    ,
    .

    NA TUR A L WA TER .

    71Wate r as i
    .t o ccurs in nature is by no means chemicall y
    , ,

    p ur e It may
    . contain solid matter in sus p ensio n as well as sub
    stances either solid or gaseous in solution The purest natural
    , ,
    .

    water is r ain wa ter This has really passed through a natural


    -
    .
    N A T UR A L WA TE R . 21

    iz e d by the sun s he at and c ondensed againby co nt act with c ol d er


    po rtions of air whereupo n it falls in the form of rain N ev ert h e


    , .

    less it contains dust particles ( in large cities more of c o ur se than , ,

    in the country ) and gas es from the air as well as traces of amm o ,

    nium salts .

    Spr in g and w ll contain in parts about 1 2 0 pa rts


    e wa t ers -

    of so l id matter consisting largely O f lime salts Well water that con


    , .
    -

    tai ns much lime is called hard Well water also contains -

    some carbo nic acid and air i n solution both of which give i t it s ,

    refreshing taste ; distilled water tastes at .

    N at u ra l water i s u sed e x tens ive ly for dri nking purposes When it .

    co mes o u t of a so il that i s c ontami nated by de c ay i ng organi c m atter as is ,

    the c ase i n m any l arge ci t i es i t i s i nj ur i o u s to health pri n ci pall y on


    , ,

    a cc o unt of the presen c e of ba c teri a I t c an b e freed fro m these by


    .

    l trat i on th ro ug h a PA S T E UR C H A M B E R L AND por c e la i n l ter ( Fig


    -
    .

    Thi s c ons i sts essent i ally of a ho ll ow c yli nder of poro us por ce l ai n ( c alled
    a c andle A thro ugh who s e walls the water i s forced by its own pres
    ,

    s ure Th e l ower end of the candl e o pens i nto


    .

    the no zzl e .

    I n l arge ci t i es it has been found muc h m ore

    p ra c t ic ab l e to p ur ify the we ll or r iv er water at -

    the c entra l stat i on and to pi pe i t then c e to the


    vari o us ho u ses Epi de mi c di seases have really
    .

    decreased re m ar kab ly s in c e the i ntroduc t i on of


    the m ethods of m odern s an i tary s cien c e .

    A water which co ntains so many substances in


    s olutio n that it has a denite taste or a t h e r ap e u

    tic e ffect is called a m in era l water There are very .

    many kinds of mineral waters differing accord ,

    ing to the amount and kind of dissolved matter


    they co ntain We distinguish betwee n S a l i n e
    .

    w a t e r s containing commo n salt b i t t e r ,

    w a t e r S with magnesium salts S u l p h u ,

    r o u s w a t e r s with sulphur etted hydrogen ,

    c a r b o n a t e d w a t e r S with carbonic FI G 9 PA S T EUR . .

    acid c h a l y b e a t e w a t e r s with iron C H AMB ERLAND


    F I L T ER
    , ,

    and many othe rs Detailed analyses of the


    '

    mineral wate rs O f numerous watering places are accessible in -

    w ork s on balneology .

    Sea water co ntai ns ab o ut 3 % of salts of wh ich


    -
    is comm on ,
    22 I N O R GA N I C CHE M I S TR Y .
    17

    s al t
    . A large num b er of ele ments V iz about thi rty h av e b ee n
    ,
    .
    , ,

    found in sea water although the most of them exist there o nly I n
    -

    extremely small qua ntities .

    Itwas stated above 1 6) that pure water i s b lu e The co l or of the .

    ri vers l akes and seas vari es howev er thro u gh m any nu an c es fro m pure
    , , ,

    blue to bro wn Thi s vari at i on i s d ue pri n ci pally to the presen c e of m ore


    .

    or less bro wni sh ye ll o w hum o u s (m arshy) s ubstan ces or an e xtre m e ly


    '

    ne oat ing slim e B oth c ondi t i ons c an produc e a browni sh ye ll o w


    .

    c ol or It i s eas il y seen h o w the c o mb inat i on of blue and ye ll o w or brown


    '

    may bring about the var i ous b l ue green or brown tints in natural waters }
    ,

    C O M PO SI TIO N O F WA TER .

    I8 . was stated above that wate r can b e


    De c o m po s itio n It .

    obtained by direct combinatio n of hydrogen and oxygen ; inversely ,

    it can be decom posed into these same elements .

    In the as k A ( Fig 1 0) so m e water is heated t ill i t bo ils vi gorous ly A


    . .

    strong e le c tri c current is then sent thro ugh the wi re a c b so that the ne ,

    pl atin um w ire c gl ows intense ly Th i s heat


    '

    p artia ll y
    . de c o m pose s the

    F IG 1 0 D E COM P OS I T I O N
    . . OF WA T ER BY G L O W ING PL A TI NUM .

    water vapor i nto hydrogen and o xygen whi c h pass out through the t ube ,

    d and are c o ll e c te d in the c y li nder C Thi s gas m i x t ure i s noth i ng but t h e


    .

    e xpl osive mixt ure 1 3 ) of hydrogen and o xygen as c an be e asil y pro ved ,

    by applyi ng a am e .
    CO M PO SI TI O N OF WA TE R . 23

    M any m etals decomp ose water o n co ntact , the hydrogen b eing


    set free and the metal uniting with the oxygen Potassium and .

    s odi u m e ffec t t h is decom p ositio n at ordinary tem peratures

    ir on zinc and other metals re q u 1r e a higher temperature ir on


    , , ,

    e g . acting at red heat


    .
    ,
    .

    19 L et us now study the quantitative com p osition of wate r


    .
    ,

    i e determine the relative amounts of hydroge n and oxygen present


    . . .

    For this purp ose both the analytic and Synthetic methods can b e
    us ed .

    ( )
    a T h e A na l ytic M et h od When an electric current is p asse.d
    through water to which has been added a little sul phuric acid t h e ,

    water is decom p osed I f t h e gases evolved at the electrodes are


    .

    collected se parately it is found that for every 1 vol oxygen 2 vols


    ,
    . .

    hydrogen are give n O ff A suitable a pparatus for this ex periment .

    is shown in Fig 1 1 . .

    Since 1 liter O f hydrogen weighs g and 1 liter oxyge n .

    weighs g both a t 0 and 7 6.0 mm


    ,

    .

    p ressure the weights of,


    2 vols hydrogen .

    an d 1 vol oxyge n must bear to each


    .

    o t her the ratio of or


    1
    ( )
    b Th e S yn th etic M eth od As early .

    as 1 82 0 the reductio n of co pper oxide by


    hydrogen was em ployed for this purp ose
    by BE R ZE L I U s ; in 1 83 4 also by DUMA S , ,

    and ST A S A weighed amount of care .

    ful ly dried co pper oxide is heated in a


    cur rent of hydrogen and water is formed ,

    which is collected and weighed The .

    weight of the oxyge n given u p by the


    c o pper oxide is found from the difference

    b etween the weight of the co pper oxide


    u sed and that of the resulting co pper .

    The weight of the hydrogen co ntained


    in the water collected is therefore eq u al
    130 the di fference in weight O f water and F IG 1 1 E L E C T R O L Y S I S . .

    O F W AT E R
    o xygen
    .

    The apparatus used for this experiment is represented in Fig 1 2 . .

    I n A the hydrogen is generated from zinc and dilute sulphuri c


    24 IN O RGA N I C CHEM IS TR Y . 19

    ci d I t is then pas se d through the permanganat e solutio n in t h e


    '

    a .

    wash b o t tle B t o free it from imp urities and also through the U
    -

    tubes C D and E containing calcium chloride sul phuric acid and


    , , ,

    p hos p horu s p entoxide res p ectively for drying it


    ,
    I n F is placed ,
    .

    t h e co pper oxide which is carefully weighed together with the tube


    ,
    .

    The water that forms is condensed in G the U tube H being


    ,

    attached t o absorb any esca ping wate r va p o r At the com pletio n .

    o f t h e ex periment F with its contents is again weighed likewis e


    , , , ,

    G an d H ; the di fferences in weigh t indicat e the am ount of

    FI G . 1 2 SYN
    . TH E S I S OF W A T ER A FT ER D U M A S

    formed . and STA S found in this way that 1 00 parts (by


    D UMA S
    weight ) of water consist O f p arts of hydrogen and
    p arts of oxygen or in other ,
    words ,
    that the mass ratio of thes
    ,
    e -

    elements is 9 80 a relatio n which agr ees with that oh


    .
    ,

    t ain e d in (a ) within t h e range of the unavoidable ex perimental


    err or .

    A nother Synthetic method which is es pecially a d a pted to t h e


    ,

    lecture table co n sists in mixing hydrogen and oxygen and deter


    -

    mining in what volume rati o these gases unite -


    For this pu r .

    p o se an a pp aratus ( Fig 1 3 ) described by HO F


    .MANN is bes t em
    p loyed .

    Hydrogen and oxygen in di fferent pro po rtions by v olum e are


    in troduced int o t h e arm of t h e U tube which can b e close d by -

    ,
    6 I N O R GA N I C C HE M I S TR Y . 20
    ~

    Under the same press u re water always has the same meltin g poin t -

    and the same boiling point in whatsoever way it may have been
    -

    O btained ; sal t always cr stalli z es in the same crystal system ; soda


    y ,

    at a de nite temperature always requires the same amount of water


    ,

    for so l ution etc , .

    When elements or compounds are brought together without any


    chemical action on each other taking plac e we have a m ixtu r e of ,

    these elements or com pounds The number of possible mixtures is .


    ,

    o f c ourse unlimited
    ,
    They are distinguished from com pounds by
    .

    the following characteristics :


    I n a mixture the pro perties of the com ponents rea ppear in many
    and important res pects G un powder for exam ple is a mixture of
    .
    , ,

    s ul phur charcoal and salt petre


    , The latter is soluble in water ; .

    s u l phur dissolves in carbon disul phide ; charcoal is insoluble in both .

    These pro perties are still evident in the constituents of gun powder .

    In a m ixture of sul phur and iron lings one can detect with a micro
    s co p e the yellow grains of s ul phur a n d the black p articles of iron ~
    .

    The iron can be drawn out with a magnet ; the sul phur dissolved
    o u t by c arbon disul phide If however a mixture of 7 p arts iron
    .
    , ,

    a n d 4 p arts sul phur is heated a glow pa s ses through the powder ,

    a d a com pound of both


    n
    iron sul phid e is fo rmed whose pro p ,

    e r t ie s are entirely di fferent from those of its elements I t is non .

    magnetic and insoluble in carbon disul phide and under the micro
    s co p e only a homogeneous scoriaceous mass is seen The constituents .

    o f a mixture sinc e they st il l preserve t heir pr o p erties can often be


    , ,

    separated from each other by m echan ica l m ean s e g by the use of ,


    . .

    microsco pe and tweezers by siftin g by treatment with solvents by


    , , ,

    washing etc
    ,
    .

    I n a mixture the ratio of the constituents can vary in all pr o

    p ortions. There are for exam ple many sorts of gun powder dis
    , , ,

    t in g u ish e d from each other by the pro portions in which their con
    s t it u e n t s are mixed When 1 p art sul phur and 1 00 parts iron or
    .
    , ,

    o n the other hand 1 part iron and 1 00 parts s ul phur are mixed we
    , , ,

    have in either case a mixture of both elements p ossessing hardly ,

    the same but at least analogous pro perties


    , ,
    .

    M oreover a mixture often has no constant physical pro perties


    , .

    Water has a constant boiling point ; the boiling point of a mixture - -

    o f ben z ene and tur p entine however rises gradually as the more
    , ,

    volatile com ponent benzene distils O ff


    ,
    The melting point of
    ,
    .
    -
    CO M P O S I T I O N O F C O M PO UN O S A TO M I C THE O R Y . . 27

    sul ph u r is constant and can be accurately determined ; that of a


    mixture of tin and lead d iffers according to the pro portion of t h e
    elements and is in many pro portions no t at all sharp there being ,

    only a softening instead of real fusion .

    In the e xam pl es ci ted here the dist i n c t i on between a co m pound an d a


    m ix t ur e i s we ll m ar ked There are however other i nstan c es where this is
    .
    , ,

    not the c ase and where i t i s therefore very difc ul t to know whether one
    is deali ng with a c o m po und or a mix t ure We Shall m eet wi th m any .

    e xam ples of thi s l ater There i s however on e way whereby a co m po u nd


    .
    , ,

    c an be dist i nguished fro m a mix t ure viz by ascertai ni ng whether or n ot


    ,
    .

    the s ubstan c e pre pared i n different ways has a c onstant co m posit i on


    , , .

    PHE N O M E N A AC C O M PA N Y I N G THE F O R MA TI O N OR
    D EC O M PO SITI O N O F A C O M PO UN D .

    The most common phenomenon of this sort is an elevation o r


    d e pression of tem perature i e an evolution or absorption of hea t
    ,
    . .

    ( caloric e ffect ) Sometimes


    . the r ise of tem p erature is so great tha t
    l ight is produced A decom position or a combination can be so
    .

    violent that it causes an ex plosion I n other instances electricity .

    may be produced by chemical action Al l these facts may be com .

    rised in this statement : C hem ica l action r es u l ts in a cha nge in the


    p
    energy su ppl y o
    -

    f th e r ea cting s u bs tan c es .

    EXP LAN ATI O N O F THE C O N STAN T C O MP O S ITI O N OF


    O
    C M P O UN S AT O M I C T H EO R Y
    D .

    2 1 It was stated that constant com position is the distinctiv e


    .

    characteris tic of a chemical com pound The pro portions in which .

    elements unite to form a certain com pound are always the same .

    This L aw of C o n stan t C o m po s itio n ( denite pro portions ) was


    nally established by P RO U S T in the beginn ing of the nineteenth
    century and at about the same time DA LT O N o ffered an e Xpl a
    '

    nation of it which is still acce pted and may b e considered as t h e


    foun dation of theoretical chemistry .

    This ex planation involves a hy pothesis as to the constitutio n


    of matter I t is p ossible to reg ard matter as innitely divisible ;
    .

    according to human conce ption the smallest particle that can really
    b e O bta ined is still ca pable of division into an innite number o f
    o thers However
    .
    even the ancients,
    were of the O i
    p nion that there
    28 I N O R GA N I C C HE M I S TR Y .
    m 21
    must be somewhere a l imi t to the divisibil ity and that we must
    n ally arrive at particles incapable of fu r ther div ision the ato m s .

    ,
    .

    Inthe fth c entur y B C there e xi sted a s c hoo l O f ph il oso phy that


    .
    ,

    of the E l eatics (so ca lled fro m the ci ty of E L EA) whose m ost pro mi nent ,

    re presentat i ve was PAR M ENI DE S He ta u ght that e verything that


    .

    exists c annot be otherwi se con ce ived than as un c hangeab le ; trans


    form at i on o f the exi stent whi c h was tho u ght to have ne ver ori gi nated
    ,

    and to be at the sam e t im e un al terable was he l d by the m to be in co n ,

    ce iv ab l e These theses they regarded i n a c erta i n sense as axi o m s


    .
    ,

    i e state m ents of tr u ths wh ic h are ac c e pted wi tho u t proof


    . . Da ily .

    e xperi en c e tea c hes one neverthe less that trans form at i on does o cc ur i n
    that whic h e xi sts a fa c t that l e d the m to suppose that everyth i ng
    ,

    O bser v ed by m en i s m ere l y a ppearance .

    Three theories were pro posed i n the sa m e century wh ic h a im to


    form a bri dge between the do c tr i ne of the unal terable e xi stent and the
    e x peri enc e that po i nts toward c ont i nu o us c hange These theor ies .

    ori gi nated w i th E M PE D OC L E S A NA X A G O RA S and the A tomis ts L E U C I PPU S


    , , ,

    a n d DE M O C R I T E S The imm utabili ty of the e xi stent i s d i s posed of by


    .

    as cr i bi ng i t to e xtre m e ly s mall un c hangeabl e and i ndestr uc t i ble part icles ;


    e very c hange i s tho u ght to de pend on the m ove ment of these s ma llest
    integral part icles toward or away fro m ea c h other E M PE D O C LES and .

    A NA X A G O RA S ass um e in thi s c onne c t i on an i n n i te d ivis i b ili ty ; the


    A to mi sts on the c ontrary regard the worl d as b uil t u p of i nd ivi s i b l e
    , ,

    part icl es ato m s a ll of wh ic h c ons i st of the sa m e pr im ord i a l s ubstan c e


    , ,

    but d i ffer i n for m and s iz e .

    N ow DA L T ON
    has used th is conce ption of the ancients regarding
    the atom to explain the fac t that the combin ing weights are c on
    stant The atoms of the various elements he assumes have dif
    .
    , ,

    fer e n t weights ; the atoms of the s am e element are alike in weight .

    A com pound of two elements is therefore produced by the associa


    tion of atoms of these elements Such a combination of two or .

    more atoms is called a m ole c u l e I t is O bvious that these supposi


    .

    tions lead directly to the l aw of con stan t proportion s; for if co pper ,

    oxide is formed by an atom of co pper uniting with an atom of


    oxygen to make a molecule of co pper oxide its com position must , ,

    according to the above hypothesis be constan t ,


    .

    DA LT O N deduced another co n clusio n from his hy pothesis and ,

    conrmed the same ex perimentally He O bserved that oxygen .

    u nites not onl y with on e very denite amount of nitrogen oxide ,

    but also with twice as much not howe v er with any intermediate
    , , ,
    TH E A TO M I C WEI G H TS O F THE E L EM EN TS . 29

    amount He also Showe d b y t h e investigation of ma rsh gas an d


    . -

    O l e a nt gas both of which are m ad e u of o nly carbo n and hydro


    ,
    p
    gen that the former co nt ains twice as much hydrogen to a certain
    ,

    weight of carbo n as the latte r It is readily seen how such O bserva


    .

    tions can be explained on the basis of the atomic theory ; in one


    c ase 1 atom of carbon is in combinati o n with n atoms of hydrogen
    ;
    in the other with 2 n atoms The observations of DA LT O N were
    .

    s ubsequently conrmed and extended es pecially by B ER ZE L I US


    , .

    The foll owing statement is therefore now acce pted as a law : When
    t wo el em en ts com bin e to form m or e tha n on e com pou nd the differ ent ,

    weights of the on e el em ent which u n it e with on e and the s am e w eight


    o f the oth er el em en t bea r a sim l e ra tio t o each other This is t he
    p .

    L aw of M u lti pl e Pr o po rt io n s .

    THE A TO M I C WE I G HTS O F THE E LE M E N TS .

    22 The absol ute weight of the at o ms is only approxi mately


    .

    kn o wn (see N eve rt heless t heir r el ativ e weights i e t he


    , ,
    . .
    ,

    w eights of the a t o ms of the various elements when that of a ,

    c erta in elemen t is a r bi tr a ril y xed have b een d eter min e d in a


    ,

    variety of ways 2 08 These rel ative wei ght s are known


    as ato m i c w e i gh ts .

    It is now c ust omary t o t ake the at omic weight of oxygen as


    The at omic weights of the remai ning elem ents then have
    t h e val ues that are given in the t able on the inside of the back
    c over of this volume The acce ptance O f 1 6 as the at o mic weight
    . .

    of oxygen has a hist ori c reason For a l ong time hydr ogen was .

    t aken t o be 1 ; it was believed that the ratio of the at omic weights


    o f hydrogen and oxygen was Inasmuch as the at o mi c weights
    o f most elements are deter m ine d fro m t he c om p osition of their oxy

    gen c omp oun ds the b asis is reall y 0 1 6 and n ot lH 1 This ma d e


    ,
    .

    n o diff erence s o l ong as the pro p o rtion


    ,
    was c on .

    s ide r e d ac curate Even when the rati o was late r fo un d t o be


    .

    a di fferent one (ac c or di ng t o investigati ons of M O R L E Y an d of


    W A N O Y E S the rati o
    . . may now be regar d e d as very
    a c cur ately determined ) it was still the simplest pl an t o preserve
    ,

    O = 1 6 as the b asis since a change woul d necessitate a c om plete


    ,

    r e cal cul ation of all the at omi c weights and t his necessity woul d ,
    o I N O RG A N I C
    _ _ C HE M I S TR Y .
    22;

    mo reove r recur as often as a new re nement of metho d s of in v es


    t ig at ion brought ab out a change in the rati o H zO .

    A few ye a r s ago there was established a permanent inter


    '

    n ational c ommission whose d uty it shoul d be t o revise the tabl e

    as the

    of at omic weights criticall y every year Those v al ues are acce pted
    international at o mi c weights which appear t o be t h e
    .

    most prob able among the determinations that have been pu b


    l is h e d The at o mic weigh t s in the t able are carried out t o as
    .

    many decimal places as may be ac ce pte d wit h cert ainty For .

    many p urp oses however it is sufficient t o use roun d n umb e r s


    , , ,

    such as N = 1 4 Br = 80 et c , ,
    .

    B es i des the atom i c we i ghts we q ui te fre quentl y use equ ivalen t ,

    w eights These are the wei ghts of the e l em ents wh ic h c o mb i ne wi th a


    .

    uni t a m o unt of a c erta in standard el em ent O n e part of hydrogen .

    co mb ines for i nstan c e wi th


    , parts of c hl or i ne and w i th 8 parts of
    ,

    O xygen These a m o unts of hydrogen c hl ori ne and oxygen are e quiv


    .
    ,

    al e n t to ea c h other The ato m i c we i ght is e i ther e qual to the equivalent


    .

    Wei ght or a m ul tipl e of i t .

    C HEM I C A L SYM B O L S A N D FO R MULZE .

    The rel ati ve or at omic weights are expresse d by symb ols


    23 .
    , , ,

    t hat were introduce d b y B E R ZE L I U S an d are O f great c onvenienc e


    in the re presentati on of c omp ounds an d the formul ation of
    c he mi cal reacti ons The symb ols whose derivati on is not at
    .

    o n ce app arent are t aken fro m the L atin names of the elements ;
    e g
    . . Sb fro m s tibiu m A u from au ru m C u fro m cu pr u m Hg fro m
    , , , ,

    h ydr argyr u m Pb from pl u m bu m Sn from s tann u m Fe fr om


    , , ,

    rr u m and A g from a rg en tu m
    f e ,
    .

    A s y m b o l stands not only for the element c o nce rn e d ,

    b ut also for the relative weight of an atom of that element If .

    the atomic weight of co pper is an d that of oxy gen


    the symb ol C u indicates p arts by weight of C o pp er t h e ,

    symbol O p arts by weight of oxygen It has been d eter .

    mine d that in c o pper oxide one atom of co pper is comb ine d with
    one atom of oxygen ; co pp e r oxid e is therefore re presente d by
    the f o r m u l a C u O which expresses rst that we are d ealin g
    , , ,

    with a c omp oun d o f C o pper and oxygen an d secon d that 1 atom , , ,

    p a r ts by weight ) of co pp er is unite d in it t o 1 atom


    24 ] S TO I C H I O M E TR I C A L C A L C UL A TI O N S . 31

    a rt s b y we i ght ) of ox ygen M any com ounds c ontain several


    p p .

    ato ms of the same element This is indicated by placin g t h e .

    r
    p p o e r gure to the right of an d b elow the Symbol Sul p huric .

    aci d for exam ple c ontains 2 at o ms of hy d rogen (H ) 1 ato m of


    , , ,

    sul phur (S) an d 4 atoms of o xygen ( 0 ) in the molec ul e Its .

    formul a is therefore H 2 S O 4
    , , .

    C hemical actions c an b e very sim ply r e presented by the use of


    these formul a ; thus the dec omp osition of mercuric oxid e into
    ,

    o xy gen an d m ercu ry by

    Hg O Hg 0;

    tha t o f po tass i um chlorate into oxygen an d p otassium c h loride b y

    K010 3 KC l so ;
    Po t a s s . ch l or a t e . Po t a s s . d
    ch lo r i e.

    t h e generation of hydrogen fro m z inc an d sul phur ic ac id by

    Zn + H2 80 4 2H 2 11 8 0 4 .

    In such e q u a t i O n S t h e sa me atoms an d the same num b e r of


    each must appear on b o th sides in acc ordance with the prin cipl e ,

    o f the I n d estructib ili t y of Matter .

    S TO I C H I OM ETR I C A L CAL C ULATI O N S .

    If the formul a of the com pounds are the m e a ns of known


    24 .


    as certaining these will be discussed in d etail later and the atomic
    weights of the elements com p osing them also known it is very easy ,

    to calculate the weights tha t enter into reactio n in all chemical


    changes A couple of exam ples may serve to make this clear
    .
    .

    1 It is r equired to know h ow m a n y l iter s of oxygen a t 0 a nd



    .

    7 6 0 m m pr es su r e can be obta in ed by h ea tin g 1 kil ogram of m ercu ric


    .

    The atomic weight of mercury is 200, tha t of oxygen is 16 ;


    mercuric oxide HgO is therefore
    , , , ,
    O u t of these 2 16
    rts by weight of mercuric oxide 16 O b
    pa .
    p arts of oxygen can be
    32 I N O R GA N I C C HE M IS TR Y .
    M

    t aine d b y heat ing ,


    ie . . fr om 1 kilo g ) can be obtained
    .

    1 000 16
    ? g Since 1 1 xygen
    . . o at 0 and 7 60 mm .
    pressure
    21

    weighs g .
    ,
    g . o ccupy a volume of
    2 How mu ch water can be for m ed fr om the hydr ogen O bta ined
    .

    by the in teraction of 1 kg zinc and the c or r es pon din g am ou n t of


    .

    su l phu r ic a cid?

    Th ereactio n of zinc and sul phuric acid is e xpresse d by t h e


    e quation
    Zn H2 8 0 4 Zn SO 4 2H

    an d t h e C om b ustion o f hydrogen to form water b y the equation


    2H O H20 .

    From these equatio n s it follows that the hy d rogen forme d b y


    t h e a ction O f 1 a tom of zin c yields 1 molecule of water For every .

    atom of zinc we obtain therefore 1 molecul e of wate r ,


    The atomic , .

    weight of zinc is 6 5 the molecular weight of water 1 8 ; therefore


    ,

    6 5 parts of zinc corres pond to 1 8 p arts of water 1 kg zinc must . .

    yield g .

    65
    3 . How ma ny gr am s o f p o ta ss iu m chl orat e ar e n eces s ary to pro
    du c e en ou gh oxygen to oxidiz e 5 00 g . copper to c opper oxide

    The reactions concerned are


    KC l O 3 HC 1 + 3 0 an d Cu O Cu O .

    Henc e 3 atoms of co pper can be oxidized with the o xygen


    d erived from 1 molecule of potassium chlorate For every 3 atoms .

    of C o pper 1 molecule of potassium chlorate must be consumed .

    The molec ul ar weight of the latter substance is


    the atomic weight of c o pper is for every
    1 22 5 6
    = 4 0 85 g otassium c hl orate are
    p arts of co pp er
    .
    p

    therefore required
    g potassium chlorate
    .
    . Hence
    .
    500 g c o pp er require
    .

    W :

    In most chemical c om putations gram m ol ecu l es are em ploye d ,

    these bein g the molecular weights of the substances in gr ams .

    The abbreviation m ol e has been suggested by OS TW A LD for this


    34 IN O R G A N I C C HE M I S TR Y .
    25

    4 . The oxygen of the air c an also serve as the O x i di z ing agent

    2 HC 1 + O E 2 0 + C 12 .

    For this purp ose a mixture of 60% of air and 4 0% of hydroge n


    chloride at ab out 4 3 0 is p assed over p orous bricks which are

    soaked with c o pp er sul phate s olution A bout 7 0% of the hydro .

    gen c hl ori d e is converted into chlor in e This metho d which is .


    ,

    known as the D eacon pr o c es s is use d c omme r cially Th e c opper


    , .

    sul p hate serves as a catalyze r .

    The progress of che m ical chan ges is o ften modie d b y t h e


    mere presence of a subst ance w hi ch has the same chemi cal c o m
    p osition after the reaction as at the begin n ing S uch a substanc e .

    is terme d a ca tal yz er and the action which it exerts is calle d


    Ca ta l ysis or ca tal ytic a ction The quantity of the catalyze r
    ,
    .

    necessary t o exert a perce ptible inuence is O ften very small .

    This is the c ase for exam ple in the c ombination of hy d rogen an d


    , ,

    oxygen in the presence of pl atinum as a c at alyzer 13 p ,


    .

    A minute trace of p lati num s p onge brought int o c ontact wit h


    det onating gas ac celerates the c ombinatio n t o such a rate that
    -

    the reaction t akes place very quickl y an d can even b ec om e


    expl osive In the D EA C O N pro cess a small quantity of c o ppe r
    .

    sul phate su ffices t o bring int o reacti on unlimited quantities of


    hydrogen chl oride and oxygen At the tem perat ur e of
    .

    there is p racti cally no reaction b etween oxygen an d hydr oge n


    c hl oride without the catalyzer That t here must nevertheless
    .
    , ,

    be a reaction al though a very sl ow on e can b e d emonstrate d


    , ,

    by t he same reasoning as in 13 The cat alyzer therefor e .

    d oes not c ause a reaction b ut o nl y ac celerates it


    ,
    OS TW A LD .

    c omp ares its action t o that of O il on the axles of a machin e


    whi ch move with very gr eat friction When oile d t he ma .
    ,

    c hin e will go much faster notwithstan d ing that the force of


    ,

    the spring (here the energy of the che mical reaction ) has no t
    chan ge d A furt her p oint in the anal ogy is t hat the oil is n ot
    .

    c onsume d .

    In m o st c ases of c at alysis it c an b e prove d that t h e c atalyz er


    takes p art in the reacti on but at t h e en d of it reapp ears i n it s
    original condition In the pl atinum catalysis o f d e t onat in g gas,
    .
    -
    C HL O R I N E .
    35

    for exam ple the m et al uni t es w ith the oxygen whereu p on the
    , ,

    resulting c om p ound reacts with the hydrogen giving water and ,

    metallic platinum The phenomenon of c at al ys I S i s u n 1 v e rs al


    .
    .

    OS T W A L D thinks it prob able that there is no k ind of chemical


    .

    reactio n that cannot b e inuenced catalytically and that there


    is no substance elemen t or com p ound which cannot ac t as a
    , , ,

    catalyzer .

    C a t alyz ers may ac celerate or retard reactio ns ; at presen t ,

    however much m o re is k no wn of the rst than of t he second


    ,

    kind .

    2 6 Physic l
    . a P r op er t ies C hlorine is yellowish
    .
    green ( hence its
    name which is derived from x71
    , greenish yellow ) and has -

    a disagreeable odor I t s Specic gravity is . taking air as


    unity or ,
    based o n O = 1 6 1 l chlorine weighs therefore . .
    , ,

    g at 0 and 76 0 mm
    ressure At 3 4 it becomes liqui d

    .
    p . .

    under ordinary pressure ; at 1 02 it solidies a nd crystallizes


    I t s critical tem perature is L iquid and solid chlorine ar e


    yellow C hlorine gas dissolves in about o ne half its volume of
    .
    -


    water ; The aqueous solutio n bears the name chlorine water

    -
    .

    It can therefore not be collected over water but a saturated salt


    , , ,

    solut io n may be used in which it is o nly slightly soluble The most


    , .

    convenient way to ll a vessel with it is by dis placement O f air t h e ,

    gas being conducted to the bottom where it remains and drives out ,

    the air above because the chlorine is denser


    ,
    .

    27 C h em ica P p i s
    . l ro er t e E ven at ordinary temperatures chlo ,

    rine combines with many elements and acts o n many com p ounds .

    I f perfectly pu re chlorine is mixed with an equal volume O f hydro


    gen the two unite in direct sunlight causing an explosion I f the
    , ,
    .

    chlorine is im pure or the sunlight diffused combination occurs ,

    slowly Whe n a hydrogen ame is intr o duced into chlorine gas it


    .
    ,

    continues to b u r n with t h e formatio n of hydrogen chloride M any


    ,
    .

    metals combine with chlorine with the evolution of light e g c op ,


    . .

    p e r ( in the form of imitation gold leaf ) nely p owdered antimony-

    , ,

    m olten sodium etc The pre cio us met als are in general quite
    ,
    .

    resistive to chemical action They are h owever attacked .


    , ,

    b y chlorine and ch anged t o chlorides i e chlorine c om p ounds ,


    . .
    , .

    G old for inst an ce d issolves in chl orine water forming gol d


    , ,
    -

    c hlori d e .
    36 IN O R GA N I C C H E M I S TR Y .
    l 27

    C ohl r ine a l s o u ni tes readily with many no n metal s e g ph os , . .

    p h o r u,
    s which burns in it with a p ale ame to phos p ho ru s

    chloride .

    The tendency o f ch lorine t o unite with hydrogen its s o called -

    chem ica l
    or t y for the latter is so strong that
    f
    a ttr a cti no
    ,
    a n it ,

    chlorine abstracts the hydrogen from many hydrogen co m p ounds in


    o rder to combine with it . A stri p of p ap er di pp ed in turpentine
    burns with a sooty ame when introduced into an atmos phere of
    chlorine ; the chlorine unites with the hydrogen of the turpentine
    and sets the carbo n free A burning candle continues to burn in
    .

    chlorine de positing soot ( carbo n) and forming hydrogen chloride


    ,
    .

    If sul phur etted hydrogen gas HzS is p assed into chlorine wate r
    , ,
    -

    hydrochloric acid and sul phur are formed .

    Wate r is also decom posed by chlorine oxyge n being lib e rated ,

    2H2 0 2C 12 = 4 HC l 02 .

    This reac t ion takes plac e under the inuence of sunlight b u t ,

    p ro ceeds very Slowly I t c


    . an b e c onveniently d emonstrated as i n
    Fig 1 4
    . . A retort is lled with dilute chlorine water inverted -

    a n d ex p o sed to the sunlight A fter a few days a bubbl e of gas


    .

    c ollects at t h e t op o f t h e r e t or t an d o n investigation wi t h a
    , .

    glowing s plinter it is found to b e oxygen


    ,
    .

    FIG 1 4 SL O W D E COM P OS I T I O N
    . .
    -
    OF W AT ER f
    BY CH LO RIN E .

    Upon this deco m position of water de pends the bl eachin g and dis infect
    in g ac tion of c hl ori ne and t hose s ubstan c es whic h generate c h l or i ne In .

    blea c hi ng t h e c o l or i ng m
    ,
    u s u ally of an organi c nat ure are ox i
    atters

    di z ed by o xygen to c o l orl ess s ubstan c es Ba c teri a are kill ed by o xi da


    .

    tion O rdi nary at m ospheric o xygen does not produc e these e ffects Lit
    . .

    m us for instance whic h i s rapi d ly de c o l oriz ed in m oist chl ori ne gas is


    , , ,
    H YD R O G E N C HL O RI DE . 37

    totally unaffe c ted by the a i r The particul arl y energet ic a c t i on of the.

    o xygen that i s prod uc ed fro m water by c hl ori ne i s e x pl ai ned by assumi ng


    that i t e xi sts in an ato mic c ondi t i on the s t at u s n asc en s regardi ng whic h , ,

    m ore wi ll be sa i d l ater Perfe c t l y dry c hl or i ne has no b lea c hing


    p ower .

    I f water i s sat urated w ith c hl or i ne at c rystal s are depos ited of the ,

    c o m pos i t i on C l 2 + 8H2 0 c h l or i n e h y drat e A t a h i gher te m perature these


    ,
    .

    are whol ly deco m posed i nto c hl ori ne and water .

    HYDR O G E N C HLO R I DE, HC l , and HY DR O C HLO R IC A C I D .

    2 Hydrochlori c ac i d of the formula HC l


    8 . is a gas
    , ,

    o ccurring in nature in the free state e g in the gases of some ,


    . .

    volcanoes I t forms an im portant although small part of the


    .
    , ,

    gastric j uice of man and other a nimals .

    So me of i t s m ethods Offor m a tion have been already given


    e g
    . .b y d ir ect synthesis fr om its el e m en t s u n de r the inuence of
    ,
    '

    light It is quite remarka b le however that ultraviolet rays


    .
    , ,

    dec om pose hyd r ogen chl oride even at ordinary temperatures .

    We saw also (l c ) that hy drogen chloride is formed by the


    . .

    action of chl orine on hy d rogen c om p ounds M oreover it can .


    ,

    also res ul t fr o m the action of hydrogen on some chlorine com


    p o un d s e g s ilver chlori
    ,
    d e. A.
    g C,
    l an d lead chloride Pb C l z , , , ,

    when hea t ed in a current of hy d rogen yiel d me t al an d hy d ro ,

    chlo r ic aci d

    A gC l + H = A g + HCL

    The or d in ary method of pre paration is by the action of a chl orine


    com pound on a hydrogen com poun d viz tha t of sal t (so d ium ,
    .
    ,

    chlori d e ) on concentrated sul phuric acid :

    N aC l H2 80 4 N aHSO 4 + HCl .

    So iu m d p
    Sul h u ric
    c hl o r i e d . a ci d .

    Th is meth o d is employed technically as well as in the labora


    tory .
    8 I N O R G A N I C C H E M I S TR Y .
    28

    The above rea c t i on ta kes pl a c e at ordinary te m perat ures If the .

    s ul phuric a ci d i s to be c o m plete l y used u p i e i f all t h e hydrogen of the


    ,
    . .

    s ul phuric a ci d i s to go o ff wi th t h e c hl or i ne of the sal t as hydro chl ori c acid ,

    the te m perature of the rea c t i on m u st be ra i sed (cf also .

    2 N aC l + m o, = N a2s o, 2 HC 1 .

    Hydrogen chloride is a colorless gas


    9
    2 . Physica l P r op er ti s
    e

    with a p ungent o dor I t s critical tem perature is


    . the
    critical pressure 86 atmos pheres L iquid hydrogen chloride b oils .

    at the solid melts at Specic gravity of the


    =
    gas 1 2 6 9 6 .
    1 1 H C l at 0 and 7 60 mm
    .
    p ress ur e

    .

    weighs gr .

    Fo r obtai ni ng hydrogen chl oride i n a pure state MO I S SAN has el abor


    ated a m ethod wh ic h i s g enerall y applic able to gases s i n ce l ow te m pera ,

    tures are ea s ily atta inabl e by m eans of liqui d a ir The freshly generated .

    gases c ontai n in m ost cases m o i st ure and other im puri t ies The gases .

    are rs t dr ied by be ing passed thro ug h one or t w o wash bottl es pl a c ed -

    in a bath of a l ower tem pe rature than A t that te m perat u re the


    tensi on of water vapor i s pra c t ic ally z ero The g ases dri ed i n th i s way
    .

    are now c ondensed by strong c oo ling to t h e soli d state Air c an then be .

    p um p ed o u t of the v esse l I f t h e te m perat u re is n o w a ll owed to r i se the ,

    soli d m ass m el ts rst ; the resul ti ng liqui d when vaporiz ed g ives the , ,

    p erfe c t l y p u re g as .

    The gas fumes strongly in the air forming a cloud with the ,

    moisture of the air I t is very soluble in water 1 vol water


    .
    ,
    .

    at 0 being able to absorb 5 03 vols HC I gas The aqueous



    . .


    s olution of the gas is called hy dro chlori c acid also m u r ia tic ,

    a c id I t is manufactured c ommerciall y o n a large s cale


    .

    Hydro chlori c acid is em ployed almost exclusively in the form


    of this aqueous solution A solutio n saturated at 1 5 c ontains
    .

    HC l and h as a s pecic gravity



    it fumes vigorously

    in t h e air The ordinary p ure concentra t ed or fuming
    .

    muriatic aci d of commerce usually has a s p ecic gravity of
    and co ntains ab out 3 8 % HC l .

    Th e g as it el f i ofte c ll e d
    s s n a
    y
    h dro h c l or ic aci d g as :
    H YD R O G E N C H LO R I DE . 9

    Hy d rogen c hl ori d e does not obey the law of HENRY 9) in


    its behavior towards water for its solubility in this liquid is n o t ,

    at all pro portional to the pressure The larger part of it is absorbe d .

    in water Without reference to the pressure and an in crease of ,

    p ressure causes only a small increase in the solub ility Such con .

    duc t indicates that a change in the com pound has occurred ; j us t


    what this change consists in we shall soon have occasion to con
    s ider 65 ,

    The sat u rated so lu t i on of hydrogen c hl ori de in water giv es o ff HC l


    o n war mi ng O n d i st illi ng i t a frac t i on i s obta ined that bo il s c on
    v

    stant at 1 1 0 an d c ontains 8 m ol s H 0 to 1 m o l HC I c orrespond i ng



    .
    .
    2 .
    ,

    to abo u t a 2 0% so lu t i on of HC l A so l ut i on of the sam e c on c entrat i on


    .

    a n d bo il i ng p o i nt res ul ts
    -
    fro m distilling a m ore d ilu te hydro c hl oric
    a ci d
    ,
    eno ugh water bo il ing o ff to ra i se the c on c entrat i on to the above
    val ue .

    3 0 The
    . c h em ica l r
    p po er t ie s of hydrogen chl oride are found t o
    b e quite d ifferent when it is in a perfectly dry condition e g con
    '

    ,
    . .

    d e n se d to a liquid than when it is dissolved in water , I n the .

    former case it does not act on metals nor change the colo r of blue
    litmus I n the latter case j ust the contrary is true Zinc iron
    . .
    , ,

    an d other metals when di pped in the aqueous solution of hydrogen


    ,

    c hloride are vigorously attacked hydrogen being given o ff


    , Blue , .

    litmus is turned red by the solution M oreover even dilute solu .


    ,

    tions taste sour N o w there are a lot of substances that undergo


    .
    ,

    a s im ilar change of pro perties when they are brought in contac t


    with wa ter and whose aqueous solutions possess about the sam e
    ,

    ro
    p p erties as those that are described here for hydrochloric acid .

    The nature of this change will be discussed later on It


    should be stated here however that these substances have a
    .

    , ,

    common name They are called a ci ds A cids have on e or mor e


    . .

    hydr ogen a tom s that be r epl aced


    by m etal s Th e com pou n ds o
    can f .

    s u ch s u bs titu tion a r e
    ca l l ed s alt s
    m eta l s tha t ar e form ed by Salts .

    can result no t only from the direct action of metals on aci d s but
    als o from the interaction of acids and b as e s The term b as es i
    .
    ,

    includes com pounds of the general type MO H where M re presents ,

    a me t al M ost of them have an alka l ine taste and turn red litmus
    .
    40 IN OR G A N I C C HEM I S TR Y . 30
    ~

    blue When sodium is dro pped into water hydrogen is generated


    .
    , ,

    and a base sodium hydroxide is forme d


    .
    ,

    Na H2 O = N aO H H .

    this hydroxide is now treated with hydrochloric acid so dium


    If ,

    chloride and water are produced :

    N aO H HC l N aC l Hg O .

    If we indicate an acid by the general formula A H and a bas e


    b y MO H the formation of salts from the in teraction of the t w o
    ,

    may be re presented thus

    MO H + HA = MA + H2 0 .

    A third way of forming salts is by the action of an aci d upo n


    a metallic oxide e g ,
    . .

    Zn O HQ SO 4 ZD SO 4 HgO .

    Zin c p
    Su l h u ric Zin c
    oxi e d . ac i d . p
    su l h at e .

    In gener al the bases are built u p from metals the aci d s fro m ,

    m etalloids .

    When hydrochloric acid is added to a solution of a silver salt for ,

    instanc e to silver n itrate a decom position of this salt takes plac e


    ,

    according to the equation

    A gN 0 3 HC 1 HN O 3 A gC l .

    Sil v e r n it r a t e Nit r ic a c i d Sil v e r


    d
    . .

    c h l o ri e .

    The silver chloride is insoluble and is precipitate d as a white , ,

    curdy mass I n this reaction the hydrochloric acid has liberated t h e


    .

    nitric acid from its salt I t is also p ossible to liberate a base fro m
    .

    a salt by the addition of another base

    A gN O 3 N aO H A gO H N aN O 3 .

    Sil v e r d
    So iu m
    hy d ro x i d e . n it r a t e .

    Such r eactions are call ed s in gl e, or s im p l e, decom positions .


    42 I N O R GA N I C CHE M I S TRY . l 3 1

    and their absolute purity the gas mixture is prepared by el ectrolysis in the
    ,

    dark and exp osed to the action of li ght i mm ed i ate l y after the tube is lled .

    FI G . 15 .
    E L E C T R O LYSI S OF H YDR OC H L O RI C A C ID .

    The fact that hydro c hl ori c a c id gas yiel ds a vol um e of hydrogen equal
    to hal f i ts o wn v o lum e can al so be shown i n another way When perfe c t ly .

    dry hydrogen c hl or i de i s treated wi th sod i u m a m al ga m a so l ut i on of


    sod i um i n m erc ury the sod ium c o mbines with the c hl ori ne sett i ng

    ,

    hydrogen free The vo lum e of the l atter i s then found to be hal f as large
    .

    as that of the hydro c hl or i c a ci d ta ken .

    Hydrogen and chlorine thus unite in a ve ry sim ple r atio by


    volume and the vol u me of their product also bears a very
    sim ple ratio to that of the com po nents I n discussing t h e
    com positio n of water 1 9 ) we already remarked that oxygen and
    hydrogen combine in a very sim ple ratio by vo l ume viz ,
    .
    ,

    By carrying out this synthesis at a tem p erature above


    so that the steam is not condensed to water it is found further , , ,

    that the volume of resulting steam bears a sim ple ratio to t h e


    volumes of its com p onents viz that 1 vol O 2 vols H gives
    ,
    .
    ,
    . .

    2 vols Hg O
    . .

    The fo ll owing arrange m ent serves t h i s p urpose ( Fig The .

    e x pl os iv e mixt ure i s i ntrod uc ed i nto the c l osed arm B of the Ut ube o ver
    m erc u ry . B i s s urro u nded by a gl ass j a cket thro u gh wh ic h the va por of
    ,

    bo ili ng amyl alc oho l (generated i n A ) whose te m perat ure i s abo u t


    ,

    is pass i ng .This v apor i s c ondensed i n C A s soon as the gas m i xt ure


    .

    h as reached this tem perature an i nd u ct i on s par k i s ashed t h rou gh an d i t is ,

    found that the volum e of s tea m form ed i s two th irds that of the mixture -
    .
    C O M PO S I TI O N O F H YD R O C H L O R I C A C ID . 43

    FI G . 16 .
    D E T ER M INA T I O N O F TH E V O L U M E R E L A TI O N s BE TW EEN ST EAM AND
    I Ts COM P O NEN T S .

    Wh at was found above to be true for hydro chloric acid and fo r


    water is a general princi ple . Gas eou s e l em en ts c om bin e in s im p l e

    pr opor tion s by v o l u m e, a nd th e vo l u m e of the pr odu ct s orm ed


    f in th e
    ga s eous s ta t e al s o bear s a s im p l e ra tio t o t he v o l u m es o f the c om

    pon en t s This law was discovered by G A Y Lu s s A C in 1 808


    .
    -
    .

    This law together with the atomic theory of DA LT O N leads t o


    , ,

    im portant co nclusions I n order to investigate the matter let u s


    .
    ,

    ass um e that the formula of hydrochloric acid is H01 ; in othe r


    words that an atom of hydrogen is in combinatio n with an atom
    ,

    of c hl orine Since o ne volume of hydrogen unites with one volum e


    .

    of chlorine to form the com pound it follows from the above as ,

    s u m ptio n that equal volumes of chlorine and hydrogen co ntain


    the same number of atoms .

    I f the formula were otherwise e g H C l m the numbers of ,


    . .
    n ,

    atoms in equal volumes of hydrogen and chlorine woul d be in the


    ratio of n zm .

    I n the synthesis of water 2 vols of hydrogen and 1 vol of oxy . .

    ge n yield 2 vols of steam I f the formula of water be Hz O p


    . .
    n ,

    the numbers of atoms in equal volumes of hydrogen an d oxygen


    must bear to each other the ratio n zp .

    G iven therefore the relative numbers of atoms in equal gas


    , ,
    44 IN O R G A N I C C H EM I S TR Y . 31

    volu m es an d t he volume ratio in which the gases unite we can ,

    det ermine t h e formula of the r esulting com p ound .

    A s to the n um ber of ato m s in equal gas volum es there was at ,

    r s t much uncerta inty Since all gases behave exactly alike to


    .

    war ds changes of pressure or tem peratur e it was reasonabl e t o ,

    suppose that the num ber sho ul d be alike for all gases ; b u t this was
    soon shown to be I ncorrect I n the synthesis of water 3 vols (2
    . .

    vols H + 1 vol O ) give 2 vols of steam ; hence the number of atoms


    . . .

    r unit volume must be differen t for steam than for th e u n c o m


    p e

    b in e d elements However all difculties were overcome by a


    .
    ,

    hypothesis which A V O G ADR O enun ciated in 1 8 1 1 to the effect tha t


    , ,

    equa l v olu m es o f a ll ga s es at the s am e t em peratu r e a nd pr es s u r e con

    t ain the s am e n u m ber o f m ol e c u l e s .

    A V O G ADR O
    further supposes tha t the molecules of oxygen h y ,

    drogen chlorine and other elements c onsis t of two ato ms The


    , ,
    .

    unio n of hydro gen and chlo rine i s then exp l ained thus : O u t of a
    molecule o f e ach two m olec ules of hydro chloric acid are fo rme d
    ,

    H2 012 2 HC l .

    1 v ol . 1 v ol . 2 v ols.

    total numb er of molecules thus remains the same after t h e


    Th e
    combination an d since the entire volume has suffered no change
    ,

    either there mus t be j us t as many molecules presen t in each of the


    ,

    two vol um es of hydrochloric acid as in each of the volumes of


    hy d rogen and chl orine .

    Th e comb ination of hy d rogen an d oxygen takes plac e t hus

    2H2 02 2 H2 0 .

    2 v ols . 1 v ol . 2 v o ls .

    Eve ry molecule of oxygen has s pli t u p into its t w o a t o m s an d ,

    each of these unites with two hydrogen atoms The number of .

    water molecules becomes therefore twice as gr eat as that of the


    oxygen molecules and equal to that of the hydrogen molecules ;
    but s inc e the vol u me of steam is also d ouble that of oxygen there
    , ,

    mus t b e in e q ual vol um es j ust as many water molecules as oxygen


    m olecules an d hy d rogen molecules .


    3 2 I t follows
    . from the above that A V O G A D RO S hy othesis is o f
    p
    im po rt anc e in two respects : ( 1 ) in furnishing us a mea ns of as c er
    C O M PO SI TI O N O F H Y DR O C HL O R I C A C I D .
    45

    t ainin g the r ela t ive weights of the molec ul es of gaseous substances ;


    (2) in putting us in a p osition to form an idea of how many atoms
    there are in the molecules .

    L et us examine bo t h points more closely As to Since .

    equal volumes of gases under the same conditions contain the same
    num ber of m olecu le s the ratio of the weights of these volumes gives
    ,

    us at once the ratio of the m ol e c u l ar w e i gh ts I f the spec ic gravity .

    of steam is 9 base d on O = I 6 and that of hydro chloric acid is


    , ,

    the rati o of the molecular weights of water and hydro


    chloric acid is 9 : The determination of the s pecic gr avity
    of gases and vap ors the v apo r den s ity , bec o mes therefore of the
    ,

    g reate st im p o rtance to chemistry The p ractical method


    . of p ro

    c e du r e is described in O R G C HEM .12 .


    , .

    For the d etermination of the s pecic gravity of gases see ,

    2 12 .


    Asto In order to understand how Av o G A DR o s hypothesis
    can fur nish an idea of the number of atoms which the molecules of
    elements and of compounds contain let us return to the exam ple ,

    of the synthesis of hydrochloric acid 1 vol hydrogen unite s . .

    with 1 vol chlorine to form 2 vols hydrochloric acid A ccording


    .
    ,
    . .

    to the above law there mus t be j us t as many molecules present


    in the two volumes of hydro chloric acid as there were molecules


    of hydrogen and chlorine together It is evident that this is .

    o nly possible in case the molecules of hydrogen and of chlorine


    divide into two parts For if the chlorine and the hydrogen
    .
    ,

    molecules consisted of o nly o ne atom each the volume of hydro ,



    chloric acid coul d not in accordance with A v o G A DR o s law be
    , ,

    double that of each of its elements but would have to be equal ,

    to it It therefore follows that an even number of atoms must be


    .

    p resent in the chlorine ,


    and in the hydrogen molecules ; whethe r
    or not this number is two as A V O G ADR O assum ed can evidently
    , ,

    not yet be determined ; we shall therefore represent the molecules


    of hydrogen and of chlorine by Hz and O l gy From the synthesis x .

    of water the same co nclusion is reached in regard to the oxygen


    molecule : 2 vols hydrogen unite with 1 vol oxygen to form 2 vols
    . . .

    steam I n each of these two vol um es of steam there must be


    .
    ,

    according to A v o G A DR o s law jus t as many molecules present as
    ,

    in the o ne volume of oxygen This is likewise im possible unless


    .

    the oxygen molecul e Splits into two parts each of which combines ,
    46 I N O R G A N I C C HEM I S TR Y . 33

    with a molecule of hydrogen so that we obtain n O as the for , z

    m ul a of wate r and 0 2 as that of the oxygen m olecule


    3 .

    3 3 The formul ae for hydrochlo ric acid for water an d for t h e


    .
    ,

    molecules of hydrogen chl orine and oxygen can be ful ly established


    , ,

    if the values so y and z are known These can be ascertained gen


    , .

    e r all y in the following way : a: mus t be at least equal to 1 ; if this is

    the c ase the molecule of hydrogen becomes H2 That a smalle r


    ,
    .

    number of atoms is im p ossible is shown by the synthesis of hydr 0 <

    chloric acid The vapor densities of a series o f hydrogen com


    .

    p ounds as,
    com p ared with that of hydrogen are then de t ermined , ,

    from which we can nd thei r molecular weights based on the ,

    hydrogen molecule as unity Thereup on these com p ounds are .

    analyzed and the amount of hydroge n calculated that is r epre


    sented in the different molecular weights It will then be found .

    that in no case is the amount less t han half of that in a molecule


    of hydrogen The following table gives s ome exam ples :
    .

    S b stanu ce . Sp G
    . .
    Q u ant ity of H .

    Hydrogen chloride 0 5 .

    Hy drogen bromide 0 5 .

    Hydrogen sul phid e


    . 17 1
    A mmonia gas 8 5 . 1 5
    M eth ane 8 2
    E thylene 14 2
    Water . 9

    Since ,
    therefore no com p ound contains less th an h alf a
    ,

    molecule of hydrogen the ato mic weight of hydrogen must b e


    ,

    half its molecular weight i e the formula of the hydrogen mole


    ,
    . .

    cule is H2 Similarly it is found that the oxygen molecule is


    .

    O z that of chlorine 0 12 ; in other words that a y and z are all


    '

    , , , ,

    equal to 1 Th e following table illustrates the case of oxygen :


    .

    Sub st an c e . Sp G . .
    Q u an t ity o f O .

    O xygen 16 16
    Water . 9 8
    Sul phur dioxide 32 16
    N itri c oxide .
    15 8
    C arb on monoxide 14 8
    C arb o n dioxide 22 16
    D E TER M I N I N G M O L EC UL A R A N D A TO M I C WE I G H TS . 47

    R ULES FO R DETE R M I N I N G M O LE C ULA R A N D A TO M I C


    WE I G HTS .

    When the atomic weight of oxygen is taken


    34 . 1 6 its ,

    molecular weight is 2 X 1 6 = 3 2 If the s pecic gravity of another gas .

    based on oxygen = 1 6 is a the molecular weight of this gas bec omes ,

    2a The following rule has therefore been prescribed for the


    .

    de te rm in atio n of t h e m o l e c u l ar w e i gh t D eterm in e the v apor .

    den sity t he co m p ou n d, bas ed = 16


    an d m u l tipl y the
    o
    f on o xygen ,

    res u l t by 2 ; the p ro du ct is the m ol ec u l a r w eight .

    For determining the ato m i c w e i gh t the following holds good ,

    ac cordin g to 33 : D eter m in e the co m


    p os itio n o f m o l e cu l a r a m ou n ts

    co m p ou n ds o f th e el em en t a s ibl th e s m a l l es t a m ou n t
    o
    f as m an y p os s e;
    th e tha t is oun d in in s ta n ce is the weight
    of el em en t f any a to m ic .

    A V O G ADR O S hyp othes is has been c on rm ed fro m a phys ic al stand


    p o i nt I
    . t i s at p resent o n e of the pr i n ci pa l l aws of c he mi stry an d
    phys ic s .

    L e t us br i e y e x a m ine a m ong others the phys ic a l arg um ents i n i ts fav or


    , , .

    The m o l e cul es of bod i es so lids as we ll as liquids and gases are i n c on


    , ,

    stant m ot i on the i ntens i ty of whic h i n c reases and de c reases wi th the


    ,

    te mperat u re I n d i fferent s ubstan c es at t h e sam e tem perat u re there must


    .

    be a de ni te rel at i on between the i ntens i t i es of the m o l e cul ar m o v e m ents .

    Th i s re l at i on has been s ucc essf ully work ed o u t fro m the theory i n the c ase
    of gaseo u s substan c es I t has been sho wn that i n all gases at the sa m e t e m
    .

    er t u r e the m ean kinet ic en ergy of trans l at i on of a m o l e cul e i s the sa m e


    p a .

    The pressure wh ic h a gas e xerts against t h e wall s of the v essel i s


    c aused by t h e impac t of t h e m ol e cul es We w ill c all t h e n umber of m ol e .

    cul es in a v olum e of the gas n the mass of eac h m ol ec ul e m and thei r ,

    m ean ve l o ci ty u It is then cl ear that the gas press ure t h e above


    .

    e xplanat i on of i ts c a u se be i ng a c ce pted mu st be pro port i onal to n and -

    M oreo ver the press ure mu st a l so b e pro port i ona l to u for i f t h e


    2
    m .
    ,

    ve l o city were i n c reased the en cl os i ng walls wo ul d re c e ive m ore im pa c ts


    fro m the m o le cules m ovi ng to a n d fro an d e very im pa c t wo ul d a lso ,

    be c o m e stronger Th e gas press ure p i s therefore pro port i ona l to the


    .

    3p
    produ c t the theory says that = z
    or =

    z
    n mu ; p nm u n 2
    ,
    mu
    e xpress i on m u is t wice the ki net ic energy of transl at i on of
    In t h is z
    '

    m ole cul es whi c h is the sam e for a ll g ases at the same tem perat ure If
    ,
    .

    3
    then p is m ade the sam e for t he di fferent gase s or n, t he number of
    mo lec ul es per uni t v o lum e must be the sam e for a ll gases
    ,
    .

    The laws of B O YL E G A Y L U SSA C and A V O G ADR O ( we refer to


    ,
    -

    the expans io n law of G A Y L U SSA C ) can be ex pressed in a single -


    48 IN O R G A N I C C HE M I S TR Y .

    c omprehensive formula which is worthy of note bec ause of its


    ,

    frequent use in physic al che mistry The laws of BO YL E and .

    G A Y L U S S A C are re present ed by the equation


    -

    P V = R T, or R,

    in which P is t h e pressure V the vol u m e and T t h e ab solut e t em


    ,

    p e r at u r e of,
    the g as and R is a cons tant which de p ends o n the
    quantity and the nature of the gas under cons ideratio n The .

    value of R however becomes the same for all gases if molecular


    , , ,

    a mounts o f them ( o ne mole each ) are taken For according to .


    ,

    A v o G A DR o s law the volume of o ne mole of every gas is the same
    ,

    under the same pressure and tem perature I n the a bove equa .

    tio n then V is co nstant for all gases and since we have already
    , , ,

    made P and T the same in each case it is evident that R must ,

    have a co nstant value I n other words if we deal with molecular


    .
    ,

    amounts the equatio n P V = R T becomes a general expressio n


    ,

    o f the l aws of B O YL E G A Y L U S SA C and A V O G ADR O


    ,
    -
    .

    The value of R may be calculated as follows : L et us consider


    1 mole oxygen at 0 and 7 60 mm pressure Since 1 1 oxygen

    . . .

    u nder these c on ditions weighs g th e volume V of 1 m ol is .


    ,

    32
    1
    . 223 9 3

    If a c orrection is a pplie d b ecause oxygen d oes not exactly follow


    the gas laws of B O YL E and G A Y LU SS A C we obtain 224 1 2 -

    The pressure of 7 6 0 mm mercury c orres ponds to a p ressure


    of g pe r sq cm i e P = 1 0 1 3 2 5 A t 0 the absolute
    . . .
    ,
    . . . .

    tem perature is 2 7 3 ( more strictly


    Substituting these
    values in the ab ove expression for R we obtain ,

    PV 1 01 3 2 5 x 2 2 4 1 2
    " 8 3 1 55
    .

    in c g units If the
    .
    -
    . .
    p ressure is ex p r essed in millimeters of m er
    cury R b ec omes
    ,

    6 23 1 3 .

    Th e p ro d uct P Va lso re presents t h e ex te rnal wo r k which is


    d one when a gas under constant pressure P i n creases its volume
    by V ( o n b eing heated for instance ) o r when a gas being generated
    ,
    50 IN O R GAN IC C HE M I S T R Y .
    35 .

    cles hav in g t he d im e n si o ns of the order of a micr on ( ja =


    , mm ) .

    or smaller exhibit when they are sus pended in a liquid It has


    , .

    n o w been
    proved that these movements are due to the im p acts
    of the molecules ) ; (3 ) the d iffusion velo city of d issolved substances ;
    ( ) the refraction of light in the atmos phere c ausing the blue c olor
    4 ,

    of the sky ; ( 5) the electric charge of the ions ( 6 ) the life


    p eriod of radium ( 7 ) the energy of the infra red s pec trum -

    The signicance of these investigations for all dep artments of


    n atural science is extraordinarily great When we see that s o .

    many wholly inde p endent methods lea d to the same absolute


    number of molecules in a gram molecule there is no
    ,

    ro o m left for d o ubt of the a ctu al exis ten ce of m ol ecu l es So long as .

    we had o n ly rough an d discordant approximations of this number ,

    we c o ul d acce pt the assum ption that matter is built out of mole


    cules and atoms as an exceed ingly useful hy p othesis whil e yet ,

    d oubting t he re al existence of atoms and molecules The satis .

    facto ry pro of o f their actual existence has pu t t h e kn owle d ge of


    matter in gener al on a secure foundation .

    O ZO N E .

    3 6 . early as 1 7 85 V AN MARUM observe d that when an elec


    As
    tric sp ark p asses through oxygen a p eculiar garlic like odor is -

    given o ff and a bright mercury surface is at once m ade d ull


    ,
    .

    S C H O N B E I N investigated this phenomenon more carefully and ,

    foun d that it is d ue to the formation of a peculiar substance which ,

    he calle d oz on e This proved to be oxygen existing in a sp ecial


    .

    c ondition The fact that it really c onsists of nothing but oxygen


    .

    is shown by its formation fro m p erfectly dry oxygen under t h e


    inuence of electric discharges e g induction sp arks The amount
    ,
    . .
    ,
    .

    of oz one thus formed is n evertheless small I t is greater when .

    silent d ischarges are used A s oz one is formed from oxygen by


    .

    ultraviolet light the formation of oz one by s ilent discharges may


    ,

    b e c aused by the ultraviolet light ac c om p anying them This is .

    o n e of the best ways of obtaining oz one although the maximum ,

    y iel d is o nl y However if the oxygen is,


    c o oled by liquid
    air an d then submitted to the silent discharge at a pressure of
    1 00 mm Hg it is wholly c onverted into o z one
    .
    ,
    .

    Fig 1 7 re presents an app aratus c onstructed by B ERT HE L O T


    .

    for the pre p aration of o z one at the or d inary pressure an d tem


    e r at u re The wid e tube to g ether with the su l tube d -
    O ZO N E . 51

    and the exit tube e are sunk in a vessel of sul phuric acid int o
    -

    , ,

    whi ch the pole o f the induct or b is di pped The other wire a o f .

    the latter ends in a tube c which is ,

    sli pped down inside f and is almost


    entirely lled The silent discharge
    .

    bet w een the two b odies of sul phuri c


    acid thus passes through a thin laye r
    o f oxyge n and has a powerful o z o n iz
    ing effe ct .

    O zo ne is fo rme d in many reaction s ,

    such as the slow oxidati on o f m oist


    p hos p ho rus also in
    ,
    a small quantity ,

    when hydrogen burns in an atmos phere


    of oxygen, The o xygen that is o b
    t ain e d by the e l ect rolysis of dilut e
    FI G 1 7 PREPARAT I O N O F . .

    sul phuri c ac i d always c onta i ns i t O ZO NE .


    .

    O z one is also gi v en o ff by the de c o m


    p osition o f p ermangani c acid that is set free in the reaction of
    p otassium pe rmanganate an d c oncentrated sul p huric aci d ( cf als o .

    When oxygen i s sub j e c ted to a very h igh tem perature (e g am e . .

    tem perature ) i t i s part i ally c onver t ed i nto o z one and the m ore so the ,

    h ig her the tem perat u re I t i s ne c essary howe ver to c oo l down , ,

    the ozoniz ed gas v ery rapi d l y beca u se t h e vel o ci ty of de c om po sit o n of


    ,

    o z one i s very great espe ci all y at high te m peratures A n instanta neous


    ,
    .

    coo ling can be a cc o m pli shed by d ire c t ing t h e fl am e ( of hydrog en carbon ,

    m ono xi de a c ety lene or other g as) u pon the s urfa c e of liqu id ai r wh ich
    , ,

    has a tem perat ure of That t h e generat i on of o z one has no c on


    n e c t io n w i th t h e c o m b u s t i on but that i t i s c a u sed onl y by the hig h te m
    ,

    p e r a t u r e to wh ic h the o x y g en i s ra i sed by t h e a m e m ay b e pro ved by ,

    t h e fa c t that an in c andes c ent pl at i nu m wi re or N E RN S T gl ower dipp ed ,

    in liquid air al so generates o z one The format i on of o z one i s also observ ed


    .

    when a rap i d cu rrent of dry air or o x ygen i s all owed to impinge against
    a hot N ERN S T gl ower When t h e a i r c onta ins m o i st u re alm ost n o o z one
    .

    is for m ed the prod uc t be i ng hydrogen pero xi de


    ,

    Physica l Prop er ties ordinary temperatures o z one is a gas ;


    .
    -
    At
    it has a p eculiar odor which is one of the most delicate tests
    ,

    for its presence O n e p art of o z o ne can still be d etecte d by its


    .

    odor in p arts of air In the l iquid state it is in d igo b lue


    .
    -
    .

    O z one boils under normal p ressure at


    52 IN O R G A N I C C H E M I S TR Y .
    36

    C hem ical Prop er tiesis characterized above all by it s O z one


    ability to oxidiz e vigorously at ordinary tem peratures es pecially ,

    in the presence of moisture Phos p horus sul phur and arsenic .


    , ,

    are oxi d ized to phos phoric acid sul phuric acid and arsenic acid , , ,

    resp e ctively ammonia t o nitric acid and silver and lead to pe r


    , ,

    oxides ; e g the metallic surface of silver especial ly when heated


    . .
    , ,

    to ab ove bec ome blue when o z oni z ed air is dire cted agains t
    it I odine is de p osited by o z one fro m a solution of p otassiu m
    .

    iodide :
    O rgani c substances are strongly oxidize d by o zone hence n o ,

    a pparatus c ontaining it shoul d have c onne cti ons of rubber Dye .

    st uff sol utions like indigo and lit mus are d e c ol ori zed (b y oxida
    , ,

    tion) O zone effectively destroys micr o organisms and is there


    .
    -

    fore use d suc cessfully in the steriliz ation of drinking water -


    .

    Th e dete ct ion of o zone


    ci ally in q u ant it ie s too s mall to b e re cog
    ,
    e sp e

    ni zed b y t h e o dor is a d i fcult m atte r be c au e e ve ral oth e r o xi diz in g u b


    ,
    s s s

    st a c e n s uch as c h lorine o
    s, b ro mine in t h e pre en c e o f w ate r t h e o xide o f
    r s , s

    n it o g e n
    r h ydro g e n p e roxi de an d t ill oth e rs give clo e ly a alogou s r e ac
    ,
    s ,
    s n

    t ions an d furt h e rmore the ir me ll at h igh d ilut ion s me w h at re se mb les


    ,
    s s o

    th at of o z one ; henc e it b e c omes n e c e ary to r t prove the ir ab se nce Th e ss s .

    te sts for o zon e a e u sually e xe cuted by mo i stenin g tri ps o f l t er paper w ith


    r s -

    t h e re ag e t an d d i ppi g the m in t h e g as c ont a in in g o z one


    n n Th e re ag ents .

    u se d for th i purpose a e le ad s ulph i de an d th allo u h ydroxide Th e tri ps


    s r s . s

    o f pap e r a e r t m o i st e ne d w i th d i l ute s o lut i o n


    r s o f t h e n i trat e s o f th e e s s

    metals an d then e xpo e d to h ydrogen l ph i de a d ammon i fume res su n a s,

    s pe c t iv e l y L e d s ul phi de is o xi diz e d b y o z on e to l e ad s ulph at e th u turn


    . a ,
    s

    in g fro m b l a ck to w h ite ; thall o us h ydro xi de w h ich i Wh ite i c onve rt e d to , s ,


    s

    bro w n th allic h ydro xi de Ho w e ve r the e c h an g e o f c o lor al


    . o ccur w ith
    ,
    s s so

    t h e oth e o xi dizing agents ment ione d A trictly ch a acte ri t ic te t fo


    r . s r s s r

    o zon e is t h e vio le t c olo pro duc e d w ith an a cet ic aci d so lut ion o f t etramethyl
    r

    p p di ami do di ph enyl me th ane ( an org an ic c o mp ound ) N i trog e n di oxi de


    -
    - -
    .

    give a straw ye llow color ch lorine an d bromine a dark b lue w h ile h ydrogen
    s -

    , ,

    p e ro xi d e p ro d uc e n o c o lorat i on at a l l s .

    is st able at o rdinary tem peratures b u t is eas ily change d


    O z on e ,

    t o oxygen o n heating I t is slightly solubl e in water . .

    T h e fo rmula of o zon e has b ee n


    3 7 For m u l a of O z on e
    .

    d etermined by L ADEN B UR G in th e following way A glass .

    globe with two c o cks was rst weigh ed when lled with pure
    oxyge n and the n when c ontaining oz oniz ed oxygen A fte r .

    r e d ucing both weights t o th e normal tem p erature and pres


    sur e t h e glob e in th e latter case w as found to be a mg .

    heavier This increas e o f weight is due t o the re placemen t


    .
    of a ce rt ain numb er o f oxyge n m ol e cules b y t h e sam e numb er
    of oz on e mol e cul e s .

    The v olum e th at t h e o z on e o c cupies i n t h e gas mixtur e can b e


    determine d b y absorbing it in turpentine Supp os e this to be .

    v c c when redu ced t o normal pressur e and tem perature Th e


    '

    . .
    , .

    We ight of this v c c o zon e can b e re presented by th e weight of an


    . . .

    e qual vo l um e of oxygen a mg and must b e therefor e (v x + a) .


    , ,

    mg .
    ,
    mg being the we ight o f 1 c c o xygen at normal pressur e
    . . .

    and temperat ure Hence the weight g of 1 c c o z one is


    . . .

    v X 1 43 + a .

    In on e of his experiments L ADEN B UR G foun d a = 16 3 . mg . an d


    = 26 0 cc hence = 2 06 mg 1 cc ozone thus weighs
    v . . .
    , g . . . .

    times as much as an equal volume of oxygen or very nearly ,

    1 2 times as much
    1 The molecule of oxygen being O z that of
    .
    ,

    ozone must be re presented by 0 3 .

    I n an oxidation by ozone the v olume of the ozonifer ous gas


    r emains unchanged O nly the third atom in O 3 has oxidizing
    .

    p ower not all three


    ,
    atoms of the molecule .

    I n ozone we have become acquainted with oxygen that is dif


    fer e n t from the ordinary kind Th is phenomenon is also seen in .

    other elements ; it is calle d all otr opi sm .

    HYDR O G E N PE R O XI DE ,
    H QOQ .

    3 8 Th is com p ound
    .
    is usually re
    p p are d by treating bari u m per

    o xide with d ilute sul p huric acid :

    13 3 0 2 H2 80 4 13 3 80 4 H20 2 .

    B ar iu m In sol u bl e
    d
    .

    p e ro x i e.

    a very c on c entrated state i t c an b e obtai ned by direct di still at i on


    In
    v acuo of a m ix t u re of sod ium pero x i de sul phur ic a ci d
    in a n d :

    N3 0
    "H
    02 i 280 4
    = N 3 9 80 4 + H20 2 .

    Hydrogen peroxide is also formed in many other ways ; e g . .

    together with ozone 3 6 ) in the slow oxidation of phos phorus ; by


    the combustion of hydrogen when the ame is cooled by a piece ,

    of ice The formation of ozone h as been often detected when


    .

    hydrogen in the nascent state comes in contact with oxygen mole


    cules We suppose that in the moment j us t after hydrogen is se t
    .
    54 I N O R G A N I C C HEM I S TR Y .
    38
    .

    free its atoms have not yet united to form molec ul es so that t he
    , ,

    in divi d ual atoms p ossess unusual chemical act ivity Th is is t h e .

    general conception of the statu s n ascen di Thus T RAU B E has .

    observe d the following instances of the production of hydrogen


    p eroxide : Zinc lin gs when shaken with water and oxygen or air
    , ,

    give hy drogen peroxide since the zinc and the water generate a
    .

    small quantity of hydrogen which unites with the oxygen Palla , .

    diu m hydrogen behaves likewise when brough t in contact with


    -

    water and air I n this case it is the hydrogen released from the
    .

    p alla d ium that unites with the oxygen M any metals such .as ,

    co pper lead and iron yield hydrogen p eroxide on being shaken


    , ,

    with air an d dilute sul phuric acid for the same reason as in t h e ,

    case of zinc and water F inally the pe r oxide is formed in t h e


    .
    ,

    e lectrolysis of water when a current of air or better oxygen p asses


    , , ,

    o ver the negative electrode ( at w h ic h hydrogen is evolved ) .

    Hydrogen p eroxide is also formed at very high tem peratures


    fr om steam and oxygen j ust as in the formati on of oz one
    under the same c onditions 3 6 ) a ra pid co oling is necessary in
    ,

    this c as e also else the c om p ound deco m p oses The formatio n


    ,
    .

    o f hydrogen p eroxide in t h e c ombustio n of hy drogen has been

    shown in the following way : A h ydrogen ame was allowed to


    burn at the mouth of a bulb tub e c ontaining a little water By .

    me ans of a very ra p id current of air the ame was blown int o


    the bulb causing a very sudden c o oling of the mixture of steam
    ,

    and air A fter a time the water in the bulb gave th e tests fo r
    .

    hydrogen p eroxide A s a further analogy to the case of oz one


    .

    it h as been sh own th at the formatio n of hydrogen p eroxide has


    no connection with the co mbustion for o n directing a ne stream ,

    o f water u p on an inc andescent N ERN S T glower some hydroge n

    p eroxide is generated in the water .

    Physical Pr operties I n the pure a nh ydrous condition hy d rogen

    p eroxide is a colorless slightly viscid liquid


    ,
    having a s p ecic g r avity ,

    of at based on water at (A density calcula t ed o n


    this basis is indicated by I t b e c om e s solid at a low tem
    '

    r at u r e and melts at
    2

    p e

    C h em ical Pr oper ties Hydrogen peroxi d e when wholly free ,

    from im purities especially from sus pen d ed particles of solid m at


    ,

    t er is rather stable and can be distilled in va cu o; when impure


    , ,

    it d ecom poses however into water and oxygen as it also doe s


    , , ,

    in dilute solution I n the latter state it is more stable in t h e


    .
    H Y D R O G EN PE R O X I D E .
    55

    p resenc e of traces of acid than in the p resence of bases I t is an .

    interesting fac t that it decom poses ra pidly in contact with pow d ere d
    substances a pparently withou t actin g upon them Finely divided
    , .

    silver gol d platinum (platinum black ) and es pecially manganese


    , , ,

    dioxide decom pose it with e ffervescence ( due to esca ping oxygen) .

    Even r ough surfaces have a disturbing e ffect ; BR iIHL observed


    for instance that a concentra t ed solution of hydrogen p eroxide


    ,

    evolves oxygen when p oured u pon ground glass Al l these actions .

    must be regarded as catalytic accelerations of the ordinaril y very


    s low d ecom position of hydrogen p eroxide The effect of h e a t .

    is here as elsewhere to accelerate the reaction ; concentrated


    , ,

    pre parations when warmed often decom pose so ra pidly as to


    , ,

    c ause an ex losion
    p .

    The oxidizing action of hydrogen perox id e is an irn por t an t


    chem ical pro perty This is always due to the surr ender of an
    .

    oxygen atom which e ffects the oxidation while w ater remains


    , , .

    Lead sul phide Pb S is oxidized by a weak solution of hyd r ogen


    , ,

    l Pb SO 4 ; s ul phuretted hydrogen H2 S
    '

    p eroxide to lead su phate , , ,

    is converted in to water and free sul phur Barium strontium and .


    ,

    calcium hydroxid es Ba (O H) 2 Sr (O H) 2 and C a (O H) 2 are pr e


    , , ,

    c ipit at e d by dilute hydrogen p eroxide from their solutions as

    p eroxides of the general formula M O Q n aq


    1
    The colorless solu -
    .

    t ion of titanium dioxid e in dilute sulphuric aci d is tur ned


    o range red by hy d rogen p er oxide
    - lemon yellow b y traces of it

    o n accoun t of the formation of yello w trioxide T l 0 This is a
    3 , .

    d elicate test for hydrogen per oxide O ther tests are fo un d in the .

    follo w ing oxidation reactions : P


    otassium iodide starch paste is at
    o nce turned blue by hydrogen peroxide in the presence of a little

    f er rous sul phate Fe SO 4 ,


    .

    The ferrous s ul phate c arries the active oxyg en of the hydrogen per
    '

    o x ide to the potassium i od i de A s a resu l t two atom s of i od ine are se t .

    free t h e ferro us sul phate be i ng o xi d iz ed a t the sam e t im e A c c ording to


    ,
    .

    M AN C H O T a higher o x ide of i ron is form ed i n th i s react i on .

    Avery characteristic reacti on is this : C hromic acid solutio n


    ( HzC r O 4 ) when treated with hydrogen p eroxide is changed to a
    , ,

    higher oxide ( see 29 5) which is blue in aqueous solutio n and


    may be taken u p by ether if shaken with the latter This test .

    is however less delicate than the two preceding ones


    , ,
    .

    1
    A q ( aq u a) ,
    . a fre qu ently u se d r viat ion for
    ab b e wa t er of crystalliz ation
    I N O R GA N I C C HEM I S TR Y 38

    Athir d gro u p of chemical effects of hy d rogen peroxi d e depends


    o n its r edu c in g p ow er When silver oxide is intro d uced into a
    .

    solution of hydrogen peroxide a vigorous evolution of oxygen ,

    o cc urs water and metallic silver bein g forme d at the same time
    , .

    Potassium permanganate solutio n loses its color when mixed


    with a hydrogen p eroxide solution acidu late d b y sul phu ric acid ,

    o xygen being given 0 3 r a pidly :

    2KMII O 4 3 11 2 80 4 5H2 0 2 K2 80 4 2Mn SO 4 8H2 0 50 2 .

    The brown peroxi d e of lead Pb O z is reduce d to re dd ish yell ow , ,


    -

    lead oxi d e Pb O ,
    .

    O zone and hy d rogen peroxide yield water and oxygen ; when


    dilute they are however able to exis t side by side
    , , , .

    There is a test for hydrogen pero xi de de pendi ng on its red u cing ,

    p ower wh i ch i
    ,
    s e v en m ore de l icate than those des c r i bed abo v e A .

    mixed so lu t i on of ferr i c c hl or i de and re d pr us si ate of potash h as a re d

    co l or O n the add it i on of hydrogen peroxi de Pruss i an b lu e is prec i pi tated


    . .

    Tra c es of the pero xide turn the so l ut ion green The rea c t i on fa il s i n the
    0
    .

    presence of free a c i d .

    The ab ility of so powerfully oxidizing a substance as hyd rogen


    p eroxide to act also as a reducing agent can be ex plained as follows : -

    O n e of its two oxygen atoms must be loosely j oined to the mole


    cule since it is easily given u p Al l the substances which are
    ,
    .

    reduced b y hydrogen peroxid v e one loosely held oxygen

    atom ; silver and o thers


    gi v e u p their oxygen at rather low tem pera t ures I t is therefo re .

    possible that the mutual attraction of the oxygen atoms which ,

    tends to make them form oxygen molecules is stronger than the ,

    fo rce by which they are held in hydrogen peroxide on the one


    h and and the res pective oxygen com poun d on the other
    , .

    Uses H
    f y g P The co l ors of o l d pai nt i ngs are often
    '

    o dr o en eroxide .
    -

    restored by means of i t The darkeni ng of the m i s du e i n m any c ases to


    .

    t h e transfor m at i on of whi te l ead s ul phate Pb SO 4 to b l a ck l ead s ul ph i de , , .

    Th e l atter i s readil y o xi d iz ed by hydro gen pero xi de ba ck to wh i te l ead


    Sul ph ate Hydrogen pero xi de i s al so of v alu e i n b l ea c h i ng i v ory s ilk
    .
    , ,

    bri st les and sponges It is al so im portant i n analysis . .

    For therape u t i c purposes at 3 0% so lu t i on of h ydrog en peroxi de is pre


    pared by M E R C K wh ic h i s perfe c t l y p u re an d i s obt a i ned by va cuum dis il
    lati on fr Om a m ore d il ute so l ut i on Before use it is strongl y d il uted It

    . .
    58 IN O R GA N I C C HEM I S TR Y . 40

    it again on the other wh ile the dissolved matter remains behin d


    ,
    .

    O n e of the ways of obtaining a semi permeable partition is by dip -

    ing a orous c u such as is used in galva ni c cells c ontaining a


    p p p
    solution of yellow prussiate of p otash into a solution of b l ue vitriol .

    A thin layer of co pper ferrocyanide is thus formed in the wall of the


    cup
    makin g it semi p ermeable If a dilute sugar solution sal t
    .
    , ,

    solution or the like be p oured into such a c u p and the c u p placed


    in a dish of water it will be found that the dissolved substance does
    ,
    '

    n o t diffuse through this sort of a p artit ion The water goes .

    thr ough however for if the c u p be closed with a perforated sto pper
    , ,

    t h rOu gh which a glass tube p asses and then di pp ed dee p enough


    un der water so that the entire c u p is submerged the water will be ,

    seen to rise slowly in the tube till it reaches a deni te height above
    t he level outside .

    The pressure exerted by this column of liquid is called the


    o sm otic pr ess u r e of the solution I f a tight t t in g p iston were
    .
    -

    ins erted in the c u p the force which one would have to exert on it
    ,

    t o prevent the inltration of the water woul d be equal to the pres


    sure of the column o f liquid for the water continues to rise in the
    ,

    tube till the pressur e of the column prevents the entrance of any
    more .

    A c cording to researches of V AN T H O FF the osmot ic p ressure


    o f dilute solutions } like the p ressure of gases, obeys the law of

    BO YL E and the ex p ansio n law of G A Y L U SS A C If the p


    -
    ressure .

    exerted at a certain tem pe r ature by a kg of a gas in a vessel b e .

    p the
    , p ressure which n a kg of the gas at the same tem p erature
    .

    ex erts in th e same vessel is n p The con cen tr a tion i e density


    .
    ,
    . .
    ,

    o f th e gas h as been multi plied n fold


    -
    .

    I f the osmotic pressure of a solution containing a pe r cen t of a


    substance be determined and found to be p the osmotic pressure ,

    will be n p if an na pe r cen t solution of the same tem perature be


    ,

    taken i e if the concentration be n times as great


    ,
    . . .

    An investigation of the pressures which a gas of constant volume


    exerts at the absolute tem pera t ures TI and T2 shows that these
    p ressures bear to each other the ratio T 1 : T2 The same ro
    p p ortion.

    is observed when the osmotic pressure of a solution o f constant


    concentration is measur e d at the sam e absolute temperatures as
    above .
    DE TE R M I N A TI O N O F M O L E C ULA R WE IGH T .
    59

    41 The laws of osm oti c pressure nd ex peri m ental Veri cation in


    .

    m easurem ents whic h were m ade by PF E FFE R pre vio u s to VAN T HO FF S

    enu n ci at i on of the l aws PFEFF E R i nvest ig ated dil ute s ug ar so lutions and
    .

    used an apparatu s not unlike the o ne j ust des c r i bed .

    Th e gas laws ar e e x pressed by the e quation 3 4)

    PV = R T, .

    in whi c h P represents the pressu re V the volum e and T the absolute


    , ,

    te m perature of a gas while R i s a c onstant The vo lum e V is inversel y


    , .
    , ,

    p ro p ort i ona l to the c on c entrat i on a c cordi,


    ng to the above de nitio n;
    1
    therefore m ay be substi tuted for V, If C in di cates the concentrati on
    C .

    Th e above equat i on then beco m es

    or, at a cons ant t tem perat ure ,

    C ons t .

    Th is e quation m ust also be applicable to osm otic pressur e This was .

    really the case in PFE PFE R s m eas ure ments of a queous s ugar so lutions

    of di fferent c on c entrations as m ay be seen fro m the foll owing brie f


    ,

    tab le The te m perature varied between


    . and and hence w as
    not perfect l y constant :

    The diere n ces in the values of


    g -
    m ust be ascribed to the variations
    of te m perature an d the unus u al e xperi mental di ffi cul ties whi ch attend
    s uch m eas ure m ents .

    From equation ( 1 ) it also foll ows when V ( or C ) is a constant that


    , ,

    C onst .
    60 I N O R G A N I C C HEM I S TR Y .
    I 41

    This c on c lusion too was de m ons trated e x per imenta ll y by PFEFFE R


    , ,

    in the c ase of sugar so lut i on as m ay be seen from the fo ll o wing tab l e


    ,
    .

    A one pe r cent so lu t i on was used :


    P
    . T .

    g .

    51 0 2 87 1 5 1 78

    544 3 05 1 78
    567 3 09 1 83

    VAN H O FF has f u rt he r shown that the nu merical value of t h e



    T

    o smotic pressure is the same as that of the gas press u re ; that is t o


    .

    s ay when a denite amount of a substance in the gaseous stat e


    ,

    o ccu pies a given volume the gas pressure which it exerts is j ust as
    ,

    great as the osmotic pressure which woul d be produced if the same


    amount of substance were dissolved i n a liquid making the sam e
    volume of solutio n .

    The measu re m ents of PFEFFE R al so furni shed experim ental proof of


    th is He fo u nd that a 1 % s ugar so l ut i on at 7 e xerts a press ure of 3 of an
    .

    atm osphere If there is really e quali ty bet w een os m ot ic press ure and gas
    .

    press ure O r in other words i f the l aw of A V O G ADR O for gases i s a lso


    , , ,

    a pplic abl e to dil ute so lu t i ons t h e c onstant R of t h e e qu at i on P V = R T


    ,

    m ust hav e the sa m e va lu e for so lu t i ons as for gases P i n t h e above case .

    was fo u nd to be e of an at m osphere or g A 1% , .

    s ugar so l ut i on contains 1 g sugar i n c c A S the m o l e c ul ar


    . . .

    wei ght of th i s s ubstan c e i s 3 42 the v o lum e V whic h c onta i ns 3 4 2 g i s


    , .

    V x 3 42 T 273 7 Sub st i t ut ing these gures i n



    .

    PV

    T
    we hav e R = 84 66 4 . The cl ose agreem ent of the two valu es of R
    ( co mpare p 4 8) pro v es
    the e qu ali ty of gaseo u s an d os m ot ic press ure
    .
    .

    4 2 I t follows from the preceding that A v o G A D



    . R o s law must

    al so hold for dilute solutions A ssuming tha t an equal number of .

    molecules of diff erent substances are dissolved in equal volumes at


    the same tem peratu r e we know from the equality of gas pressure
    , ,

    and osmotic pressure that the various substances will exert the
    same osmotic pressure ; inversely in equal volumes of solution hav ,

    in g the same tem perature and osmotic pressure there is the sam e
    num ber of mole cules .

    This is a ve ry im por t ant extensio n of A v o G A DR o s law We



    .

    are thus able not o nl y to com pare the weights of equal gas volum es
    at the same tem perature and pressure and calculate therefrom t h e
    molecul a r weight but we cana pply the same principle to soluti o ns
    , ,
    D E TE R M I N A TI O N O F M O L E C UL A R WEI GH T .
    61

    since w e know that in solutio ns of the same tem perature and the
    s ame osmotic pressure the quantities of the dissolved substances

    c o ntained in equal volumes of solution are to each othe r as thei r

    molecular weights .

    Jus t as it is p ossible to ascertain the molecular weights of


    g aseous b odies from determinatio ns of tem p erature p ressure , ,

    we ight and volume it is also possible to nd those of substances


    .

    i n dilute solutio n by measuring the volum e of liquid the tem pera ,


    ~

    ture the quantity dissolved and the osm otic pressure


    , T he .

    molecula r weights of all substances tha t dissolve in some liquid or


    o t her can be determi n ed in this way and since the number of
    , ,

    s o l ub l e s ubstances is very large there are not a few wh ose m ol e c


    ,

    ular weights were r s t dete rmi ned in this way


    I n worki ng out this method however there is a practical , ,

    diffic ul ty The osmotic pressure is very hard to measure


    .

    directl y This would rende r the whole method of little value if it


    .
    ,

    were not for the fac t that the calculatio n o nl y requires that it be
    known wheth er two solutio ns have the sam e osmotic pressur e not ,

    t he absolute amount of the latter ; the law of A VO G ADR O sim ply


    r equires the equality of volume of tem perature and of pressure
    ,

    ( osmotic or gas ) withou ,


    t rega rd for the absolute value of these
    factors ( betwee n certain limits ) N o w it is easy to measure
    .
    ,

    magnitudes which are pro portio nal to the osmotic pressure and ,

    from which it may be seen whether equality of osmotic pressure


    e xists or not These magnitudes are the de pr e ssio n of t h e f re ez in g
    .

    p oi n t and the e l e v a tio n o f t h e b oili n g p oin t A n ex-

    p lanation of
    .


    these terms is perha ps necessary When a substance is dissolved
    in a liquid the maxi mum tensio n of the va por is less above the solu
    tio n than above the p ure solvent at the same tem perature for the ,

    p articles of the dissolved body attract the molecules o f the sol v ent ,

    hindering the formatio n of vap or o n the one hand and o n the other , ,

    hand facilitating the return of va por molecules into the liquid


    ,
    .

    This lowering of the va por pressure necessarily causes a de pressio n


    of the freezing point and an elevation of the boiling p oint as may
    -
    -

    be proved by the following diagrams I n Fig 1 8 a bc re presents . .


    ,

    the va por pressure curve of a solvent in the neighborhood of its


    -

    freezing point b ; the part a b gives the pressures for the frozen
    -

    matter ; the part bc for the liquid solvent This latter part is .

    always more nearly horiz ontal than the former as has been proved ,
    62 I N O R GA N I C C HE M I S TR Y I 4 2~

    bo t h e x perirn e nt all y
    and theoretically The freezing point of a .
    -

    liquid is that tem perature at which the solid and liquid states can
    exist sid e by si d e inde nitely This condition requires that t h e .

    s olid and t h e l iqui d substance have the same va or tensio n If


    p .
    ,

    for instance t h e vapor tension of the solid were greater than that
    ,

    o f the liquid we should have at a co ns tant tem erature the va o r


    , p p , ,

    given off fro m the solid co nde ns ing to a liquid and the former grad

    FI G . 18 . FI G . 19 .

    u all y tur ni ng into the la t te r Inversely if t h e va po r tensio n of t h e


    .
    ,

    solid were less than that of the liquid the entire li q uid would , ,

    under similar conditions solidify ,


    .

    The freezing p oint b can thus be regar d e d as the intersectio n of


    -

    the va por pressure cu rves a b and be of the solid and the liquid r e

    ,

    L e t us now co nsider the c u rve b c Of a solutio n



    s pe c t iv e l y . It s .

    va por pressure is lower than that of the pure solvent so its inter ,

    sectio n with the cu r ve a b must lie more to the left that is it s , ,

    freezing point is lowered O n the other hand the boiling point


    -
    .
    ,
    -

    of a solutio n is that tem perature at which the tensio n of its va po r


    equals o ne atmos phere I f O d in Fig 1 9 re presents this tension
    . .
    ,

    a line dd parallel to the axis of abscissas will intersect the vapor
    p ressure curve a c of the p ure solvent at a lower tem p erature than ,

    it will the curve a o of the solution The latte r must therefore



    .
    , ,

    have a higher boiling p oint -


    .

    The c onne c tion between these m agnit u des and the os m otic
    43 .

    pressure will be better understood after the fo ll ow i ng cons i derat i ons :

    1 . S ol u tion s in the s am e s ol ven t , sep ar ated by a s em i per m eabl e p ar ti


    -

    tion , c an on l y be in equ ilibr iu m when they are isotonic, i e when they exer t
    . .

    the s am e os m otic pr es su r e .
    D E TE R M I N A TI O N O F M O L E C UL A R WEI GH T . 63

    Le t i m agine the so lu t i ons in an apparat us c ons i st i ng of two Cyli nders


    us

    that are c onne c ted by a t ube c onta i ni ng a se m i perm eab le part i t i on I n -

    both c yli nders the l eve l of liqui d i s ke pt at the sam e he i ght c o ns t ant ly by
    addi ng or re m ovi ng so m e fro m t im e to t ime .

    The so lu t i on wi th the greater os m ot ic press ure will e xtract solvent


    fro m the other for be c au se of the stronger press ure whic h t h e dis so lved
    , ,

    m ole c u les e xert upon t h e free s urfa c e of t h e liqui d t h e rst so lu t i on ,

    w ill endeavor to i ncrease i n vo lum e at the e x pense of the se c ond .

    E quili br ium will be estab li shed so soon as the sa m e press ure is e xerte d
    by the d isso lved m o le cul es u pon t h e u ni t area of t h e free s urfa c es of the
    li qui ds fro m both s i des of the se mi permeab l e part i t i on ; in other words
    -

    when the so lu t i ons are i sotonic .

    2 . I s oton ic s ol u tions with the s am e s ol ven t h ave the s am e v ap or tens ion


    at the s am e temp er atu re .

    FI G . 20 . FI G 2 1
    . .

    The p roof of t h i s state ment lies i n the contradic tion to which the
    assurn pt io n that i soton ic so lu t ions hav e u ne qu a l va por tens i ons l eads .

    The a cc o m panyi ng di agram Fig 2 0 re presents a cl osed v esse l that


    ,
    .
    , ,

    is se parated by the se mi perm eab le part i t i on HH i nto two parts wh ic h


    -

    conta i n the i sotonic so lu t i ons A an d B N ear the t o p the two parts .


    .

    are c onne c ted with ea c h other As s umi ng that the vapor tens i on of A
    .

    i s greater than that of B vapor must pass o u t of A and c ondense in B ;


    ,

    the res ul t is that A be c o m es m ore c on centrated B m ore dilu te and , ,

    they are no l onger i sotonic In s uc h a c ase a cc ordi ng to t h e rst pri n


    .
    ,

    c ipl e the so lv ent wo ul d then begi n to pass thro ugh HH fro m B to A


    ,
    .

    The ass um pt i on of perpet u al m ot i on whic h i s thu s m ade ne c essary c an


    onl y b e avo i ded by s u ppos i ng that t h e v apor tens i on is the sam e .

    3 . I soton ic s ol u tions with the s am e s ol v en t h ave the s am e reez in g


    f
    poin t .

    Let u s again ta k e the sam e apparat u s c ontai ni ng in addition to , ,

    the i soton ic so lu t i ons A and B a pi e c e C of the so lvent in t h e so li d


    , , ,

    state ( Fig L e t u s al so ass um e that A and C hav e t h e sam e va por


    .

    tension We then have a c cordi ng to de nit i on (see


    .
    ,
    the t em
    64 IN O R GA N I C C HEM I S TR Y . 43 s

    pe rat u re of the free z ing point of A However if A and B are i sotonic


    -
    .
    , ,

    they hav e the sam e vapor tens i on B will therefore have t h e sam e .
    , ,

    vapor tens i on as C Hen c e B and C must a lso be at the i r only c oe xi st


    .

    en c e te m perature the free zi ng po i nt of B A t the i r free zi ng po i nts


    ,
    -
    .
    -

    A and B therefore hav e the sam e te m perature as C i e they possess


    , , ,
    . .

    the sa m e free zi ng po i nt -
    .

    4 I s ol on ic
    . sol u t ion s wit h the s am e s ol ven t h ave the s ame boilin g
    p oin t .

    As we saw i n 42 the bo i l i ng po i nt of a so lu t i on is that te m perat ure


    ,
    -

    at w hi ch the tens i on of i ts v apor e qu al s one at m osphere Two so lu t i ons .

    wi th a co mm on so lvent therefore have the sam e vapor tens i on at their


    , ,

    bo ili ng po i nt N o w it was shown above that so lu t i ons havi ng the


    -
    .
    ,

    sam e te m perat ure and vapor tens i on are i sotoni c If these so lut i ons .

    hav e the sam e v apor tens i o n (at the i r bo ili ng po i nt) and are isotoni c -

    they mu st also have the sam e te m perature .

    Si n c e as has j u st been de m onstrated is o t o n is m re qu ires li ke free z i ng


    , ,

    po i nts and bo ili ng po i nts i t i s -


    e vi dent the de press
    ,
    i on of the free zi ng
    po i nt and e l e v at i on of the bo ili ng po i nt mu st be the sa m e in i so
    -
    ton i c
    so lu t i ons wi th t h e sam e so lvent .

    In the depressio n of the freezing po m t and the elevation of the -

    boiling point we thus have a means of deciding whether solutio n s


    -

    ar e isotonic Us e is made of this fact for t h e determination o f


    .

    molecular weights in t h e following way : The freezing p oint of a -

    liquid e g water acetic acid phenol et c is rs t determined


    ,
    . .
    , , ,
    .
    ,
    .

    Thereu p on a gram mole cule of a substance whos e molecular


    weight is known is dissolved in a given weight (hence also in a
    given volume ) of the liquid A de pression of the freezing p oint . .
    -

    is observed This de pressio n will always be the same no matte r


    .
    ,

    what the substance is that is dissolved in the liquid p roviding ,

    that o ne gram molecule is dissolved in the same volume of liquid .

    The de pressio n of the free z ing p oint for o ne gram molecule of - -

    solute is thus a constant for the solvent .

    N o w if we p re p are a 1 % solutio n of a com p ound whose


    molecular weight M is unknown and measu r e the freezing p oint
    , ,
    -

    d e pression A we have , ,

    AM C onstant .

    This formula is also a pplicable t o th e elevation of the b oiling p oint -

    as can be readily seen M is the o nly unknown and can therefore .

    b e calculated .
    6 IN OR G A N I C C H E M I S TR Y .


    hav e sin c e been found to be r ic h i n potass ium salts bro mi des and other
    valu abl e mi nerals so that the waste sal ts of form er days are now the
    ,
    ,

    l eadi ng so ur c e of m any c ommerc i ally and s ci ent ically im portant c o m


    pounds .

    The pur ication o f these Stassfur t salts is accompl ished by


    solution in water and partial eva poration of the latter Vario u s
    substances crystallize out while the remaining liquid ( mother
    ,
    .


    liquor still contains the most soluble salts among which is mag ,

    n es iu m bromide M g Br z From this mother liquor the bromine is


    ,
    .

    obtain ed by the use of c hl orine which sets bro m ine free fro m ,

    bromides thus : ,

    MBr C l = M C I+ Br .
    (M Met al ) .

    The process em ploye d is an a pplication of the pr in cipl e of t he


    coun ter current -
    The mother liquor i s allowed to ow down
    -

    through a tower lled with round stones so that the expos ed sur ,

    face of the liquid is greatly enlarged A current of chlorine is .

    p assed into the tower from below and as it rises t h


    , e g as is ,in con ,

    stant touch with the bromide liquor the most concentrated gas ,

    being in contact with liquor which has already yielded the greater
    p art of its bromine so that p
    , ractically all the bromine is thus
    easily obtained The bromine pre pared in th is way always con
    .

    tains a little chlorine from which it is freed by distil lation over


    ,

    nely powdered bromide of p otassium .

    A nother metho d co mmon in t h e Unite d States of ob t aining


    , ,

    the bromine from the mother liquor is by distilling the latter -

    w ith manganese dioxide ( or p otassium chlorate ) and sul p h u ric


    acid corres p onding to the meth o d of making chlorine
    ,

    Still another metho d is to electrolyz e the bromide solutio n an d


    b oil o ff the bromine .

    The bromine thus obtained st ill contains a little water I t is



    .

    drie d b y shaking it with concentrated sul phuric acid and then dis
    t ill ing again .

    Physica l Pr op erties Bromine is a liquid at ordinary tem pera


    tures ; it is the only element excep ting mercury that dis plays this
    , ,

    p pro erty I t sol


    . i d ies at and boils at I t is dark brown ,

    and is trans parent only in thin layers A t the temp erature o f .


    H YDR O BR O M I C A C I D .
    67

    liquid hydrogen (205 absolute ) it becomes colorless ; M O I SSAN


    showed the same to be true of chlorine and uorine as well It .

    is quite volatile at ordinary tem peratures givin g o ff brown fumes ,

    of an extremely irritating and d isagreeable odor whence its name ,

    Sp g at
    . 1 00 parts of water
    .

    dissolve p arts of bromi ne The addition of potassium bromide


    .

    to the water increases its solubility a little Its vapor density is .

    The ch em ica l pr op erties of bromine are com pletely analogous to


    those of c hl orin e but the action of the former is less energetic
    , .

    While for instance chlorine combines with hydrogen in the day


    , ,

    l ight at ordinary tem peratures bromine does not ,I t s a fnity for .

    many elements is however very strong I t reacts vigorously with


    , , .

    phos phorus ; and powdered arsenic and ant imony take re when
    s prinkled u pon bromine I t is an interesting fact that of the two
    .

    closely related alkali metals potassium and sodium the former


    , ,

    r eacts vigorously with bromine while the latter does not react with
    ,

    it at all at ordinary tem peratures .

    The br om in e m ol ecu le cons ists of two atoms ; for since its va po r ,

    density is ( see ab ove ) its m olecular weight must be


    ,

    Inasmuch as a gram molec ule of no one of the very numerous


    bromin e c om pounds c ontai n s less than g bromine but often .
    ,

    simple multipl e s of this quantity its atomic weight is t ak e n to ,

    be based on O = 1 6 The molec u le therefore c ontains


    .
    , ,

    2 atoms .

    HYDR O G EN BR O M I DE, or HYDR O BR O M I C A C I D, HBr .

    45 This gaseo u s c om p ound c an b e obtained by direct syn


    .

    thesis fro m its elements ; for this p ur p ose it is necessary to p ass


    hydrogen together with b ro mine va p or t hrough a hot tub e c on
    , ,

    t aining platinum gauz e This is the most practical meth o d of


    .

    manufacturing it .

    Hydrob romic acid can also b e obtaine d by the actio n of h ydro


    gen o n brom in e com pou n ds Silver bro mide A gB r for ex am ple
    .
    , , ,

    is reduced by hydrogen at a high tem p erature to metallic silve r


    with t h e f or matio n of hyd r ogen bromide .
    IN O R G A N I C C HE M I S TR Y . 45

    Ou the other hand it is also fo rmed by the actio n of b romine o n


    ,

    hydr ogen com pou nds For this purpose numerous organic com
    .
    -o

    pounds can be used For exam ple bromine reacts with n aph
    .
    ,

    t h al e n e C 1 0H8 at ordinary tem peratures to form hydrogen bromide


    , , ,

    somewhat im pure however from the presence of orga ni c sub


    , ,

    s t ances Hydrogen bromide is also produced togethe r with free


    .
    ,

    sulphur when hydrogen sulphide is led into b r omi ne unde r water :
    ,

    s BI 2 '
    S ZHBr .

    Hydrobromic acid may also be pre p are d by the decom p osition


    o f a bromine com p ound with a hydrogen com p ound phos phorus ,

    p e ntabromide PB r5 and water being em ployed :


    , ,

    P h o s p h o ric
    aci d .

    A s ph O Sph O I l C
    '

    acid is not volatile but the desired substance is t h e , ,

    two products of the reactio n can be e as ily sep arated .

    Phys ica l Pr oper ties A t ordinary tem peratures h y drogen b r o


    mide is a gas I t can be co ndensed by cooling to a liquid whi ch
    .
    , ,

    boils at ( under mm pressure ) and by still farthe r .


    , ,

    cooling to colorless crystals which melt at


    , , I t has a
    p ungen t odor and a sour taste I n cont a ct with moist air. it forms
    dense clouds like hydrochloric acid
    ,
    I t is very soluble in
    water 1 vol water dissolving about 600 vols at
    ,
    . its solu .

    b il it y is thus eve n greater than that of hydrochloric acid .

    C h em ica l Pr op er ties Here too the acidic nature is stro ngly, ,

    dis played Various metals such as zinc and magnesium are


    .
    , ,

    acted upo n by hydrobromic acid forming a salt and free hydrogen ,


    .

    The most of its salts are soluble in water ; silver bromide however , ,

    is i ns oluble and lead bromide difc u l t l y soluble .

    A very high tem perature is required to decom pose hydrogen


    t
    bromide into its elements .

    The com pos ition of hydr obrom ic a cid can be determined i n the
    same way as that of hydro chloric acid Since its va por density is .

    it has a m olecular weight of The atomic weight of


    bromine being O = it follows that the formula of hydro
    (
    bromic acid must be HBr M oreover t h e dry gas c an be de c o m
    .
    ,
    IO DI N E .
    69

    posed with sodium amalgam where b y it is found that half of its ,

    vol u me consists of hydrogen ; this co n r ms the ab ove molecul a r


    formula .

    I O DIN E .

    46 . This eleme nt a crystalline solid was discovered b y C O UR


    ,

    To l s in 1 8 1 2 b u t its elementary natur e was rs t recognized in 1 8 1 5


    ,

    by G A Y L U SSA C L ike chlorine and bromine it does not o ccur in


    -
    .
    ,

    the free state b u t is frequently found in nature in combinatio n


    ,

    with some metal A n im portant source of iodine com p ounds is


    .

    the mother liquor 44 ) remaining in the puricatio n of C hili


    -

    salt petre ; another the ash of seaweeds known in Scotland as


    , ,

    help and in N ormandy as var ec which co ntains iodides The , .

    extractio n of the iodine is accom plished either by passing chlorine


    into the solutio n or by distilling with manganese dioxide and
    sulphuric acid in the same manner as for bromine and chlorine .

    The commercial iodin e is puried by warming it gently with the


    addition of a little potassium iodide the iodine subliming in the ,

    p ure state free from


    ,
    traces of chlorine and bromine that may
    have been present Finally it is dried in a desiccator over sul
    .
    ,

    p h ur ic acid .

    Phys ic a l Prop r ties


    e I odine forms tabular crystals of a dark
    gr ay metallic lustre I t s s pecic gravity is . at It
    melts at and boils under 7 6 0 mm pressure at .

    I t s va por is characterized by a beautiful dark blue color which -

    gave the element its name I n water it is only


    slightly s oluble enough however to color the water yellow I t , , .

    dissolves easily in a solution of potassium iodi de the latter being ,

    turned brown In various other liquids such as alcohol ether ;


    .
    , ,

    carbon disul phi d e and chloroform iodine is also easily soluble I t , .

    is a peculiar fact that the alcoholic and the ethereal solutions are
    bro w n while the sol utions in carbo n disul phide and chloroform
    ,

    are violet ; other solvents e g ben z ene gi ve solutions of an inter4


    ,
    . .
    ,

    me d iate c olo r The ex planation of this diversity of c olor is


    .

    that in the brown solutions the iodine has formed a comp ound
    with the solvent whereas in the violet solutions which have very
    , ,

    n early the same c olor as iodine va por the element exists in the ,

    free state .
    70 IN O R G A N I C C HE M I S TR Y . 46

    This c onclusion is reached in vari ous ways ; on e is fr o m t h e


    f act that the addition to the vi olet iodine solution of a smal l
    amount of a liquid that dissolves iodine with a brown c olor does
    not alter the freez ing p oint of the solution -
    The n umber of .

    molecules free to move has thus not been change d by this


    addition ; in other words the iodin e has unite d with t he a dd e d
    ,

    liquid .

    The v a p o r d e n s i t y o f i o d i n e i s ( a i r = 1 ) at about
    A s the te mperat u re ri ses i t grows stead ily s m al l er howe v er
    , ,
    .

    A t 1 5 00 we nd i t i s redu c ed to a lm ost hal f of what i t i s at


    Later 4 9 ) we shall ha v e o c cas i on to d i scuss th i s pheno m enon


    .

    known as d i s s o c i a t i o n whic h has been observ ed with many


    ,

    s ubstan c es .

    47 . Th e chemica l p p
    ro er ties o
    f iodin e r esemble very stron gly
    those of chlorine and bromine I t s affi nity for other elements is
    (
    .

    in general weaker however than t hat of the two hal ogens men
    , ,

    t io n e d I t c ombines with metals e g mercury d irectly to form


    .
    , . .
    , ,

    salts ( iodides) A ch ar acteristic test for iodine is the intense blue


    .

    c oloration which it imp arts to starch solution ; the slightest traces


    o f iodine c an be thus detected The blue c olor disappears on .

    b oiling an d r e appears on c o oling provi d e d the b oiling was no t t o o


    ,

    p rolonged .

    Th e b l u e
    substance form ed fro m i odine and starch i s not a c om
    p ound b
    ,
    u t i s to be regarded as a p rod u ct of the a bsorp tio n of i od i ne by

    star c h ; for the quant i ty of i od ine ta ken u p by star c h fro m the so l ut i on


    in K I depends l argel y on the c on c entrati on of the sol ut i on and does not
    beco m e c onstant ev en when a l arge e xc ess of so lu ti on is present I t is
    , .

    the rea c h in g of a constant rat i o that chara c teriz es c he mic al co m binat i on .

    The m o l ecu l e of iodin e in vestigated by the same method as w as


    ,

    employed with b rom ine is foun d to c onsist of two atoms at


    ,

    hence the formula is I 2 A b ove 1 500 it must c ontain o nl y on e


    .
    0

    at om fo r t he vap or d ensity is only half as great


    , .
    H YDR OG EN I O DIDE . 71

    HYDR O GEN IO DIDE, or HYDR I O DIC A C ID, H1 .

    4 This com poun d can be obta ined by dir ect synthesis from
    8 .

    its elements and that is really the best method for pre paring it
    ,

    in a perfectly pure state For this purpose hydrogen and iodine .

    va por are conducted together over heated platinum black which -

    a ccelerates their combination .

    Hydrogen iodide can also be ob t a ined by the reaction of iodine


    with hydrogen com po u nds O rganic hydrogen com pounds are .

    p referable es p ecially C,olo phonium and C o paiva o il This method .

    is also used for the laboratory pre paration of the gas but the ,

    hydrogen iodide thu s obtained is more or less adulterated with


    organic substances When iodine acts on hydrogen sul phide water
    .

    hydrogen iodide is formed sul phur being liberated ,

    A s an exam ple of the action of hydrogen on an iodine com pound ,

    we may mention the reduction of silver iodide by hydrogen from ,

    which hydrogen iodide results .

    Finally the action of an io d ide on a hydrogen com pound is


    ,

    il lustrated by the decom position of a phos phorus iodide PI 3 or ,

    PI 5 by water
    , As was ex pl ain ed in 4 5 it is possible to use
    .
    ,

    p hos p horus iodine and wate r,


    This method with some va r iation .
    ,

    o r other is the preferable one for the preparation of hydriodic


    ,

    a cid .

    A c c ordi ng to G A TT E R M A N N it is best to rst add ye ll ow phosphorus


    ,

    ( 4 g ) i n very s m all pi e c es to 44 g iodi ne and then de c o m pose the res ult


    . .
    ,

    ing c o m pound with a littl e water In order to re m o ve t h e free i o di ne .

    fro m the hydrogen i odi de for m ed the gas i s all owed to pass over red ,

    phos phor u s .

    The de c o m pos i t i on of the hal ogen sal t by sul phuric a ci d is even less
    ava il ab l e for the pre parat i on of hydr i od ic than for hydrobro m ic acid ,

    s i n c e the for m er is m ore eas il y deco m osed by s ul h ur i c a ci d than t h e


    p p
    l atter .

    Physical Pr oper ties Hy d rogen iodide is a colorless gas whos e


    .
    -

    s pecic gravity is I t fumes st r ongly when exp ose d


    to the air and possesses an acid reaction and a pungent odor A t
    , .


    0 and 4 atmos pheres pressure it condenses to a colorless liquid ,

    wh ich boils at 3 4 1 4 under a pressure of -


    mm The melt
    -

    .

    ing point of the solid is


    -
    Hydrogen iodide is very soluble
    72,
    IN O R GA N I C C HE M I S TR Y 48

    in water ; 1 vol Hg O a t 1 0 d issolves 4 25 vols HI Th is solution


    .

    . .

    fumes strongly and turns dark brown after a time b ecaus e of t h e


    , ,

    liberation of iodine .

    C h ica l
    e m Pr op r ti
    e e s Hydrogen iodide has all the charac
    .

    t er is t ic s of an acid With metals it forms salts ( iodides ) hydrogen


    .
    ,

    being given o ff These are ahn os t all soluble with the exceptio n
    .
    ,

    of the iodides of s ilver and me r cury L ead iodide is slightly solubl e


    . .

    at ordinary temperatures I n addition to its acidic character


    .
    ,

    hyd riodic acid possesses another pro p erty which is not found in ,

    hydrochloric and hydr obromic acids Since it Splits u p readily .

    into hydrogen and iodine it can act as a strong reduc ing agent
    ,
    -

    especially at high tem peratures I t has already been remarke d .

    that the aqueous Solution of the gas turns brown iodine bein g ,

    set free by the oxidiz ing action of the air ; this change is greatly
    aided by the inuence of light A t a high tem perature hydr ogen
    .

    iodide is decom posed into H2 and 1 2 as is shown by t h ea ppearanc e ,

    of the violet iodin e va por I n organic chemistry p articularly


    .
    , ,

    frequent use is made of the reducing p ower of this acid -

    Form u la of Hydr iodic A cid The va por d ensity of this sub


    stance has been found to be I t s molecular weight is ther e
    fore The at omic weight of iodine being
    it is seen that the molecular weight c orres p onds very closely to t h e
    formula HI = an d no other formula is p ossible .

    DI SSO C I AT I O N .

    49 . When hy d rogen iodide is subj ected to a slow increase of


    temperature it co m mences to decompose at a denite temp eratur e
    ,

    slightly above 1 80 into hydrogen and iodine vapor As the heat



    .

    ing continues the decom position grows gradually gr eater til l a


    ,

    p oin t is nally r eached when the gas mixture contains only t h e

    individual elements I f the m ixture is then l w l y cooled t h e


    .
    ,

    same stages are passed thr ough in in verse order so that the degre e ,

    o f decom p osition at any one tem perature is found to be the same ,

    no matter whether the temperature was a pproa ched from above


    o r below it being only necessary that the p articul ar tem p eratur e
    ,

    s hould be maintained for a sufcient length of time in both cases .

    The phenomenon j ust described is to be observed with a grea t


    74 IN O R GA N I C C HE M I S TR Y . 49

    from a syste m re m a ining at constant te m perat u re but according to t h e ,

    p r i nc i pl es of ther m odyna mi cs t h i s i s im poss i b l e s i n c e


    ,
    t h e p rod u ction of

    work is always acco m panied by a fa ll of te m perature .

    The question now arises how such an equilibrium comes ab out


    , ,

    an d why the d ecom p osition of a com poun d that begins at a cer


    ~

    t ain tem peratur e does not complete itself To th is the kinetic



    .

    theory of gases fu rnis h es a satisfactory answe r A ccording to this .

    theory the molec ul es of gases are co nstantly in motion Whil e .

    a constan t m ean velocity of the molecules may be assumed to exis t


    '

    fo r every tem perature the velocities of the individua l molecules


    ,

    m ust be considerably d ifferent because of their very frequen t


    ,

    c oll isions with each other The atoms of a molecule mus t also b e
    .

    s u pposed to be ca pabl e o f changing their res pec tive positions fo r ,


    f

    t h e re p eated collisions o f the molecul es dis place the at o m s fr om their


    p ositions of equilibriu m These. movements of the ato m s are t h e

    more violent the greater the velocity of the molecul es It is easy .

    to conceive that they may at las t become so violent as to thr ow '

    t he atoms out of their s phere of mutual attraction Th e m ol ecul e .

    is thus broken u p In a body of gas at a denite tem perature this


    .

    will however only occur in those molecules whose velocity is


    , ,

    above c ertain limits ; henc e we see a reaso n for par tia l decom msi

    tion . The ex planation of partia l com bina tion is exactly analogous .

    Th e atoms set free from the molecules o f the elements en t er into


    the s pheres of mutual attraction and if their velocities are n o t
    ,

    g r eat enough to resis t the attraction the di ff erent,


    atoms unit e .

    In the case of the form ation and deco m position of hydrogen iodide
    this can be c on c eived as foll ows : Two HI m o l e c ul es m eet in s u ch a
    state of ato mi c m ove m ent that the H ato m s enter the spheres of attrae
    t i on of ea c h other and the I ato m s like wise so that H2 and I2 are form ed
    , ,
    .

    O n the other hand these m o l e c ul es H2 and I 2 m ay aga i n m eet i n s uc h a


    ,

    way that ea c h H ato m enters the s phere of attra c tion of O n e of the


    I at oms whereupon two HI m o l ecul es are for m ed
    , .

    A ccording to the above the state of equilibrium is to be ao


    counted for by su pp os ing that in the unit of time j ust as much
    p ass es from the one system into the other as v ic e ver sa U nt il .

    the state of equilibrium is reached the amoun ts which pass fro m


    ,

    o n e system into the o ther in the unit of t ime are unlik e .


    DI S SO C I A TI O N 75

    or d e r to d ene more clearly this condition of equilib rium w e


    In
    m us t in tro d uce the concep t of r e ac tio n v e lo c ity By th is term .

    we understand the number of moles transformed from one system


    in t o the other in the unit of time Suppose that in the unit of .

    volume (one liter for instance ) there are a moles of a substanc e


    ,

    A whi ch can un dergo a chemical change into a substance B If

    .
    ,

    in the unit of time (say one m m u t e) moles of A are converte d

    into B, the reaction velocity S will b e expressed b y


    Z . In cas e
    there ar e originally o nl y %a moles of A per liter ex periments ,

    have shown that the number of moles converted per minute is


    1 a
    We thus p erceive that the r eaction v el ocity is pr opor tional
    2 n

    to the number of gram molecules per liter or in other words to


    -

    , , ,

    t he con cen tr a tion This is a princi ple of very wide a pplication ;


    .

    it is ordinarily called the l aw of c h em i c al m as s a ctio n I t nds .

    a general ex pression in the equation

    in which K is a constant factor the re ac tio n c o n stan t , or


    , l
    v e oc ity
    c o n st an t .

    5 0 L et. us assume that the molec ul es of a com pound are dis


    s oc iat e d by heat into two others the process being expressed by,

    A =R +a
    in which A B and C re present single molecules O f the su b
    ,
    .

    stanc e A a gram molecul es were originally present but in t h e


    ,
    -

    course of a denite time t x gr am molecules have undergone the


    , ,
    -

    above decom p osition The problem is to ex press the reaction


    .

    velocity at any moment A t the beginning ( during the rst


    .
    .

    minute ) the reaction velocity is pro portional to a ; after the time


    t when the concentration has fallen to a x the amount converted
    , ,

    during the succeeding minute will be pro portional to a x The .

    r eaction velocity thus constantly dim inishes This being the case it '
    .
    ,

    =
    is evident that s k a and s h (a x) are not the true expressions
    = o

    respectively, for the reaction velocity in the rst minute and in the
    minute fo l lowing the time t They woul d be correc t if the con .
    ,

    c entration remained constan t dur ing these minutes in stead of


    76 IN O R G A N I C C H EM I S TR Y .
    50

    d im inishing as ,
    it
    does in real ity However we can a pproach .
    ,

    the real velocity by consideri ng n o t one minute b u t a very small


    fraction of this unit of time which we will call At ; the smaller At
    ,

    is taken the less is the concentration change Supposing tha t .

    t he quantity of A which is transformed in this very short period


    At is Ax , the expression must be very close to the real velocity ,

    because it indicates the quantity transformed in a unit of time


    so small that the concentration scarcely dimin ishes during it .

    We a pproach the true velocity nearer and nearer according as


    w e take At smaller and smaller and when it is made in ni t ely ,

    Ax
    small becomes the exac t expression o f the velocity It is
    22
    .

    customary to expres s such innitely small quantities by the letter


    d, thus
    if The mathematical ex pression for the velocity at
    a time t,
    when the concentration is a x , thus b ecom es
    A :

    dl
    7

    K b eing the velocity constant .

    The above reactio n is te rmed u n im ol ec u l ar Wh e n t wo ( like o r .

    d ifferent ) molecules react with each other the reactio n is called ,

    bim ol e c u l ar ; it may be re presented by the equatio n

    A +B= C m

    The equatio n fo r the reactio n veloc ity is different in this latte r


    c ase A ssuming that originally a gram molecules of A and b gram
    .
    -

    molecules of B take pa rt i n the reactio n and that x gram molecul es ,


    -

    o f A and of B are decom p osed at the end of the period t there must ,


    be res pectively a x and b x of the two substances present at
    , ,

    this mo m ent The r eactio n velocity will the n b e propo rti o nal t o
    .

    t h e pro d uc t of t h es e quantities thus ,

    Si
    g; K '
    <
    a x > b x
    ( >.

    in which K is again a co nstant ; for su ppose that ther e were o nly


    o ne molecule of A p resent ; the p ossibility of its reacting with a


    D I SSO C I A TI O N 77

    molecule of B woul d then b e pro portio nal to the number of mole



    c ules of B Whe n there are a x molecules of A this possibility
    .

    '

    becomes a x times as large .

    I t is assumed in the above that the tem perature is Constant .

    We shall see in 1 04 that this factor has a great inuence o n the


    r eactio n velocity .

    5 1
    . The manner of ex p ressing the conditio n of equilibri u m is
    now plain A ssuming that the reactio n velocity of the o ne system
    .


    is S and tha t of the other S eq u ilibrium must exist when
    ,

    S=S

    .

    The s ta t e o f may therefore b e dened as that s ta te


    equ il ibr iu m

    in which the r ea ction v e l ocities of both s yst em s ha ve becom e equa l .

    L et us a pply these co ns ideratio ns to the dissociatio n of hy d ro


    ge n iodide T hi
    . s may be ex pressed by
    lg .

    If a gram molecules HI per unit vo l um e are present originally an d


    -

    x of these are decom posed after a give n period the reactio n velocity ,

    at this moment ( since in this case a = b and the r eactio n is evi ,

    de n t l y bimolecular ) is
    S C (a x) 2
    ,

    C being a co nstant .

    F r om the x gr am molec ul es of hydr o gen io dide


    -

    g gr am m ol e
    -

    c ul es of hydrogen and an equal amount of iodine have been fornie d .

    The vel ocity of formatio n of HI from H2 and 1 2 is therefore ex


    p ressed by the equa t io n
    =
    S C I

    in which C
    is a co ns tant . A ccordingly equilibrium will e xis t
    when
    C (a

    in which K is substituted for


    78 IN O R G A N I C C H E M I S TR Y . 51

    This equa t io n may b e writte n in a slightly differen t way sin c e ,

    in gases the number of molecules per unit Volume is pro po rtio nal
    to the pressur e A ssuming that at a given moment t h e
    pressur e of the hydrogen iodide still present is p that of the hydro ,

    ge n is pl and that of the iodine vapor pg the equilibri um constant


    , , ,

    K can be r epresented by the expressio n


    ,

    ff
    lp
    k
    2
    x .

    It has b een ascertained that the dissociation is less if t h e hy


    drogen iodide was originally mixed with hydrogen or with iodine
    va por The necessity of this being true follows immediately from
    .

    the above equation for the additio n of these gases amounts to an


    ,

    increase of pl or pg I f K is to remain constant p or in other


    .
    , ,

    words the mass of undissociated hydrogen iodide mus t increase , .

    We see also from the equation that the same increase of Hz or of


    1 2 must have the same inuence o n the equilibrium A further .

    conclusion from this equatio n is that when p p 1 and p2 are in , ,

    creased n fold i e when hydrogen iodide undergoing dissociatio n


    -

    ,
    . .

    is com pressed or expanded at a co nstant tem perature the d egree ,

    o f dissociatio n must remain unaltered since ,

    This t oo is co n rmed by ex periment


    , ,
    .

    I n the dissociatio n of hydrogen iodide the gas volume d oes no t


    change since two molecules ( 2 H I ) yield two molecules (H2 and
    ,

    I n all such cases the degree of disso ciatio n must be inde pendent
    of the volume because an increase or decrease in the latter causes
    ,

    changes in the co ncentratio n of the reacting gases which are pr o


    p ortional to each other and hence the factor re
    , p resenting t he
    concentratio n falls out of the equatio n .

    Hydrogen i od i de is al so de c o m posed by is a pe culi ar fa c t light . It


    that thi s di sso ci at i on i s u nim o le cular ( HI whil e that c au sed by
    ri se of te m perat ure i s b im o l e cul ar Thi s m ay be de m onstrated by the
    .

    fo ll o w i ng very general m ethod Wh en the react i on i s unim o l e cul ar


    .
    ,

    dx
    the e qu ation for the vel oc i ty of deco m pos i t i on i s
    ?
    t
    a
    K (a -

    )
    x . When ,
    52 ] FL UO R HVE .
    79

    however ,
    it is b im o l e c ul ar t he e quat i on be c om es
    dx
    =K 2
    Wi th the he l p of i nte gra l c alcul us these e quat i ons c an
    a ( a x ) .

    be so lved for K; from the rst we nd

    K=
    % ma

    where l og i s the nat ura l l ogar i thm and fro m the se c ond
    e ,

    J .


    (
    '

    t a a x )
    If now we determi ne x for var i o u s values of t the val ues of K can , be
    c alc ul ated ; they mu st be c onstant I f this constancy appears in .

    the rea c t i on i s unimo le c ul ar if in b im o lec u lar , .

    FLUO R IN E .

    5 2 This element
    . was rst isolated from it s com pounds b y
    M O I SSAN in 1 886 It o ccurs in nature chiey in combinatio n with
    .

    calcium as u or s par C a and in certain rare minerals


    , , .

    The great difculty in obtaining it in the free state is due to


    its very great afnity which makes it unite with other elements
    ,

    even at ordinary tem peratures As yet it has o nly been success .

    fully pre pared by the electrolysis of pure anhydrous hydrouoric


    acid in which potassi um uoride h as been dissolved to make the
    liquid a co nductor .

    The m anner i n whi c h M O I SSAN ac c o m plished this is interest i ng .

    A mix t u re of abo u t 2 00 g anhydr o u s hydro u or i c a ci d and 6 0 g


    . .

    hydro gen potass i um u ori de i s i ntroduced i nto a c o pper Ut ube ( Fig .

    22) of a ca pa ci ty of abo u t 3 00 c c whi c h has two l atera l exi t tubes


    . .
    ,
    -
    .

    The o pen ends of the U t ube are cl osed w i th sto ppers FF m ade of
    -

    u or s par and wra pped i n very thin sheet pl at i num .

    The c yli ndric al e lectrodes ti of plati num i ri dium pass th rough the -

    sto ppers and are he l d i n pl a c e by the c o pper s crews EE which t t ight ly ,

    to the ends of the Ut ube w ith the he l p of a band of lead P


    ,
    .

    During the e l ectro l ys i s the a pparat u s i s k e pt at the constant t e m


    p e r at ur e of 2 3 (by bo ili
    -
    ng
    m ethy l c hl or i de ) T h e free u or i ne .
    ,

    whic h i s given o ff as a gas at the pos i t ive e l e c trode is rst passed thro ugh ,

    a pl at i num vesse l that i s c oo led by a mix t ure of so li d carbon di o xi de


    and al coho l i n order to condense the ac i d fum es which were carried
    ,
    IN O R G A N I C C HE M I S TR Y . 52*

    o ver with it The last traces of the a c id are re m oved by c ondu c t i n g


    .

    t h e gas t h ro u gh two pl at i num tubes c ontai ni n g sod i u m uor i de wh ic h ,

    absorbs the hydro u oric a ci d The free u or i ne gas was c o ll ected by


    .

    M O I SS AN i n a pl at i nu m t ube whose two ends were c l osed w i th plates


    ,

    of u or Spar so that one co ul d l oo k thr o ugh .

    FI G . 2 2 PREPARAT
    . IO N OF FL U O R I NE BY E L E C R O LYS IS
    T .
    ( A FT E R M O I SS AN )
    .

    Later M O I SS AN fo u nd that perfe c t l y pu re uorine attac k s gl ass but


    Very sl owl y so that the gas
    ,
    m ay be coll e c ted i n gl ass vesse l s .

    Physica l Pr oper ties .



    Fluorine is a gas with a ve ry pungent
    o dor and a greenish yellow color which is somewhat paler than
    -

    that of chlorine A s a liquid it boils at 1 87 and is bright yellow


    .

    .

    l t can be co ndense d in a glass vessel


    a When cooled by liquid .

    hydroge n it freezes to a white mass that melts at The ,

    Specic gravity of the gas is 1 9 tha t of the liquid

    C hem ica P p ti s
    l r o er e Of
    all the elements now known uorine
    p

    has the stro ngest tendency to fo rm com pounds I t co m b in es .

    with hydrogen in the dark at ordinary tem peratures in an ex pl o


    s ive manner M O I SSAN demo nstrated this with the hel p of the
    .

    ab ove a pparatus by reversing the electric curr ent while uorin e


    82 IN O R GA N I C C HE M I S TR Y . 53

    tio n of t h e aci d which fo r t h e a b ov e r easo n mus t b e pres erve d in


    ,

    bottles of lead or caoutchouc .

    By direct synthesis from its elements 52 ) hydrouoric acid


    may also be obtained A nother method is by the actio n of hydro
    .

    gen o n a uorine com pound ; e g silver uoride when heated . .


    ,

    in a current of hydrogen gives hydrogen uoride ,


    .

    '

    Still other methods ar e b y the actio n of uorine o n hydrogen


    com pounds 52 ) and by the direct decom positio n of certain com

    p ounds ,
    such as hydrogen p otassium uoride K F H F which . ,
    -
    ,

    Splits u p o n heating into the two uorides This las t r eactio n is .

    made use of when anhydrous acid is sought .

    Phys ica l Pr oper ties A nhydrous hydrouoric acid is a color


    less liquid at ordinary tem p eratures It boils at 1 9 5 and solidies .

    at Sp g ( H = 1 ) . at . I t has an extremely

    p ungent o dor and is very p oisonous . when inhaled I t is very .

    soluble in water .


    C hem ica l Proper ties The aqueous solution of hydrogen
    .

    uoride the hydrouoric acid o i c o rmn erc e p oss esses entirely


    ,
    '

    the character of an acid ; it evolves hydrogen with most metals ,

    the precious metals however and also lead being un affected by it


    , , ,
    .

    The uorides of the metals are in general soluble in water ; some , , ,

    however such as those of C o pper and lead dissolve with difculty


    , , ,

    while those of the alkaline earths ( C a Sr and Ba) are insoluble ,


    .

    I t is a p eculiar characteristic of the alkali uorides that they a r e


    able to combine with a molecule of the aci d forming double uorides ,

    like that described above K F HF ,


    -
    .

    Thi s chara c ter i st ic i s probabl y d ue to the fa c t that i n a qu eous solu


    t i on the m o l e cule of hydr o uor ic a ci d is H F Th e form at i on of suc h z 2
    .

    do ubl e m ol e cules i s o ften obser ved for a ci ds (espe ci all y org anic a ci d s) I t .

    i s c all ed a ssociation T hus liqui d water cons i sts i n all probability of


    .

    H 02 4 m o l e cul es
    . I?

    The mos t irn por t an t pro perty of the gas for practical purposes
    is th at it attacks glass ( f c A s a result .it nds extensiv e

    u se in e t c h i n g g l a s s

    G l ass m ay be et c hed in two ways with a so lu tion of the gas or with
    the gas i tse lf In the rst c ase the et c hi ng i s shiny and transparent ;
    .

    i n t h e second dul l Th e gl ass obj e c t i s c overed wi th a coat of wax i n


    .

    wh ic h the gures or l etters whic h one des i res et c hed on the gl ass m ay
    be dra w n w i th a sty l us Then the ob j e c.t is e i ther d i pped i n dil u t e
    H Y DR O FL UO R I C A C ID .

    hydro uoric a c ra for a whil e or se t o ver a l eaden di sh whic h c ontains a


    mixt ure of s ul phur ic a ci d and c alcium u ori de kept s li ghtly warm by a
    l ow ame O nly the pl a c es where the c oat ing was rem oved are att acked
    .

    so that when the l atter i s s ubse qu ent ly d isso lved o ff (by t ur pentine or
    ,

    alcohol ) the etchg u re i s vis ible .

    M O I SSA N h as proved that gl ass is a lso attac ked by perfe c t l y dr v


    hydro uor ic ac i d gas .

    The form u l a of hydrou oric acid gas is HF which can be de t er ,

    mined in exactly the same way as was done for the analogous
    chlorine and bromine com pounds .

    C om pou n ds of th e Hal og en s wit h e ac h ot h er.

    54 . Th e hal ogens or s alt formers i e t h e el ements uorine ch lorine


    ,
    -

    ,
    . .
    , ,

    b romine an d i o di n e ( s o c all e d b e c au s e th ey form salts w ith m et al s b y d ire c t


    -

    c o mb inat ion) c an unite w ith e ach othe r to for m rathe r u n stab l e c ompounds
    , .

    I n g e n eral t h e mo s t st ab l e o f th e s e c o mpo u n ds ar e tho se w h os e c o mp onent


    h al og e n s s h o w t h e gre at e s t d i ss imil ari ty .

    I o di ne uni te s w ith uor ine t o form a c om po und I F w h ich c an e xi s t e ven 5,

    in t h e g ase o u s s t ate Th e re is al s o a Br F ; c h l or in e a n d u or i n e h ow e ve r
    .
    a , ,

    do n o t co mb in e w ith e ac h other .

    C h lorin e an d b romine at l o w te mp e ratur e s give an u n bro ken s eri es o f


    mixe d cryst al s 2 1 2 b u t form n o c ompo un d
    ,
    W ith i o din e ch lor in e give s .

    t w o c o mpo u n ds I C l an d I C 1,
    I t de pe n d s o n t h e qu an t ity o f ch l or in e prese n t
    3 .

    a s to w he th e r t h e forme r or t h e l att e r is o b t a ine d I C l is a re ddi sh b ro w n o il .

    th at eve ntu ally y ie l ds c ry st al s me l ting at it bo ils at W ater


    de c ompo s e s i t i n to io dic aci d i o di n e an d h y dr ogen chl ori de
    ,
    I t exi sts in t w o .

    mo dic ation s I C l crystalliz e s in lon g ye llo w n ee dl e s an d o n fus in g dis


    .
    3

    s o ci at e s almo s t c ompl e t e ly into 1 C ] an d C I I n a sm all qu ant i ty o f w at er 2 .

    it di s solve s almost u n ch an ge d ; b u t a l arge r qu an t ity of w ater de compose s it


    p a rt i all y i n to h yd ro g e n c h l or i de a n d i o d ic a ci d .

    B romi ne an d io di n e give only o n e c ompound BrI w h ich is c o n s i derab ly , ,

    di sso ciate d in t h e liqui d as w e ll as in t h e g aseou s state .

    O xygen C o m po u n ds of the Hal o ge n s .

    With t he exce ption of uorine the halogens are known to form ,

    various oxygen com pounds havin g the common pro perty of ,


    .

    instability i e of being easily decom posed M ost of them can


    ,
    . . .

    combine with water forming acids O xides which show this latter
    ,
    .

    pro perty are called a c i d an h ydrides The acids which are thus .

    formed from the halogen oxides contain each but 0 n e hydro


    gen atom and this can be re placed by a metal A cids conta in
    ,
    .

    ing one hydrogen atom which can be thus substituted are called
    m on o b a s i c .
    84 IN O R GA N I C C HE M IS TR Y . 55

    HY PO C HLO R O US O XI D E . C HLO R IN E M O N O XI DE, C l .

    '

    55 This com
    .
    p ound can be re
    p p ared by p assing c h l o rin e 0 v er
    dry mercuric oxide at a low tem perature

    Hypochlorous oxide is a brownish yellow gas at or d in ary tem -

    p e r a t u r e s I t can
    . be condensed by strong cooling to a dark brown -

    liquid which bo ils at


    ,
    It is an extremely dangerous sub
    stance e s pecially in the liquid state since the slightest mechanical
    , ,

    disturbances make it ex plode vigorously breaking u p into it s ,

    elements I t is possible to distil it without decom position only


    .
    ,

    when everything with which it comes in contact is entirely fre e


    from dust ( organic matter) It acts upon s u l phur phosphorus
    .
    ,

    and com pounds of carbon with ex plosive violence .

    The composition of this com pound w as de t e rm in e d by BA LARE


    in the following way : He in t roduced 50 vols of the gas into a .

    tube over mercury and decomp osed it by gently warming He .

    thus obtained a mixture of chlorine and oxygen which occupie d


    somewhat less than 7 5 vols Af ter the chlorine was removed by
    .

    caustic potash 25 vols remained i e 50 v o l s c h l o r in e were present


    , .
    ,
    . . .
    .

    the slight difference which was observed being ascribable to t h e


    fact that a little chlorine had united with the mercury in the tube .

    1 vol hy pochlorous oxide yielded therefore 1 vol c hl orin e an d


    . .

    1; vol oxygen
    . This indicates the formula C 12 0 :
    .

    2Cl gO 2C l z 02 .

    2 v o ls . 2 v ol s . 1 v ol .

    Th e vapo r d ensity of the com pound was foun d t o b e


    ( ai r or ( 0 I t s molecular weight therefore b ecom es

    c o rres ponding to the formula C l C l = 7 1 O = 1 6 sum


    ( 2 ; ;

    HY PO C IILO R O US A C I D , E C l O
    -

    56When chlorine monoxide C l


    . is p asse d in to wa te r it is
    , , ,

    ab sor b e d ; t h e solu t ion c ontains hy pochlorous aci d :

    C 12 0 HgO 2 HC l O .
    H Y PO C HL O R O US A C I D .
    85

    This c ompound is known o nl y in aqueous solutio n Its c om .

    p osit ion is studie d in its salts :


    l l h e same aqueous solution can also be o b tained b y add ing
    r

    n ely p owdered mercuric oxide to chlorine water .

    Hg o + 2 01 2 + H 20 = Hg01 , + 2 010 H .

    So l u l eb .

    Up on distillation a pure aqueous solution of the aci d is


    obtained .

    Still another method of pre paring the acid solution is to lead


    chlorine into the solution of a base e g potassium hydroxide a t
    ,
    . .
    ,

    the ordinary tem perature whereupon a salt of hypoc hl orous aci d


    ,

    hy
    ( p och l orite ) is formed :

    2 K O H + C 12 KC l + KC l O + 1 1 2 0 .

    By carefully treating the hypochlorite with the equivalent


    amount of nitric acid the hy p ochlorous acid is set free and can be
    se parated from the salts by distillatio n .

    Whe n concentrated the aqueous solutio n of hy p ochlorous acid


    ,

    has a golden color I t is unstable ; only dilute solutio ns can b e


    .

    distilled without decom positio n I t oxidizes vigorously breaki ng


    .
    ,

    u p into oxygen and hydrochloric acid :

    2C l O H 2 HC l + 0 2 .

    On the addition of hydro chloric acid all the chlorin e of b oth


    com pounds is set free

    HC l O HC l C 12 Hg O .

    The hy pochlorites act j ust like the free acid since the presence ,

    of v ery weak a cids e g the carbo nic acid of the air serves
    ,
    . .
    ,

    to liberate hy p ochlorous acid They are therefore extensively


    .

    em ployed as bleaching agents A solution of p otassium


    hy p ochlorite ( eau de Ja vell c) is used for this purp ose but chloride ,

    of lime bleaching p owder 2 5 8) deserves p articular notice The
    ,
    .

    latter is obt ained by treating lime with chl orine at or d inary tem
    86 IN O R GA N I C C HE M IS TR Y .

    p e r at u The b leaching actio n of hy po chlo r o us acid is twi ce


    r es .

    as great as that of the chlorine which it co ntains would b e if t h e ,

    latter were to act in the free state :


    2Cl Hg O 2 HC l O and 2 Cl O H 2 HC l 20 .

    However it should be remembered that tw o atoms of chl orine


    ,

    we r e necessary to form the on e HC l O molecule


    2 KO H Olg KC l KCl O Hg O .

    On shaking an a queo u s solut i on of hypo c hl oro u s a c id with m ercury


    a bro wn i sh ye ll o w pre ci pi tate of m er cur ic o xy c h l or i de a O HgC l z is
    -

    ,
    '

    form ed whic h i s i nso lubl e i n hydro c hl ori c a ci d C hl or i ne water on the


    ,
    .
    ,

    other hand when sha ken wi th m er cury gives white m er curi c c hl ori de
    , , ,

    HgC lz (s ub lim ate) These rea c t i ons enabl e us to d i st i ng ui sh between


    .

    the two s ubstanc es .

    I n a d il ute a queo u s so l ution of c hl orine we have the fo ll owing e q uilib


    ri u m :

    Cl2 H,o HC 10 ,
    as is shown by the facts that the so lu t i on reacts distinct ly a c id toward
    litmu s an d that the hypo c hl oro u s a c id c an be separated fro m t h e hydro
    c hl or ic a ci d by dis t ill at i on .

    Th e di fferen c e i n the a c tion of c hlorine water and a so l ut i on of hyp o


    c hl oro u s a ci d on mer cury i s d ue to the fa c t that i n the above e quilibr i um
    t h e syste m C lz l HzO is by far the predo minant one
    - -
    .

    C HLO R I N E DIO XI DE, 0 10 2 .

    57 This gas
    . is formed when p otassium chlorat e KC l O 3 is , ,

    treated with co ncentrated sulphuric acid C hloric acid is at rs t .

    set free and this decom poses as follows


    3 HC 10 3 HC l O 4 2Cl O g HzO .

    C h l o ric P e r c h l o ric
    aci d . ac i d .

    C hlorine dioxide is a dark yellow gas I t can b e con d ense d t o -


    .

    a liquid which boils at 9 9 and solidies at 7 9 to a yellow



    ,

    crystalline mass I t has a peculiar odor resembling chlorine and


    .

    burned sugar .

    C hlorine dioxide is extremely ex plosive ; warming j arring o r ,

    co ntact with organic substances causes it to ex plode with vio


    lence L ight slowly decom poses it
    .
    .
    C H L O R I N E DI O X I DE .
    87

    The following e xperi m ents give one an idea of the vigor with wh ic h i t
    c a u ses o xi dat i on ( 1 ) Wh en ne l y powdered s u gar i s mixed caref ull y
    .

    wi th potass ium c hl orate and a dro p of c onc entrated s ul phur ic a ci d i s


    added t h e who l e m ass b ursts into am e Th e c hl ori ne di o xi de set free
    ,
    .

    m a kes t h e s u gar b u rn at ordi nary te m perat ure ( 2) Pl a ce a fe w pi e c es .

    of ye ll ow phos phor u s and so m e c rysta l s of potass ium chl orate u nder


    water and all ow a few dro ps of c on c entrated sul phuric a ci d to ow down on
    t h e two s ubstances The phos phor u s at on c e b urns un der water w i t h
    .

    a brilli ant l i ght .

    C hlorine dioxide is soluble in water Such a solutio n ca n be .

    easily pre pared by oating a little porcelain c u p in a large crystal


    l iz in g dish with a at brim and co ntaining 220 c c water putting
    -

    . .
    ,

    into the c u p 1 2 g potassium chlorate and adding a cooled mixture


    .

    of 44 c c co nce ntrated sul phuric acid and 1 1 c c water The


    . . . . .

    crystalli z ing dish is the n covered with a glass plate The chlorine
    .

    dioxide evolved dissolves in the water forming a yellow solutio n , .

    When a base is added to a chlorine dioxide solution a chlorite ,

    58) and a chlorate are formed :


    2 KO H 2C l O z K C 10 2 K C 10 3 Hg O .

    Po t . c h l o r it e . Po t . c h l o rat e .

    This reactio n proceeds very slowly Ti dil u t e solutio n .

    The com position of chlorine dioxide was determined by G A Y


    L U SSA C as follows : He allowed the gas to ow through a ca pillary
    tube with three bulbs By heating the part of the tube in fro nt
    .

    of the bulbs he decom posed the gas the actio n being non ex pl o ,
    -

    sive i n so narrow a s pace Thus there was obtained in the bulbs


    .

    a mixture of oxygen and chlorine in the same pro portio ns as they


    are contained i n the com p ound The chlorine was absorbed by .

    p otash and the residual gas ( oxygen ) was p assed over into a
    measuring tube The ca pacity of the bulbs being known it was
    -
    .
    ,

    p ossible from these data to calculate the volume ratio of oxygen


    and chlorine I t was found that
    . v ols of the oxide yield 9 87 . .

    vol chlorine and


    . vols oxygen The c ombining ratio is ve ry
    . .

    close t o that o f 1 : 2 re presented by the formula C 10 2


    ,

    2 010 2 C 12 20 2 .

    2 v ol s . 1 v ol. 2 v o ls .

    This form ula is also conrmed by the v a por density which was ,

    f ound t o be at while the formula C l O z demands


    16
    88 I N O R G A N I C C HE M I S TR Y . 58

    C HLO R O US A C I D, E GIO

    58Th is ac i d i s unkno wn in t h e p ure state It s sodi um sal t is form e d


    . .

    by the a c t i on of sodi um pero xi de so lu t i on on a ch l or i ne dio xi de so lu t i on :

    2 010 , N ap , zN aCio, o, .

    The s ilver sal t A gCl O z is a ye ll ow crystal line powder as is al so the l ead


    , , ,

    s a l t Pb ( C l O z) ; they are both dif c u l t l y so lu b l e i n water and brea k u p


    , 2 ,

    e ven on warmi ng to 1 00 i n an e x pl os iv e m anner The anhydri de of



    .

    chl orous ac i d correspondi ng to t h e for m ul a Cl 3 is not kn own


    , , .

    C HL O R I C A CI D, HC 10 3 .

    59 The chlorates of potassium o r b arium are the usual start


    .

    i g points for the pre paration of chlori c acid


    n When dilute .

    sul phuric acid is added to the solution of the barium chlorate ,

    barium sul phate is pre ci pitated and a dilute solution of chloric


    acid is obtained which may be ltered o ff from the sulphate and
    ,

    dried in a vacuum desiccator over concentrated sul phuric acid .

    In this way a 4 0% solution of the acid may be obtained O n .

    concentrating it any farther decom position takes place oxygen


    , ,

    being evolved and perchloric acid formed The concentrated .

    acid is a powerful oxidizing agent ; wood or paper ignites when


    brought in contact with it I t oxidizes hydro chloric acid chlo
    .
    ,

    rine being given o ff further sul phuretted hydrogen sul phurous ,

    a cid and others even in dilute solution The following reaction


    ,
    .

    is very characteristic of chlori c acid When indigo solution is .

    added to a dilute solution of the acid the former is no t decolori z ed


    ,

    however on the addition of a little sul phurous acid the color dis
    ,

    a ppears since the chloric acid is thereby reduced to lower oxides


    , .

    The sal ts are all soluble in water that of potassium being ,

    somewhat difcu l t l y so however ,


    .

    The com position of chl oric acid was ascertained by STA S from
    an analysis of silver chlorate A n accurately weighed amount of
    .

    the latter was reduced by a solution of sul phurous acid to silver


    chloride and this was ltered o ff and weighed Since he knew .

    from pre vi ous i nvestigat ions t h e exact com position of silve r


    chloride the analysis of the silver chlorate was complete
    , .

    ST A S found thus that silver chlorate consists of


    90 IN O R G A N I C C HE M I S T R Y . 60

    The salts of p erchlo ric acid p e r c h l o r a t e s a re all solu ,

    ble in water ; that of p otassium and es pecially that of rubi dium


    are however very difcu l t l y soluble in cold water
    , ,
    .

    The com p osition of p erchlori c acid has been dete rm ined as in ,

    the case of chloric acid by the analysis of a salt in this i ns tance


    , ,

    the potassium salt A weighed amoun t o f the latter is heated to


    .

    drive off all the oxygen The loss in weight indicates the amount.

    of the latter The analysis of the remai ning potassium chloride


    .
    ,

    KC ] shows the amounts of potassium and chlorine


    ,
    From these .
    _

    d ata it is found in th e same manner as with chloric acid that the


    , ,

    em pirical formula of the salt is K C l O 4 that of the acid therefore , , ,

    HC l O 4 .

    Ch l ori n e h e pto x de ,i Cl O is the o xi de corresponding to perc hl oric


    acid :
    2HC l O , H O Cl
    Z .
    . 7

    It m ay be obtained by s l owly addi ng per chl ori c a ci d to phosphor u s pent


    o x i de c oo l ed be l ow B y di st ill at i on on a water bath t h e o xi de i s
    obta i ned as a c o l orl es s liquid whic h bo ils at It i s m ore stab l e than
    ,

    t h e other o xi des of c hl or i ne ; i t ne i ther atta cks pa per nor acts on sul phur
    or phosphorus in the co l d .

    O XYG EN C O M PO UN D S O F BR O MINE .

    6I . Al tho u gh
    no c o m pounds w i th o xygen al one are known there are ,

    two oxygen a ci ds viz hypobro m o u s and bro mic


    ,
    .
    , .

    Hy po brom ou s aci d HBr O c an be obta i ned i n the sam e way as HC l O


    , , ,

    nam e l y,by sha ki ng u p bro mi ne water and m er cur ic o xi de together The .

    di lu te so lu t i on c an be di st ill ed in v acu o and has pro pert ies ent i re ly anal ,

    o g ou s to those of hypo c hl oro u s a ci d .

    Br om ic ac i d HBr O B c an be obta i ned fro m t h e barium sal t with sul


    , ,

    p h ur ic a ci d or fro m the s ilver sa l t wi th bro mi ne water : -

    5A gBr O 3 3 Br2 3 HzO 5A gBr 6 HBr O 3 .

    In s o l .

    It is also form ed when c hl ori ne i s passed i nto bro mine water -

    B r2 5012 6 HZO 2 HBr O 3 1 0HC l .

    It corresponds in its behavi or with chl oric a ci d Many reducing agents .


    -

    such as hydrogen s ul ph i de and su l ph u ro u s a ci d are abl e to e x tra c t all ,

    it s o xygen M ost of its sal ts are difc u l t l y solubl e in wat er When


    . .

    h eated they give u p a ll the i r o xygen


    ,
    .
    O X Y GE N C O M PO UN DS O F I O DI N E .
    91

    O XYG EN C O M PO UN D S O F IO DINE .

    62 When io dine i s i ntrodu ced i nto a c o l d di l ute so l ution of causti c


    .

    p otash or s oda a c o l orl ess liqui d i s obtai ned wh ic h has other propert i es
    , ,

    when fresh than i t has l ater When freshl y pre pared i t de c o l oriz es i ndigo
    .

    s o l ut i on and i od i ne i s li berated on the add i t i on of very wea k a ci ds


    '

    .
    Late r on these two pro pert i es di sappear It i s therefore to b e s u pposed .

    that a hypo i odi te K I O i s rst form ed and that this i s c hanged sl owl y
    -

    t o K I and K I O s A t the bo ili ng po i nt the c hange ta kes l a c e a lm ost


    p
    -
    .

    Io din e pe n to xi de , I 2 0 5 is the anhydride of io dic aci d s ince i t ,


    ,

    can be obtained by heatin g this acid to

    2 HI 0 3 HzO I zO 5 ,

    an d yiel d s the same acid when dissolved in water It is a white .

    crystall ine substance whi ch breaks u p in to its elements at


    ,

    I o di c a c i d H I O 3 is pre p ared by the oxidation of iodine with


    , ,

    n itric acid or b etter with nitrogen pentoxide


    , , , .

    3 I2 1 0HN 0 3 6 HI O 3 1 0N O 2 HzO
    Nit d Nit d
    .

    r ic a c i . i
    r c o xi e .

    Iodic acid is crystalline and easily soluble in water I t is a p ower .

    ful oxidizing agent setting free chlorine from hydrochl oric acid
    -

    , ,

    for exam ple .

    2 HI O g 1 0HC l 12 5C 12 6 HzO .

    It reacts instantaneously with hydriodic acid ,


    all the iodine of b oth
    com pounds being preci pitated :
    5 HI +H1 0 3 3 Hz O + 6 I .

    The salts of this acid the i o d a t e s are in general not very,

    soluble in water ; however those of the alk ali metals dissolv e ,

    r ather easily .

    O n heating i od ic ac i d w i th concentrated s ul phuri c ac i d oxygen is


    ev o lved and the co mpo und i o di ne di o x i de i s form ed Th i s i s a , .

    l emon yell ow c rysta lline powder that brea k s u p into i ts el e ments above
    -

    Wi th hot water i t rea c ts quickly to form i od i ne an d i od ic a ci d :


    5 1 2 0 4 + 4 H2 0 = 8HI O 3 + 1 2 .

    Per io di c i d, HI O 4 + 2 H2 0 is forme d b y the action of iodine


    ac ,

    on p erchloric acid :

    HC l O 4 I 2 H2 0 HI O 4 Q HZO 01 .

    It is a c olorless crystalline solid that is entirely decompose d at


    1 40
    into iodine pentoxide oxygen an d water ,
    I N O R GA N I C C HE M I S TR Y .

    N O M E N C L ATUR E .

    63 Th e sys t em of naming the various halogen o xy ge n acids is


    .
    -

    a general one which is also used for the acids of other elements
    , .

    The bes t k nown acid usually has the sufx ic e g chloric acid o
    - -

    ,
    . .

    _ ,

    p hos p horic acid sul p hur ic acid etc A cids that


    ,
    conta in m o r e ,
    .

    0 x y g e n have in addition the prex p er thus perchl oric acid


    i
    and p ersul phuric acid A cids contain ing f e s s o x y g e n h ave

    .

    the sufx O u s e g chlorous acid sul phurous acid phosphorous


    -

    ,
    . .
    , ,

    acid etc Thos e which conta in still less oxygen have the sufx
    ,
    .

    -
    ou s and also the prex hyp o e g hyp ochlorous acid h yp osul . .
    ,

    ph ur o u s acid and hy o
    p p hos phorous acid .

    The nam es in u se i n pharm a c e u t ic a l c he mi stry (se e the N at i onal Phar


    m aco poeia) fo ll ow t h e L at i n Thus w e hav e A cidu m s u lphu ricu m (su l .

    ph u r ic a ci d) and A cidu m s u lp hu r os u m ( s ul ph u ro u s a ci d) .

    The names of the s al ts of the best known ic) acids end in - -

    -
    a te
    ,
    e g p otassium
    . . c hlorate sul p hate phos p hate T h e salts of ,
    -

    ,
    -
    .

    the ou s ac ids have the ending ite as potassium chlorite sul phite
    -
    .
    -

    , ,
    -

    hos hite The salts of h yp o o u s acids are called h it s


    y p

    -
    p p . o e
    -

    thus so diu m h ypo ch l o rit e hyposul phite hypo phos phite


    ,
    -

    ,
    -
    .

    The names of the anhydrides corres pond to those of the ir acids .

    I n naming oxi de s the name of the element with or without the


    ending i c i s used unless there is more than one oxide Where
    -

    , .

    there are two oxides the name of the one with the more oxygen ,

    ends in ic that of the other in ou s e g mercuric oxide arsenic


    -

    ,
    -

    ,
    . .
    ,

    oxide mercurous oxide arsenious oxide


    ,
    An oxide with less ,
    .

    oxygen than the ou s com poun d is given the prex hypo and one
    -

    with more than the ic oxide the prex per as in the case of acids -

    thus hy pochlorous oxide lead peroxide I n some cases for the ,


    .
    ,

    sake of eu phony the sufx is added to the L atin instead of the


    ,

    English stem as cu prous ferric etc , , ,


    .

    For h i storic al reasons m any nam es now in u se do not conform to this


    syste m I n so m e i nstan c es the o xi de rst di s c o vered too k the s u fx ic
    .
    -

    and those s ubse qu ent ly di s c o vered were nam ed a cc ordi ngly a s i n the ,

    case of the ni trogen o xi des


    I t i s not unco mm on to s pea k of oxides of the genera l form ul a M2 0 3 as
    4 I N O R G A N I C C HE M I S TR Y . 65

    E LE C T R O LY TI C DI SSO C I A TI O N .

    65 In 3 0 it was stated that the pro perties of a n aqueous


    .

    solution of hydrogen chloride differ widely from those of the dry


    gas I t was also stated there that many o ther substances undergo
    .

    a similar change of pro perties when they are dissolved in wate r .

    We may n o w consider the na t ure of this change .

    I f we investigate the freezin g p oint de pressio n of the aqueous


    -

    solutio n of an acid base or salt of known concentration we nd


    , ,

    that the de pressio n does n ot corres po nd with that calculated from


    the acce pted molecular weight The freezing point de pres -

    sio n a nd the boiling p oint elevatio n are both greater than they
    -

    sho ul d be A 1 % sodium chloride solutio n would for exam ple


    .
    , ,


    9
    be expected to Show a de pressio n of the molecula r
    g 5
    de pressio n for water 4 3 ) being 1 9 i e A M = I 9 and the m ol e c
    ,
    . .
    ,

    ular weight of sodium chloride I n reality however t h e , ,

    de pressio n is found to be times as great namely As, ,

    the osmotic pressure i s pro portio nal to the freezing p oint de pre s -

    sio n it must also be greater than the calculated amount .

    The fact at o nce o c curs t o us that gases to which dissolve d ,

    substances have been found t o show close analogy also exhibit ,

    a simil ar phenomeno n I n numerous instances the pressur e


    .

    exerted by a denite weight of gas o c cu pying a denite volum e


    at a denite tem p erature is greater than the c alculatio n indi

    cates This is but another phase of the observatio n that t h e
    .

    va p or density of some gases is ab normally low at certain tem


    This is ex lained by assuming a breaking
    p e r at u r e s p
    u p of the gas molecules ; the number of p articles free t o move
    ab out is thus increased and ac cordingly the p ressure becomes
    greater This pheno meno n is known as diss o cia tion
    .

    In the case of abnormal osmotic p ressure we are led to a


    similar ex planatio n by assuming that the molecules are s plit u p
    into several inde p endent p articles A difculty arises h owever
    .
    , ,

    when we try to conceive the nature of this division I n solu .

    tions of s a l t s in water it would be p ossible t o assume a


    hydrolytic se p aration i e into free b ase and free acid (p
    ,
    . . .

    which would necessarily be com plete in dilute solutions of the salts


    of strong acids and b ases inasmu ch as the osmotic p ressure of such
    ,

    solutions in c oncentrations o f 1 3 normal


    3
    for instanc e ,
    E L E C TR O L Y TI C DI SSO C I A TI ON .

    amounts to d ouble the calculated p ressure There are howev er .


    , ,

    s e rious objectio ns to such a hy pothesis I n the rst place it has


    .
    ,

    n ever yet been p ossible to se parate such a solutio n by diffusio n int o

    the free base and free acid which it is supposed to co ntain A


    .
    .

    seco nd and still more serious obj ectio n is that an acid or base in
    an aqueous solutio n by itself exerts a n osmotic pressur e greate r
    than that calculated Here however hydro lytic dissociatio n is
    .
    , ,

    im possible .

    The questio n as to the real nature of the divisio n has found its
    a nswer in a co nsideratio n of the relation which exists betwee n the

    ab normal osmotic pressure and the transmission of the electric


    current A RRHEN I U S observed that only those substances which
    .

    conduct the el ectric current in aqueous solution namely acids , , ,


    bases and salts show the above mentio ne d ab normalities in osmotic
    ,

    p ress u re
    . When these substances are dissolved in another liquid
    t h an water the resulting solution is a non co nductor but at t h e
    ,
    -

    same time its osmoti c pressure again assumes the normal Thes e .

    f acts enable u s t o p erceive the connection between the a pp arently


    disconnected p henomena of abnormal osmotic pressure and elec
    t ro l y t ic c onduction .

    I n o rder to understand this relation it is necessary to know


    the usual ex planation of electrolytic c onduction L et us take .

    hydro c hl oric acid as an exam ple Perfectly d ry hydrochloric acid


    .

    gas is a no n conductor as is also perfectly pure water Howeve r


    -

    , .
    ,

    when the gas is dissolved in water a solutio n is obtained which


    ,

    transmits electricity very well Evidently a certain reactio n m us t


    .

    have resulted from the mixing of the water and the hydrogen
    chloride We were led to surmis e this above
    . when it w as
    found that this gas solution does not obey H ENR Y S law Sinc e
    .

    during the transmissio n of the current the hydrogen chloride is


    broken u p into hydrogen and chlorine while the water remains
    unchanged it must be assumed that the hydrogen chloride molecules
    ,

    are the ones which have undergo ne a change .

    The phenomena of electrolytic conduction now nd their com


    .

    p l e t e ex planation in the assum p tion that the change wh ich t h e

    hydrochloric acid underwent consisted in a se paration of its mol e


    cules into electric ally ch arged atoms (ion s ) This se para
    tion may h ave b een com plete or p artial the extent de pending u p on
    ,

    the c oncentratio n amo n g other things When a current p asses .

    t hrough the solution the negatively


    ,
    charged chlorine ions ( e
    t h
    96 I NO R G A N I C C HE M I S TR Y . 65

    ) are d rawn toward the p ositive electro de ( a n o d e ) ; t h ey


    a n io n s

    become electri cally neutral o n c ontact with the latter and esca p e

    fro m th e liquid Similarly the p ositively charged hydrogen ions
    .

    ( ion s ) wander toward the negative electro de ( 0 a t h o d e


    ca t
    I n this way c onduction goes on the undivided molecules h aving
    ,

    no p art in it This division of the molecules is known as el e c tr o


    .

    l yti c di s s o c i atio n , or io n i z a tio n .

    Th e exis ten ce of fr ee io n s in the solution of an electrolyt e


    isdemonstrated by OS T W A LD in the following manner The t u b e .

    a bcd ,
    Fig 23 is nearly lled with d ilute sul phuric acid
    .
    , Th e .

    FI G . 23 .

    narr owe d po rtion be is about 4 0 cm long A rod of amalgamated . .

    zinc is lowered into a to serve as the p ositive electrode while a ,

    platinum wire is fused into d at p for a negative elec trode I f .

    connection is made with a battery of ten accumulators there is ,

    an imm edia te evolution of hy drogen at p The p assage of the .

    current through the liquid resu it s in the formation of zinc sul


    .

    phate around the bar in a :

    ZIl H2 SO 4 ZUSO 4 H2 .

    N ow if this hydrogen has to pass through be t o p it must c ove r ,

    the 4 0 cm in a very brief s pace o f time However it has been


    . .
    ,

    shown both by investigations which canno t be described h e re


    and by calculus that this migration would take many hours Th e .

    hydrogen appearing at p as soon as the circuit is closed cannot ,

    therefore come from a ; the most natural ex planation is to su p


    ,

    p ose that there are already free ions in the neighborhood of p


    and that they are discharged by the current and given off from
    the liquid as free hydrogen .

    T O L MAN has shown that when a long tube c ontaining a solu


    ,

    tion of an alkali iodide is rotated as the sp oke of a wheel at 3 000


    98 I N O R GA NI C C HE M I S TR Y .

    by the two m ethods The values o pposi te ro were calc ul ated fro m the
    .

    observed free zi ng po i nt de press i ons and those o ppos i te 7 fro m the c on


    -
    6

    du c t iv it ies of the sal t solu t i ons The c onc entrat i on t hr o u ghout i s 1 g pe r


    . .

    li ter .

    N aN O

    0 0 0 0 0 0 0 0 0 0 0 0

    66 . I on ic Equ ilibriu m In
    a case of electrolytic disso ciation w e
    h ave an equilibrium to deal with namel y that between the u n , ,

    disso ciate d molecules o n the one hand and th e l ons on the other .

    In the case of a monobasic aci d this e quilibrium may be re pre


    se nte d by
    A HZ ZA
    H
    '


    H the hy d rogen ion

    where A is t h e acid radical ( anion) an d

    ( cation ) Fo r a b ase we.have



    M oHe l M OH
    .

    We may ly here the equilibrium equation d educed in 4 9


    app .

    G iven a gram molecules of A H per unit volume of which a: ar e


    - -

    divide d into two ions each then the equil ibrium is r epresente d b y ,

    From this equation it necessarily follows tha t the diss ociation is


    dim in ished by the in tr odu ction in to the f with s ol u tion o a s u bst a n c e

    l ik e ion s (j ust as the addition of hydrogen or iodine re d uces t h e


    disso ciation of hydrogen i odide gas T his e ffect ( which is ,

    called the comm on ion effe ct ) may be produced on a salt in
    soluti on by the additi on t o t he s oluti on of a salt of the same base
    or a salt of the same acid The equation then b ecomes .

    a x =K

    p being the concentration of the adde d ion K can only r emain .

    constant provided a: diminishes .

    I t also follows that the degr ee of diss ocia tion depen ds on the con e

    c en tra tion I f the latter be increase d n fol d we have from t h e


    .

    ,

    above equation
    x) = K n 2 x2
    ) = K 2
    n ( a , (a x -
    n x
    -
    .
    E L E C TR O L Y TIC D I S SO C I A TI O N . 9

    If n is 1, must diminish ,i e
    a: . . the ion ization decreases with
    in cr ea sin g con cen tra tion I f n is < . 1, must increase i e the
    11:
    ,
    . .

    ion ization in cr eas es with the dilu tion . When n is in ni tely small ,

    we have a =x
    ,
    in other wor d s ,
    at inn ite dil u tion the ionization is
    com pl ete .

    We are now ab l e to give another de ni tion of acids an d bases


    than that of 3 0 A c i d s are those su bstances which give Hions
    .

    in aqu eou s s ol u tion ; ba s e s u nder the s ame condition give O H

    Al l the pr o p erties of acids bases and salts are closel y c on ,

    n e c t e d with the degree of their ioniz ation among others that


    ,

    which is indicated b y the rather vague term s trength of a n a cid


    or base .

    As early as the eighteenth century it was observ ed that an


    a cid can sometimes ex p el another acid from its salts O n adding .

    hydrochloric acid to sodium carbonate for in stance so di um , ,

    chloride is formed an d carbonic acid given off The same is true .

    o f bases Wh en a solution of caustic soda is added to a solution


    .

    o f iron chloride ir on hy d roxide is p reci pitate d and sodium chlorid e


    ,

    is also formed The acid or base that can ex pel another from its
    .

    salts was considere d b y B ER G MANN ( 1 7 3 5 1 7 84 ) to be



    s t r o n ge r f

    than the one expelled .

    Ex perience has taught that those aci d s an d bases are stro n g


    e st which are the most i o n i z e d for the same dilution Hy d ro .

    chl oric acid is for exam ple stronger than hydrouoric acid At
    , , .

    a dilution of one g r am molecule p e r liter the former is almos t


    -

    c om pletely ( about s plit u p into ions the latter only ,

    It was remarke d above 3 0) that acids tur blue litmus re d


    n ,

    an d bases red litmus blue I t is only natural to seek the caus e of


    . .

    these common pro perties of acids on the one hand and bases o n
    the other in that which all acid solutions have in common namely , ,

    hyd rogen i ons an d in that which all solutions of bases have in


    ,

    common n amely hydroxyl ions T h e


    , ,
    reactions be .

    tween acids bases and salts in aqueous solu,

    t i o n ar e a l m o s t i n v a r i a b l y r e a c t i o n s b e
    t w e e n t h e i r i o n s We shall explain this later in many .

    ins tances ; the following exam ple may sufce for the present .

    Wh en dilute solutions of a base an d an acid are mixe d we have ,

    a salt solution In order to un d ers tand what reaction has


    1 00 I N O R G A NI C C H E M I S TR Y .
    66 .

    take n pla ce we must know t hat in dilute sol uti on mos t salts are
    almost wholly s plit u p int o i ons Water itself however i s split .
    , ,

    up only in an ext remely small amount In the equilibrium .

    H2 O H OH
    ,

    there is thus very little of the system on the r ight han d si d e -


    .

    The a m ount of t h e i on iz at i on of water has been deter mi ned in vari ous


    ways wh ic h c annot b e ta k en u p here but are dis cu ssed in te x t books of
    , ,
    -

    el e c tro c he mi stry The res ul ts of the d i fferent m ethods agree well and
    .

    show that the c on c entrat i on of hydrogen or hydro xyl i ons i s v ery , ,

    nearl y 1 0 X 1 0 ; i e 1 g H i ons and 1 7 g O Hi ons are c ontained in


    .
    7
    -

    . .
    ,
    .
    -
    .

    ten milli on li ters of water .

    N ow ,when a base an d an aci d are mixe d we have together in the


    solution M + O H and

    O f these ions M and A can exist

    ' '

    freely side by side ; but not so with H O H for these must unite

    '

    to form water accordin g to t h e above equilibrium In the forma .

    tion of the salt we therefore have only the H and O H ions unitin g
    '

    p roducing undissociated molecules of water .

    It is now easy to understand also why a strong acid (i e o n e . .

    almost com pletely ionized ) expels a weak (slightly ioni z ed ) acid


    from its salts To use an exam ple su ppose We add to a liter of
    .
    ,

    a sodium uoride solution contai ni ng one mole of the salt a , ,

    similar solution of hydrochlo ri c aci d In the mixe d s olution w e .

    have the ions

    Since the equilibrium E Fzi H + F is conditione d on the presence


    '
    -


    of only 3 % of H ions and F ions there is a large excess of these ,

    ions in the liquid and almos t all of them must unite with each

    other whil e the N a and C l ions remain free ; in o ther words
    '

    , ,

    hydrouoric acid an d sodium chloride ( dissociated ) are formed .

    It also becomes manifest that the old notion once very gen ,

    e r all y held that the stronger acid ex pels the weaker one from its
    ,

    salts com pl etel y is incorrect When the ex pelled acid or base escapes
    .

    from the solution as a gas or is precipitated the expulsion may in ,

    d eed seem to be com plete ; we shall examine the cas e more tho r
    o ughly in 73 .

    We can now go a ste p farther It was stated above that water .


    66


    solution of potassium iodide retaining our il lustration contains

    neither free p o tassium nor free iodine but ion s of pota ss iu m and
    ion s of iodin e The atoms however must possess an altogethe r
    .
    , ,

    different energy su pply than the ions whose elec tric charges are ,

    very heavy as can be proved by different methods I t is this


    ,
    .

    en ergy su pp l y on w h ich t h e p ro p erties of bodies de pend ; and since

    this is apparently much different wi th the ions than with the atoms ,

    i t is perfectly natural that the latter should display o ther pro pe r


    ties than the former .

    SUL PH UR .

    67 . was k n own to th e ancients I t o ccu rs fre e i n


    Sul phur .

    nature prin ci p ally in the vicinity of active or extin ct vol canoes


    ,
    .

    Sicily is its most im p ortant lo cality closely followe d by L ouisiana


    ,

    in the United States but large quantities are also found in other
    ,

    p arts of t h e United States and in I celand Ja p an and M exic o , ,


    .

    FI G . 24 D
    . I ST ILL AT I O N OF SU L PH UR .

    It is se parated fro m t he ac co m p anying ro c k ,


    or mat rix ,
    by
    fusion .
    67 1
    - S UL PH UR .
    1 03

    In Lou i s i ana th is i s a cc o m pli shed by the FRA S C H p roces s whereby ,

    hot water under pressure i s forced thro ugh p ipes s u nk thro ugh the
    g round to the sul ph u r depos i t thus m e l t i ng the s ul phu r wh ic h i n a
    , , ,

    m ol ten form i s for ced u p to the surfa c e by c o mpressed air


    , .

    The crude sul ph ur th u s obta i ned i s st ill im pure It i s re ned ( Fig 24)

    . .

    by istill at i on After be ing m e l ted in B i t i s let down i nto t h e c ast iron


    d
    -
    .

    cyli nder A W hJC h 1 s heated to a te m perat ure abo ve the bo ili ng po i nt of


    0

    s ul phu r The v apor is c ondu cted i nto a l arge brick chamber e qui pped
    .
    ,

    with a safety valve for the rel ease of a i r If the dist ill at i on is condu c ted .

    so s l owly that the te m perature of the c hamber does not e xc eed the
    bo ili ng po i nt of s ul phur the l atter is de posi ted in t h e form of a ne
    -

    owder ca ll ed j u st as water va or when s u dden l y


    p ,
    o w er s of s u l p h u r
    p ,

    c oo l d be l ow t u rns to snow R api d d i st ill at i on however yie l ds a


    e
    .
    , ,

    layer of liqui d sul phu r on the oor It m ay be l e t out thro ugh the .

    o pening C and cast i nto s li ghtl y c onic a l wooden m o l ds This is the roll .

    sul phur or the r oll brims ton e of c o mm er c e


    , ,
    .

    B esides ccurring in the free state sul phur is also foun d in


    o

    n umerous com p ounds from some of which it is ob tained e g


    , , . .

    py r ite o r i,
    r on p y rites F 6 82 which yields sul phur on heating
    , ,

    3 F6 82 F6 3 S4 28 .

    th er c o mpounds of t he element with metals the s u l


    M an y o
    " i ) i
    ,

    p h i d e s o ccur in nature e g ga l en t,
    e .
    ( lead . sul p hide z n c ,

    blende ( s phalerite , zinc sul phide ) s tibn ite ( antimo ny sul phide ) , ,

    Cinnaba r ( mercu ry sul p hide ) r ea lgar an d,


    or p i m e n t ( a rsenic s ul

    p h id es ) and ch a l co py ri t e co
    ( pp er p yrites C o pper and iron sul ,

    h id ) S ul hur also occurs in the natural su l p hates of which


    p e .
    p ,

    m C S O 2 H 0 ) is the most im ortant I t is also found


    gyp s u ( a 4 1 2 p .

    in the organic world as a constituent of the albuminoids .

    Physica l Proper ti s e Sul phur is known in various modications .

    ll
    '

    At ordinary tem eratures the stable form is a y e ow crystalline


    p
    solid ; melting p oint -

    ,
    A little ab ove its melting p oint -

    sul phur is a mobile yellow liquid With a co ntinue d rise of tem .

    e r a t u r e it bec o mes much darker i n c olor and very viscid ; at


    p
    1 8 0 it c an no longer be p oured ; at a higher tem perature es pe

    ,

    c ial l y
    ab ove it again beco mes mobile the dark color remain ,

    it b
    oils roducing an ora ge c olored va or A t
    ing ; at 4 48 p ,
    n p .

    5 00 the va p or is re d ; ab ove this tem perature it becomes clearer


    again During c o oling these phenome na rea ppear in invers e


    .

    8 0 sul phur is c olorless



    order A t .
    .
    1 04 IN O R G AN I C C H E M I S TR Y . 67

    Sul phur is in s ol u b l ein water and diicu l t l y soluble in alcohol


    '

    and in ether ; it is easily soluble in carb on disul phide and in s u l phur


    monochloride 8 2 0 12 1 00 p arts C S2 dissolve 4 6 p arts S at
    ,
    .

    The m ol ec u la r weight of this element more than that of any ,

    other d e p ends on the tem perature B elow the b oiling p oint t h e


    , .
    -

    molecular formula is SS acc ording t o the determination of t h e


    ,

    b oiling p oint elevation in carb on disul phide (boiling p oint


    - -

    a n d
    the freezing p oint de pression of fused na phthalene ( melting
    oint I the gaseous state the density air = 1 varies from
    p n ( )
    at to at 860 and then remains c onstant even

    as high as indicating that at the lowest tem p erature s


    sul phur va p or c onsists of S8 molecules and ab ove 8 6 0 of only ,

    Sz molecules .

    A b ove 1 8 00 the molecu l e S2 begins to dissociate int o its


    atoms ; at 2 000 and atmos phere pressure the disso ciation has

    reached about ac cording t o an investigation of N ERN ST .

    6 8 A ll o tr opic M O di catio n s A t least four solid forms are


    . .

    known while in the liquid state there are two more The solid
    ,
    .

    allotro pic c ondition s can be divided into crystallized and amor


    p h o u s A
    . s for the former sul p hur is dimor p hic forming
    ,
    r h o m bi c ,

    as well as m on o cl in ic crystals The former are transformed int o .

    the latter on heating


    R ho mbic sul phu r can be obtained in bea u t i ful crystal s by all owi ng a
    so lu t i on of s ul phu r i n c arbon d i s ul ph i de or c hl oroform to sl owly e v aporate .

    Mono cli nic s ul ph ur i s eas il y obta i ned i n the fo ll owing m anner : So m e


    s ul phur i s fu sed i n a l arge c rucibl e and all owed to c oo l s l owly unt il a c r us t
    form s on t h e s urfa c e Th e c r ust i s the n bro ken thro ugh an d the liqui d
    .

    s ul phu r po ured o u t ; the s i des of the c ruci bl e are fo und to be c o v ered


    t h l ong ye ll ow trans parent needl es
    ,
    I n t h e c o urse of a fe w ho u rs these
    .

    be c o m e o pa que and bri ttle ho w e ver and c r um ble at t h e slig htest to u ch


    , ,

    to a powder whic h i s fo und to c ons ist of rho mb ic crystal s ( cf


    ,
    .

    A mor phous sul phur may be either soft and soluble in carb on
    disul phide or p owdery and in s ou b l e in this liquid .

    The so lub le ki nd res ults fro m the deco m pos it i on of c erta i n sul phur
    co m po unds When hydrogen s ul phi de water i s e x posed to t h e ai r s ul
    .
    ,

    phu r s l owl y se parate s i n t h e for m of a wh i te powder Th e po lys ul phi des .

    ( C aS KZS e t c ) yi e l d when de c o m posed by an a ci d a cl o u dy milk lik e


    n, n, .
    , ,
    -

    liqui d whic h i s found to c ontai n e x trem ely ne part icles of am orphou s


    ,
    1 06 I N O R G A N I C C HE M I S TR Y .

    69 . C h em ica l comb ines directly with


    Properties . Sul phur
    many elements not o nly metals but also metalloids I t has b een
    ,
    .

    already stated 1 0) that it burns with a blue ame when heated


    in air or in oxygen The halogens and hydrogen unite with it
    .

    directly Powdered Iro n and sul phur when mixed and heated
    .
    , ,

    combine energetically producing great heat C o pper takes


    ,

    re in the va por of boiling sul phur When mercury and sulphur .

    are rub b ed together in a mortar black mercuric sul phide HgS is , , ,

    fo rmed The sulphur com p ounds of the metals are called s u l


    .
    -

    p h i d e s .

    THE TR A N SI TI O N PO I N T .

    70 . state d in 6 8 s ulphur can crystallize i n two mo d i


    As

    c at io n s rhombic and monoclinic


    ,
    These modications can b e .

    r eadily transformed into one another The peculiar phenomena .

    connected with this transition d eserve a closer study A t ordi .

    n ary tem p eratu res sul phur is rhombic and rema ins so till the

    tem perature is reached abov e whi ch there be gins a slow b u t ,

    c om plete transformation into the monoclinic variety I nversely .


    ,

    when the monoclin ic modication is subj ected to a tem perature


    below a complete change into the rhombic form occurs .

    A t the tem perature named the two mod ications are equally
    stable and can exis t side by side in any pro portions for an indenit e
    p eriod ; above it only the monoclinic below it only the rhombic , ,

    form can exist permanently Such phenomena are not infrequent . .

    The tem perature at which the one system passes into the other
    is called the tr an sitio n poi n t also poi n t of i n ve r sio n This transi
    , .

    tion point possesses great analogy with the melting p oint Just -
    .


    as ice for e xam ple is changed into water above 0 and water into
    , ,

    ice below so in a system of substances possessing a transition


    p oint only one system is stable below that p oint above it only ,

    the other .

    T h e theoretical ex planation of both phenomena is exactly the


    same L et us consider a body ice for exam ple at tem peratures
    .
    , ,

    slightly below its melting point and re present graphically in the


    -

    d iagr am O TP ( Fig 2 5) the values of the vapo r tension corre


    .

    spo n din g to different tem peratures The result is the line marke d .

    ice in the gur e This vapor tension curve if prolonged through


    .
    -

    and beyond the melting point is found to bend sharply at t h e


    -

    ,
    THE TR A N S I TI O N PO I N T . 1 07

    latter and take a new dir ection This deection is very slight in
    .

    the case of ice and water ; i t can be nevertheless ex perimentally


    d etected ; it is much more evident with benzene and many othe r
    s ub stances .By carefully coolin g water it can be made to remain
    liqui d even under such a liqui d is said to b e s u p e r c o o l e d
    The v apor tension Of this supercooled water is greater than that of
    ice at t h e same tem perature an d the curve representin g the former
    is b ut a continuation of the va por tension curve for water
    -
    Sinc e .

    the va por tension of su percoole d water is gr eater than that of ice ,

    water at tem peratures below 0 mus t accord in g to previous con



    ,

    c l u sio n s 43 ass into ice when the two are in contact How
    ,p .

    e ver,
    the va por tension of water at a tem perature slightly above

    FI G 2 5
    . . FI G 2 6 . .

    0

    will b e l ess than that of ic e and we shall have t he ice trans
    formed in t o water It is therefore e v i d ent that b oth ab ove
    .

    an d bel ow t he mel t ing po int one of t h e sys tems will n ecessarily


    -

    d isappe ar .

    Exac tly the same explanation can b e o ffered fo r t he tran sition


    p oi n t B
    .
    elow the va p or t e n sion of r hom b ic su l p hur is less
    than that of monoclinic sulphur ; ab ove the vapor tension of t h e
    ,

    rhomb ic variety excee d s that of the monoclinic There is therefore .

    a com plete transformation from one system to the other when

    the tem perature is other than for the same reason as in the
    case of the melting po int ; moreover jus t as ice and water un d er
    -

    or d in ary press u re can exist side b y side indenitely only at so


    b oth mo d ications of sul phur are coexistent onl y at sin c e
    o nl y then is the va por tension the same for b ot h syst ems
    ( F ig .

    O f the vari ous meth ods fo r the de t e r m in atio n of t h e tr an s itio n


    1 08 IN O R G A N I C C HE M I S TR Y . 68

    poi n t a convenient one is the dil atom etric m ethod It is based on .

    the change of volume (s pecic gravity) which a body usually


    undergoes on passing through the transition p oint I n measuring .

    this a d i l a t o m e t e r is used an instrument which may be


    ,

    compare d to a thermometer of very large dimensions A fter .

    rhombic sul phur for exam ple has been placed in the dilato meter
    , ,

    the latter is lled with a chemically indi fferent liquid (kerosene ,

    linseed oil ) and pu t in a large water bath ; the temperature is


    then slo wly raised B elow the transi t ion point the volume is
    .

    seen to slowly and steadily increase with the temperature on


    a ccount of ex p ansion ; as soon as the tem perature gets a trie ,

    above however a marked increase of volume is observed


    , ,

    even if the temperature be maintaine d constant ; thereup on


    e xpansi o n again p ro cee d s gradual ly as befo r e if the tem
    , ,

    p e r at u r e is allo wed t o rise The . marked change of volume


    indicates t he transition of the rhombic sulphur int o the mon o
    clin ic m o d i cati on .

    STAB LE,

    M ETA STA B LE ,
    AND
    LA BI L E .

    T hese terms are coming to be so frequently used in chemistry


    that they need to be distinctively dened They are borrowed .

    from mechanics for which reason it is desirable that they be


    ,

    em pl oyed in chemistry in the same sense as in mechanics I n the .

    latter an equilibrium is c alled l a bil e ( apt to slip) when the slightest


    dis placement su f ces to trans p ose the body into a new p osition of
    equilibrium A n exam ple is a ffor d ed by a c one standing on its
    .

    a p ex . I t cannot rec over from even the slightest disturbance ,

    but gets further and further fro m the vertical p osition and nally
    tumbles over A labile condition is thus really a limiting c ase
    .

    which c annot actually be realize d ; not even for the c one though ,

    its apex were a mathematical p oint resting on an absolutely hard


    surface .

    A l l actually oc curring equilibria are stable ; but there c an be


    different degrees of stability When a m aterial c one is sto o d on
    .

    its a pe x its equil ibrium has very little stability O n the c ontrary .
    1 10 IN O R GA N I C C HE M I S TR Y . 71

    ph as e s . Wate r and its va por constitut e t w o phas es ; ice w at e r ,

    and steam three phases .

    A heterogeneous system can never hav e mo re than o n e


    gaseous phase because all gases are miscible in all pro po rtions ;
    ,

    it may however c onsist of di fferent liquid p hases in cas e it


    , , ,

    c ontains immiscible liquids The number of these liqui d phas e s


    .

    is seldo m mor e than two ; that of t h e soli d phases is u n


    limite d .

    A furthe r c once pti o n intro duc e d b y G I B B S is tha t o f t h e


    , ,

    c o m po n en t s of a system If the system is c om p osed of only


    .

    o n e element then this element is the only c om p onent


    ,
    Systems .

    made u p of one c om p ound have in most cases this c om p oun d


    as t h e only c om p onent A syste m c onsisting of molten an d .

    gaseous sul phur O r of water and st eam has but one c om p onent
    , ,
    .

    In this case all phases have the same c om p osition There are .

    systems however in which this is not the case ; viz systems


    , ,
    .

    that are made u p of more than one c om p onent We select as .

    the c o m p o nents those c om p ounds of which the smallest numbe r


    is necessary t o form the di fferent phases The choic e of such .

    c om p ounds may b e somewhat arbitrary b ut thei r n u mber is


    always fully dened .

    L et us c onsider fo r exam ple the system G lau b er s salt


    ,

    ,

    water This salt has the c om p osition N aQ SO 4 1 OH2 0


    . In ,

    .

    o rder to determine t h e c om p ositio n of the p hases that are p ossible

    here ( solid salt solution va p or) it is best to cho ose N a2 SO 4 and


    , ,

    H2 0 as c om p onents We might indeed take G lauber s salt itself


    .

    as one of the c om p onents ; but then in case the solid phase was ,

    the anhydrous salt it would b e necessary to regard water as a


    ,

    negativ e p art of it whi ch is undesirable Sul phuric acid an d


    ,
    .

    so dium hydroxi de are not c om p onents b ecause they do not o c cu r ,

    inde pendently in any phase neither are they found in any other ,

    r elatio n in the phases than as a p art of the salt itself It is a .

    p pro erty of the c om p onents that they c an o c cur in some o f the


    p hases in varying ro
    p p ortions ( e g in saturate d and unsaturated
    . .

    s olutions ) .

    L et us now take for e xam ple a saturate d solution of salt an d


    , ,

    wate r in a vessel that is close d with a movable piston Unde r .

    t his Solution le t ther e b e a l ittl e soli d salt a b ov e i t t h e vapo r of ,


    THE PH A S E R UL E O F G I BBS . 111

    t he solution Th e sys t e m c o nsists manifestly of t wo su b s t anc es


    .

    and three phases .

    So long as t h e tem p erature remains c onstant the va p or of t h e ,

    salt solution p ossesses a denite tension I f we increase t h e .

    volume by raising the piston a denite amount of water will eva p


    ,

    orate ; since the solut ion was saturated the result will be that a ,

    little salt will be de p osited ; in the end the quantities of va p or ,

    solution and s alt will therefore h ave altered but the co m p osition ,

    of each phase will remain the same The tension and hence als o .
    ,

    the c oncentration of the va p or remain unchanged since t h e


    , ,

    tem p erature is c onstant ; there is likewise no change in the co n


    c e ntration of the salt s olution The same is true in case t h e
    .

    Volume be diminished I t therefore follows that the equilibrium


    .

    of s uch a sys t e m is inde p endent of the quantities of the various

    p hases . I t is d e p en d ent only on t h e tem p erature chosen ; if


    t his is c onstant the whole syste m is dened O r if we should
    ,
    .
    ,

    select an arbitrary value for the c om p osition the tem p erature ,

    and pressure would b e fully dened I t is therefore evident .

    that the system is c om pletely dened as soo n as one of thes e


    magnitudes is arbitrarily chosen The system has only O n e .

    de gr ee of fr e e do m Such an equilibrium p ossesses the following


    .

    characteristic : A t a given c onstant tem p erature the va p or pres


    s ure is denite Under an even slightly greater or smalle r
    .

    p ressure one of the p hases will gradually and c om p letely dis


    a ppear provided the tem p erature remains c onstant O n in
    ,
    .

    creasing the pressure the gaseous phase wholly c ondenses so tha t ,

    o nly s olution an d salt remain A decrease of p ressur e r esults in


    .

    the c om p let e e va poration of t h e solu t ion v a po r and salt only ,

    b eing left .

    Th e s am e is t ru e wh e n t h e pressur e r emains c onstant an d t h e


    t e m p eratur e varies
    A n entirely di fferent b ehavior is shown by a system made u p
    o f an unsatura t e d salt solution and its va p or A t a constant .

    tem pe rature and a denite p osition of the piston the va p or tension


    has a d enit e value as in the former case I f however t h e
    ,
    .
    , ,

    volum e o f va p or b e change d the tensio n will corres pondingly


    ,

    va ry fo r if t h e volume b e increased for exam ple more wate r


    , , , ,

    will eva p orate t h e solut i o n will bec ome more concentrated an d


    ,

    t h e v a po r t e nsio n o f cours e lessen Th erefor e for e very de ni t e


    .
    1 12 IN O R G A N I C C HEM I S TR Y .
    71

    tem perature there are not sim ply o ne but innitely many pres
    sures under which this system can be in e quilibrium The result .

    is that the slightest change of volume or pressure does 11 o t


    necessitate the disa pp earance of o ne of the phases T w o .

    magnitudes may be chosen a rbitrarily b efore the system is fully


    dened ; it has two de gr e ss of freedom I t is evident in this .

    exam ple that the number of degrees of freedom increases by one


    when the number of phases decreases by one .

    The phase rule ex presses a relation between the numb ers of


    the com p onents S the phases P and the degrees of freedo m E
    , ,
    .

    It is of the following form :


    F+P= S +z

    or in words
    , ,
    -
    The su m o f th e n u m ber o f th e degr e e s offr eedo m a n d
    th e n u m ber f
    o th e pha s es of a s ys tem ex c eeds th e n u m ber of co m

    p o n en ts by two .

    L et us a pply the phase rule in the rst place water a system to ,

    of one c omp onent ; the sum of the degrees of freedo m and t h e


    p hases must therefore b e three .

    In t h e foll o w m g gra phic re presentation Fig 2 7 t h e tem pera ,


    .
    ,

    Sol id L iq u id R h om b ic

    G a s e ou s

    FI G . 27 FI G . 28 .

    tures t are plotted as a b sciss as the p ressures P as ordinates


    , , , , ,
    .

    L et us rst consider liquid water ab ove The number of t h e


    hases is two ( liquid and va or ) the system has therefore o nly
    '

    p p ;
    o n e degree of freedom or as we say it is u n iv ar i an t To every
    , , , .

    tem p erature there c orres p onds a denite va p or tension Th e .

    o rdinates o f every p oint in the line O B indicate these va por ten


    1 14 IN O R G A N I C C HE M I S TR Y .
    m 7 1;

    p la in t he r elati o n between these p hases B el o


    . w sul p hur is
    rh ombic ; the two phase s are rhombic sul phu r and va p or Th e
    (
    .

    line O A forms the b oundary between the two regions A t .

    the rhombic phase passes into the monocli nic phase The or di .

    nates of the line O B represent the va por pressure of monoclini c


    sul phur at the tem peratur es The two crystallizabl e
    p hases can exist side by side at the p oint O ( the transition p oint ) .

    A ccording to researches by R E I C H B R this transition point de pends


    o n the ressure ; an increase of ressure of one atmos here raises
    p p p
    it about The boundary between the crystallized phases is
    therefore furnished by a lin e O C which shows that a very sligh t
    ,

    rise of tem perature is followed by a very considerable increase of


    p ressure A
    . t 0 we have therefore a tri p le p oint i e a p oint
    ,
    com . .

    mon to both crystall ized phases and the gaseous phase A t B the .
    ,

    melting point of monoclini c sulphur there is a second tri ple point


    -

    , ,

    which is wholly analogous to the melting point of ice Finally it -


    .
    ,


    should also be noted that the line B C which se parates the liquid ,

    and the solid phases mus t indicate a rise of melting point for an
    ,
    -

    increase of pressure s ince sul phur melts higher the greater t h e


    ,


    p ressure The
    . lines O C and B C are not p arallel but intersect ,

    according to TA M M A N N S exper iments at 1 5 1 an d 1 28 1 atmos



    ,

    p h e r e s
    . A s the sum of the p hases and degrees of freedom is als o

    three with sul phur the p hase rule indicates that all four phases
    ,

    cannot e xist in the p resence of each other at the same time not ,

    even when the system has bec ome non variant -


    .

    A t the tri ple p oint neither the tem p erature nor the p ressure
    can be changed without altering the kind of equilibrium Here .

    the system is n o n var ia n t A long the lines O A O B and O C it


    -
    .
    ,

    is u niv a ria n t When the state of the system is re p resented by a


    .

    p oint within one of the areas it is d iv a r ia n t c onsisting then of


    ,

    only one phase I n the suc ceeding cha pters we shall have
    .

    o ccasion to c oncern ourselves with systems of mor e than o ne


    c om p onent .
    H YD R O GE N S ULPHIDE . 1 15

    HY DR O G EN SUL PHI DE, SUL PHUR E TTE D HY DR O G EN ,


    72 .This gas occurs in nature chiey in volcanic regions C er .

    t ain mineral waters es pecially the s o called sul phur s prings


    ,
    -

    contain it It is also found as a putrefactive product of organic


    .

    bodies .

    Hydrogen sul phide can be obtained from its elements by


    synthesis They unite almost com pletely when heated together
    .

    for a long time ( about 1 68 hours ) at


    I t can also be obtained by the action of hydrogen on sul phur
    com pounds as well as by the action of sul phur on com pounds of
    ,

    hydrogen ; the reduction of silver sul phide A n with hydrogen , ,

    at high tem peratures illustrates the former case while the boiling ,

    of turpentine o il with sul phur is an exam ple of the latter .

    N one of the above methods is ada pted to the pre par ation of
    the gas in the laboratory For this purpose the interaction of a
    .

    sul phide with a hydrogen com pound is em ployed iron sulphide ,

    and dilute acids being generally used :


    Fe S 2 HC l Fe 012 H2 S .

    In order to h ave s ul phuretted hydrogen a l w ays at hand it being in con


    stant de m and i n analyt ic a l work ( cf a very c oI IVe n i e n t a pparat u s
    .

    was de vi sed by KI P P whic h c an b e u sed for the ge n jfat ion (at ordi nary
    , .

    te m perat ures) of other gases as we ll It s c o n s t ru ct ibn i s shown i n the


    .

    gu re (s ee nex t page) .

    The l ower gl obe i s j o i ned to the basa l port i on by a narrow ne ck wh ile ,

    the u pper gl obe tape rs i nto a l ong t ube whic h ts t i ght ly i nto t h e l ower
    ,

    gl obe and e x tends nearl y to t h e botto m of t h e generator witho u t c o m


    l t e l y lli ng the ne ck Th e i ron s ul phide i s pu t i nto the mi ddl e port i on
    p e .

    and the d ilu te a ci d i s poured i nto the u pper port i on t h e sto pc o ck rem ai n ,

    ing o pen A s soon as the basal part i s lled wi th t h e a ci d the c o ck i s


    .

    c l osed and the t o p part i s ha l f ll ed wi th m ore a ci d When the c o ck i s .

    O pened the liqui d s i n k s in t h e t o p part a n d r i ses i nto the mi dd l e port i on ,

    where i t rea c ts wi th the i ron s ul phi de to prod uc e hydrogen s ul phi de ,

    whic h es c a pes thro ugh the c o ck O n cl os i ng t h e l atter t h e g as c ont inues


    .

    to be e v o lv ed t ill i t for c es t h e liqui d ba ck o u t of the part c ontai ni ng the


    iron s ul phi de The rea c t i on thu s c eases a u to m at ic ally and the generator
    .

    is ready at any t im e to s u ppl y n e w quant i t i es of gas on o peni ng the c o ck ,

    t ill e ither a ci d or s ul phi de i s e xhau sted The spent a ci d c an b e l et o u t


    .

    th ro ugh a sto ppered o peni ng near t h e botto m .

    O n acco unt of t h e free i ron u s u a lly present i n iron sulphide the gas ,
    e I N O R GA N I C C HE M I S TR Y . 72

    pre pared in this m anner c onta i ns so m e hydro gen . Pe rfectly pure


    hydro gen s ul ph i de i s obta ined by warmi ng sul phide s Ss
    , ,

    wi th concentrated hydro c hl oric a ci d .

    FI G 2 9
    . . K I PP G ENERA T O R .

    Physical Properties
    Hydrogen sul phide is a colorless gas of
    disagreeable odor when diluted reminding one of ro tten eggs
    , .

    Under a p ressure of about 1 7 atmos pheres it becomes liquid at


    ordinary temperatures ; liquid hydrogen sul phide boils at
    and freezes at 1 l H 2 S gas weighs
    . g at 0 and .

    7 60 mm pressure
    .

    water dissolving
    The gas is rather soluble in water 1 vol
    .

    vols H ZS at 0 ( hydrogen sulphid e


    .
    , .

    water
    C h em ica l Pr op er ties Hydrogen sul phide is c ombustible and
    yields on c ombustion either sul p hur dioxide and water or water
    and sul phur ac c ording to the air su pply
    ,

    In aqueous solution it is slowly oxidized by the oxygen of the


    air sulp hur being set free ; this d ec omp osition is aided by light
    ,
    .

    In order to preserve hydrogen sulphide water it must be pr e ,

    p are d fro m b oile d ( air free ) water and p u t in to a dark bottle ,

    lled entirely and closed air tight The latter condition is best
    -
    .

    met b y placing the bottle sto pper downwards in a glass of water


    , , .

    I t is p oisonous ; as an antidote very dilute chlorine may be inhale d .


    118 I N O R GA N I C C HE MI S TR Y . 73

    C dS, the brown stannous sul phide SnS the yellow stanni c sulphide

    , , ,

    SnSz and the yellow sul phides of arseni c A Sg Sg and A szS5


    ,
    Th e ,
    .

    r est of the sul phi des named are black O ther metals such as .
    ,

    nickel cobalt iron manganese zinc chromium aluminium etc


    , , , , , , ,
    .
    ,

    are no t precipitated by hydrogen sul phide from acid solution but .

    are p reci pitated by amm onium sul phide Still other metals such .
    ,

    as barium strontium calcium magnesium and the alkalies are


    , , , , ,

    not precipitated from their solutions even by ammonium sul


    p h ide so ,
    th at w e therefore p ossess in sul phuretted hydrogen an d
    its ammonium com pound a means of se parating these el e ments .

    A n answer to the questio n why some elements are preci pi t ated


    ,

    from a cid solutio n by hydrogen sul phide a nd others are not is


    .

    furnished by the ionic theory L et u S take for exam ple a dilute


    .
    , ,

    solutio n of co pper sul phate into which hydroge n sul phide is being
    ,

    p assed C o pp
    . e r sul phate is almos t entirely ioni z ed hydroge n ,

    s ulphide only to a ve ry small degre e We therefo re have in


    t he solutio n :

    Cu S0 4 + 2 OH +

    t he cations being re prese nted by a point a nd the a nio ns b y a line


    above and to the right and the number of these points or lines
    ,

    i ndicating the ionic valence


    Some of the co pper ions a nd sul phu r io ns will the n unite t o
    form undissociated molecules C u S which are only slightly soluble
    , ,

    in water and are therefore precipitated A s S ions thus disa ppear .


    -

    the equilibrium betwee n hydro gen sul phide a nd its ions is dis
    t u rb e d ; new HzS molecules are then Spli t u p into ions so tha t ,

    there are again S ions prese nt whi ch can unite with co ppe r an d
    -

    , ,

    s o on The actio n pro ceeds according to the equatio n


    .

    0 11 80 4 s Cu S 11 2 8 0 4 ,
    In so l .

    o r, if o nl y the ions which take p ar t i n it are re present e d



    Cu S = C uS .

    This t akes plac e quantitatively if the co pper solutio n is dilut e


    a nd no co nsiderable amount of any stro ng free acid was added .

    However if these co nditions are not ful lled and as a result the
    , ,

    ,
    H Y D R O G EN S UL PHIDE 19

    c oncentration of the hydrogen ions is rather high the presence ,

    of these ions reduces the ionization of HQ S so much 6 6 ) that


    no p reci pitate can be formed The a pplication of the mass
    .

    actio n law to the case is very sim ple C o pper sul phide when in .
    ,

    c ontact with water dissolves to an extremely small extent ; in


    ,

    this solution we have the equilibrium :



    Cu S CuS .

    If the co ncentratio ns of the two io ns are a an d b and that of the ,

    undissociated co pper sulphide is c we have the equatio n


    -

    ab= k -
    c,

    k being a co nstant for a xed tem perature


    The product a b has a denite value for every saturated solu
    tio n (since c is denite ) This value is known as the s ol u bility
    .

    p r o d u c t of the su b stance i n questio n I f in any case the product


    .

    a b is less than this value no ne of the substance can separate out


    , ,

    because the solutio n will then be unsaturated ; if however the , ,

    p ro d uct is greater than the solubility p roduct the substance will ,

    be preci pitated .

    A s soo n then as the co ncentratio n of the S ions becomes so -

    small (because of the reductio n of the io nizatio n of hydrogen sul


    p h id e by the H io
    -
    ns of the acid ) that it makes the value of a b
    smaller than that of the solubility product for co pper sul phide no ,

    p reci p itate will be formed I f however


    .
    ,
    the liquid is diluted the , ,

    co ncentratio n of the Hions decreases ; then if hydrogen sulphide ,

    is passed in the co ncentratio n of the S io ns increases The value


    ,
    -
    .

    of the solubility product can in this way be exceeded i n which ,

    event co pper sul phide will be preci pitated .

    I f a small quantity of stro ng acid be added to a preci pitate of


    co pper sul phide sus pended in water only a very s m all amount ,

    of the sul phide will dissolve ; to be sure the H ions of the strong
    -

    acid will remove a part of the S io ns y ielding some undissociated


    -

    hydrogen sul phide so that in order to establish equilibrium a trace


    ,

    of co pper sul phide must go into solutio n ; but soon the point will
    b e reached whe n so many C u and S ions are again in the solutio n -

    that the value of the solubility product is reached A fter this .

    moment no more co pper sul phide goes into solution Since t h e .

    value of the solubility product is ve ry low the solubility of the ,


    1 20 I N O R G A N I C C H EM I S TR Y . 73

    sul phide in dilute strong acids is very slight ; this accounts fo r


    the p racti cally c om plete preci pitation of the co pper sul phide .

    O n the o ther hand if the solubi l ity product of a sul phide is


    ,

    greater as in the case of iron sul phi de the addition of sulphuretted


    , ,

    hydrogen to the solution of an iron salt e g ferrous sul phate ,


    . .
    ,

    Fe SO 4 will cause no preci pitate of iron sul phide and iron sul phide
    , ,

    will unlike the previous case be dissolved by dilute strong acids


    , ,
    .

    When hydrogen sul phide is led into a solution of ferrous sul phate
    t o the point of saturation the concentration of the S ions is on
    ,
    -

    account of the slight ionization of hydrogen sulphide no t great ,

    enough together with that of the Feions to reach the solubility


    p roduct of iron sul p hide hence no p reci p itate
    ,
    fo rms M oreover .
    ,

    when dilute hydrochloric acid is added to iron sul phide the H ions ,
    -

    and the S ions form undissociated H2 S molecules and the coneen


    -

    t rat io n of the S ions therefore becomes too small in comparison


    -

    wi th the value of the solubility p roduct to pre vent solution ; hence


    in the presence of enough acid all the iron sul phide goes into solution .

    I t now becomes clear t o o why iron solutions are preci pitated


    , ,

    by ammo nium sul phide This takes place according to t h e equa


    .

    tion
    Fe SO 4 (N H4 ) 2S F EES i ( N H4 ) 2 SO 4

    In this case there are no H ions in the solution to act on the iron
    -

    sul phide .

    The reason for the non preci pitation of metals like barium -

    etc either by sul phuretted hydrogen or ammo nium sul phide lies
    .
    ,

    in the easy solubili t y of their sul phides .

    Hydro g en Per su l ph ide .

    74 . a
    Ifs o l ut i on of sod i um s ul ph i de N a S i s d i gested
    , w ith s ul ph
    , u r
    , ,

    the sul phur di sso lv es and the liqui d c ontai ns c o mpounds c all ed pol y
    s u l ph i des and havi ng for m u l ae fro m N a S u p to N a s ac c ord ing to the
    z 2 ,

    a m o unt of sul phur e mpl oyed O n po u ring s uc h a soluti on i nto c o l d


    .

    d il ute hydro c hl oric a ci d an o il separates out whic h by d i st ill at i on under ,

    l ow pressure yi el ds two c o mpounds having t h e formul ae H S and H S


    , , 2 2 2 3 .

    The h ydrogen disu l ph i de i s at ord inary te mperat u res a yell ow i sh water ,

    c l ear liqui d wi th a c onsi sten c y so m ewhat like that of water Wi th .

    alk ali es i t de c o mposes v i ol ently Under ordinary pres sure the liq ui d
    .

    bo il s wi th part i al stabili ty at 7 4 I t s spe cic gravi ty i s It s


    fu m es atta ck the eyes and m ucous m e mbranes vigoro u sly .
    I N O R G A N I C C HEM I S TR Y . 75

    chlorine d ecr ease in volume and this d iminuti on is g re at est whe n


    ,

    the comp osition c orres p onds to SzC l z + C 12 ( )


    3 O n distilling .

    under 4 mm pressure 8090% of the liquid coul d b e dist illed over


    .

    almost c onstant at A t o rdinary pressure the c om p ound



    b oils at about 59 60 with dec om p osition
    .

    Su lph u r t etra c h lo r i de , SC l 4 c an be obtained as a ne white


    ,

    owder a arently not crystalline when a chlorine sul hu r


    p , pp p ,

    mixture of the c om p osition S + C l 4 or S + 016 is c o oled to


    ( where it solidies ) and then centrif u ged The tetrachloride melts .

    at about giving o ff c hlorine abundantly The exact tem .

    p e r at u r e c ould not be determined Here to o the for m of


    . the , ,

    freezing p oint curve indic ates unquestionably the f o rmula of the


    s ubstance vi z ,
    SO 14 .
    ,
    Cf 23 7
    . . .

    With bro m in e and io di n e s S anal ogo u s c om


    p ound s

    Fl u o r in e unites with s u l ph u r to form a gas of t h e fo r m u l a SF6


    an d of rather sur prising pro perties I t is c ol o rl e s s , 6 dorl e s s and


    inc o mbustible A t
    . 5 5 it solidies with t h e fo r m at ion of crystals

    .
    '

    N otwithstan ding its high p ercentage of uorine it is chemically


    s o ind ifferen t that it almost resembles ni trogen in this res pect

    ( see p . Fo r instance it is n o t decom p,


    osed by fused alkalies
    n o r by C o pp e r oxide at dull red heat I t can be heated with
    -
    .

    hydrogen without yielding hydroge n uoride M oreover sodium .


    ,

    can be fused in sul phur h ex a u o ride without losing its metallic


    s urface the gas no t being attacked by the metal till the boiling
    ,

    p oint of the l atter is reached .

    VA L EN C E .

    76 . elements have the pro perty whereby their atoms


    C ertain
    c an combine with only one atom of ano ther element The halogens .

    o n the one hand and hydrogen on the o ther are able to form only

    comp ounds of the typ e This pro p erty of t h e


    a toms is called u n iv al e n c e .

    I n the case of o ther elements like oxygen an d sul phur each


    ato m can enter into com p ounds with two univalent atoms ( exam

    p les : H g S Hg O ) These
    ,
    are therefore
    . called b i v al e n t .

    The number of univalent ato m s that can combine with o n e


    ato m of a given element serves in an analogous way as a measure

    o f valence in general A n at om of nitrogen for instance unites


    .
    , ,
    V A L EN C E . 23

    with three ato m s of hydrogen ; nitrogen is therefore trivalent ;


    carbon is quad rivalent etc , .

    The valence is ordinarily indicated by lines , as in O /


    H \H
    N H, each l in e re p resenting a valence unit (unit bo nd ) .

    \H
    The valence of one and the same element may be different
    according t o the nature of the u nivalent elements with whi ch it
    combines Sul phur for instance can o nl y unite with two hydrogen
    .
    , ,

    ato ms but wi th univalent chlorine it forms the com pound SC 14


    , ,

    wi th uorine even SF6 The valence of Sul phur in these cases is


    .

    therefore four and six The prep aration of sul phur compounds .

    with m ore than six univalent atoms has not yet been accomplishe d ;
    hence it s m axim u m v al e n c e is six .

    The halogens are univalent towards hydrogen but in relatio n ,

    to each other they dis play more than o ne valence as may be seen ,

    fro m the com pounds 1 013 and 1 015 ; in the com pound C l 7 6 0)
    the maximum valence of chlorine can even be assumed to be seven .

    It has been very generally observed th a t when the maximum


    valence of a n element is an ev e n or an uneven number its lower ,

    vale nces are of the same sort ; the halogens and sulphur illustrate
    this However these are exce ptions t o this rule
    .
    ,
    .

    vale ce al o d pe nd u p n t h te mpe r ture We h ll oon ee th at


    Th e n s e s o e a . s a s s

    S0 3 di ci ate t a h igh t e mperatu e in t SO a d oxyge n ; w h il e ul ph u is


    s so s a r o Z n s r

    O
    xivalent tow ards oxygen at l o w e r tempe ratu / it on ly qu adri
    se re s 2 0
    is

    valent tow rd o xyg e n ab o ve 7 00


    ( S Th e val e n c e must al so de pend

    a s

    on t h e pr e ss ur
    l tt e x e rt a g t i nu e n ce o n t h e di o ci tion
    e, fo r t h e a er s re a ss a .

    Th e b i f th bov rt f f rmul ae i t h i de b r w d fr m g anic'

    as s or e a e so o o s e a, o ro e o or

    ch mi try t h t t h t m f a m le cul e m y t
    e s ,
    a e a o ume y co c ivab l e
    s o o a no ass an n e

    arra g m n t w h t o e ve b t th t th e i d it o der in e ve y mo le cul e


    e en a s r, u a re s a e n e r r .

    F or so me extensio ns of the idea of valence see 3 17 .

    Vale n c e I on s I n
    the solutio n of an electrolyte the sum s of
    of .

    all the p ositive and all the negative a m ounts of electricity must

    b e equal for the solutio n acts as electrically neutral I n a solu


    ,
    .

    tio n of hy drochloric acid the positive charge of the H io ns mus t -


    1 24 I N O R GA N I C C H E M I S TR Y . 7 6;

    be numerically equal to the negative charge of the and l


    C ions ,

    since the same number of both io ns are present each C l io n mus t ,


    -

    carry a charge equal but o pposite in sign to that of an H io n


    , ,
    -
    .

    In a sulphuric acid solutio n however the two H io ns togethe r , ,


    -

    mus t possess j us t as much p ositive electricity as the SO 4 io n nega -

    tive electricity The S0 4 io n is t herefore called bivalent in re



    .

    Spe ct to the hydroge n io n I t is readily seen how the valence of


    .

    other io ns can be determined in an analogous manner for it is ,

    equal to the numerical value of their electrical charge th at of ,

    t h e hydroge n io n being take n as unity .

    C o mpo u n ds of Su l ph u r with O xygen .

    77 . O f those
    o nly the two elements three are known
    c o n t a1 n 1 n g ,

    viz S 2 0 3 SO Z and SO 3
    .
    , ,
    E s pecial im p ortance attaches itself
    , .
    ,

    however only to SO 2 and SO 3 ; the two others have been little


    ,

    studied .

    l
    Su ph ur Se s q ui oxi de ,
    820 3 .

    Th i s i s obtained when s ulphur i s treated w i th i ts tri oxide I t i s a .

    b lu e liquid wh ic h c ongeal s to a m al a c h i te green m ass an d i s so lub l e in


    ,
    -

    fum ing su lphuric a c id giv ing a blue so l ut i on O n being warm ed it


    ,
    .

    brea ks u p into s ul ph ur and t h e di oxi de


    2 82 0 3 3 SO 2 S .

    Water de c o m poses it with the form at i on of sul phur sul phuro u s a ci d and ,

    po l yth i on ic ac i ds .

    SUL PHUR DIO XI DE, SUL PHUR O US A NHYDR I DE, so,

    7 This gas o ccu rs in nature in volcanic gases It is forme d


    8 . .

    when sul phur burns in the air or in oxygen ; the well known odo r -

    o f burning sul phur is due to it A li t tle trioxide is also formed .

    b y this combustio n The laboratory method of preparatio n con


    .

    s ists in decom posing sul p huric acid with co pper .

    2 H2 8 0 4 CH 011 80 J "80 2 H2 0
    4 r 2 .

    Fo r this pur pose co ncentrated sul phu ric acid is heated with c op
    e r tur ni ngs no act io n taking p lace at ordinary tem p eratures
    p ,
    .

    The pro cess can be ex plained by supposing that at the high tem
    "
    1 26 IN O R G A N I C C HEM I ST R Y .
    Q

    is ve ry soluble in wate r ; at vol Hg O dissolves


    .

    vols .

    SO z at,
    20

    vo l s SO z . . B oiling the solutio n ex pels all t h e
    gas
    C h em ica l Prop er ties dioxide i s an acid a nh ydride ;
    Sul phu r
    I t s aqueous solutio n has an acid reactio n and behaves in general

    like tha t of an acid I t is easily oxidi z ed by oxidizing


    agents to the trioxide This occurs for instance when a mixture
    .
    , ,

    of s ul phu r dioxide and air or oxygen is passed over hot s pongy


    platinum or platinum asbestos I n aqueous solutio n this oxidatio n
    .

    takes place readily at ordinary tem peratures The oxidatio n of .

    the dioxide can also be brought about by chlorine water bromine -

    and iodine :

    012 2H2 0 S0 2 Hg SO 4 2HCl

    also b y chromic acid which is reduce d to chromium sul phate or


    , ,

    b y potassium permanganate which is re duced to a mixtur e of ,

    manganese an d potassium sul phates and therefore loses its colo r : ,

    2KMn O 4 5SO z 2H2 0 K 2 SO 4 2 Mn SO 4 2H2 SO 4 .

    L ea d peroxide glows faintly in a current of sulphur dioxi d e


    an d is re d uce d to lea d sul phate from brown to white

    Pb O z S0 2 Pb SO 4 .

    It is to its reducin g action that the bleaching e ffect of sul


    ph u r o u s oxide on vegetable coloring matters is due A red rose -

    .
    ,

    for exam ple loses color in it The gas probably reacts with
    ,
    .

    water settin g hydrogen free which latter effects the re d uctio n


    , ,

    an d hence the b leaching :

    80 2 2 H2 0 11 2 80 4 H2 .

    In this case therefore bleaching depends on a reduction ; as a


    , ,

    matter of fact the color returns in many instances when the ,

    b leached article is exposed to the oxidizing action of the air Silk .


    ,

    wool and stra w i e substances that c annot stand the chlorine


    ,
    . .

    b leachin g are whitened commercially with sul phurous oxide


    , .

    It also n d s use as an antiseptic .


    S UL PH UR D I O X I DE .
    1 27

    The reduction of iodic a ci d by s ul ph u r d i o xi de is so meti mes e m pl oyed


    as a test for t h e l atter For thi s pu rpose stri ps of paper are di pped i n a
    .

    so lu t i on of potass ium i odate and star c h whic h t u rns b lu e i n t h e presence


    ,


    of s ul phur d i o xi de i odi ne be i ng s e t free
    I f the react i on i s c arr i ed o u t i n dilu te so lu t i on a pec uli ar pheno m enon
    ,

    is observed ; the b lu e c o l or of star c h i odi de does not a ppear d ire c tly when
    t h e so l ut i ons of s ul ph u r d i o xi de and i odic a ci d are mixed b u t i s w i th ,

    he l d for a c ertai n nu mber of se c onds (de ni te for e very c on c entrati on


    at constant te m peratu re) when i t s u ddenly appears The fo ll owing
    , .

    reactions co m e into pl ay

    I . 3 SO zaq HI o, 3 H2SO 4aq HI .

    The hydriodic a c id thu s form ed i s at on c e o x i diz ed by the iodic aci d


    still present :
    II . SHI 11 1 0 3 3 H,o 61 .

    So l ong as s ulphur d i o xi de is present it reduces the io dine in this,

    dil ute so l ution to hydr i odic a ci d

    I II . 21 SO zaq 2 H2 0 HzSO 4aq 2 HI .

    N ot nt i l a ll the d i o xi de is used Up by the rea c ti ons I and I I I does the


    u

    free i odi ne s u ddenl y a ppe ar a cc ordi ng to II .

    There are some substances which are able to extrac t oxygen


    from sul phur dioxide i e the latter can also act as an oxidizing
    ,
    . .

    agen t . Ignited magnesium ribbon continues to burn in sulphur


    di oxide forming magnesium oxide and sul phur
    ,
    Hydrogen sul .

    ph id e and sul phur dioxide have res p ectively an oxidi z ing and a
    reducin g effec t on each other which follows mainl y the equation :
    ,

    2 11 2 8 80 2 2 H2 0 + 3 8 .

    Sul phur dioxid e is decom pose d by electric s parks in to sul phur


    an d the trioxide .

    The a c t i on of the e l e c tric s parks i s to be as cr ibed so le ly to the sudden


    and enorm o us r i se of te m perat ure whic h they produc e an d t h e rapi d c oo l
    ing that i mm ed i ate l y fo ll ows for t h e g as part icl es whic h hav e be c o m e
    ,

    heated by the s par ks are imm ed i ate ly c oo led aga i n by s urro unding
    obj e c ts A s a res ult t h e produc ts form ed do not have t im e to rea c t i n
    .

    the o ppos i te di re c t i on Th e c orre c tness of thi s vi ew was dem onstrated


    .

    by ST C L A I R E DEVILLE with t h e he l p of an apparatus whic h m ade i t pos


    .
    1 28 IN O R G A N I C C HE M I S TR Y .
    7s

    s ible to cool obj e c ts very rapi dl y fro m a very high te m perature Th is .

    apparat us the c o l d h o t t u b e c ons i sts of a rather wi de porcel ai n


    ,

    t ube whic h i s heated to a br i ght gl ow i n a furna c e and wh ic h contains


    ,

    a con c entric thinner m etalli c t ube through whic h c o l d water i s forced so


    ,

    rapi dly that the t ube m ai ntai ns a l ow te m perat ure When DEVI LL E .

    introduced sul phur d i oxide i nto the s pa c e between the two t ubes i t was ,

    seen after so m e t im e that the i nner t ube whic h was m ade of s ilver plated
    ,
    -

    co pper had t urned bl a ck be c a us e of the form at i on of s ilver s ulphi de


    , ,

    wh ile at the sa m e t im e the for m at i on of s ul phu r tr i oxide c oul d be dete c ted


    (by i ts prod uci ng s ulphu ri c a ci d wi th water a prec i pi tate be ing giv en by
    ,

    barium c hl or i de) .

    The com position of sul phurous oxi d e can b e d etermin e d in the


    following manner : When sul phur burns in oxygen no chan ge of
    volume is observe d after cooling Therefore j us t as many mole
    .

    cules of sulphurous oxide have been formed as oxygen molecules


    co n s u med The sul phurous oxide molecule must therefore con
    .

    tain two atoms of oxygen The s pecic gravity of the gas has
    .

    been found to be or (o so that its


    molecular weight is I f we subtract from this for
    two atoms of oxygen there remains
    ,
    for sul phur the atomic ,

    weight of which is 3 2 We thus see that only one atom of sul


    .

    p hur is p resent in the mo lecule of sul p hurous oxi d e an d that t h e

    formula of the latter is S0 2 .

    SULPHUR TR I O XI DE, SULPHUR IC AN HYDR I DE , so,

    79 This
    . c om p ound is found in a small amount in th e fume s

    o f burning sul p hur A s was stated above oxyge n and ,

    sul phur dio xide u ni te t o form the trio xide in the p resence of
    p latinized asbestos O n the other hand
    . the trioxide breaks up
    ,

    into the dioxide and oxygen at an elevated tem perature so that ,

    the formation of the trioxide fro m the dioxide an d oxygen is


    evi d ently a reversible proc ess which is expresse d thus
    ,

    2 80 2
    02 3 280 3 .

    If we c all the pressureof SO 2 in the equilibrium c ondition pl , that


    13 0 I N O R G A N I C C HE M I S TR Y .
    80

    Fuming sulphuric acid ( oleum) is a solution of


    sul phur trioxide in sul p huric acid ; the anhydride can be obtained
    fro m it by distillation .

    8 0 Physica l Pr op erties
    .
    Perfectly dry sul p hur trioxide melts at
    1 7 7 and boils at I t looks much like ice but usually a ppears

    .

    in another mo dication viz long asbestos like needles with a


    , .
    ,
    -

    s ilky lustre T hese crystals have no shar p melting poin t but


    .
    -

    s ubl ime on heat ing This modication is the stable one for the
    .
    ,

    other goes over into it Spontaneously This transformation is .

    gr eatly accelerated by traces of water The asbestine m o dic a .

    tion consists of double molecules ( SO 3 ) 2 the glacial form of simpl e ,

    molecules ( SO 3 ) This is shown by the de pression of the free z ing


    .

    p oint of p hos p horus oxychloride The rst is therefore called a .

    p lym er of the second


    o I t is also worth noting that the SO 3
    .

    mo d ication is very rea d ily soluble in co ncentrate d sul phu ric


    aci d while the other ( SO 3 ) 2 d issolves with difficulty
    , , ,
    .

    C h em ica l P p
    r o er ties Sul phur trioxi d e u nites ver y easily with
    water to form sul phuric acid

    80 3 HgO 11 2 80 4 .

    It therefore fum es vigorously when exposed to mois t air O n .

    introducing it into water combin ation and great evolution of heat


    , ,

    accom panied by sizzling results It reacts energetically with , .

    many metallic oxides also forming sulphates Baryta for exam ,


    .
    ,

    p l e glows
    ,
    in contact with it When its va p or is p asse d . through
    a r ed hot tube it is decom posed into the dioxide and oxygen
    -

    , .

    C om s itio n The decom osition j ust mentioned ermits us


    p o p p
    to establish the com position of sul phuric oxide The dissociation .

    p roducts S 0 2 ,
    and 0 2 are formed in the
    ,
    volume ratio 2 : 1 N o w .

    t he Specic gravity of sul phuric oxide is from which


    the molecular weight is calculated to be This gure corre
    Spo n ds to the formula and it also harmonize s
    with the above dissociation ; for it is clear tha t 2 vols SO 3 mus t .

    th en yiel d 2 vols S0 2 and 1 vol O z . .

    2 80 3 2 80 2 02 .

    2 v ol s . 2 v ols . 1 v ol .
    O X Y G EN A C I D S O F S UL PH UR . 13 1

    O xyg e n A ci ds of Su l ph u r .

    81 . forms an unusually large number of acid s


    Sul phur
    o xygen and hydrogen namely nine They are as follows
    , .

    1 . Thi os ul ph uri c a ci d H2S2 0 3 .

    2 . Hypos ul ph u ro u s a ci d H2S2 0 4 .

    3 . Sul ph uro u s a ci d .

    4 . Sul ph u r ic a ci d .
    H2SO 4 .

    5 . Pers ul ph u r ic a ci d . HzSzO S .

    6 . Di thion ic a ci d HZSZO G

    7 . Tri th i onic a ci d H2 S3 O B .

    8 . Tetrath i oni c a ci d . H2S4O e .

    9 . Pentath i oni c a ci d Hs O B .

    I t is an M port an t fact however that of these n in e aci d s only


    , ,

    sul phu r i c aci d has really been isolated ; all the others are kn own

    o nly in aqu eo us solution or in the form of salts The two hydro .

    gen atoms which each o f these acids possesses are both replaceable
    by metals ; they are therefore diba sic acids With such acids it .

    is possible that j ust one of the hydrogen a toms be re placed b y a


    metal The salts thus formed are called ac i d salts
    . .

    By different methods e g the cryosco pic metho d it is found


    ,
    . .
    ,

    that the aqueous solution of dibasic acids A H2 contains c hiey the


    ions H and HA ; it is only when these solutions are very dilute
    '

    that the anion HA s plits u p further into H and A



    In the case

    of the M2 A salts however there is an ioni z ation into 2M + A ;


    , ,

    but in that of the acid salts MHA the ions are chiey M and HA '
    .

    How far the anion HA is Split u p does not de pend m erely o n the

    .

    concentration but also to a considerable degree on the strength


    ,

    of t he acid HA being more ionized in s trong than in weak acids



    ,

    o f t h e same concentration .

    THI O SUL PHUR I C A C I D, 11 2 820 3 .

    82 This aci d can only exis t in dilute aqueous solution an d is


    .

    e ven then very unstable decom p osing com pletely in a short time
    ,
    .

    The salts are however s table and can be prepared in the following
    , ,
    13 2 IN O R GA N I C C H E M I S TR Y .
    M 82

    1 . By b oiling the solution of a sulphite with sulphur


    N a2 S0 3 + S = N a2 S2 0 3 ;
    So iu m d sul p h it e.

    SO 3 S S2 0 3

    o nly the anion b em g changed .

    2 By the oxidation of sul phides in the a 1 r


    .

    2 08 82 3 02 2 03 82 0 3 .

    C al c iu m di
    su l p hi d e .

    3 . By the action of sul phur dioxide on the soluti on of a sul e

    ph ide

    4 N ag S 68 0 2 4N a2 S2 0 3 S2 .

    The most im portan t sal t is the sodium thiosul phate formerly ,

    and even yet often called sodium hyp osul phite or abbreviated
    hyp o
    I t is very soluble in water ; the solution when used in
    .
    ,

    ,
    , ,

    excess has the pro perty of dissolving readily the halogen com
    ,

    p ounds of silver hence i ts extensive,


    use in p hotogra p hy ,

    I t is easily oxidi z ed by oxidizing agents usually t o the sul phate -

    , .

    This takes place with p o tassium p ermanganate ni t ric acid and ,

    chlo rine for example Practical use is also made of this latter
    ,
    .

    ro
    p p erty by em p loying sodium thiosul p hate as an a n tichl or in
    bleaching i e to remove the last traces of chlorine which cling t o
    ,
    . .

    the bleached material very obstinately and have an inj urious effec t .

    When a dilute acid is added to a dilute solution of sodiu m


    thiosul phate the following decomp osi tion takes place :
    ,

    820 3 2H HS0 3 + H + S '


    '

    A n io n o f s u l hur
    o u s ac 1

    b e however that the ions rst u nite


    , , p a r tially to
    which s pl its up into Hg O S and S0 2 ,
    .

    It is an interesting fa c t that i n this de c o m pos i t i on in a dil ute so lu ti o n


    the s ul phur prec i pi tate i s not at onc e vi s i ble be i ng r st noti c eab le after ,

    so m e seconds or e ven mi nu tes ac c ordi ng to the d ilu t i on I t was form erl y


    , ,
    .

    supposed that the thi os ul phu ric a ci d re m a i ned ent ire ly unc hanged u nt il

    the appearan c e of the s ulph u r an d the de c o m pos i t i on r st be gan at thi s


    4 IN O R G A N I C C H E M I S TR Y .
    84

    however the solution obeys this law pretty well A fact in con
    ,
    .

    rm at io n of this is that all the sul phur dioxide can be ex pelled fro m
    the solution by boi l ing it the combination being then wholly ,

    destroyed The compound H2 SO g itself has however not yet been


    .
    , ,

    isolated The salts have the com position M 2 S0 3 and M HSO 3


    .

    M being an atom of a u nivalent metal ) The acid salts are almost


    ( .

    all s oluble in water while of the neutral salts only those of the,

    alkalies are soluble The acid sodium sul phite N aHSO 3 (sodium
    .
    ,

    bisul phite) is frequently employed in organic che m istry Su l


    , .

    p h it e s in soluti o n gradually absorb oxygen from the air form ,

    ing sul phates I t is a very strange fac t that minute quantities of


    .

    organic substances e g only of alcohol and as little as 1 0 5


    ,
    . .
    -

    gram molecule of stannous chloride greatly hinder this oxida ,

    tio n We have here one of the few exam ples of a retarding


    .

    catalytical action O n the other hand traces of co pper sul


    .
    ,

    p hate c o nsiderably ac celerate the oxidatio n .

    SULPHUR I C A C I D, H ,So , .

    J
    85 Sul phuric
    ac id is the most im p ortant a c id of sul p hur It .

    can b e obt ained in various ways ; in the rst place by direct


    synthesis from its elements A ccording to 7 9 sul phur trioxide .

    can be formed directly from sul phur and oxygen and this yields ,

    sul phuric acid on the addition of water .

    The acid can be obtained from its salts by distillin g them wi th


    p hos p horic acid I ts formation from. the action of oxygen on
    sul phur com pounds is illustrated by the oxidation of an aqueous
    SO z solution by the air
    -
    O n the other hand the ac tion of sul phur.

    on oxygen comp ounds may also give sul phuri c acid ; thus it is
    formed when concentrated nitric acid HN O 3 is boiled with sul , ,

    hur and again otassium sul hate is fo r med by hea ting sul hur
    p ; p p , p
    with saltpetre ( K N O g) .

    8 6 For the c om m er cia l ma n u fa ctu r e of sul phuri c acid two


    .

    p rocesses are now i n use the lead chamber p ro cess a nd the co


    ,
    n -

    t act process E normous amounts o i the acid are produced by


    .

    these two methods .

    The l e a d c h a m b e r p r o c e s s is based o n the follow


    -

    ing reactio ns : 1 the oxidatio n of sul phur dioxide by nitric acid


    .

    in the prese nce of water ; 2 the oxidatio n by the oxyge n in the .


    S UL PH UR I C A C I D .
    13 5

    air of lower oxides of nitrogen formed from the nitric acid in the
    p revious reactio n These .are p artly reconverted to nitric acid
    a nd partly changed to certain stages of oxidatio n of nitrogen
    which oxidize sul phur d ioxide anew to sul ph uric acid By this .

    last pro cess the lower nitroge n oxides are again formed but are ,

    soo n reoxidized by atmos pheric oxygen and so o n O n e might .

    suppose that a certain amount of nitric acid would suffice to co n


    vert unlimited amounts of sul phur dioxide into s ulphuric acid
    with the aid of the air I n practice this is not true ,however ; for
    .

    the nitrogen oxides are to a small extent still farther reduced by


    s ul phurous oxide so that nitrous oxide or nitrogen are formed
    , ,

    and these are no lo nger able under the conditio ns of the indus
    ,

    trial process to combine with oxygen


    , .

    The chemical pro cesses which lie at the basis of the manu
    facture of sul p huric acid will be taken u p a little later
    From a techni cal stand point the lea d cham b e r pro cess fall s -

    into th r ee se parate parts


    1 The pre paratio n of sul phur dioxide ;
    .

    2 The oxidatio n of sul phur dioxide ;


    .

    3 The concentratio n of the resulting acid


    . .

    ( 1 ) The material for the productio n of the dioxide is sul phur


    or pyrite ( iro n pyrites Fe Sg ) Sul ph ur yields a purer ac id th an
    '

    .
    ,

    p yrite ; that re
    p p ared from the latter almost always co ntains
    arsenic The roasting of the pyrite is carried o n in furnaces the
    .
    ,

    constructio n of which varies co nsiderably I n all of them how .


    ,

    e ver the sul phur dioxide leaves the furnace m ixed with a good
    ,

    deal of air The furnace gases pass through a canal in which the
    .

    dus t particles carried along by the draught are de posited .

    ( )
    2 The oxidation of the sul phurous acid is car r ied out in a

    str ucture c onsist ing chiey of thre e parts the G lover tower , ,

    the lea d chambers and the G ay L ussac tower


    ,
    -
    The gases .

    enter the b otto m of the G lover Tow e r , which is made of


    shee t lead lined with acid proof brick I t is lled with lump
    -
    .

    stone over which is laid a layer of smaller p ieces of c oke O n


    ,
    .

    t op of the tower is a reservoir for c ollecting the nitroso sul p huric


    acid (see below ) that c o mes from the G ay L uss ac tower and t he -

    lead chambers and is to be c oncentrated in t he G lover tower I t .

    ows down over the stone in the tower fro m a horiz ontally re v ol v
    ing tube From the G lover tower the gases enter the l ead c h am
    .
    13 6 I N O RGA N I C C H E M I S TR Y .
    86 ;

    ber s . These are three or four in number and have a t otal c ap acity
    of 4 000 5000 cubic meters Their form is that of a p arallelo piped

    .
    ,

    whose cross section is nearly a square L ea d has been chosen as


    -

    the material fo r the walls of the chambers be c ause it is the only ,

    one of the c ommon metals which is only slightly attacked by


    sulphuric acid and the substances used in its manufacture The .

    lea d c hambers are c onnected with each other with the G love r ,

    tower an d with the G ay L ussac tower by means of lead p ipes -


    .

    Th e r st two chambers are also furnishe d with o penings for


    intr o d ucing steam .

    The oxi d ation of dioxide t o trioxide having been ac complished -

    in the lead chambers the residual gas p rincip ally nitrogen p asse s
    , , ,

    t o the G ay L u s sac tow er


    -
    .

    Usually this is entirely lle d with c oke O n t op of the tower .

    is a reservoir c ontaining 60 62 sul p huric acid ( B AUM E see -



    ,

    which c omes fro m the G lover tower The G ay L ussac tower (


    .
    -

    serves to c ollect the nitrous vap ors that are still present in t h e
    gas as it leaves the lea d chambers These va p ors dissolve in t h e .

    sul p huric acid forming the nitroso sul phuric acid which is use d
    ,

    in the G l o ver tower In this way the loss of n it rl c aci d is much


    .

    reduc ed .

    L et us n ow examine t h e task that befalls each of these thre e


    the G lover tower the lea d chambers an d the G a L ussa c
    y
    -

    tower .

    The gases that c ome from the pyrite furnace c onsist of a mix
    ture of sul phur dioxide and air a larger pro p ortion of the latte r ,

    than is require d for the oxidation They have a tem perature of .

    ab out 3 00 when they e nter the G lover tower A at the o pening w



    , , , .

    The gas current rising in the tower meets an acid mixture ow


    ing d own from ab o ve The l atter c onsists of the nitroso aci d

    fro m the G ay L ussac tower dilute d with the acid ( cha m ber a cid)
    -

    ( 3 ) The acid p ro d uced in the chambers contains about 67 %


    Hg SO 4 (53 BAUM E)


    In this condition it is em ployed dir ectly
    .

    in the manufacture of fertilizers ( su perphos phate For


    alm os t all other pur poses it must first be concentrated O rdinary
    -
    .

    sul phuric aci d of commerce is of about 66 B ie



    . . .

    9 6 9 8% H2 SO 4
    It is prepared from the chamber acid by ev dp
    .

    orating it rst in lea d pans to about 7 8 % (60 B ) and n ally in


    .

    a platinum vessel .
    13 8 IN O R G A N I C C H E M I S TR Y .
    86

    e xamined with t h e eye to see whether it is perfectly trans pare nt


    an d free from nebulous masses Eve n when this o ptical test is
    .

    quite satisfactory the cataly z er suffers a loss in activity if the


    gas is not entirely free from arsenic c o m po u n ds the least traces
    a

    o f the latter have a n inj urious e ffect The presence of arsenic .

    com pounds in the furnace gas is due to the o ccurrence of arsenic


    in the pyrites 8 6 1 ) used for roasting
    ,
    KN I E T SC H has nally .

    succeeded in com pletely elim inating the arsenic com pounds by


    b lowing steam into the gas mixture .

    (3 ) A s already set forth in 7 9 the equilibrium ,

    2 80 2

    is expressed by the e quation

    2
    29 1 19 2 K P3 2
    ~

    A c c ording to this equatio n the formation of sul phur trioxide is


    more c omplete in the p resence of an excess of either sul phur
    dioxide or oxyge n for as p l or p 2 in creases p3 must also increase
    , .

    Since the obj ect in v 1 ew 1 s to c onvert the dioxide as com pletely as


    p ossible into the trioxide it is advantageous
    ,
    to provide a large
    excess of oxy gen This e x plains why more than the theoretical
    .

    amount of oxygen is taken C om p are .

    The equilibrium must also d e pen d on the pressure fo r if this , ,

    is i ncreased n times the equation becomes


    ,

    or 2
    p1 p = K 2
    2 p3 ,

    from which it is evident that at a higher p ressure (n > 1 ) the for


    mation of the trioxide is more nearly c om plete 1 02 Th e ,

    manufacturer does not nd it necessary h owever t o em p loy , ,

    high p ressure which would involve moreover a great com plica


    , , ,

    tion of the app aratus .

    I f it is desired that the combination of sul phur dioxide and oxy


    gen should be as complete as p ossible the temperature must b e ,

    kept at about Since however the heat of formation of t he


    , ,

    trioxide is great viz


    ,
    .
    ,

    C al ,
    S ULPH UR I C A C ID . 13 9

    the a pp aratus must b e c o oled This is done most practicably b y


    .

    the aid of a fresh p ortion of the gas mixture as the next p aragraph ,

    sets forth .

    The construction of the app aratus is as follows : The tubes ab


    ( Fig. 3 1 ) c ontain the plat inize d asbestos b su pp orted on little ,

    sieves (shown in the middle tubes ) The puried furnace gases


    .

    rst p ass around the outside of the tubes and are thus warmed to

    FI G 3 1 C O N T A
    . C T PR O C E SS
    -
    A PPAR A T US .

    the desired tem p erature at the heat exp ense of the gas system
    within When the pro p er tem perature is reached the gases are
    .

    allowed to enter the tubes where sul p hur trioxide is formed with
    ,

    the evolution of more h eat By increasing or diminishing t h e


    .

    rate of ow of the gas current the tem p erature can be regul ated
    very satisfactorily When the O peration is started the app aratus
    .

    must rst be warmed to


    ( )
    4 The r eaction between sul p hur trioxide and water is an
    energetic one N evertheless the manufacture of sulphuric acid
    .
    ,
    40 I N O R GA N I C C H E M I S TR Y . 86

    from these two c ompoun d s invol ved some difficulty inasmuch as ,

    sulp hur trioxide fumes invariably esc aped when this substance was
    introduced into water or dilute sul p huric a cid O nly when sul .

    p h u r ic acid of 9 7 9 8 % is used as the absorbent and c are is taken


    to kee p the acid at this c onc entration by the simultaneous addition


    of water does a c omplete and immediat e absorp tion o c cur .

    This is due to two circumstances : rst that traces of water ,

    change s u l ph u r t r io x ide into the asbestine modic ation


    '

    which is only slowly absorbed by sul p huric acid ; sec ond that at ,

    t h e concentration o f 9 7 98 % H2 SO 4 the system xS0 3 + s O


    h as a minimum of va por tension which is very l o w , .

    8 7 Physi l Pr ope ti s
    . ca r e The pure com p ound hy droge n sul ,

    p hate ,
    is an oily liquid at ordinary tem p eratures solidifying at a ,

    low tem p erature and melting again at Its Spe cic gravity
    in the liquid state is
    C hemica l Pr oper ties The co nce ntrated aci d o btained by ( 1 1 8
    .

    bil l at io n is n o t the sim ple com pound Hg SO 4 for it still co ntains ,

    about of water I n order to pre pare the absolutely pure acid


    .

    the distilled produc t must be mixed with the theoreti cal amount
    o f s ul phur trioxide Whe n pure sul phuric acid 1 s heated it begins
    .
    ,

    at 3 0 t o give o ff fumes of sul phur trioxide ; this co ntinues until


    the b oilingp oint 3 1 7 at 7 5 0 mm Hg p ressure is rea ch e d


    ,

    . .
    , ,

    when an acid with water distils over O n heating the va p or .

    of sul phuric acid ab ove the b oiling p oint it begins to break u p -

    into water and the anhydride ; this disso ciatio n is com plete at
    for the va po r density at that t em perature is found to be
    while that of S0 3 + HzO is theoretically
    Whe n sul phuric acid is mixed with water a stro ng evolutio n ,

    o f heat o c curs The mixing must therefore be do ne with great


    .

    care pa rticularly in glass vessels the acid bein g poured in a ne


    , ,

    stream i nto the wate r an d the liquid being steadily stirred O n .

    mixing them in the reverse way by pouring the water into the ,

    sulphur ic aci d the inte nse heat tha t is produced may cause the
    ,

    glass to crack However when the acid is mixed with ice i n a


    .
    ,

    certain pro portio n a stro ng cooling follows


    ,
    .

    The mixing of sulphuric acid and wate r is attended b y a co n


    t ractio n i e the volum e of the dilute acid is sma l ler than the s um
    ,
    . .

    of the volumes of water and aci d I t is known that sul phuric .

    acid is able to form h y d r a t e s with water


    1 42 IN O R G A N I C C H E M I S TR Y . 87

    If thes e pyrosul phates are heate d still higher they give off , sul p ur h
    t rioxide and form neutral salts :
    N a2 S2 0 7 N a2 so4 80 3 .

    88 Uses Sul huric


    acid is of enormous practical value , it s
    .
    p
    u ses b eing most va rie d It is employe d in the pre paration of almost
    .

    all other mineral aci d s from thei r salts In the manufacture of soda
    .

    after L E BL AN C i t is use d in astonishin gly large amounts an d in


    nearly all o ther b ranches of chemical indus try it is of some servic e
    o r other In. the laboratory it is often em p loye d as a drying agent .

    A moist substance is dried very thoroughly when placed in a close d


    app aratus near a dish of the concentrated acid For t his purp os e .

    Special pieces of a pp aratus are constructed called des ic ca tor s , .

    The determ ina tion of the con cen tra tion of su l ph u ric acid is an .

    O peration that is frequently necessary O rdina rily the s peci c


    .

    gravity is made use of for this can be determin ed rapidly with an


    ,

    areometer T here are tables so pre pared that the pro p ortion of
    .

    H2 SO 4 o r SO 3 in a dilute aci d whose Specic gravity and tem pera


    ture are known can be quickly read B AUM E a chemist of the .
    ,

    latter part of the eighteenth century constructed an areomete r ,

    w ith an arb itra ry scale t h e zero point of which in d icates pur e


    ,

    water an d the point 1 0 bei n g reached in a 1 0% sal t solution A l l -


    .

    the divisions are equal 1 00% H2 SO 4 would then be represente d


    .

    by the line I n the arts the strength of sul phuric acid is


    still given as so many degrees B AUM E
    .

    F u m in g s u lph u ri c a c i d is the name of a sul p huric acid that


    c ontains sul phur trioxide in sol ution I t is obtained by dissolving
    .

    the oxide in c oncentrated sul p huric acid .

    Fuming sul p huric acid is a thick oily liquid which fu m es ,

    vigorously in the air throwing o ff the trioxide Sp g


    ,
    . . .

    C HL O R I DES O F SULPHUR I C AC I D .

    89 . Wh en phosphoru s p enta c hl or i de a c ts on s ulphuri c a ci d a c o m


    p o u nd SO 3 HC l , c h l or o s u l ph o n i c a c i d, i s form ed

    The sam e c o mp o un d res ul ts fro m th e d i re c t un i on of s ulph u r tri o xi de


    and hydrochl oric a ci d I t i s a c o l orl ess liqu i d whic h f um es vi goro u sly on
    .
    ,
    C H L O R ID E S OF S UL PH UR I C A C ID . 1 43

    e x pos ure to the a i r Sp g = 1 7 6 6 at . Bo ili n g po i nt


    . .
    On . -

    the addi tion of water a vio l ent rea c t i on o cc u rs produ cing hydro c hloric ,

    a ci d and s ul phur ic a ci d :
    so,HC I + H, o H,s o, + HC L

    90 c o mpo und SO C I lph u ryl h lo i d is obtained by the dire c t


    . A , Z Z, su c r e,

    uni on of s ul phu r di o xi de an d c hl ori ne m ost eas ily by rst saturat ing ,

    cam phor wi th s ul phu r di o xi de (whic h readily di sso lve s in i t) an d then


    pass i n g c h l or i ne o v er i t Th e c a m phor re m a i ns u n c han ged
    .
    S ul ph u ry l .

    chl ori de i s a c o l orl ess liqui d w h ic h bo il s at has a penetrat ing odor


    ,
    ,

    fum es strongly in t h e ai r and has a spe cic gravi ty of at


    Th e add i t i on of a li tt l e water c onv erts i t into c h l oros ul phoni c a ci d and
    hydro chl oric acid m uc h water to s ul phur ic and hydro c hl ori c aci ds :
    ,

    so,ol , + HCI .

    H,so, + 2 HCI .

    The se de c o m pos i t i ons of s ul phu ryl chl ori de can be represented in the
    fo ll owing way :
    1
    0 1 H | O H
    802 SO 2 + 2 H0]
    [C l H IO H \ 0H

    In thepl ace of the two c hl ori ne ato m s we have therefore two O H , ,

    ( hydroxyl) g ro u ps enteri ng Fo r this reason i t i s ass um ed in cl ose


    .
    ,

    anal ogy wi th the m ethods of organ ic c he mi stry that s ulphur i c a ci d con ,

    ta ins two hydro xyl gro u ps .

    Sul ph uryl u or i de c an be obta ined by the d i re c t u n i on of sul ph u r


    di oxide and uorine I t has the sa m e re m ark ab l e stab ili ty as the c o m
    .

    p o u nd SFo I t i s a c o l orl ess an d odorl ess gas liqui d at 52 a n d -



    ,

    so li d at I t c an be heated w i th water in a seal ed t ube to 1 50


    w i thout un dergo i ng de c o mp os i ti on A lkali es absorb i t though very .


    ,

    s l owly Sod ium c an be fused in i t without be ing attacked


    . .

    Pe r su l ph u r ic A c id, m , os .

    91 The p otass i um sal t


    . or st ill better the a mmoni um sal t
    , , , ,

    of t h l s a ci d c an be obta i ned by the el ec tro l y s is of a c o ld


    satur ated so l uti on of the c orrespond ing s ul phate in s ulphuric a ci d of
    Sp g I n s uc h a so lu t i on we m ay ass u m e w e hav e t h e i ons K an d
    '

    . .

    HSO
    , the l atter are d i s c harged at the anode an d c a n then uni te to
    form H S O wh ic h form s wi th the K i ons present the difc ul t ly solubl e
    z z s,

    p otass i um sa l t K S O Th i
    z s se
    z p arates out
    s. as a wh i te crysta lli ne m ass .
    1 44 I N O R G A N I C C HE M I S TR Y .
    91

    However, the c om b inat i on of two HSO groups only ta kes pl ace when 4

    the i r concentrat i on at the anode i s qui te h i gh ; for if thi s i s not the


    c ase there is m ore O pport uni ty for secondary react i ons such as a uni on ,

    wi th water to form 2 H 80 and 2 O H the latter of wh ic h i s deco mposed


    2 4 ,

    into H 0 an d 0
    2 Suc h a h i gh c oncentrat i on at the anode i s reached
    .

    by us ing a v ery s m all e l e c trode The el ectric c urrent therefore has a .

    h i gh dens i ty at the anode ; that is a l arge q uant i ty of el ectri c i ty m ust ,

    p ass through a s m a ll s ur face The e ffect thereof i s that th . i s l arge


    q uant i ty d ischarges a great m any HSO i ons into a sm all space or in ,

    ,

    other words produces eno ugh HSO groups to m a ke the concentrat i on


    , 4

    very hi gh there .

    As l ow as 1 00 i t deco mp oses i n the fo ll owing way


    2 K 2S20 8 2 K28 20 7 02 .

    K -
    py r os u l ph at e .

    The barium sal t of persul ph uric a ci d i s so l ubl e i n water as are also ,

    m ost of t h e other known sal ts .

    Th e a c t i on of 1 00% hydrogen peroxide on s ul phur tri oxide or on


    c hl o rs ul ph o n ic a ci d y i el ds C A R o s acid

    ,

    8 0 3 + H20 2 HzSO s,

    2 2 + HC I .

    \ C l + H20 2 \ O OH '

    It crystalliz es very prett ily and m el ts at about 4 5 wi th sli ght dec om

    p os i t i on .

    C A R o s a ci d reacts w i th another m o l e c ul e of c hl o rs ul ph on ic a ci d

    accord ing to the e qu at i on


    OH OH HO
    / /
    2 + 01 so,0 H so,
    \ o OH- \ o o
    .

    form i ng persul phuri c a cid wh i ch can be obta ined in th is way pure and
    ,

    crystalliz ed w i th a m el t ing p o int of 6 0 ( attended by sli gh t de c o m


    ,
    -

    p
    os i t i on ) A
    .
    so l u t i on o f C A R o s a ci d in sul phu ric a ci d can be prepared

    in a s im pl e way by mi xi ng H O w i th an e xc ess of strong s u l phuric a ci d


    g , .

    O n the bas is of this m ethod of form at i on B A EYE R ga v e the co mpound the


    nam e su l ph o m on o peraci d
    - -
    .

    I t has v ery strong oxi dizing p owers I t sets i od ine free fro m .

    p
    otass i u m i od i de ox,
    i d iz es s u lphu r d i oxide to tri oxide and ferro us t o ,
    I N O R G A N I C C HE M IS TR Y .

    Us e o f So dium Thiosulphate in Volum e t ric


    A nalysis . I odometry .

    93 . On
    adding sodium thiosul phate to an iodine solution t h e ,

    intensely brown liquid loses it s color sodium iodide an d s o dium ,

    te trathionate two colorless compounds being formed


    , ,

    2 N a2S2 0 3 2T N a2 S4 0 6 2 N aI ;

    or, w riting o nly the ions that take p art in the reacti on _

    =
    2 S2 0 3 + 2 I S4 O e + 2 I .

    The d isa ppearance of the color is thus due t o the fact that t h e
    molecules of iodine are transformed into I ons by taking u p t w o .

    n egative charges from 2 S2 0 3



    Upon this fact a method is base d
    .

    for deter m ining the amount of free iodine in a solution This is done .

    by allowing a solution of sodium thiosul phate whose concentration ,

    ( t itr e) is known to ow dro p by


    ,
    dro p into a denite volume of iodin e

    solution ( For letting out a certain amount of liquid a pipe tte


    .

    ( Fig .3 2 ) is com m o nl y em p loye d ) T h e color gradually b righ


    . t e n s
    and nally a p oint is reached when the liquid is only slightly ti n ge d
    and the addition of ano ther dro p causes the color to entirely dis
    a ppear This transition can be very accurately detected The
    . .

    iodine molecules have now enti rely disa ppeared Since according .

    to the above equation a molecule of thiosul phate is consumed for


    each atom of iodine the percentage of iodine in the solution can
    ,

    b e calculated from the amount of thiosul phate used .

    To make the calculation of the result of such a determination


    ( titration ) as easy as possible the thiosul phate solution is so s ta n d
    '

    ar diz ed that it bears a certain relation to an equivalen t o f iodin e


    1 27 i e a certain amount bleaches exactly this much iodin e
    N o rm al sol u ti on
    . .

    is a name a pplied to a solution containing


    .

    the equivalent weight 2 3 ) in grams (gram equ iv a l en t) in o n e


    liter Frequently use is also made of a
    .
    2 TE, or a twice thrice , , ,

    etc normal solution N ormal hydrochloric acid contains


    .
    ,
    . g .

    HC l normal sul phuric acid 4 9 g H2 SO 4


    ,
    gram molecule ).
    ,

    a normal iodine solution 1 2 7 g iodine per liter Detail ed dir e c .


    , .

    VO L UM E TR I C A N A L Y SIS . 147

    tions fo r pre paring such solutions can b e foun d in t he text books -

    of analytical chemistry .

    In order to determ i ne read ily the volume of thiosul phate solu


    tion that is r equired in the analysis use is made of a b ur ette ,

    ( Fig
    . a glass tube that is divided into 3
    1
    7, c c and closed at . .

    the lower end with a glass sto p cock or with a rubb er tube an d

    p inch clam
    -

    p I n titrating the iodine solution the thiosul phat e


    .

    FI G . 32 PI PE T TE
    . . FI G 3 3 B URE T T E S
    . . AND SUPP O R T .

    solution is allowed to ow out slowly an d nally dro p by dro p , , ,

    while the liquid is being stirred .

    Exam pl e For 50 of an io d ine solution whose s trength is


    .

    to be determin ed c c 1 3 normal thiosulphate solution was


    1
    . .
    .

    necessary before the color com pletely disa ppeared R equired the .

    num ber of grams of iodine contained in 1 liter of this solution .

    1 000 c c {5 normal N a2 S2 0 3 solution ( see above ) decolorizes


    . .

    1
    13
    equivalent of iodine ( = l2 7 c c therefore decolori
    . z es . .

    {
    ix - E g iodine
    . . This amoun t is contained in 50 of
    1 000
    14 8 IN O R G A N I C C HEM I S TR Y .
    m
    the io dine solution in questio n Hence 1 liter of the latter con.

    tains g iodin e . .

    Various other substances which liberate iodine from p otassium


    iodide can be determined by titrating the amount of iodine dis
    p laced ; for exam ple chlorine and bromine may
    , be thus determined ,

    sinc e they set free the equivalent amount of iodine from potassium
    iodide solution .

    SEL EN IUM .

    94 . l e nSe
    i u m was discovered by B ER ZE L I U S in 1 81 7 I t .

    took its name from d e liriu m ( the moon ) because it p ossesses great ,

    Similarity to the element tellurium ( named from t ell u s = the earth


    ) ,

    discovered a Short time previously I t is rather widely distributed .

    in nature but it o ccurs only in small quantities I t is found


    , .

    native is frequ e ntly found in pyrite and also a ppears in som e

    rare minerals When this sort of pyrite is em ployed in sul phuric


    .

    acid manufacture the selenium collects in the chamb er mud


    ,
    -

    o f the lead chamb ers ; fro m this it is usually obtained .

    The pro c ess i s as foll ows : Th e sel enium de pos i t is heated with nitric
    a ci d wh ic h o xi d iz es t h e se l en ium to se l en ic a ci d H Se O
    ,
    Th e so lu t i on , z 4.

    thu s obtai ned i s rst bo iled wi th hydro c hl oric a ci d whereby sel eni o u s ,

    a ci d H Se O i s form ed wi th t h e e v o lu t i on of c hl ori ne Thi s l atter a ci d


    , Z 3 ,
    .

    is then red uced by means of sulph u ro u s o xi de to sel enium whi c h separates ,

    in a m orpho u s r e d a kes .

    Selenium dis plays analogy with sul phur in many res pects ; fo r
    instance in o c cu rr in g in various allotro pic co nditio ns A ccording
    ,
    .

    to SAUNDER S there is an amorphous red modicatio n that is


    , ,

    s oluble i n carbo n disul p hide From this solutio n the selenium


    .

    se parates as a seco nd modicatio n which is the red crystallin e ,

    selenium fusing at 1 7 0
    ,
    The n there is a metallic form fusing

    at This modicatio n a ppears when amorphous seleni u m is


    heated to at which p oint a sudden and marked rise of tem per a
    ture o ccurs ; or whe n molte n selenium is suddenly cooled to 2 1 0

    and ke pt for a time at that te m perature I n this metallic stat e .

    selenium has a metallic lustre is insoluble in carbon disul phide a n d


    ,

    conducts electricity I t s conductivity strangely d e pen d s very


    .

    much o n the intensity of its illuminatio n however , .

    The meltingp oint of selenium is its boiling point -

    A s in the cas e of sulphur the va p or density decreases with rising


    1 50 IN O R G A N I C C H E M IS T R Y 94

    when bromine is added to it s e l e n i c a c i d, H2 Se O 4 is formed I n , , .

    the pure state this is a crystalline solid melting at The 9 5 % ,

    solutio n of it is an oily liquid which has the appearance of sul ,

    ph u r ic acid The barium. sal t of the acid like that of sul p huric ,

    acid is extremely difcu l t l y soluble


    , .

    O n boiling with hydrochloric acid selenic acid is r educed t o ,

    selenio us acid with the evolut io n of chlorine .

    T e ll u riu m .

    95 . Te lluri um is of rare occurren c e ; it is kno wn in the n ative condi


    t i on and al so in c o mb i nation with b i smu th and with go l d or s ilver ( i n ,

    s yl v a n ite or gr a phic te l l u r iu m )
    ,
    I t is fo und c hi e y i n Transylv an i a and
    .

    in the A l tai m o u ntai ns and al so i n Bo ul der C o C o l orado I n the am or


    ,
    .
    ,
    .

    h o u s c ondition te ll uriu m is a b l a ck powder b u t after fus ion it is s ilver


    p y ,

    white of a m etalli c l ustre and a c ond uc tor of heat and electricity The
    , .

    vapor density as in the c ases of se l enium and s ul phur de c reases w ith


    , ,

    increas ing te m perat ure and does not re m a i n c onstant t ill abo u t
    it then c orres ponds to a Te2 m o le cule .

    Hydr o g e n t e llu ri de H2Te res ul ts fro m the a c tion of hydro c hl ori c acid
    , ,

    on zi n c te lluri de Zn Te The produc t thu s obtai ned c onta i ns m ore or


    ,
    .

    less hydrogen It i s very po i sono u s and di sso ci ates readily Fro m so lu


    .
    ,
    .

    t i ons of the heavy m etals i t pre ci pi tates the i r te lluri um c o m po unds


    Ge l l u r id e s )
    Tel l u riu m Te 0 2 is for med on burning te lluriu m in the air
    dio xide , ,
    .

    It is very difcu l t l y so lub l e in water .

    Te ll u r ou s ac id HzTe O 3 i s obta i ned by d i ssolving te ll uriu m in nitric


    , ,

    ac i d It disso lves in water wi th great dii cu l t y and brea ks u p on warmi ng


    .

    into Te O 2 and H20 .

    Tell u ric aci d HZTe O 4 is pre pared by f u sing the m etal or the d i oxide
    , ,

    with soda and sal tpetre and se parat i ng the a ci d fro m the te llu rate form ed .

    The c o m pound HzTe O 4 + 2H20 crysta lliz es o u t fro m t h e a q ueous so lu t i on ;


    it l oses i ts water of crystalliz at i on at The free te llur i c a ci d HZTe O 4 , ,

    re
    p p ared i n th i s way i s a wh i te p owder d if c u l t l y so lu b l e in c o l d water ,
    .

    Te lluri c a ci d has only feeb ly a ci d pro perti es .

    Se l enium and te ll u r i u m both c o m b i ne wi th potass i u m c yanide when ,

    they are fused wi th i t for mi ng co m po u nds c orrespo ndi ng to K C N S v iz


    , ,
    .
    ,

    K O N Se and K C N Te N everthe l ess whil e potass ium t e l l u r o c yani de


    .
    ,
    -

    is at once de c o m posed by the o xygen of t h e a i r wi th the se parat i on of


    t e llu ri um potass ium s e l e n i o c yani de i s m ore stabl e and does not
    ,
    -

    de co m pose wi th the se parat i on of se l eni u m u nt il i t i s bo il ed wi th hydro


    S UM M A R Y O F TH E O X Y G E N G R O UP . 1 51

    chloric acid We have here a m eans of dete c t i ng selenium in the pres


    .

    enc e of t e ll urium and of separating the two .

    SUMM A R Y O F THE O XY G EN G R O UP .

    96
    The elements oxygen sul phur selenium and tellurium
    .
    , , ,

    like the halogens form a natural group particularly in two res pects
    , ,

    their com pounds corres pond to a general typ e and their physical
    an d chemical pro perties vary gradually with increasin g atomic
    weight Their hydrogen com pounds have the formula R Hz t heir
    .
    ,

    oxygen com pound s and their acids the formulae R 0 2 and H2R 0 3 ,

    an d also R O 3 and H2 R 0 4 O zone may be considered with referenc e


    .

    to these types as analogous to sulphur dioxi d e ; O 0 2 ozone ; S O z - -

    sul phur dioxide .

    Th e following table shows the gradual change o r pro gr es si on , ,

    of the physical pro perties :

    At o mic w e ight
    Spe m c gra vity . 1 95 2 0 7
    .
    -

    M e lt in g p o i nt -
    .

    Boi n li g po in t
    -
    .

    l
    C o or

    As the ato m ic weight increases the values of the physical con


    ,

    st an t s also increase as the table shows A t the same time t h e


    ,
    .

    external a ppearance approaches that of the metals ; in tell urium


    the metall ic a ppearance is quite marked .

    The insta bility of the hydrogen com pou nds increases from oxygen
    to tel lurium ; the str ength of the oxygen acids diminishes rapidly ,

    sulphu ric acid b elong ing to the strongest and telluric acid to t h e ,

    very weak acids , .

    I t should also be note d that all of these elements a pp ear in

    al l o t r O pic mo dicatio ns .
    1 52 IN O R G A N I C C HE M I S T R Y . 97

    TH ER M O C H EMI STR Y .

    97 . state d ab ove
    I t w as 2 0) that a chemical comb ination o r
    d ecomposition is accomp anied by an evolution or abso rption of
    heat in other words by a heat change or c al o r i c e ff ec t In many
    , ,
    .

    cases this caloric effect has been carefully measure d The work .

    of B ERT HE L O T an d of T H O M SEN along this line has been es pecially


    fruitful Tha t pa rt of chemistry which deals particularly with
    .

    these calo ric effects is called therm ochem istry .

    The calo ric effec t is always given for molecular amounts of the
    r eacting substances , since in this way only is it possible to compare
    substances from a chemical stand point Hence when the h e at of .
    ,

    fo rm atio n o f water is said to be calories ( kil ogram calories ) ,

    it is im pli ed that this number of calories is evolve d b y the union


    o f 2 g hy dr ogen with 1 6 g oxygen
    . .

    2H O Hg O C al .

    In this equation H and 0 stand for gram atoms .

    In e xpr essing a c aloric effec t it is necessary to in dica t e the s t a te


    o f m a t t e r of the reacting an d the resulting substances in so ,

    far as this is not self evident because the latent heat of fusio n
    -

    o r va porization mus t be taken into co nsideration Th e abov e .

    amoun t ,

    2H O H2 0 1iq uid C a1 .
    ,

    r efers formation of water and its conversion t o a l iqui d I t


    t o t he .

    therefor e includes the hea t of condensation Since this amounts .

    to C al pe r gram it would in this case (for 1 8 g ) be


    .
    ,
    C al ; . .

    hence t h e caloric e ffec t of the combustion of hydrogen to steam at



    1 00 is
    2 H + O = HzO g as + C al .

    The caloric e ff e ct is also inuence d by the state of matter


    in which the subst ances react i e whether solid liquid or gas
    ,
    . .
    , , , ,

    inasmuch as solution is almost always accom panie d by a heat


    change I n the formation of sodium chloride by the mixture of


    .

    dilute solutions of sodium hydroxide and hydro c hl oric acid (this


    being indicated by aq after the formul ae of the su b stances) t h e
    calo ric e ffe ct is :
    N aO Ha q HO ] , q N aC l a q H 20 C al .

    1 54 IN O R G A N I C C HE M I S T R Y .

    is contradic to ry to the above princi ple A few exampl es will .


    '

    s erve to make this law more clearly u nderstood .

    ( a ) A di lute solution of sodium sulphate can be p re pared


    from sodium hydroxide sul phuric acid and water in various ways
    , .

    For instance two gram molecules of the base can be treated at


    ,
    -

    o nce wi th dilute s u lphuric acid ; or one grammolecule of t h e


    base can be mixed with the acid at rs t and the second added
    afterward A ccordingly we get the following caloric effects :
    .

    ( )
    1 2 N aO H HQ SO 4 aq N a2 8 0 4 a q 2 H2 0
    N aO Ha q Hg SO 4 a q N aHSO 4 a q Hg O
    ( )
    2
    N Q O Haq
    I N aHSO 4 a q N a2 8 0 4 a q Hg O

    C al .

    bFrom ammo ni a hydrogen chloride and water a dilute solu


    ( ) ,

    tion of ammo nium chloride N H4 C I can be p re p ared either b y


    , , ,
    -

    letting dry ammonia gas combine wi th dry hydrogen chloride gas


    a n d dissolving the resulting ammonium chloride in water or by

    rs t dissolving ammonia and hydrogen chloride in se p arate po r


    tio ns of water and then mixing the solutions I n the rst case w e .

    have the equations

    N H3 g a s HC l g as N H4 C l s o l id
    N H4 C l s o l id aq N H4 C l aq

    C al .

    in t he secon d case

    N H3 aq N Hg aq
    Hcl aq HC l aq

    N Hgaq HC l q a N H4 C l aq

    C al .

    The nal effec t s in the two cases are found to be alike withi n t h e
    l imit s of ex perimental error .

    With the hel p of HE s s s law the determination of the c alo ric


    effec t is rendered p ossible in many reactions whi ch cannot b e

    d eal t w ith di rec tly or are u n suitable for calorimetric measure


    m e nts I n general this is done by making thermochemic al meas
    .
    THE R M O C HE M I S TR Y .
    55

    ure m en t s fo r a series of processes in which the reaction plays a


    p art and n ally calculating the caloric effect of the reaction as
    the single unknown as will be more fully explained in the examples
    ,

    below .

    Supp ose it were required to nd the heat of formation of hydro


    g e n s u l hi
    p de T his compound can be formed di rectly from its
    .

    elements b u t the reaction is unsuitable for thermo chemical


    study We will t herefore sta rt with the syste m H S and O and
    .

    , , , ,

    consider the two ways b y which it can form water and sul p hur
    dioxide : ( 1 ) hyd rogen an d s ul p hur are burned dire ctly t o water
    and sul phur dioxide ; (2) (a) hydrogen and sul p hur combine and
    (b) the resulting hydrogen sul phide is burned to wate r and sul p hu r
    d io xi d e Sin ce we started with the same system and in t h e en d
    .

    reache d the same result in each case the caloric e ffect must be t h e ,

    same according t o HE s s s law so that if we m easure ( 1 ) an d (2b)



    , , ,

    we can equate ( 1 ) an d (2) an d solve fo r ( 2a) thus : ,

    Heat of combustion of 2 H + heat of combustion of S


    heat of formation of HZS heat of combustion of H28 .

    H
    0 H20 ) S 2 0 SO Z)
    ( 2 (
    H H
    ( 2 + S 2 S) (H2S + 3 0 SO Z -
    H20 ) .

    68 0 + 50 +

    x= ( S + 2 H -
    HzS)

    1 00 In usi n g these values of the heat of formation and heat of


    .

    d ecomp osition it should be no ted t h at they do no t represent the


    amounts of heat liberated by the combination of ato m s to form
    molecules but that the heat of decom position of the molecules
    ,

    of the elements (i e the amount of heat required to break these


    . .

    molecules u p into atoms ) is always included When for example .


    , ,

    chlorine u nites with hydrogen to form hydro chloric acid C al , .

    are given o ff That which is measured is the total c a lo ri c diffe r


    .

    e n c e between the initial system H2 + C 12 and the 2 HC l forme d

    from it I n the i n direct determination of a heat of formation


    .

    with the hel p of HE s s s law the calculated calori c e ffect als o


    includes t h e heat of decom p osition of the molecules of the ele


    ments I n the determination of the heat of formation of hydrogen
    .
    1 56 IN O R GA N I C C HE M I S TR Y

    sul phide fo r instanc e in the ab ove way the caloric e ffect of


    , ,
    t he
    c ombustion of this gas is com p osed of the follo wing parts :

    2 (2 H
    s H2 S) + 3 (2 o oz ) 2 soz + 2 n zo C l
    p a .

    t hat of the combustio n of hydrogen of the following

    2 (2 H H2 ) ( 0
    2 0 2) 2 H2 0 q C al.
    ;

    t hat of the combus tio n of sulphur of

    (2 S S2 ) 0 2) 2 S0 2 + r C al

    ( 0
    2 etc indicating the heat of decom positio n of molecules
    .
    ,

    o f the elements .

    The heat of formatio n of hydrogen sul phide is r + q p Dedu c .

    ing the value of r + q p from the above equations we have ,

    from which it follo ws that the heats of formatio n of the sul phu r
    an d hydrogen molecules a r e included in the hea t of formati o n

    found .

    C HEM I C A L A FF I N I T Y .

    101 When a com pound is formed we attribute the phe


    .
    ,

    n om e n on to the afnity which exists between the combin ing sub



    stances . The term afnity comes d own from an age when
    it was thought that o nl y those substances coul d combine with

    ( were in
    o n e another which were in a certain agreement with each other

    love with each other


    as E M P ED O C L E S and
    ,
    later also
    G L A U B E R ex pressed it ) .

    This afnity was originally c onsi d ered as a force T H O M SEN .


    ,

    for exam ple dened it as the force which holds the p a rts of a
    ,

    c o m po und together C oncerning the magnitude of this force


    .

    o u r knowle d ge was for a long tim e o nl y q ualitative If the .

    substances A B an d C interacte d t o f orm A C and B it was said ,

    that the afnity of A for C was greater than that of A for B .

    C om parative study of such reactions le d t o the arrangement of


    a series of the elements in d e creasing ord er of afnity ; but the
    absolute or even relative magnitu d e of these afnities was
    , ,

    a s it were a close d b o ok He n c e it was a great ste p forward when


    .
    1 58 IN O R G A N I C C HE M I S TR Y . 1 01 .

    to m ea sure the force with Whi ch an a ction t en d s t o pro ceed ,

    we often make use of an O pp osing force of kno wn magnitude ,

    which is j ust great enough t o sto p the action I f this O pp osing .

    force is to o small the internal driving force of the system will


    ,

    overp ower it and thereby do a certain amount of work and this ,

    amount of work will be the greater the greater the counter force ,

    that is overc ome or in other words the smaller the di fference


    , ,

    between this counter force and the driving force of the system .

    For measuring af nity we can thus make use of the sim ple
    mechanical n otions which serve for the measurement of forces
    in general as for instance in an ordinary weighing We o ppose
    , , ,
    .

    the for ce to b e m e asured with another of known but variable


    magnitude and allow the latter to c hange until equilibrium is
    established There is then equality between the known force
    .

    and the force to be measured .

    The free energy is in general not equal to the total energy


    that co mes into play in a reaction ; but fre quently the di fference
    is n ot great as for instance in reactions between solid c om
    , ,
    '

    p ounds o r in solution Herein lies the ex p lanation of


    . the e x c e p
    tions to B E RT HE L O T S princi ple as well as the reason fo r i t s

    agreement with ex p eriment .

    The total energy c ontent of a body c ons i sts accord ing to HEL M
    -

    H O L T Z of free an d bound en e
    ,
    rgy Th e free energy al one i s c apab l e .

    of transform at i on i nto other form s of wor k The bound energy i s .

    i nv olved i n s uc h c hanges as those of state When ic e m el ts a c on .

    s iderab l e a m ount of heat i s absorbed whic h cannot be transform ed

    i nto work but only seem s to in c rease the m o l e cular m o vem ents of the
    ,

    water m o l ecul es The bound energy of water i s therefore greater than


    .

    that of ic e at t h e sam e tem perature Similarly there are vari o u s other .


    ,

    p ro c esses where t h e bo u nd energy i s c hanged .

    I t c an be pro v ed theoret ic a ll y that in e v ery a c t i on pro c eed i ng of i ts


    ow n a cc ord t h e free energy mu st de c rease .

    I n the c ase of an e x othermic rea c t i on the e v o lu ti on of heat i s due


    in part to the de c rease of the free energy of the syste m
    ,
    Further the .
    ,

    bo und energy c an at t h e sam e t im e e i ther be partly c onv erted i nto .

    heat re m ain u n c hanged or i n c rease l ess than the de c rease of free


    , ,

    energy call s for ; howe ver i f t h e de c rease of free energy i n a r e ac


    ,

    t i on i s l ess than the i nc rease of bo und energy the whol e c al oric ,

    effe c t mu st be negat iv e wh ic h i s to say that t h e rea c t i on i s endo


    , ,

    thermi c .
    TH E R M O C HE M I S TR Y . 1 59

    For the measuremen t of af nity it is therefore necessary t o


    determine this maximum work or free energy whic h is involved
    in chemical reactions Two means are available one the deter
    .
    ,

    mination of the ele ctromotive force that can be created by it ,

    and secondly the determination of the equilibrium constant of


    , ,

    t h e reaction in question .

    We shall learn in the cha pter on electro chemistry that


    reactions can in many cases be conducted so as to produce an
    electric c urrent If the reaction is reversible it can be brought
    .
    ,

    to a sto p by sending a current of the same energy through the


    system in the o pp osite direction The energy of an electric
    .

    current is re presented by the product of two factors the amount ,

    of electricit y (ex pressed in coul ombs ) and the electromotive


    force (ex pressed in volts ) N ow the deco m position of an equiv
    .


    al e n t amount of each com p o und requires according to FA R A DA Y s
    ,

    law the same amount of electricity namely


    , ,
    c oulombs ,

    r equivalent weight ; whence it follows that the electromotive


    p e

    force must be pro p ortional to the afn ity ; in other wo rds that ,

    the ele ctromotive force is a measure of the afnity A ccordingly .


    ,

    the afnity whic h seeks to brin g about a chemical transformation


    must be O pposed by an electromotive force j ust great enough
    to p revent the reaction This electromotive force is then the
    .

    exact measure of the afnity whose action it prevents .

    The fre e energy or maximum amount of work whic h the


    r eaction produces is ac cordingly equal t o the energy of the
    electric current produced .

    The second general method for mea suring afnity is a pplicable


    in all cases involving a chemical equilibrium We learn from .

    thermodynamics that the equilib rium constant K and the maxi


    mum amount o f work A done by the reaction bear the following ,

    relation to each other :


    A = R T l og , K ,

    when unit concentrations of the reacting substances are in


    volved . R is the gas constant 3 5) and T the absolute
    tem perature . K is also de pendent on a function of) the
    tem perature .

    The studen t will nd it interesting to learn from the ap


    o i t e text books of p hysical chemistry h o w these t w o
    p p
    r r a
    -
    1 60 I N O R GA N I C C H E M IS TR Y .
    1 02

    m et hods are utilize d for the l c al cul at ion of afnity in a variety


    of s pecial cases .

    THE DI S P L A C EMEN T OF EQ U I L I B R I UM .

    When t wo systems are in e quilibrium with each othe r


    1 02 .

    ( g
    e . 2 H 2 +
    .
    , the position of this equilibrium is d e pen d
    ent on various circumstance s The relati onshi p is ex presse d b y .

    the rul e of LE C HA T E L I E R Z
    Wh en an y s ys tem is in physical or c h e m ica l equ ilibriu m a ,

    c ha n g e in on e o
    f its equ il ibr iu m fa c tor s p r o du c es a c h a n ge in the
    s ys t em , ec t is opp osite to tha t of th e form er chan ge
    w hos e e .

    This ru le or theorem which can be called the pri n ci pl e of t h e


    , ,

    r e sistan c e of t h e r eac tio n to t h e ac tio n furnishes us with a con ,

    v e n ie n t means of foretelling in many instances the dire ction which

    a reaction will foll ow Some exam ples may be given to illustra t e


    .

    the rul e .

    ( 1 ) When a system of water an d ice is subj ected to increase d


    p ressure the ice melts
    , ; that is t hat p ro cess goes on which in volves
    ,

    a contraction for by this contraction the system diminishes the


    ,

    p ressure exerted on it .

    (2) M onoclinic sul phur when com pressed near the transition ,

    p oint ( the tem p erature of e quilibrium for ordinary p ressure ) p asses ,

    over into rhomb ic sul phur since this pro cess involves a lessening ,

    o f volume and in the end also a diminution of p ressure as in the


    , ,

    p revious case .

    (3 ) When a solution is d iluted the osmotic p ressure decreases



    ac cordin g to B o Y L E s law ; in the case of a solution of an electr o
    lyte dilution will be followed by fu rther d is sociation since this ,

    increases the osmotic p ressure .

    (4 ) When a liquid is heated mo re va p or is forme d ; since the ,

    va p ori z ation absorb s heat its e ffect is o pposite to that of the


    heating .

    ( )
    5 I n p artially disso ciated N 2 0 4 an increase of p ressure drives
    back the disso ciation while diminution of pressure increases the,

    disso ciation The former c hange carries with it a pressure


    .

    decrease the latter a pressure increase


    ,
    .

    VAN T HO FF s princi pl e of m o b il e e qu ili b ri u m is a s pecial



    I O 3 .


    c ase of L E C HA T E L I E R s rule but was derived from thermodynamics ,
    1 62 IN O RG AN IC C HE M I S TR Y . 1 04 1

    wo ul d un doubtedly liberate free energy do not o c cur A cco rd .

    in gl y we have to assume that circumstances can arise to p revent


    ,

    the o ccurrence of a strictly p ossible reaction Such hindering .

    conditions can be com prehensively termed pa ssive r es i stan c e s .

    Their e ffect is noticed for instance in the retarding o f reaction


    , ,

    velo city e specially at low tem peratures We saw an exam ple of


    ,
    .

    this in 1 2 in a mixture of hydrogen an d oxygen M oreover .

    PI C T E T has shown that sodium which reacts rather vigorously ,

    with alc ohol at o rdinary tem peratures oats on it quietly at ,

    80 without any a pp arent reaction ; even c on centrated hydro


    -

    chl oric acid and marble d o n ot react u pon each othe r or at ,

    least only very slowly when they are cooled to a low tem pera
    ,

    ture I n general the rea ction velo city lessens as the t em p erature
    .
    ,

    falls It is t o this c irc umstance in many c ases that we have to


    .

    attribute the non o ccu rrence of reaction s which are therm odyna m
    -

    ic all y p ossible .

    I t has been found that the variation of the reaction velo city

    with the tem perature may in general be ex pressed thus : when the
    tem perature increase s arithmetically the velo city in creases geo ,

    metrically Experience has also shown that a tem perature rise of


    .

    ten degrees in the neighb orh oo d of ro om t em peratu e generally r

    involves ab out a doubling o r trebling of the reaction velo city .

    I t is not difcul t to see what an excee d ingly im po rtant r 61e the


    p assive resistances ab ove referre d to play in n a ture Were it not .

    for them the phenomenon of co mbustion and the oxidation of


    ,

    metals etc could take place at ordinary tem peratures ; every


    ,
    .
    ,

    thing combustible would then burn and there could be no animal


    and vegetable life on the ea rth .

    N I TR O G E N .

    1 05 This element occurs free in the air which contains ab ou t


    .
    ,

    80% nitrogen and 2 0% oxygen I n combination it is found in the .


    ,

    salts of nitric acid e g salt petre and also in the albuminoids


    ,
    . .
    , ,

    which form an im portant c o n st it u t e n t of animal and v egetable


    o rganisms .

    N itrogen can be easily isolated from the air by removin g t h e


    o xygen This is accom plished in various ways
    . Phos pho ru s .
    ,

    when burned in the air absorbs the oxygen to form phos phorus ,
    N I TR O G E N . 1 63

    p entoxide and the residual gas aside from slight admixtures


    , ,

    is nitrogen A ga in air can be passed over heated co pper


    .
    ,

    in a n ely divided condition whereupon co pper oxide is formed an d


    ,

    n itrogen lef t .

    In th i s process the oxygen of the a i r soon converts a ll the c o pper into


    copper oxi de so that of c o urse only a limi ted am ount of ni trogen c an thu s
    ,

    be obtained wi th t h e a i d of a g iv en a m ount of c o pper However if .


    ,

    the ai r i s rst passed thr o ugh amm oni a water t h e pro cess can be c arri ed ,

    on c ont i nu o us ly s in c e the hydrogen of the amm onia N H3 constantly


    , , ,

    reduc es the oxi diz ed co pper .

    C o ppe r ca n also absor b the oxygen of t h e air at o r din a ry tem


    er t r es if it is treated with a solutio n of ammo nia and am
    p a u ,

    m o niu m carbo nate M ois t phos phorus combines with oxygen even
    .

    at ordinary tem peratures so tha t a volume of air which remains


    ,

    in co ntact with pieces of phos phorus for some minutes loses its
    o xygen .A n alkaline solutio n of pyrogallol also has the ability to
    ab sorb oxygen at ordinary tem p erat u r es These r eactio ns are .

    made use of i n gas an alysis .

    1 06 . Pure nitrogen is obtained by the direct deco m p ositio n o f


    c ert a in o f its c o m p o u nds es p ecially by heating ammonium nitrite
    ,
    .

    N H4 N 0 2 N2 2 H2 0 .

    This is usuall y ac c o m pli shed by boili ng a so l uti on of e q ual parts by


    weight of potassi um ni trite K N O Z sal amm oni a c N H4C1 and potassium
    , , , ,

    di chr o m ate KzC r20 7 i n 3 parts of wate r The N H4C1 and K N O 2 react to
    , ,
    .

    form K Cl and N H4N 0 2 .

    By heating ammo nium chromate ( N H4 ) 2 C r 0 4 ( a m ixture of ,

    ammo ni um chloride and potassium dich r omate is mo r e co nvenient ) ,

    nit r ogen is also set free :

    K2 0T20 7 2N H4 Cl N2 l C I '

    20 3 2 KC l 4H2 0 .

    A n exam ple of the form at io n of nitrogen by the indirect dec o m


    -

    sitio n of its com o unds is the reduction of n it r oge n o xi d es


    po p
    b y hot co ppe r :
    Q NO 2 011 N2 2 0 11 0 .
    "
    1 64 I N O R G A N I C C H EM I S TR Y . 1 06

    Phys ica l Pr oper ties N itrogen


    is a colorless a nd tasteless gas
    Its s p ecic gravi t y based o n air is its density com pared

    with hydroge n is therefore 1 l N weighs g at 0 . .

    an d 7 6 0 mm I t is one of the mos t di fcult gase s to co ndense


    .
    ,

    its critical tem p erature being I t s boiling p oint is -

    At 2 1 4 it becomes solid

    I t is o nly slightly soluble in wate r ,
    .

    e ve n less so than oxyge n .

    C h em ica l Pr operties N itroge n is chemically ve ry indifferent ;


    it uni t es wi t h no eleme nt at ordinary tem peratures and at highe r
    tem peratures with o nly a few B oro n silico n tita nium barium .
    , , , ,

    stro ntiu m calcium magnesium chromium and also certain rare


    , , ,

    e leme nts combine directly with nitroge n at red heat form ing ,

    n i t r i d e s The direct union of nitrogen with a large numbe r


    .

    of elements notably metals is b est ac complished by a s pe cial


    , ,

    ex p erimental arrangement as follows : I n a liquid mixture of 9 0%


    ,

    argon and 1 0% nitrogen an electric arc is produced between a silver


    anode and the element c oncerned The low temperature of the .

    bath prevents the decomp osition of the nitri d es forme d in the arc .

    N itrogen unites wit h oxygen un d er t h e inuence of induc


    tion s p arks directly (re d dish b rown N O 2 being formed) ; with
    hydrogen it combines in a similar way When a mix t ure of .

    hy d rogen and n itrogen together with a fe w d ro ps of c on ce n


    ,

    t r at e d hydrochloric acid is introduced into a tube over mercury


    , ,

    and induction s parks are sent through clouds of amm on ium ,

    c hl oride N H4C 1 are produced the nitrogen and hydrogen having


    , , ,

    united to form ammonia N H3 These last two reactions and


    ,
    .

    the fact that nitrogen is not able to su pport comb ustion serve fo r
    the identication of nitrogen gas .

    The m ol ecu l e of n itr ogen consists of two atoms this having ,

    been demonstrated in the same way as for oxygen an d other gaseous


    elements .
    1 66 I N O R G A N I C C H E M I S TR Y .
    7
    10

    he himse l f regarded as a i r devo i d of phl ogiston de ph l o gi st ic ated ai r


    L A V O I SIE R howe ver re c ogn iz ed thi s s ubstan c e as t h e essent i a l pri n ci ple
    , ,

    of all b urning and o xi dat i on I t now re qui red only a ste p to rea c h the
    .

    c on c e pt i on that ai r is n o t an e l ement b u t c ontains another gas i n addi t i on ,

    to o xygen and that th is g as does n o t s u pport c o mb u st i on The e x peri


    , .

    ment by whic h L A V O I SI E R de m onstrated thi s has been al ready des c ribe d


    By m eas u ri ng the a m o unt of n i tro gen wh ic h re m a i ned after the
    absor pt i on of the o xygen by hot m er c ury he was ab l e to deter mi ne fa i r ly

    a ccurate ly the c om pos i t i on of ai r .

    1 08 . C on s titu en ts
    f th e B esides oxygen an d
    o A t m os pher e

    nitrogen air co ntains argon and the other elements described in


    1 1 0 hydrogen and also variable amounts of water va p or
    , , ,

    carb on dioxide (very nearly on the average ) ammonia , ,

    o zone and p erha ps hydrogen p eroxide (the last three in extremely


    ,

    small quantities ) I ncidentally sul phur dioxide and other gases


    .

    are found in the air in the vic inity of volcanoes ) The .

    lower strata of air always c ontain oating dust particles m i crobes , ,

    etc .

    A n al ys is of A ir The pro p ortional amounts of oxygen and


    .

    nitrogen in carefully dried air free from carb on dioxide et c hav e , ,


    .
    ,

    been re peatedly determined with all due p recaution A c cording .

    to the metho d of DUMA S and B O U SS I N G AU L T this can be done


    as follows :
    The tube a b ( Fig 3 4) c ontaining c o pp er turnings is c onne cted
    ,
    .

    with th e globe V all air having b een removed from both The en d
    , , .

    o f the tub e marked b is attached to th e various p ieces of a p p aratus

    C B and A which are to remove the carbon dioxide an d wate r


    , ,

    va por from the in o w in g air The globe V is rst carefull y .


    , ,

    weighed without air Thereu pon the tube is heated by means of a


    .

    furn ace and a slow current of air is allowed to pass through it to


    the globe by partially O pening the sto p cocks u and r the oxyge n -

    being meanwhile asb o rb e d by the hot co pper By subsequently .

    w eighing the globe the amount of nit r ogen which it contain s can
    b e determined and by weighing the tube before and after we can

    m t h e l tt e an d l b r t ry n otes o f SCH EE L E pub li sh e d b y Baron


    Fr o e rs a o a o ,

    N O RDEN S KI O L D ( St ck h lm
    SC H EE L E
    o

    it is e vi d t th t xyg n w s k w n to
    o

    r th t PR I E ST L E Y ; h e c all d it F
    soon e an o l ft
    ,

    H w e v e r th is e
    en a

    e ue r u
    o e

    .

    a

    o
    no

    d i c v y did n t e m t l d h im n y n re r th n PR I E S T L E Y to a c o rre c t
    s o er o s e o ea a ea a

    un de rsta din g f t h phe o me o f b urn in g


    n o e n na .
    TH E A T M O S PH E R E .
    7

    nd the amoun t of oxygen In this way the ratio of oxygen to


    ni tro gen in air can b e ascertained .

    A NA LYS IS AIR .

    An other method is the eu diom etric m ethod A known volume .

    of air is mixed with a sufcient known volume of pure (electro


    lytic ) hydrogen O n allowing an electric s park to pass through
    .
    ,

    the hydrogen and oxygen unite to form water which is de posited ,

    on the sides of the vessel I nasmuch as 2 vols hydrogen comb ine


    . .

    with 1 vol oxygen one third of the volume tha t disa ppeared must
    .
    ,
    -

    have been oxygen .

    1 09 These and other methods of investigation have shown that


    .

    the c om pos ition of the a ir is n ear l y con sta n t I n all parts of the .

    earth as well as at the highest altitudes which balloons have


    ,

    reached it consists of
    ,

    oxygen an d nitrogen by volum e ; an d


    weight .

    The observed variations from this ratio amount to hardly i 0 1 % . .

    M oreover the com po sition does not a ppear to change with time ;
    ,

    our present analyses agree wi t h those of DUMA S and B O U SSI N G AU LT


    made in 1 84 1 .

    This r esult seems sur prising at rst thought because oxygen ,

    and nitrogen are constantly be ing removed from the air and again
    r eturned to it and it does not necessarily follow indeed it is rather ,

    an im probability that the losses and gains will exactly balance


    ,
    .
    1 68 IN O R G A N I C C HE M I S TR Y . 1 09

    Th e o x yge n passes through the following cycl e : Fr e e oxygen


    is consumed in all sorts of oxidations of which the m in er aliza tion
    o f organic matter is the most im ortant B the term minerali
    p y .

    z at io n is meant th e oxidatio n of the residues of plants and


    animals by th e oxygen of the air w ith the aid of bacilli The .

    c arb o n o f these residues is oxidize d to carb on dioxide


    '

    ; the nitro
    gen ph os phorus sul phur and other elements return t o t h e
    , ,

    mineral state as nitrates sul phates etc A long with this
    , , ,
    .

    p ro cess there are the other oxygen c o nsuming p rocesses of t h e


    -

    res piration of animals and plants and the burning of fuels carb o n ,

    dio xide being formed in all cases This c arb on dioxide is em .

    p lo y ed by the p lants in their p ro cess of assi milatio n the oxygen ,

    in it being again given bac k to the air I t will therefore de p end .

    o n the relative magnitude of this p rocess as to whether j ust as

    much oxygen gets b ac k into the air as was previously taken u p in


    the formatio n of c arb on dioxide The oxygen which serves fo r .

    o t he r oxi d atio ns d oes not necessarily return t o the air .

    Di fferent i nvest i gators ha v e atte m pted to est im ate the amount of


    carbon whic h annually enters i nto the c y cl e of organ ic li fe Du B O I s .

    c alcul ated that every year the plants assimil ate milli on milli on
    kil ogram s C 0 whic h i s alm ost i s of the total carbon d i o xi de i n t h e
    2,

    at m osphere The am o unt of C O given o ff by the ent i re an im al worl d is


    .
    2

    est im ated at m il li on milli on kil ograms whi c h br ings u s to t h e ,

    startling resul t that onl y about 2 % of the exi sti ng pl ant m ateri a l i s
    engaged in the c yc l e w i th the anim al li fe Al l the rest of the carbon.

    d i oxi de re quired by the pl ants c o m es fro m the process of m ineral i z ati on .

    The am ount of c arbon d i o x i de prod uc ed by t h e burn i n g of c oal e t c is , .


    ,

    estim ated by C R E D N E R at milli on m il li on kil ogram s .

    N itrogen p asses through a cycle t o o M ost of the nitroge n.

    that o c curs in the form of organic co m p ounds in animal an d v e ge


    table tissues remains in the co mbined state after the death o f
    the organism either as ammo nia or as nitric aci d or in other n it r o
    ,
    e

    genous p ro ducts D uring the pro cess of decay the co mbined


    .

    n itrogen is partially liberated ; in the burning of plant and animal

    r emain s all of it is Se t free O n the other hand certain plants t h e


    .
    , ,

    L egu m in osce are able by symbiosis with bacteria to absorb fre e


    ,

    nitrogen from the air directly There are also bacteria which.
    ,

    acting alone can assimilate nitrogen M oreover in storms som e


    ,
    .
    ,
    170 IN O R G A N I C C H E M I S TR Y . 1 09

    free nitro gen and free o x ygen ) (3 ) The ratio of t h e solubilities


    .

    of the o xygen and the nitrog e n of the air in l iquids is the same
    as that c alculated fro m the solubilities of the p ure gases oxyge n
    an d nitrogen after taking int o accou n t their p artial p ressure s
    ,
    .

    This c ould not be the ca se if the air c ontaine d a c om p ound of


    oxygen and nitrogen ; (4 ) when liquid air b oils the rst part of
    the distillate is chiey nitr o gen .

    The l iqu efa ction of air is now carried o n in c ommerce Th e .

    meth ods used by L I NDE and by H AM PS O N are b ased o n the sam e


    p rinci p le namely
    ,
    co oling ,
    the air by ex p ansion Furthe r details .

    may b e found in text bo oks o n physics -


    .

    L iquid air is very mobile and has a bluish tint I t is usually .


    ,

    s omewha t cloudy becaus e of Sl i Spe n Cl e d p articles of ice ( congeale d

    atmos pheric moisture ) and solid carbo n dioxide These may b e .

    r emoved by ltration through l t e r paper I t boils at about -


    .

    I t is now extensively used in producing and de m o n s t rat ,

    ing the e ff ects of very l ow tem peratures When carbo n dioxide


    ,
    .
    ,

    for exam ple is led into a ask co ntaining liquid air it falls in
    , ,

    the solid form like snow ak e s I n s pite of its low tem perature
    -
    .

    liquid air can be poured u po n the hand without danger ; it doe s


    not even feel cold ( o n account of the LE Y DE N FR O ST phenomenon) .

    L iquid air is much richer in oxygen than the gaseous air of t h e


    atmos phere containing about
    ,
    I f a glowing Splinter is
    d ipped int o the liquid the wood begins to burn very vigorously
    ,
    ,

    p roducing a violent r eactio n I t can b e p r ese


    . r ved fo r a r a t h er
    long time in vacuum asks By fractional distillation of liqui d
    .

    air practically p ure oxy gen and nitrogen can be obtained .

    A c cording to E RDMANN pure nitrogen is obtain ed in the cooling


    d own of liquid air whereup on nitrogen crystalli z es out
    ,
    .

    AR G O N , HELI UM AN D C O M PAN IO N ELEM EN TS .

    1 10 r g o 11 Des pite the fact that air had been already


    . A .

    a naly z ed times without number it was rs t discovered in t he ,

    course of investigations by R A YL E I G H a nd R AM SA Y in 1 89 4 that


    there are other elements in the air than nitroge n and oxygen .

    O n e of these named argon by its discoverers is even found to


    , ,

    the extent of by volume or by weight It was ,


    .

    o n account of its extraordinary resemblance to nitrogen that it


    A R GO N , HE L I UM A N D C O M PA N I O N E LE M E N TS . 171

    was s o long overlooked The r s t indicatio n of its presence was


    .

    the observatio n that the Specic gravity of the nitrogen Isolated


    from the air is somewhat higher than that of the nitrogen pre
    pared from a m mo nium nitrite and other com pounds 1 liter of .

    nitrogen from air weighed g wh ile the same amount


    . from
    ,

    chemical compounds weighed g in both cases at 0 and .


    ,

    7 60 mm There must therefore be another gas heavier than


    .
    :

    nitrogen mixed in with the nitrogen of the air


    , .

    O n e of the sim plest methods for obtaining argon f r o m the


    air is to heat a 1 r with a mixture of 1 g magnesium ,
    g .
    ,
    ,
    .

    sodium and 5 gr freshly ignited lime O n ac co un t of the high


    . .

    tem perature free calcium is formed :

    M g + C aO = M g O + C a,

    an d it is in such a nely divided condition tha t it absorbs oxygen


    greedily and also nitrogen so that only argon is left
    , .

    A rgon can also be isolated with the hel p of calcium carbide .

    When cal cium carb ide (better mixed with 1 0% calcium chl oride )
    ,

    is b rought in c ontact with air at ab out it abso rbs b oth


    oxygen and nitrogen :

    2 GaC 2 02 2 C a0 4 0 ; C aC 2 N2 C aC N2 C .

    This is a suitable method f or pre paring argon in large quan


    tities
    .

    A fter argo n had been once discovered it was fo und elsewhe re


    t han i n the atmos phere ; some mineral waters co ntain it in solution ,

    ce rtain rare minerals yield it when heated etc . .

    A rgon is a colorless odorless gas having a va p or density of


    , ,

    I t has been condensed to a colorless liquid that b oi l s at ,

    by c o oling with boiling oxygen and co m pressing to about


    atmos pheres ; it s olidies at l 89 6 I t is somewhat more .

    .

    soluble in water than is nitrogen p arts in 1 vol at 0 .


    and 7 60 mm p ressure ) A s t o its chemical nature it is interest


    . .
    ,

    ing that no one has yet succeeded in p re p aring a com p ound of argon .

    I t is certain that what is now called argon is neither a mixture


    "
    :

    nor a c om p ound but an element The boiling p oint and the


    ,
    .
    -

    melting p oint are constant and the va por p ressure of argon like
    -

    ,
    :
    172 IN O R GA N I C C HE M I S TR Y E
    110

    w ise re m ains constant during the l iquefaction so long as any gas ,

    is present M oreover when a certain volume of argo n is three


    .
    ,

    fourths dissolved in water the undissolved gas shows exactly the ,

    same s pectrum as t he dissolved Al l of the ab ove are charac .

    t e r is t ic s of a homogeneous substan ce The extraordinary stab ility .

    o f the gas in the p resence of all sorts of reagents is a stro ng


    a rgument against its being a c om p ound .

    I I I . d i s c o v ery of argon R A M S A Y an d TRAVE R S dete c ted fo u r


    A fter t h e
    other rare gases i n t h e atm osphere though the i r qu ant i ty i s v ery s m all ,
    .

    These are heliu m n eon k ryp ton an d xen on I n a spe c tros c op ic in v es


    , , ,
    .

    t igat io n 2 65) N O R M AN L O C K YE R had dete c ted i n the at m ospheres of


    t h e s u n and m any x ed stars c ons i derab l e qu ant i t i es of a gas u n known on
    t h e earth ; he na m ed i t hel iu m I n 1 8 9 5 R A M S AY and TRA VE R S s ucc eeded
    .
    ,

    howe ver in obta in ing i t in s m all a m ounts on heat ing the rare mi neral
    ,

    c l eveite . A fterward i t w a s al so m e t w i th as a c o m pan i o n of argon i n


    c ertain other c hi e y u ran i ferous mi neral s as well as in mineral springs
    , , ,

    for instan c e those of B ath ; and at l ast i t was a lso d i s c o v ered in the a i r
    , .

    A t ord i nary te mp eratures helium i s a co l orl ess gas I t i s of a ll gases the .

    m ost d i fcul t to c ondens e ; y et K A M E R L I N G H O NN E S re c ent l y a c hi e v ed


    the tas k Heli u m bo il s at 2 4
    . abso l ute te m

    p erat u re 2 69 By

    quickl y e vaporat ing i t a te mperat ure of abso lu te was rea c hed .

    w h ic h i s the l owes t th u s far atta i ned The c ri t ic al press ure i s 2 3 at m os


    .

    D ens at abs = n water he li um i s l ess so l ub l e



    p h e r es
    . 4 2 9 . O I 22 I
    . . .

    than argon For its re l ation to radium see 26 7


    .
    , .

    Heli u m and neon wt of a i r) are found in the m ost v o l atil e


    .

    p art of liqui d a i r D E W AR p ro
    . v ed that he li u m and neon c an be i so l ated
    d ire c tly fro m the a i r by bringing the a i r i n c onta c t w i th i gn i ted c harc oa l
    at The c harc oal has the cu ri o u s property of c ondens i ng i n i ts
    p ores a ll the other gases of the a i r and a gaseo u s res i,
    d u e i s here obta i ned
    wh ic h shows c l early the spe c tra l lines of He and N e .

    Wh il e helium and neon were found i n the m ost v o l at il e part of the a i r ,

    k r y p t o n and x e n o n were obtained on the c ontrary fro m the , ,

    res i d u e after a l arge quant i ty of liqui d a i r had been all owed to e vaporate
    ,

    sl owly The i r separat i on was rendered poss ibl e by t h e fa c t that k rypton


    .

    st ill has a rather l arge v apor tens i on at the te m perature of liq u i d a i r ,

    whil e the v apor tensi on of x enon i s then im percept ibl e .

    B oth these el e m ents oc cu r onl y in e x trem e l y s m a ll a m ounts in the


    at m osphere K rypton m a kes u p
    . x enon (by wei ght)
    o f the a i r .

    In the fo ll ow i ng tab l e so m e of the data of these el e m ents are g i ve n .

    The el e m ents form a natural group .


    1 74 I N O R GA N I C C HE M I S T R Y .

    C om po u n ds of N it r o gen an d Hy dr o gen .

    1 1 2 . Until recent years onlyc omp oun d of hyd rogen an d on e

    n it r o gen has been known viz a m m on ia N H3 ,


    A t p resent how
    .
    ,
    .
    ,
    ,

    ever we kn ow f i v e : the others being hydrazin e N 2H4 hydraz oic


    , , ,

    a cid N 3 H an d t he com p ou n ds of th e l a tt er wi th a m m on ia a n d wit h


    , ,

    hydraz in e (N Hs N sH an d N 2 H4 N 3 H)-
    O f these ve c o m p oun d s
    ~
    .
    ,

    however ammo nia is by far the most imp o rtan t


    ,
    .

    AM M O N I A .

    The material now used for obtaining ammonia is t h e ammonia



    liquor of the gas factories and c oke ovens -
    The gases that .

    are given off in the d ry distillation of c oal are passed th rough


    water which dissolves the ammonia
    ,
    .

    In order to obta in a pu re am m on i a the a mm on i a liquor i s heated wi th


    ,

    milk of lim e and the e xpell ed amm oni a i s l e d i nto con c entrated s ulph uric
    a ci d In thi s way crystalliz ed amm onium sulphate i s obtained I t i s
    . .

    p ur i ed by recrysta lliz at i on and aga i n d i st ill ed w i th lim e to re c over the


    free a mm on i a .

    A mmonia can b e pre pare d synthetical ly b y the following


    metho d s The d irect synthesis from the elements was given
    .

    ab ove There are also exam ples of its formation b y t he


    direct d ecom p osition of its c om p ounds Thus we obtain it by .

    he ating the ammonia c om p ounds of c ertain salts as xC aCl z yN H3 ,

    and xA gC l yN H3 A number of organic com p oun d s yield nitrogen


    .

    in t he form of a mm o nia on heating M oreover ammonia results .


    ,

    from the action of hy d rogen on certain nitrogen com p ounds as , ,

    for exam ple when nitric aci d HN 0 3 c omes in contact with


    , , ,

    nascent hy d rogen ( generate d from zinc or iron lings and dilute


    sul phuric acid) or when a mixture of nitric o xi d e N O with
    , , ,

    hy d rogen is passe d o ve r platinum black

    2N O 5H2 2 N H3 2H2 0 .

    The formation of ammonia by the action of free n i trogen on


    h ydrogen com poun d s has not been b rought a b out but the gas can ,

    be produce d b y the interaction of a hy d rogen com po un d with a


    n itrogen com p oun d An illustration of this is the d ecom position
    .

    o f magn esium n it ri d e by w ater

    M g3 N 2 3 H2 0 2 N H3 3 M g0 .
    A M M O N IA .
    1 75

    The putrefaction of organic matter (faeces urine etc ) evolves , , .

    a mmonia B y the actio n of e l e c t r ic sp ar k s on mo ist air am


    .
    ,

    m on iu m nitrate is produced These l ast two methods of for .

    mation are res p onsible for the slight traces of ammonia in t h e


    ai r .

    For the fo rmation of ammonia from calcium cyanamid e ,

    see O R G . C HE M .
    ,
    2 66 .

    P hysica l Pr op er ti es A mmonia
    at ordinary temperatures is
    a gas with a characteristic o d or that excites one to tears Its , .

    ( O = 1 6) or 1 ) 1 1 N H3 at 0 an d
    s pecic gravity is (air .

    7 60 mm pressure weighs . g It can be easily liqueed ; it .

    b oils at and b ec omes solid at it then forms white


    translucent crystals It is extremely soluble in water ; at 0 an d
    .

    normal pressure 1 vol H,O dissolves 1 1 4 8 vols or .


    p arts by .
    ,

    weight of N H3 The s pecic gravity of the sol ution of ammonia


    ,
    .

    in water grows smaller as the concentration increases Th e .

    eva p orat ion of liquid ammonia involves a considerable de pr e s


    s ion of tem p erature This is the p rinci ple of most of t h e ice
    .

    m achines now in use .

    C hem ical Proper ties The characteristic pro perty of this com
    .
    -

    compoun d is that it com bin es with a cids directl y to form s al ts

    N H3 + HC 1 N H4 C l . N H3 HN 0 3 N H4 N 0 3 .

    Am m o n iu m Am m o n iu m
    c h l o ri d e . m t rate .

    2 N H3 H2 80 4 ( N H4 ) 2 80 4 .

    Am m o n iu m
    sul ph at e .

    thes e salts (which are almost all readily soluble in water)


    In
    the atomic group N H4 plays the part of a metal ; they correspond
    in every respect to the com pounds K C l K N 0 3 K 2 SO 4 etc The , , ,
    .

    group or radi cal N H4 has been given a particular name ; it is


    , ,

    called am m o n i u m M ore than one attem pt has been made to


    .

    isolate this ammonium but always in vain However when ,


    .
    ,

    sodium amalgam comes in contact with a concentrated ammo


    nium chloride solution the mer cury swells to a sof t s pongy mass,

    that ra pidly decom poses at ordinary tem peratures into ammonia


    and hydrogen and is in all probability therefore ammonium amal ,

    m
    ,

    g a m I f
    .
    sodium amalgam is allowed to react with am onium
    io di de dissolved in liquid amm onia a t a hard metallic mass
    1 76 I N O R G A N I C C H E M I S TR Y . 1 12

    is obtained which swells with rising tem perature because of de c o m


    ,

    p osition into mercury hydrogen ( 1 vol ) and ammonia


    , ( 2 vols ) . .

    2 N H4 2 N H3 H2 .

    The aqueous solution of ammonia reacts strongly b asic ; so do


    the moist fumes of ammonia We must therefore assume that .

    this solution contains a com pound N H4 O H ammonium hydroxide , ,

    and hence also the ions N H4 and O H in analogy with other soluble
    b ases e g p otassium hydroxide K O H A S a matter of f act
    ,
    . .
    ,
    .
    ,

    h owever the solution of ammonia conducts the ele ctric current


    ,

    mu ch more p oorly than a solutio n of so dium hydroxide of e q u iva


    lent concentratio n A mmonium hydroxide has not yet
    been isolated When the solution of it is eva p orated N H4 O H
    .
    ,

    Sp lits u p into N H3 and H2 0 C oncordant herewith is t h e well .

    known fact that ammo nia can be entirely ex pelled fro m its
    a queous solutio n b y b oiling .

    Am monia does n o t burn in the air but does in oxygen ; in addi


    tion to water and nitrogen traces of ammonium nitrite N H4 N 0 2 , ,

    and nitrogen dioxide N 0 2 are also formed A mixture of


    , ,
    .

    ammo ni a and oxygen ex plodes violently when it is ignited The .

    oxygen conveyed by soil bacte ria may also cause the oxidation of .

    ammonia producing nitric acid C hlorine takes re when passed


    ,
    .

    into ammonia forming n itrogen N 2 and hydrochlo ri c acid ; the


    , , ,

    latter then unites with the remaining ammonia to form sal am


    moniac N H4 C 1 The hydrogen of ammonia is replaceable by
    ,
    .

    metals M agnesium e g burns in amm o ni a fo rmin g magn esi u m


    .
    ,
    . .
    ,

    n it ri de Mg gN z
    ,
    When ammo nia is conducted over hot potassium
    .

    o r sodium p o tassium amide


    ,
    N H zK or sodium a m ide N HzN a is , , , ,

    formed These and analogous metal compoun ds are decomposed


    .

    by water yiel ding ammonia again and also metal oxide o r


    ,

    hydroxide A t high temperatures ( produced by induction s parks )


    .

    ammo ni a Splits u p almost completely into its elements the volume ,

    being doubled :
    2 N H3 N2 3 11 2 .

    2 v ol s . 1 v ol . 3 v ols.

    On the other hand n i trogen an d hydro gen c an un i te to form


    ,

    am m onia under the inuence of i ndu c t i on spar ks E quilibr i um


    1 78 I N O R G A N IC C HE M IS TR Y . 1 1 4_

    Ifa l arge e xc ess oi am m o n ra i s present i t a c ts upon the c hl oram ine with


    '

    the form at i on of hydra zine hydro c hl ori de :


    u

    N HZ C I

    The add i t i on of certa in s ubstan c es e g a s m a ll a m ount of a lbum en ,


    . .
    , ,

    in c reases the yi el d givin g as muc h as 8 0% of the theoret ic al yi el d


    ,
    .

    By fra c t i ona l d i st ill at i on of t h e a queo u s so l ut i on the hydrate


    N H H 0 i s obta ined wh ic h bo il s c onstant at
    2 4
    -

    2 ,
    i t i s a liquid at
    ord inary te m perat ures an d free z es be l ow
    L O B R Y D E B RU Y N showed that t h e m o l e cul e of water c an be re m o v ed
    b y tre at m ent w i th barium o xi de and that the fr ee hydr a zin e c an be
    obtained in t h e pu re state by d i st ill at i on u nder red uc ed press ure Thi s
    '

    s ubstan c e i s liqui d at ord inary tem p erat u res c ongeal s at and boil s ,
    :

    under ordi nary pressu re at Sp g at I t u n i tes w i th. .

    water to form t h e abo v e hydrate w i th the e v o lu t i on of heat Both the .

    free hydra zi ne and it s a qu eo us so lut i on hav e a strong red uci ng a c t i on .

    Th e form er grad u all y o xi d iz es i n the a i r rea c ts vi goro u s ly w i th the ,

    hal ogens e t c Th e a qu eo u s so lu t i on pre ci p i tates t h e m etal s fro m


    ,
    .

    so lu t i ons of sal ts of c opper m er cury Silv er et c at ord inar y t em , , . .


    ,

    e ra t u r e s
    p .

    Hydra zine ,lik e amm oni a u ni tes w i th a ci ds d ire c tly to form sal ts; i t
    ,

    can t a k e u p e i ther on e or two m ol e cul es of a m onobas ic a ci d N H HCl , 2 4


    ~

    an d N H 2 HC 1 being both known


    2 4
    -
    Th e a qu eo u s so lut i on of hydra
    .

    zine i s strongly bas ic I t s sal ts are eas ily so lubl e in wat er e xc ept ing
    .
    ,

    the sulphate N H H SO wh ic h i s rather difc ul t l y so


    , 2 4
    -
    2 4, .

    HYDR A Z O I C A C I D,

    5
    1 1 Th i
    . s interest i ng c o m p o u nd lik e the p re c ed i ng one w a s rst
    , ,

    d i s c o vered by C UR T I U S in the de c o m p osi t i on of an organ ic c o m pound .

    I t c an now b e prepared in a good yi e l d by treat i ng hydra zi ne hydrate


    wi th n i tro u s a ci d Thi s i s best done by bo ili ng an alc oho lic so lu ti on of
    .

    hydra z ine hydrate w i th a m yl n i tri te and sodi um al coho l ate whi c h giv es ,

    t h e sod i um sal t of t h e hydra z o ic a ci d .

    A n aqu eo u s so lu t i on o f t h e free a ci d i s best obta i ned by d i stilli ng


    lead hydra z oate Pb ( N 3 ) 2 wi th d ilu te s ul ph ur ic a ci d By fra c t i ona l
    , , .

    d i st ill at i on of thi s so lu t i on the pu re a ci d c an be obta i ned .

    Pure hydra z o ic a ci d i s a liqui d wi th a penetrat i ng u nbearab l e odor ; it ,

    boils at 3 7 and is e xtre m e l y e x pl os iv e even in aqueo u s so lut i on



    , .

    It is a strang e fa c t that hydra z o ic a ci d d i s pl ays m ore or l ess ana l ogy


    wi th the hydro g en a ci ds of t h e hal o gens ; i t form s lik e the m dif c u l t l y , ,

    so l ub l e sa l ts of s i l ver m ercury ( o u s) and l ead , These are however .


    , ,
    C O M PO UN DS O F N I TR O G E N W I TH T HE H A L O G E N S . 17 9

    so lub le i n strong mineral a ci ds They are al so very e xpl os ive hence


    .
    ,

    e x tre m e ly dangero u s the sod ium salt be i ng the least so A n aqueo u s


    , .

    1 % so lu t i on of t h e a ci d i s only i oniz ed ; i t i s thus a rather weak


    a ci d ; i t g iv es o ff hydrogen in c onta c t wi th m any m eta ls e g Zn Fe ,
    . .
    , ,

    C d and M g
    ,
    I t is c hara c ter i st ic of the m eta l h ydr az oat e s ( or a zi des )
    .

    that they c rystalliz e anhydr o us and y ie l d the pure m eta l when heated .

    C o m po u n ds of N it r o g e n with th e H al o g e n s .

    1 1When chlorine gas is allowed to ac t on a concentrated


    6 .

    solution of a m monium chloride most conve niently by in verting a ,

    ask full of chlorine over the warm (3 0 solution oily dro ps


    ,

    are formed which are best collected in a leaden saucer placed


    ,

    un der the mouth of the ask These dro ps contain some hydrogen
    .

    as well as nitrogen and chlorine By treating with chlorine once .

    more pure n itro g e n t ri chl o ri de , N C 13 is obtained as a yellowish ,

    oil with a disagreeable pungent odor a nd a s pecic g ravity of


    This is one of the most dangerous of substances because it ,

    e xplodes in a most violent manner no t only on contact with certain ,

    organic s ubstances ( e g tur pent ine ) but very o ften s pontaneously


    . .
    ,
    .

    I t disso l v e s in carbon disul phide benzene and o ther solvents form


    .
    , .

    ing yellow solutions These solutions are relatively harmless ; they


    .

    d ecom pose in the sunlight .

    C oncentrated hydrochloric acid decom poses nitrogen trichlori de


    acco rding t o the equation :

    N or3 411 01 N H4 C l 3 012

    aq u eo u s a m m o n ia also breaks it up in a similar way

    N C 13 4 N H3 3 N H4 C 1 + N 2 .

    N itrogen trichloride is strongly e n do t h erm rc

    N 3 Cl N C 13 C al .

    When a so l ut i on of sod ium a zi de N aN i s mix ed w i th a so lut i on , 3,

    of sod i um hypo c hl ori te in t h e rel at i on of m o l e cul e for m o l e cul e an d the


    mixt ure is a cid ied t h e liqui d ass umes a yell ow c ol or an d gives o ff a
    ,

    c ol orl ess gas wi th an odor like that of hy p o c hl oro us a ci d an d having


    the c o m pos i t i on N C l showing i t to be c h l ora z i de O n be in g passed
    3 ,
    .
    1 80 I N O R G A N I C C HE M I S TR Y 1 16

    i nto c au stic soda i t form s sod i um a zi de and sodi um hypochl orite in


    e quival ent a m o unts

    N C l + 2 N aO H
    . N aN 3 + N a O C l + HzO .

    The chl ora zi de is likew ise e x tre m el y e xpl os i ve .

    I o di I
    N itrogen i de
    a solution of iodine in p otassium
    71 1 .

    iodide is mixed with ammonia sol ution a p reci p itate is usually ,

    o btained of the co m p osition N I 2 H ; if the co nditions are slightly

    altered another c om pound N 2 1 3 H3 (i e N H3 + N I 3 ) is de p osited


    ,
    . .
    ,

    which breaks u p on co ntinued treatment with water int o ammonia


    and nitrogen tri iodide These com p ounds are likewise very
    -
    .

    ex plosive .

    A nother meth o d is t o digest p ulverized iodine with ammonia


    water The pro duct so obtained is still more ex p losive often

    .
    ,

    ex plo ding even when d am p or when it is being washed with water


    o r by the action of hydro chloric acid In the presence of ammo ni a
    .

    solutio n it is stable .

    N itrogen iodide is decom posed by dilute hy d rochloric aci d ,

    forming ammonia and chlorine iodide :

    N HzI HC l N H3 1 01.

    N itrogen iodide is also decidedly endotherm i c .

    Hydr o xyl am i n e , N H2 O H .

    Hydroxylamine is a r eduction produc t of many oxygen


    1 1 8 .

    com pounds of nitrogen intermediate to the formation of ammonia ;


    e g
    . it is formed when tin acts on dilute nitric acid
    . Here the .

    nascent hydrogen effects the reduction :


    HN 0 3 3 H2 N H3 O 2 H2 O .

    It is manufactured by the electrolytic reduc tion of nitric acid dis a

    solved in sul ph ur ic acid .

    Th e free hydro xyl amine i s best prepared by heat ing the phosphate .

    I t i s a c rystalliz ed so li d m el t i ng at 3 0 an d bo iling un der 6 0 m m



    .
    ,

    p
    ress u re at W hen heated in the a i r i t e xpl odes wi th a ye ll ow
    am e
    182 I N O R GA N I C C HE M I S TR Y .
    l 1 19

    T his method is analogous to that of pre parin g nitrogen fro m


    ammonium nitrite I f the nitrate is heated above .

    the gaseous pro duct partially decom poses .

    Physical Pr operties N itrous oxide is a colorless an d odorless


    gas which when liqueed boils at 87 and solidies at

    ,

    The evaporation of the liquid produces a great depression in t h e



    temp erature w hi ch may even reach 1 4 0 under reduced pressure
    , .

    Its s p ecic gravity is ( based on air ) or for O 1 6,


    1 1 :
    . .


    N 2 O at 0 and 7 60 mm p ressure weighs . g It is rathe r .

    soluble in water ( 1 vol H2 O dissolves . v ol N 2 0 at henc e .

    it must be collected over hot water I n alcohol it is still more .

    s oluble .

    C hem ical Properties N itrous oxide su pp orts combustion


    . .

    Phos phorus carbon and a glowing Splinter burn in it as in oxygen


    ,
    .

    A mixture of nitrous oxide and hydrogen ex plodes like detonating


    gas when it is ignited o nl y not quite so loud These pro pe rties
    ,
    .

    m ight lead one to confuse it with oxygen on a su p ercial examin a


    tion However it is very easily distinguished from the latter by
    .
    ,

    the fact that it gives no red fu mes when mixed with nit ric oxide
    1 2 0) and always leaves residu al gas ( nitrogen ) after a combustion .

    A faintly burning piece of sul phur is moreover extinguished by


    nitrous oxide .

    N itrous oxide is endothe rm ic : 2 N + O N O = C al


    2 .

    B ERT HE L O T has made the general observation that endothermic


    substances can suffer an ex plosive dec om position ; in this case this
    may be brought about by touching off the gas w ith fu l rnin at in g
    -


    mercury It is easy to ex plain B E R T H E L o r s observation When
    .
    '
    .

    an en dothermic substance d ecomposes heat is evolved N ow we ,


    .
    ,

    saw in 1 3 and 1 04 that chemical reactions are ac celerated in a


    very high degree by rise of tem perature Su pp ose th at a sudden .

    decom p osition is caused at a certain p oint in a mass of an endo


    thermic co m p ound The heat given o ff raises the tem p erature
    .

    of the surrounding molecules and they to o s plit u p suddenly ,

    evolving still more heat and so o n The wh ole mass will thus
    ,
    .

    reach a co ndition of sudden dec om p osition th at is it will ex plo de , , .

    To bring this ab out it is only necessary th at the rst im pulse be


    v igorous enough for the sudden deco m p ositio n of s o many mole
    cules that the heat evolved is su i cie n t to raise the surrounding
    o nes to the tem p erature of dec om p osition .
    N I TR I C O XI DE . 1 83

    C omposition Un d e r
    the protracted action o f in duction s parks
    the gas s plits u p into a mixture of nitrogen and oxygen the volume ,

    o f which is half again as great as that of the nitrous oxide Wh en .

    p otassium and sodium are burne d in the gas potassium and so dium ,

    o xides res p ectively are formed together with nitrogen ; the gas ,

    volume after cooling is unchanged B oth of these observations point .

    t o the same formula N 2 0 and t his is conrmed by the fact that


    , ,

    the relative density of t h e gas which should theo reticall y b e ,

    w as foun d to be

    NI TR I C O XI DE, N O .

    This gas is onl y obtained by the reduction o f nitric o r


    1 20.

    nitrous acid The ordinary method of pre paration is by allowing


    .

    co pper to act on nitric acid or else by cove ring co pper (in the form
    o f thin sheets ) with a saturated solution of salt petre and ad d in g

    concent rated sul phu ric acid drop b y dro p

    3 Cu 8HN0 3 3 C u (N 0 3 ) 2 4 H2 0 2N o .

    In this reaction the hydrogen which would b e expe cted t o b e ,

    given off reduces another portion of the acid


    ,
    .

    I n order t o p re p are nit ric oxide by the reduction of nit ric acid
    or a ni trate a boil ing hot solution of ferrous chl o ride EeC l g in
    -

    , ,

    hydrochloric acid is foun d very satisfac t ory ; the ferrous chlo ride
    is conve rted into the fe rric chlo ride FC CI3 b y t h e reac ti on : , ,

    Perfe c t ly pure
    ni tric oxi de i s obtai ned by treat ing a mix ture of yell ow
    pruss i ate of p otash and potass i um n i tr i te w i th a c et ic ac i d :

    2K 2K N O 2, + 4 0,H 0 2 + 4 K C, H3 0 , + 2H,o + 2N O
    Ye ow p rus Po t n i
    .
    -
    A ce t . ac i d . p
    R e d ru s Po t . a c e t at e .
    s ia t e . t r it e s ia t e
    .

    Physica l Proper ties N it ric


    oxide is a colo rless gas whose
    " ,

    Specic gravity has been found to be I t can b e


    condensed to a blue li q u id which boils under ordi na ry p ressure at
    ,
    1 84 I N O R G A N I C C HE M I S TR Y . 1 20

    The critical tem perature is the critical pressure


    atm It is not very soluble in water but dissolves easil y in a
    .
    ,

    solution of ferrous sul phate Fe SO 4 ; strange to say this solution is


    , ,

    quite dark brown in color although the ferrous salt solution is pal e
    ,

    green and nitric oxide colorless The com p ound which is formed .

    here has not been isolated but it has been shown to consist of
    ,

    Fe SO 4 and N O in equimolecul ar p ro p o rtions .

    C h em ical Proper ties I t is characteris t ic of this gas above all


    .
    ,

    o ther p ro p erties that


    ,
    it combines with oxygen immediately ,

    forming nitrogen dioxide a reddish brown gas , O n heating it


    -
    .

    with hydrogen no ex plosion o c curs ; the mixtu re burns with a


    white ame forming water and nitrogen If burning ph os phorus
    ,
    .

    is intro duced into the gas it continues t o burn ; a lighted c andl e


    ,

    is h owever extinguishe d ; sul phur and charco al do not burn in


    , ,

    it either A mixture of nitri c oxide and carb o n disul phide burns


    .

    with an intensely luminous b lue ame that is very rich i n ,

    chemically e ffective rays .

    N itric oxide is a stro ngly endothermic com poun d ; it can b e


    made to ex plo de by fulminating mercury A c c ording t o
    1 03 N O must be formed at a high tem pera t ure N ERNST .

    p roved that the reaction N 2 + O 2 z2 2 N O ac c ords strictly with the


    law of mass action -
    fro m whichever side one starts t h e ,

    r esults are in agreement with th ose c alculated assuming b oth ,

    rea ctions t o b e bimolecular Se e further 1 2 7 . .

    The formation and the decom positio n of N O are much slower


    than in the case of oz o ne A c c ordingly a sh ort h eating of air
    .
    ,

    followed by a ra pid c o oling pro duces oz o ne while a slower


    , ,

    heating and co oling yiel d N O o z o ne being broken u p during t h e


    ,

    extended p erio d of c ooling The following ex p eriment illustrates


    .

    this : When moist air is directed with a vel o city of less th an 7 m .

    p e r sec
    . against an incandes cent N ERN S T lament 2 9 1 ) N O is
    formed ; a more ra pid current gives oz one .

    C om pos ition When sodium is heated in contact with a measure d


    amount of nit ric oxide sodium oxide and nitrogen are formed ; the
    ,

    latter takes u p exactly half the volume of the ori ginal gas The .

    Spec ic gravity of nitric oxide is 1 5 ( H hence its molecula r


    weight is 3 0 A c cording to the above decom position the gas con
    .
    e

    t ains one atom of nitrogen ( 1 4 p a rts by weight ) There remain .

    for the oxygen therefore 1 6 pa rts by weight i e j ust one atom


    , , , . . .

    Hence the form ula is N O .


    I N O R GA N I C C HE M I S TR Y .
    1 22

    oi the former to be A s the tem perature rises the vap or ,

    density steadily decreases till about 1 50 is reached when it becomes


    ,

    constant at There is evidently complete dissociation of N 20 4


    molecules in this cas e ,

    N 2 0 4 Tf 2 N 0 2 ,

    1 v ol . 2 v ols .

    an d, inasmuch as the color of the gas grows darker we must su p ,

    p ose that N 0 2 is dark brown while N 2 0 4 is colorless which is t ru e


    , ,

    o f the latter in the solid state This su pp osition is su pp orted by


    .

    the fact that not only can the degree of dissociation be e s timated
    from t h e intensity of the color but that it can even be measure d ,

    quantitatively in this way .

    A ccording the equilibrium between t h e t w o g as es is


    e x pr esse d b y the e q u ti on

    =
    P x hx2
    ,

    where P is the total pressure of the gas mixture and x that o f t h e


    dioxide It being a constant From this equation it follows that
    ,
    .

    the disso ciation ( at a constant tem perature ) de pends on the p res


    s ure which has been shown to be the c as e Th is also fol .

    l ows from the theorem of L E C H AT E L I ER


    O n bringing nitrogen tetroxide in contact with water or better , ,

    with alkalies nitrous and nitric acids are formed ; we may therefore
    ,

    c ons ider it as a m i x e d a n h y d r i d e of these two aci d s :

    1\ 8
    5 9
    > o H
    + zo = N O 2 O H+ N 0 O H ~
    .

    Nit r ic a c i d . Nit d
    r o us a c i .

    Bo th N O 2and N 2 O 4 possess strong oxidizing power ; many


    s ubstances burn in t heir va p or ; they preci pitate iodine from solu

    b le iodides .

    The com position of n itr ogen dioxide follows from its synth esis
    eq uation 2 N O H O 2 an d from t h e va po r d e nsity

    .
    , ,

    Nitr oge n Pento xide , N2 0 5 .

    1 23 Thi s c o m pound c an be obtai ned by the action of chlorine on


    .

    Silver n i trate or by d i st illi ng f u mi ng ni tr ic a ci d wi th phos phor u s pent

    o x i de I t i s a c o l orless c rysta lli ne so li d me l ts at


    . I t and at 5 50
    4 .

    brea ks u p givi ng o ff brown f umes I f the heat i ng ta kes place rather


    ,
    .
    H Y PO N I TR O US A C ID .

    1 87

    rapi dly the deco m pos i t i on i s ex pl os ive i n nat ure ; so m et im es a spon


    t an e o u s ex pl os i on ta kes pl a c e hence i t ca n not be kept l ong, .

    As ni trogen pento xi de i s strongl y endother mic i ts spontaneous ,

    e x pl os i on must be e xpl a i ned in the sam e way as i s i ndi cated in 1 1 9 .

    O nly we mu st c on clu de i n t h i s c ase that the de c o m pos i t i on at ordi nary


    te m perat ure s is v i gorous eno ugh to s u f ci e nt ly heat t h e ne i ghbori ng
    m o l e cul es .

    I t u n i tes wi th water formi n g n i tri c a ci d wi th t h e e v o lu t i on of m u ch


    ,

    heat As m i ght be e x pe c ted i t has strongly o xi dizi ng pro pert i es Phos


    .
    , .

    h u s and p otass ium for i nstan c e b u rn w i th g reat br illi an c e in the


    p or , ,

    slightl y warmed anhydri de .

    Th e c o m pos i t i on of n i tro g en pento xi de is as certained by heat i ng w i th

    p owdered c o p per ; the a m ount of n i tro g en e v o lv ed c orre s ponds to the


    for mul a N O 2 5

    O xy g en Ac i ds of N itr o gen .

    1 24 . F our acids of nitrogen are known : hyponitr ou s ac id,


    H2 N 2 O 2 ; n itr oh ydr ox yl a m in ic a cid, H2 N 2 0 3 ; n itr o u s a cid, HN O 2 ;
    n itr ic a cid, HN O g
    The nitrous acid is known only in dilute
    .

    aqueous solution ; n it r o h y dro x yl am in ic acid is known o nly in its


    salts ; but the others are known in the pure state .

    O nly cert ain ones of the ab ove nitrogen oxides can b e regar d e d
    as aci d anhyd rides The pentoxide is undoubtedly one an d the
    .

    tetroxide may be co ns idered as a mixed anhydride of nitric and


    nit rous acids N itrogen trioxide gives a solution of nitrous
    acid when mixed with water at a low temperature ; however this ,

    solution undergoes a decom position slowly at ordinary more rapidly ,

    at higher temperatures nitric acid and nitri c oxide being fo rme d


    , ,

    3 HN O 2 = HN 0 3 + 2 N O + H2 O .

    The acid corres p onding to nitric oxide N O is n it r oh y dr ox yl , ,

    aminic acid However no one has yet been able to obtain this
    .

    a ci d fro m nitric oxide and water The same is true for nitrous .

    oxide t o which hy p onitrous acid corres p onds


    ,
    .

    Hypo n i tr o u s A c i d, H2N202 .

    1 25Thi s acid is form ed when ni trogen tri o xi de is introduced i nto a


    .

    m ethyl alc oho lic solu t i on of hydroxyl amine Th e free a ci d does not
    -
    .

    liberate i o dine fro m potass ium i odi de at on c e ; t h e reac t i on i s del ayed


    88 I N O R GA N I C C HE M I S TR Y .
    M 1 25

    for a t im e probab l y on acco unt of a de c o mpos i t i on by which ni tro us


    , ,

    ac i d i s form ed .

    Hypon itro u s a c id belongs to the cl ass of weak acids ; it s a q ueo u s


    solu t i on i s a poor c ondu ctor Both neutral and acid sal ts of th i s ac i d
    .

    are k nown .

    N it roh ydr bxyl am inic A c d, i

    Thi s a ci d does n o t e xi st i n the free state be i ng known onl y i n sal ts , .

    I t s sod ium sal t is obta i ned by m ix i ng an alc oho li c so l ut i on c onta i n ing


    sodium al coho l ate and hydro x yl amine with ethyl n itrate :

    02H50 N 0 2 N HzO H Cs O H

    i
    H2N 20 3 o

    Et h y l Nit r at e

    The alc ohol ateis a dded in order to c on vert t h e free a ci d d ire c tly i nto its
    sod iu m sal t If the atte m pt is m ade to li bera te i t by addi ng a s t ro nger
    .

    acid i t i s imm edi atel y de c omp o sed a cc ordi ng t o t he e quat i on :


    ,

    N a,N ,O 2 Hcl 2 N aCl 2N O H,O .

    The sod ium sal t heated in a queo us so lu t i on gives sod i um nitrate a n d


    , ,

    n i tro u s o xi de When the sodium s al t i s heated dry unt il it begins to


    .

    m e l t i t i s deco m posed i nto n i tr i te an d hypon i tr i te


    ,

    2 N 3 2N 3 0 3

    2 N 3 N 0 2 i N azN 20 2 .

    NI TR O US A C I D, H N 0 , .

    It was remarked above that this aci d is o nly known


    1 26 .

    in dilute solution at ordinary or low tem peratures : its salts


    are h owever stable
    ,
    I n order to pre pare them we usually
    ,
    .

    em ploy p otassium o r sodium nitr ate which gives o ff oxygen ,

    w hen heate d an d is co nverted i nto nitrite This decom positio n .

    takes place more readily if lead is added du ring the heating


    as a re ducing agent :

    2K N 0 3 2 KN 0 2 02 .
    1 90 IN O R G A N I C C HE M I S TR Y . 1 27

    In the cast iron retort ( C Fig


    -
    salt petre and sulphuri c ac i d
    ,
    .

    chamber acid are mixed in ro ortions corres onding to the abov e


    ( ) p p p
    equation a slight excess of sul phu ric acid however being ad d e d
    , , , ,

    because this makes the residue easier to remove from the reto rt .

    The reto rt is connected with a row of earthenware bottles (EE ) '

    containing a little water These receive the distilled aci d The


    . .

    las t b o ttle c onnects with a cok e towe r thro ugh which wat e r is

    FI G .
    M ANU FA C T URE or N I T R IC A CI D .

    trickling d own to dissolve the uncon d ensed aci d vapor . By


    p rocess a liquid of a Sp ecic gravity of and containing 6 0%
    acid is obtained I f the salt petre is previously dried and c o n cen
    .

    t rat e d sul phuri c acid is used a nitri c a cid of s p g


    ,
    an d almos t . .

    1 00% pure can be obtained .

    In some cases two molecules of saltpetre are use d to one of


    sul phur i c acid I f heat is moderatel y a pplied the reaction pro
    .
    ,

    c e e ds according to the above equation but on heati n g to a highe r ,

    tem perature the acid sodium sul phate that is formed acts on t h e
    second molecule of n itrate also forming nitric acid :
    ,

    N aN 0 3 N aHSO 4 N a2 SO 4 HN 0 3 .

    A large part of the nitric acid however dissocia t es a t the sam e


    , ,

    time as follows :
    2HN 0 3 2N O 2 H2 O O

    The N O 2 fumes dissolve in the distillate The liqui d thus


    -
    .

    o btained is red and its Sp eci c gravity is

    strongly in the air and is known as r ed fu m in g n itric acid


    it fume s
    .
    N I TR IC A C ID .
    19 1

    F o r som e y e a rs t h e d is t illation of saltpetr e wi t h sul phuric aci d


    h as b e en carrie d o n n a v acuum
    i
    Th e yiel d of aci d in such a c as e
    .

    app roaches closely t o t h e theoretical an d t h e pr o d uc t obtai ned is

    e n t i r ely fre e from nit r ous fumes .

    A n e ntir ely d istinct metho d for t h e in d us t rial pr e paration of


    n i tr ic aci d was in v rn t e d a few y e a r s ago b y BI R K E L AND an d

    EY D E . They make u s e of t h e ni tr og en an d oxyg e n of t he a t mos


    p h e re
    . T h e p roblem o f mak ing ni t r i c aci d from t his rathe r in
    e xh austible source has b een studie d fo r many y e a rs b ut thes e ,

    m en are t h e rs t t o handle i t with suc cess o n a c o mm ercial scal e .

    Th e solutio n of t h e problem b ecam e a r eally pressing mat t e r ,

    b e cause t h e princi pal mat erial fo r t h e pr ep ar a t i on o f nit r ogen


    c o mp oun d s C hili salt p et r e b ids fai r t o be e xh aus t e d in thi r ty
    , ,
    "
    v e yea rs an d s alt p etre h as not o nly a la r g e s ig ni c anc e in t h e
    ,

    , in d ustrial worl d b ut a s till large r o n e in ag ri cul t ure as a ni tro


    g e no u s fertiliz er .
    .

    Th e m e t h o d of BI R K E L AND an d E Y D E is b ased o n the lon g


    ~

    e s t ablish e d fac t th at o xides of nitrogen are fo r med in an e l e c tr i c

    ar c b urning in the air Th e .

    r eason why p revious investiga


    t ions did not suc cee d lies in
    t he fact th at an ordinary electri c
    arc has t o o s mall a volume an d ,

    t herefore c annot let a sufcient


    ,

    q uantity of air p ass This dif .

    c ulty is now obviate d b y mount

    in g t h e arc b etween the p oles


    PP of a very p owerful electri c
    m agne t E E (Fig The ar e
    .

    is produced between t w o hol


    l ow b ars of c o ppe r which are ,

    kept c o ol by ci r culating wate r


    in them . Wh en an alternat e
    c urrent is use d fo r p roducing

    t h e arc the latte r s p rea ds out FI G 3 6 D I A G RAM o r B IR K E L A N D AN D


    , . .

    in t h e Sha pe of a at disc that ,


    E Y D E N I T R IC A CI D A PPARAT U S
    ,
    .

    r eaches a diamete r o f 2 m in .

    t h e industrial form o f the a pp a r atus ; t h e t e nsion e m ploy e d


    is 5000 volts This ame disc is inclose d in a b ox th r ough
    .
    1 92 IN O R GA N I C C HE M IS TR Y .
    1 27 ,

    which a ra pi d current of air is force d and the c ontact with ,

    the ame is suf cient to form somewhat more than 1 % of N O '

    I nstead of b roa d ening out the electric arc t o a sun sha ped dis c -

    by the action of p owerful magnets SC H ONHERR ( B adische A nilin ,

    un d Sod a fabrik) forms an arc in the insi d e of an iron pi p e


    through which air is p assed Un d er these circumstances the.

    arc is develo pe d in a peculiar manner When the current is .

    turne d on the arc forms at the rst instant in the l ower par t
    ,

    of the metal pi pe between the pipe itself w hich serves a s an


    , ,

    electrode and a secon d electro d e which is se p arated by only


    , ,

    a few millimeters from the lower en d of the pipe Forth with .


    ,

    however the arc is carried along u pwar d in the p i pe b y the


    ,

    current of air which is given a tangential motion as it is passe d


    ,

    into the pipe so that the arc comes to o c cup y the p ortion of
    ,

    air along the ax is o f the p i pe an d d oes not t ouc h the wa l l of


    '

    the pipe (or the e f u x e n d of the pipe or a s pecially d evise d


    se parate electro d e) until a c onsiderable distance fro m the lower
    electro de is reached Th u s t h e re is established in the axis of
    .

    the pi pe a continuous and quietly b urning column of light of


    very p owerful actinic e ffect In this long drawn out ar e the
    .
    - -

    p assing air is p artially transforme d into nitric oxide This is .

    quickly chilled by contact wit h the wall of the pipe , which is .

    externally exp osed to the at mos p here and so prevente d fr om ,

    r e de c o m po s it io n The gaseous p roduct is half again if not


    .
    ,

    twice as rich in nitric oxide ( yield ab out


    ,
    as b y the B I R K E
    L AND E Y DE pro cess
    -
    .

    The N O must b e lo oked u p on as the primary pro d uct which ,

    subsequently unites with oxygen to form N O 2 the latter being ,

    carried to water absor ption towers much like the G A Y L U SS A C


    - -

    t owers in sul phuric a cid plants The N O 2 cannot be the primary


    .

    p roduct ,
    for it diss o ciates at ab out 6 00 into N O an d 0 2 With

    .

    the water the N O Z fo rms nitri c acid and nitrous acid :


    '

    N2O 4 H2 O HN 0 3 HN O 2 .

    The latter yields N O 2 and NO , however when the li quid bec o me s


    ,

    more concentrated :

    2 HN O 2 H2 O NO2 NO .
    I N O R G A N I C C HE M I S TR Y .
    I 1 27

    acid o n the metals is not the same in all cases I t d oes no t attack .

    gold or platinum Sil ver mercury and co pper are only im per
    .
    , ,

    c e pt ib l y dissolved at ordinary tem eratures but on warming they


    p ,

    dissolve with the evolution of nitric oxide This and the other .

    N O com pounds are p owerful cataly z ers in the dissolving of t h e


    above named metals for nitric acid which is per fe c t y free from
    -

    them does not dissolve these metals while the reaction immediately ,

    begins as soon as a little of these substances is added ; I t may b e


    su pposed that on warming nitric acid traces of N O com pounds
    are formed which together with the elevation o f the tem perature
    ,

    accelerate t h e reaction I ron zinc and magnesium reduce nitric


    .
    , ,

    acid to nitrous oxide and even to ammonia Under the action of .

    iron lings and dilute sul phuric acid the reduction of nitric aci d
    to ammonia in d ilute solution is quantitative There are also .

    various denitrifying bac teria known B a cil l u s p yo cya n eu s being t h e


    ,

    b est studied of them .

    N itric acid frequently acts as a powerful oxidizing agen t ,

    es pecially at an elevated tem perature I f sul phur is boiled with it ,

    the sul phur is conv erted to sul phuric acid similarly phos phorus to ,

    p hos phoric acid A glowing


    .
    p iece of charco al dro pp ed u p on t h e

    concentrated acid continues to burn with a bright glow In all .

    these cases t h e highest oxidation stages are formed N itric aci d .

    is used particularly in the organic branches of chemical industry .

    The com pos ition of nitric acid can be deduced from that of its
    anhydride A weighed amount of the latter is introduced into
    .

    water ; nitric acid is formed which is neutralized w ith bary t a


    ,

    water B y eva p oration it is p o ss ib e to determine how m any


    . .

    arts by weight of barium oxide B a O comb ine with the an hyd ride
    p , ,
    .

    ( = O
    It is found that p arts 1 B a ) combine with
    p arts 1 N 2
    O 5) of the anhydride ; t h e formula of barium nitrate

    thus b ecomes hence that of nitric acid itself m ust b e


    HN 0 3 .

    i i c Ac i d HN O
    Pe rn t r , ,.

    Pern i tric a ci d i s for m ed in v ery d il ute a q ueo u s so l ut i on by the


    oxi dat i on of ni tro u s a ci d wi th hydrogen pero xi de :
    2 H20 2 + HN 0 2 "
    HN O 4 i 2H20

    N i tric a ci d does n ot yi el d i t when treate d in t h e sa m e way ; o n th e


    c ontrary ,
    t he p ern i tr ic a ci d brea k s u p e v en in a c o l d d ilu te a q ueo u s
    D E R I VA TI VE S O F TH E N I TR O G E N A C I DS . 1 95

    so lu t i on i ns i de of abo u t an ho ur c o mpl ete ly i nto n i tric a ci d an d hydrogen


    p ero xi de :
    HN O 4 + H20 HN 0 3 + H20 2 .

    Pern i trica ci d has the v ery c h ara c teri st ic pro perty of liberat ing bro mi ne
    fro m potass ium bro m i de so lu t i ons so m ething that ne i ther hydro gen
    ,

    p eroxi de nor n i tro u s a ci d nor n i tr ic a ci d does .

    De riv ativ e s of t h e N itr o ge n A c i ds .

    12 .discussing the manufacture of sul phuric aci d


    8 In 86)
    we already referred to the c h am b e r c ry stal s , H SO 5 N They are .

    formed in the lead chambers in case not enough steam is su pplied .

    The following equation expresses the action that takes place :

    2 80 2 N 20 4 + O Hg O Q SO 5 N H .

    The or d inary method of preparing this substance is by conduct


    ing carefully dried sul phurous oxide into cooled fuming nitric aci d

    S0 2 HN 0 3 SO 5 N H .

    The crystalline mass obtained is s pread out on porous earthenware


    to allow the adhering liquid to be absorbed .

    The chamber crystals have the a ppearance of a coarse crystal


    line colorless mass ; they melt at
    ,
    They are at once de c o m
    osed by water into s ul phuric and nitrous acids :
    p

    SO 5 N H H2 O H2 SO 4 HN O 2 .

    For this reason the com pound is considered as the m ixed an ky


    dride of su l phu r ic a nd n itr ou s acids A ccording to.9 0 the s t r u c

    ture SO 2 < 83 can be ascribe d to sul phuric aci d ; to nitrous acid the
    s tructure HO N O
    -
    s inc e a hy d roxyl group is assumed
    ,
    1 29) to
    e x is t in i t For the chamber crystals we therefore hav e
    .

    OH

    n itrosyl ,
    Sinc e t h e atomic grou p N O is known as the rational
    n ame for the com p ound is n itr o s yl s u l phu r ic acid .
    1 96 ,
    I N O R G AN I C C HE M I S TR Y . 1 28

    N itr osyl l ph u ri c a c i d plays a very im p o rtant role I n the


    su

    lead chamber process I n its dec om p osition by water it forms


    -
    .

    sul p huric and nitrous acids ac cording t o the equation given ,

    ab ove N itrous acid reacts with sul p hur d ioxide formin g


    .
    ,

    n itr o so s u l ph o n i c a c i d
    -

    HN O , + so, = O N so,H,
    which is very unstable however and unites at once with a , ,

    sec ond molecule of nitrous acid t o form n itr osi s u l ph o n i c a c i d -

    and nitric oxide :

    O N S0 ,H HN O , ON /
    \ So, H

    but the nitrosi sul phonic aci d likewise very unstable so on s plits
    -

    , ,

    u p under the conditions p revailing in the lea d chambers int o

    nitric oxi d e an d sulphuric aci d :

    ON
    < s o, H

    The nitric oxi d e nally oxi d iz es very q uickly in the oxygen


    , ,

    always present in the lea d chambers back again into nitrous ,

    acid :
    2N O O H,O 2 HN O , .

    These four equations explain the whole lead chamber p ro cess


    ,

    accor d in g to R A SC H I G He suc c eeded in p re paring the nitroso


    .

    and nitrosi sul phonic acids ; see 1 3 0


    -
    .

    C oncentrated sul phuric acid dissolves nitrosyl sul phuric aci d


    without change Th is solution is very stable ; it can be distille d
    .

    without decom position I t is formed in the G ay L ussac tower of


    .
    -


    the sul phuric acid factory and is cal led nitrated acid o r
    O n d ilution with water th is Solution is n o t

    nitrous vitriol .

    altered until its s pecic gravity reaches 4 8


    ( 5 1
    then the nitric oxides begin to esca pe es pecially when warmed ,
    .

    Wat er an d sul phurous oxide act on the nitrated acid producing


    the following reac tion :

    851 8g
    0
    2 s0 2 2R 20 80 2 3 s0 2 + 2N o

    This action takes place in the G lover tower .


    1 98 I N O R GA N I C C HEM I S TR Y . 1 29

    therefore bears the name aqu a regia It was known even to t h e .

    alchemists p articularly G E B ER who prepared it by dissol v rng sal


    , ,

    a m moniac N H4 C 1 in nitric acid


    , ,
    .

    O THER N I TR O G EN C O M PO UN D S .

    1 3 0. organi c che mi stry a c id der iv at ives are k nown which are


    In
    form ed through the s ubst i tut i on of the hydro xyl gro u p by a ha l ogen
    ato m or the ami do group N H, The form er class are called a c i d
    ,

    0 h l o r i d e s the l atter a m i d e S O f the i norgani c a ci d c hl ori des


    we hav e a lready be c o m e a cqu ai nted wi th those of s ul phur ic a ci d
    N it rosyl chl ori de i s a l so an a ci d chl ori de .

    Upon mixi n g c on c entrated so l ut i ons of sod ium n i tri te and sod ium
    b i s ulph i te the liqui d heats strongly and a react i on ta k es place a cc ord i ng
    to the fo ll o w i ng e qu at i on

    N aN O , 3 N aHSO 3 N ( SO sN a) 3 N aO H HZO .

    The resul ti ng c o m poun d to wh ic h has been assi gned the structura l


    ,

    formul a N after R A S C H IG i s regarded as a mm oni a i n


    ,

    whic h three hydro g en ato m s hav e been repl a c ed by s ulpho groups -

    ( SO H) ; i t bears the na m e s o diu m n i tr il o su lph on a t e


    3 I t i s v ery so lu b l e
    -
    .

    i n water ; b u t i f the liqui d mixt ure is po u red i nto a c o l d saturated


    ,
    -

    potass ium c hl ori de so lu t i on the difc u l t l y so l ub l e N ( SO K )


    ,
    i s pre 3 3

    c ipit at e d O n bo ili ng i t for a short t im e w i th water or better by l ett i ng


    .
    , ,

    i t stand for a day m o i stened wi th d ilute sulphuri c a ci d i t form s ,

    po tassi u m im ido su l ph o n at e

    N ( SO 3 K ) 3
    1 H20

    N H ( 80 3 K ) 2 "
    i KHSO 4 .

    If the boi l ing is continued for a l ong period , am ido su l ph onic acid is pro
    du c e d
    2 H,o = N H,so,H K, so, K HSO , .

    Si mil ar
    derivat ives of hydro xylam ine are al so kno wn The potassium .

    sal t of hydro xyl a mi ne d i s ul phonic ac i d HO N (SO 3 K) 2 + 2 H,O i s form ed


    -

    ,
    -

    when so lut i ons of a ci d potass i um s ul phi te and potassi um n itrite are


    m ixed
    K N O 2 + 2 K HSO 3 = HO N ( SO 3 K) 2 KO H .

    By bo iling th i s c o m po u nd with water hydro xyl ami ne i s set free

    + 2 H,
    0 = HO N H,
    2 s o,K H .
    PHO S PHO R US .
    1 99

    O xi dat i on of sodi um hydro xylam ine d i sulphonate wi th perm anganate -

    so lu t i on giv es an i ntensely vi o l et c o l ored liqui d Thi s c o l orat i on i s due


    -
    .

    to t h e N a sal t of the n i tros i s ul phon ic a ci d m ent i oned in 1 28 A ddi


    -


    t i on of col d sat urated potass ium c hl ori de so lut i on c auses t h e separat i on of
    orange c rystal s of the c orrespond i ng potass ium sal t wh i ch i s al so so l ub l e ,

    i n water wi th a Vio l et c ol or .

    I f a so lut i on of c ha mber c rysta l s in c on c e n trated s ul huric a ci d i s


    p
    Sha k en wi th m er cu ry t h e so lu t i on be c o m es s k y b l ue on a c co u nt of
    ,
    -

    the red uc t i on of the n i trosyl s ulphu ric a ci d to n i tros i sulphonic a ci d -

    Th e c opper s al t of t he l atter i s m ore stab l e an d c an be


    obt i ned by sha ki g
    a abo v e m ent i oned so lut i on wi th c o pper fo i l
    n t he -

    c li pp i ngs The add i ti on of water or o xi d i zing agents


    . n i tri c a ci d)
    d estroys the b lu e co l orat i on .

    The a i de of nitric ac i d nit r


    m a m ide H ,

    N 2 N O 2 has so far be en obtained
    , ,

    only fro m an organic c o m po u nd n it ro u re t h an e N O ZN H CO zC s , ,


    -
    .

    Thi s a mi de a ppears i n c o l orl ess c rystal s that m e lt at 7 2 wi th de co m

    pos i t i on The a queous so lut i on rea c ts strongly a ci d I t i s a v ery


    . .

    unstab le substan c e de c o m pos i ng on be i ng mixed wi th co pper o xi de


    , ,

    p owdered g l ass or the lik e I t i s imm ed i ate l y bro ken u p by alk ali es
    .

    and even by sodium a c etate at ordi nary te m peratures ni trous oxide ,

    and water bein g form ed in the latter case .

    PHO SPHO R US .

    1 3 1 . Phos pho rus


    does not occur free in nature inas much as i t ,

    combines very eas ily with oxygen N evertheless salts of phos .

    h ric acid are widely distributed and occur in large quantities


    p o .

    Tricalcium phos phate C a3 ( PO 4 ) 2 phosphor ite is found in large


    , , ,

    de posits ; other phos phates which are frequently met with are :
    3 C a3 ( PO 4 ) 2 + C aC 12 or C a ) v ellit e 4 A l P O4+
    a pa tite , ( ; w a ,

    and vivian ite F Phos phates


    ,

    a re also found to a small extent in granite and volcanic rocks ;

    when these weather the ph os phates enter the soil A bout .

    o f ph os p hates ( calculated as P2 0 5 ) is p resent in soil of average

    fertility B ones contain a considerable p ro p ortion of tricalcium


    .

    p hos p hate .

    Phos phorus has been known for a long time I n 1 6 7 4 the .

    a lchemist B RAND discovered it at Hamburg by eva p orating urine

    a n d heating the residue with sand in an earthen retort SC H EE L E .


    2 00 IN O R G A N I C C H E M I S TR Y . 13 1

    rst pre pare d phosphorus from b ones b y a pr ocess wh ic h in the


    m ai n is stil l employed .

    For the m anu fa ctu re of phosphoru s bones or phos phorite are


    used B y treatment with sul phuric acid gy psum and monocalcium
    .

    p hos phate are formed A s the latter


    . remains soluble while t h e

    former is preci pitated the phos phate solution is readily p oured o ff


    , .

    Gy p sum .

    On being heated this phos phate loses water and is converted into
    calcium metaphos phate :
    C HH4 <PO 4 > 2 C a ( P0 3 ) 2 2H2 0 .

    The latter [ or in some pro cesses the original phos phate material ] .

    is mixed with p owdere d coal and sand and reduced in a con '

    t in u ou sl y o perated electric arc furnace whereu p on phos ph oru s ,

    d istils over :

    The phos phorus thus obtained is blac k because of adherin g


    particles of charcoal and c ontains still other im purities
    , It can b e .

    p uried by distilling with steam in a n atmos p here of carb on dioxide .

    Fin ally the p hosphorus is c ast int o sticks and in this form enters
    the market .

    1 3 2 . Ph ysical P op er ties
    r A t or d inary tem peratures phos
    .

    p h o ru s is a crystalline solid of a light yellow c olor and having a


    s pecic gravity of at When c old it is brittle on ac c ount
    o f its crystallin e t e xture ; above 1 5

    it becomes s oft an d waxy and
    melts at 44 4 to a yellow strongly refractive liqui d Its boilin g

    ,
    .

    p oint is it then turns to a colorless va p or In the sunligh t .

    it becomes yellow and coated with an O paque pink layer Phos .

    h ru s is insoluble in water slightly soluble in alcohol and ether


    p o , ,

    but easily soluble in carbon disul phide from which it c rv s t alliz e s ,

    in crystals of t h e regular system .


    The v apor den sity of phos phorus at temperatures between 5 1 5
    an d 1 0 4 0

    is 4 50 I t s molecular weight is there
    fore I nasmuch as the smallest amount of phos phorus that
    is found in one grammolecule of any of the numerous phos phorus
    compounds investigated is 3 1 g this number therefore re presents
    .
    ,
    02 IN O R GA N IC C H E M I S TR Y .

    tem perature is low the velocity of transformation of the yellow


    ,

    form is so small that it seems perfectly stable .

    The re d phosphoru s i s not a ho m ogeneo u s s ubstan c e ; i f i t i s st i rred


    u p w i th water so m e vi o l et c o l ored p art icl es of m etallic l ustre an d a
    -

    spe cic grav i ty of are l eft on the botto m HI TT O R F prepared .

    thi s m e t al l i c ph o sph oru s m any years ago by heat ing phosphoru s w i th


    l ead i n a seal ed t ube ; the phosphoru s d isso lv es i n m o lten l ead and
    crystalliz es o u t i n the m etalli c form on c oo ling The spe cic gra vi ty of .

    the red phosphorus vari es between and a cc ord ing to the d u rati on
    and tem perat u re of the heat i ng I t i s probab l e that i t represents a
    .

    so li d so lut i on of whi te phosphorus i n m etallic phosphorus The rat i o .

    in whic h these two m od ic at i ons o cc ur in r e d phos phor u s c hanges w i th


    t h e te m perat u re ; an e quilibrium estab li shes i tse l f between the m for
    e v ery te mperature A t abo u t 500 t h e pro port i on of whi te phosph orus
    .

    rea c hes a mi nimum .

    A cc ord i ngl y onl y the wh i te and the m etallic phosphor u s are to be


    regarded as well c hara c teriz ed a ll otro pic m odic at i ons .

    1 34 . C hem ical Pr oper ties Phos phoru s


    has a great ai nit y for
    m any elements ; it combin e s directly with all elements excep t
    n itrogen an d carb on the combination o ccu rri ng with great vigo r
    ,

    in many cases e g when phos phorus is brought in contact w ith


    ,
    . .

    sul phur or bromine C e rtain comp ounds of the metals (phos


    .

    p h id es ) are know n w hi ch are called


    , p hos phor bronzes
    Es pecially characteristic of phos phorus is its very strong afnity
    for oxygen ; yellow phos phoru s takes re in the air at so

    that contact with a hot glass rod is sufcient to ignite it Th e .

    b u rning is accompanied b y a vigorous evolution of light an d heat ,

    p hos p horus p ento xide P 2 0 5 being forme ,


    d O n ,
    account o f th is .

    s trong af ni ty for oxygen phos pho ru s is a p owe rful reducin g ag e nt


    -
    .

    Sul phuri c acid when warmed with it is reduced t o sul phur dioxid e ;
    , ,

    concentrate d nit ri c acid oxidizes it with explosive violence ; dilute


    acid e volves ni trous fumes oxidizing the phos pho rus t o phos
    ,

    h ric aci d M any metals are p reci p itated by p hos p ho r us fro m


    p o .

    t hei r salts p hos


    , p hides being formed to some extent S il ve r .

    nitrate for instance gives silver and silve r phos phide A g3 P with
    , , , ,

    p hos p horus ; on warming p hos p horus with a solution o f co pp e r


    s ul phate co ppe r phos p hide C u 3 P2 is de p osite d , ,
    .

    1 3 5 The slow O xidation of phos phorus by oxygen at ordinary


    .
    PH O SPHO R US . 3

    temperatures is accompani e d b y the emis sion of a bluish light .

    This l u minosity of phosphoru s is very plain in the dark .

    This phenom enon is due to various circu m stances so m e of which ,

    are very mysteri ous The o xi dat i on and hen c e the l uminosity is
    .
    , ,

    p revented by the p resen c e of tra c es of c erta i n substan c es su c h as hydro ,

    carbons amm oni a et c Further the lumi nosity depends on the t e m


    , , .
    ,

    p e rat u re ; be l o w 1 0 it i s e xtre m e l y wea k



    The gas press u re has a .

    p ec ul iar in u en c e ; at ord i nary te m p erat u res phos phor u s does not e mi t


    l ight i n pure o xygen of at m os pher ic press ure b u t i f the pressure is ,

    redu ced a po i nt i s rea c hed at whic h lumi nosi ty co mm en c es ; thi s i s at


    ,
    '

    666 m m fo r .
    ,
    and at 7 60 mm for The o xi dat i on i s there
    .

    fore m ore vi goro us i n d il ute o xygen (i e oxygen mixed wi th another . .

    gas su ch as n i trogen) than i n c on c entrated


    ,
    VA N M ARU M observed .

    as early as 1 7 98 that a pi e c e of phosphoru s l a i d on wadding (whi ch


    serves as a poor c ondu c tor of heat) in a cl osed vesse l shi nes the m ore
    bri ghtly as the o xygen is pum ped out and m ay even take r e in very ,

    dil u te gas .

    The fa c t that o xi dat i ons are m ore energ et ic u nder red uc ed oxyg en
    press u re has been ob ser ved i n m any other c ases Se e 13 7 . .

    Detection P hosphoru s Poisoning s by yellow


    f o
    p hos phoru
    .
    s

    o ccur now and then In order to detect it in such cases use is


    .
    ,

    made of its luminosity For this purp ose the contents of t h e .

    stomach whic h are to be tested for phosphorus are diluted with


    , ,


    water in a distilling ask connected with a condenser by a tub e ,

    doubly bent at right angles O n heating the ask water distils .

    over with a little phosphorus vapor ; if the whole apparatus is


    p laced in a dark roo m a lum inous r ing is noticed during this
    ,

    d istillation at the place where the steam is c onde n sed i e wher e ,


    . .

    the phos phorus va po r c o mes in contact with air in the condenser .

    The distillate c ontains p hos p horic aci l (M I T S C H E R L I C H S te st )


    .

    Use Phos hor


    p us
    used c h iey for t h e m a n u f a c t u r e o f
    is


    m a t c h e s Th e m at ches in u s e to day m ay b e cl assed as safety matches

    -

    m atches wh ic h l atter m ay b e of t h e ( a) parl or



    an d s trike a nywhere ,

    Sl n gl e dip typ e or ( b) dou b l e dip wi th c o mb u st i b l e b ulb or ( 0 ) do ub l e


    -

    ,
    -

    dip w i th safety bulb I n the Sw ed i sh safety m at c hes t h e head c ons ists


    .

    c h i e y of a mix ture of potass i um chl orate an d ant im ony sulph i de .

    They are li ghted by striking the m on a s u rfa c e c oated w i th r ed phos


    204 IN O R G A N I C C HE M I S TR Y .
    M 13 5

    ph o ru s account of thei r re qui ring a spec i a l i gn i t i on surfa c e and


    . On
    the i r quick burn ing and dropping they are not as p opul ar in A m eric a
    as t h e strik e anywhere m at c hes O f the l atter the do ub l e dip safety
    -
    .
    -

    b ulb m at c hes are best be c a u se they c an be i gn i ted by fri ct i on of t h e


    t ip on ly not by s i de fri ct i on
    ,
    .

    Phosphoru s i n so m e form i s u sed i n the prod uc t i on of a ll m at c hes


    , , .

    Y e ll ow pho sphor u s i s generally u t iliz ed in t h e prod uc t i on of A m er ic an


    m at c hes b u t s in c e i t i s v ery in ju ri o u s to t h e heal th of the wor km en
    , ,

    m ost Euro pean c o u ntri es forb i d i ts u s e an d e m pl oy non po i son ous



    -

    substi t u tes The red phosphorus and phosphoru s ses qui s ulphi de
    .

    -

    P S are the c h i ef non p o i sono u s s ubst i t u tes for ye ll ow phos phoru s


    4 3,
    -

    and are to be utiliz ed i n A m eric an strike anywhere m at c hes as fast -

    as practi cabl e C o m pare 1 3 3 . .

    C o m p o u n ds of Ph o s ph or u s an d Hy dro gen .

    There are three c om pounds of phos phorus and hydrogen known


    ( ) g
    1 as eo u s hydrogen p hos p hide PH , (also called p hosphine ) ; ,

    ( ) q
    2 l i u id hydrogen p hos p hide P2 H4 ; and ( 3 ) s o lid hydrogen ,

    p hos p hide ( P2 H)6 ,


    .

    HYDR O GEN PHO SPHI DE . PHO SPHINE, PH, .

    This com p ound can be p re pared from the elements by


    13 6 .

    b ringing phos phorus together wit h z inc and dilute sul phuric a cid ,

    i e with nascent hyd rogen ; when thus p re pared it is mixed with


    . .
    , ,

    a large quantity of hydrogen .

    The generation of hydrogen phos phid e by heating phos phorous


    an d hy po phos phorous acids is another exam ple o f it s f o rm at i o n b y

    t he dire c t d e c o m position of phos phorus com po un ds

    4H3 PO 3
    PH3 i 3 H3 PO 4
    '
    .

    P h os p h o r o us P h o s ph o ric
    ac i d . a c l d.

    Th e o r d in ary metho d of re
    p p aration is b y t h e a c t ion of phos
    ph o r us o n ca u stic potash :

    P4 3 KO H 3 11 20 PE 3 3 H2 K P0 2 .

    Po t h po p h o s
    p
    .

    te .

    eaction is really m ore co m plicated than this e quation ind ca t es


    i

    The r ,

    for in addition hydrogen P21 1 4 and other substan c es are form ed (See
    ,
    4
    .

    al so
    2 06 IN O R G A N I C C H EM I S TR Y . 136

    p ose d b y d il u t e a cids with the format i on of h ydrogen p hos


    ph ide .

    The pe rfe c tly pure gas is n e w b est obtained by c ondensa


    tion and sub sequent fra ctionation at a very low tem perature as ,

    was describe d in 2 9 .

    Physical Pr op er ties Hydrogen phosphide or phos phuretted


    .
    ,

    hydrogen PH3 is a gas at ordinary tem peratures ; it becomes


    , ,

    liquid at
    8 5 and solid at
    It has a p eculiar disagree
    able o d o r that reminds one o f s poiled sh I t is slightly soluble
    ,
    .

    in wate r more so in alcohol Sp g = 1 7 (O =


    ,
    . 1 liter weighs
    . .

    g at O an d 7 6 0 mm p ressure
    .
    0
    . .

    13 7 C hem ical Pr op rti


    . e es Hy d rogen phos phi d e is very poison
    .

    ous ; it burns very easily yielding phos phoric acid ,


    I n the .

    resence O f oxygen of ordinary pressure it remains unchanged ;


    p
    if however the pressure is diminished an explosion results This
    , , ,
    .

    conduct reminds one of phos phorus which is luminous (because ,

    of oxidation ) only below a certain limit of pressure


    The combusti on of hy d rogen phos phide may be ex presse d b y
    the equation :

    2 PH3 40 2 P2 0 5 3 H2 O .

    A c cordingly the reactio n w ould b e h e x a m o l e c u l ar VA N


    D E R ST AD T demonstrate d by a meth od Si milar to that referre d ,

    to in 51 that the rst stage o f the reaction is bimo l ecular an d


    ,

    corres ponds very closely to the following equation

    PHs 02 H2 PO 2 H,
    M e t ap h o s
    p h oro u s a c id.

    if the gases slowly d iffuse into each other in a d ilute d con d ition .

    I n general ex perience has taught that the mechanism of a


    ,

    reaction is decidedly sim ple and that chemical processes are almos t
    always mono or bimolecular A ccordin gly when the quantita .
    ,

    tive course of a reaction is re presented by an equation indicatin g


    the participation o f several molecules it is probable that several ,

    intermediate reactions are involved .

    Hydrogen phos phide can unite with halogen hydrogen aci d s -

    d irectly t o form com pounds of the typ e PH4 X in


    analogy with ammonia The best known of these com pounds
    .
    H YD R O G E N PH O S PH I DE . 2 07

    is PH4 I ph o sph o n iu m io di de a c olorless well crystallized co m


    , , ,
    -

    p ound ,w hic h is formed when dry hydrogen p hos p hid e and hydro
    gen i odide are mixed In conta ct with water it brea ks u p into
    .

    PH3 and H I ; the former esca pes as a gas while the latter remains ,

    d issolve d in water .

    Phos phonium iodide is very unstable This is even more the .

    ca se with p hos p honium b romide w hi ch is a lso a solid but is , ,

    com pletely disso ciated into the t wo hydrogen com poun ds PH3 ,

    and HB r as low as
    ,
    Phos p honium chloride is disso ciated
    even at o rdina ry temperatures and pressures and can only exist
    below 1 4 or under more than 20 atm pressure C onsidering

    . .

    these p ro pert ies it is not surprising that phos p honium PH4


    , , ,

    like ammonium should be impossible to isolate N o other a cids


    ,
    -

    exce pt those mentione d unite with hydrogen phosphide The .

    general behavio r of the latter thus shows that it is very much less
    basic than a mmonia .

    It i s for thi s reason that PH I i s de c omposed by water The wea k


    4 .

    basic c hara c ter of phosphonium hydro xi de all ows the i od i de to b e


    hydro ly z ed i nto PH O H and HI whereupon the PH O H brea ks u p
    , ,

    forthw i th i nto PH and H 0


    3 2 .

    Hydrogen p hos phide p ossesses reducing pro perties Fro m .

    solutions of silve r nitrate of co ppe r sul phate it p reci pitates a


    mix t ure of metal and phos phide ; this pro perty can be made use
    o f to se parate the gas from other gases When m ixed with chlo .

    r ine it ex plodes vigorously forming hydrochloric aci d and phos


    ,

    p h o r u s trichloride .

    The c om pos ition of hydrogen phos phide was determined by


    p assing a known volume over co pp er turnings in a heated tub e .

    The co pper combines with the phos phorus so that the increase ,

    in weight of the tube shows the pro portion of p hos phorus The .

    esca ping hy dr ogen is coll ected and measur ed I n the e x per i .

    ment it was found that hydrogen phos phide co ntains


    hos horus and hydrogen The s ecic gravity for O = 16
    p p p .

    was found t o b e 1 7 ; the molecular weight is therefore 3 4 I n .

    3 4 p arts there are ac cording to the above com p osition 3 1 p arts


    , ,

    of phos phorus and 3 p arts of hydrogen ; the com position of the


    com pound is therefore ex pressed by PH3 This agrees with the .

    results of the decom position of hydrogen phos phide b y inducti on


    2 08 IN O R G A N I C C HE M I S TR Y .

    s p arks o r b y the electric ar e ; 1 vol PH3 yields 1 3 vols hydrogen . .

    and also amorphous phos phorus which is de posited o n the sides ,

    of the tube and o n the platinum wires ( or carb ons ) .

    2 PH3 3 H2 2P .

    2 v ol s .
    3 v ol s . s o l id.

    Liqu id Hy dr o g e n Ph os phide , P2H4 .

    1 38 . certai n cases thi s c o m po und is form ed as a b y product in


    In -

    the preparat i on of phosphi ne Espe ci ally i s i t form ed i n the de com


    .

    pos i t i on of c alcium phosphi de wi th water It a l so res ults fro m the .

    Ix idat io n of phos ph i ne by var i o u s substances for i nstan c e ni tro gen , ,

    d i o xi de by wh ic h ord inary hydrogen phosphi de c an be m ade spon


    ,

    t an e o u s l y i n amm ab l e Th e mixt u re of PH, and P2 H4 can be se parated


    .

    by pass ing it thro u gh a we ll c oo led t ube ; the latter substan c e con


    denses 130 a c o l or less liqui d whic h bo il s at 57 58 (under 7 3 5 m m )

    ,

    .

    and has a spe cic gravi ty of It is eas ily de c o m posab l e and can
    not be preserved be c au se i t rapi dly c hanges to the gaseo u s and the
    ,

    so li d hydrogen phosphi des Th e sam e de c o m pos it i on i s al so effe c ted


    .

    by hydro c hl or ic a ci d It m ust be c ondensed i n the dark as sunlight


    .
    ,

    a i ds de c o m pos i t i on The e m pi r ic al c o m pos i t i on is i ndic ated by the


    .

    for mul a PH2 ; b u t s i n c e phos phor u s i s tr iva l ent we ta k e P2H4 i e , ,


    . .

    HgP PHZ as the for mul a of the m o le cul e



    ,
    Li quid hydrogen phosphide .

    t h u s beco m es ana l ogo u s to hydra zi ne .

    li
    So d Hydrogen Ph o sph de , i
    1 39 Thi s substan c e i s form ed by the de c o m pos i ti on of the precedi ng
    .

    one e spe ci ally eas il y when phosphine c harged wi th P H vapor as i t


    , z 4 ,

    i s e vo lved fro m the deco m posi t i on of C a P w i th water i s l ed o ver gran u 3 2 ,

    l ated c al c iumc hl ori de The so li d hydrogen phosphi de separates out as a


    .

    bri ght yell ow powder of the e m pi ri ca l formula P H whose m o l ec ul ar wei ght z ,

    has been determined c rys o copicall y to be Pl ( u s i ng ye ll ow phosphor u s ,

    as a so lvent) O n be ing heated to about 2 00 i t brea ks u p i nto phos


    .

    phine and a n e w so li d hydrogen phosp hi de of the e mp i r i ca l for m ul a


    P9 H 2 Thi s l atter c o mpound i s al so form ed when PU H i s treated wi th
    .
    6

    liq ui d amm on ia When heated in the ai r Pl


    . catches re at ,

    I t is i nso l ub l e in water .
    2 10 I N O R G A N I C C H E M I STR Y .
    141

    PHO SPHO R US PEN TA C HLO R I DE, P015 .

    1 41 This substance is pre pared by passm g chlorine ove r phos


    .
    e

    p h or u s trichloride Fine
    . l ight yellow crystals
    -
    at once a p p ea r and
    the entire mass nally becomes solid indicating that all is con ,

    verte d into penta chloride This comp ound fumes strongly in


    .

    mois t air being imme d i ately decomposed by water with the forma
    ,

    tion of hydrochloric and phos phoric acids When heated it Su b .


    ~

    limes wi thou t melti ng In the transition to the gas eous state it


    .

    b reaks u p at a rathe r low tem perature into the trichloride and


    chlorine ; this dissociatio n is c omplete at for at that p oint


    the va po r density is j ust half of that calculate d for the penta
    chloride The vap or which at moderately low tem peratures is
    .
    ,

    almos t colorless takes on the yellow color of chlorine for the ab ove
    ,

    reason as the tem perature rises The di ssociation products


    ,
    .
    ,

    p hos p ho rus trichl oride and chlorine can be se p arated by di ffusion .

    Phosphorus pentachlo ride eva porates in an atmosphere of the tri


    c hlo ride with almost no dissociation (cf .

    By the ad d ition of a little wate r i t is conve rte d in t o ph o sph o ru s


    oxychloride

    PCl 5 H2 O PO C l 3 2 HC l .

    With more wate r pho sphoric and hydro chloric acids are produced .

    Phos pho rus pentachloride is u sed i n organic chemistry t o


    replace hydr oxyl gr ou ps with chlorine In inorganic chemistry .
    ,

    it can also b e em ployed for the same purpose ; thus sulphuric ac i d


    reacts with it in the following mann er 8 9)


    1 0 013 4
    3 -
    11 01 .

    PHO SPHO R US O XYC HLO R I DE , PO C l , .

    1 42The best method of pre paring this com poun d is by t he


    .

    oxidation of the trichloride with sodium chlorate :

    In or d e r t o m o derate the grea t vigor of this reaction s od ium chlora t e


    C O M PO UN DS O F PH O SPHO R O US . 21 1

    is placed und er phosphorus oxychlori de and the trichlori d e is


    then added slowly by means of a dropping funnel -
    .

    Phos phorus oxychloride is a colorless m obile liquid that b oi l s , ,

    at 107 2 and when solid melts at


    .

    , Sp g ,
    at . .

    In the presence of water with which it is not miscib le i t slowly


    , ,

    changes to phosphoric and h ydroc hl oric acids :


    P0 013 + 3 H2O = H3 P0 4 + 3 11 01 .

    THE C O M PO UN DS O F PHO SPHO R US WI TH THE O THER HA LO GEN S .

    1 43 These are very anal ogo u s to the chl orine derivatives They are
    . .

    l ikewi se pre pared by d ire c t synthes i s fro m the e l e m ents I nas mu c h as .

    the rea c t i on i s very v igorous it has to be m oderated by di sso lvi ng the


    ,

    p hos phor u s and the ha l ogen se parate l y in carbon d i s u l ph i de s l ow l y ,

    addi ng one to the other and then d i st illing o ff the so lvent The u ori des .

    hav e spe ci al m ethods of pre parati on A l l these c o m po unds are bro ken
    .

    u p by water lik e the c orr es pond i ng c hl orides the uorides however , , ,

    q uite sl owly .

    The com position of t hes e com pou n ds can be asce rtained in t h e :

    following way : on being decomposed by water they yield phos

    h ric or phos phorous a cid an d a halogen acid so that the quan


    p o ,

    tities of phos phorus and halogen present can be foun d by deter


    minin g the amounts of these acids M oreover the molecula r .
    ,

    weight can b e ob t ain e d by measuri n g the vapor density though


    it must be born e in mind however that compoun d s of the type , ,

    PX5 are usually dissociated in the gaseous state .

    O xyg en C o m po u n ds of Ph o sph o ru s .

    44 Three
    1 com poun d s of this class are known : phosphoru s
    .

    tr ioxide, P2 O 3 ; h o s phoru s t etr ox ide P2 0 4 ; and phosphoru s


    p p nt
    e ,

    oxide o r pho sphor ic an hydride P2 0 5


    ,
    O nly t h e last is of any great
    ,
    .

    importance .

    Ph os ph oru s Trio xide , P20 3 .

    Thi s co m pound is produ c ed when phos phorus burns in a slow cur


    rent of dry a i r in a t ube The pr i nc i pal produ ct is phos phorus pent
    .

    oxi de wh ic h c an be co lle c ted by a wad of g lass bers The phosphorus


    ,
    .

    tr i o xi de passes through as a v apor and is condensed in a we ll c oo led -


    212 I N O R GA N I C C H EM I S TR Y . 1 44

    tube It is a white waxy substance when thus form ed but it c an also


    .
    ,

    be obtained in c rystal s ; the latter m e l t at 22 5 and boi l at ( in


    a ni trogen at m osphere) The vapor dens i ty has been fo und to be


    .

    w hil e t h at ca lcul ated for P4 O G i s 1 1 0 O n be i ng heated to 44 0 i t i s


    .

    de c o m posed i nto red phosphoru s and phosphoru s tetroxide It t urns


    yell ow i n the li ght which e x pl a ins the fa c t that M sph oru s pentoxi de
    .

    so m etim es takes on a ye ll ow c o l or It d i sso lves sl owly i n co l d water


    .

    formi ng phosphoro u s a ci d ; with hot water i t produ ces red phosphorus ,

    sel f in am m ab l e hydro gen phosph i de and phosphor i c a ci d in a vig or


    -

    o u s rea c t i on W hen heated to 50 60 i n the ai r it takes re an d burns


    .

    to the pentoxide .

    i
    Ph os ph oru s Tetr o x de , P20 4 ,

    is obta ined fro m the P2 0 , co m po und as was stated above It form s , .

    co l orl ess gli stening crystal s that break u p i n water into phosphorous
    ,

    and phosphor i c a ci ds I n thi s respe c t i ts c on du c t i s anal ogous to that


    .

    of n i tro gen tetroxi de whi c h y i e l ds n i tro u s and n i tr i c ac i ds with water


    , .

    PHO SPHO R US PEN TO XI DE, P,o, .

    This com poun d is the product of the c ombustion o f phos pho rus
    in oxygen or an excess of dry air I t forms a white voluminous .
    , ,

    snow like mass that takes u p water rapidly to produce phos pho ri c
    -

    a cid It is the most p owerful desic cating agent known M O R L E Y


    .
    -
    .

    ascertaine d that it dries the air down to 1 mg water va por in .

    1 air I t exists in two m o dications b oth of which ar e


    . .
    ,

    formed simultaneously in the ab ove proc ess The one is crystal .

    line subliming at
    ,
    the other amor phous and not volatile
    below red heat ; the va p or condenses crystalline When heated .

    ab ove 2 50 the crystalline modicatio n p asses over into t h e



    ,

    amor pho u s form .

    Heating with charcoal reduces it to phos pho ru s .

    The vap o r de n sit v of phos phoric anhyd ride at b right redn es s


    was found to corres pond to the formula (P2 0 5) 2 .

    A c i ds of Ph o sph o ru s .

    1 . O nly
    two of the above described oxides of phos phorus
    45 ,

    viz P2 O 3 and P20 5 form corresp onding a cids ; these oxides c an


    . ,

    u nite with different amounts of water to form acids Fro m P20 5 .

    we have :
    21 4 I N O R GA N I C C HE M I S TR Y . 1 45

    This way of l oo king at them m akes pl a i n not only the c onne c t i on


    b e tween the di fferent ac i ds but a lso the i r str u ct u ra l form ul ae
    ,
    The .

    sa me m ethod can be appli ed to m any other cases As an exa m pl e .

    we m ay se le c t the per iodic acids I n 6 2 only one was m ent i oned


    -
    . .

    There are sa l ts however of var i ous pe r i od i c ac M 1 0 4 M3 I O 5



    , ,
    e g -

    ,
    . .
    , ,

    M51 0 6 et c
    ,
    These c an be derived fro m a h yp et ical a ci d I ( O H) 7
    .

    in whi ch i odine i s j o i ned to as m any hydro xyl s as correspond to i ts


    m aximum valen c e M5 1 0 6 wo ul d c om e fro m I ( O H) 7 1 H,O ; M,IO 5
    .

    fro m I (O ) 7
    H 2 H, O ; and M I O 4 fro m I ( O H) 7
    3 H, O .

    O R THO PHO SPHO R I C A C I D, H,Po, .

    1 46
    This acid can be obtained by direct synthesis from its
    .

    elements ; phos phorus burns to the pentoxide and the latter yields
    the acid on dissolving in water Its formation by the action of .

    nitric acid on phos phorus was mentioned in 1 3 4 I t can also be .

    obtained by the oxidation of com pounds containing phos phorus


    and hydrogen ; phos phine and the lower acids of phos phorus are
    oxidized to phos phoric acid .

    O rdinarily this acid is prepared by the oxidation of phos phorus


    with nitric acid or by liberating it from its salts particularly the ,

    calcium salt C a3 ( PO 4) 2 The latter is stirred i nto the theoretical


    ,
    .

    amount of dilute sul phuric acid formin g calcium sul phate which , ,

    is only slightly soluble in water and phos phoric acid which goes , ,

    into solution O n eva porating this solu t ion the acid remains
    . .

    A t ordinary tem peratures ortho phos phoric acid is a crystallin e


    solid I t melts at
    . is odorless and extremely soluble in water ,

    forming a strongly acid solution .

    It has the character of a stro n g acid ; however it is consider ,

    ably less ionized than hydrochloric acid ; a solution of 1 mole


    p hos phoric acid in 1 0 1 water contains about o n e fourth as many
    .
    -

    hydrogen ions as hydrochloric acid of the same molecular con


    c entration I t is ionized chiey into H and H2 PO 4
    '

    . I t generates .

    hydrogen with metals all three hydrogen atoms being replaceable


    ,

    by metallic atoms ; it is therefore trib as i c Three classes of salts .

    are p ossible and known to exist ; these are the pr i m ary, se c o n dary
    and t e r ti ary salts O f the alkali salts all three kinds are soluble ;
    .

    of the alkaline ea rth salts only the primary the tertiary and ,

    secondary being insoluble The other phos phates are insolubl e .

    in water but are dissolved by mineral acids .


    O R THO PH O S PHO R I C A C I D . 215

    This latter pro perty is due to the fact that phos phoric acid is
    a w e ak er acid than the strong mineral acids hydrochloric nitric
    '

    , ,

    and sul phuric O n treating an insoluble phos phate with one of


    .

    these acids e g h ydrochloric undissociated molecules of phos


    ,
    . .
    ,

    h o r ic acid are formed in the liquid ; the more hydrochloric acid


    p ,

    the more the association since the hydrochloric acid reduces the ,

    ionization of phos phoric acid H2 PO 4 and H ions thus disa ppear


    and in case enough hydrochloric acid is added the concentratio n


    , ,

    of the H 2 PO 4 ions remainin g will not be great enough together


    with tha t of the metal ions presen t to reach the value of the solu
    b il it y product ; hence all the phos phat e must dissolve
    For the same reason a s a gen er al r u l e sa l ts that are insolu ble
    , ,

    in wa ter wil l on l y diss ol ve in acids that a r e s tr on ger tha n the acid

    of the The only


    salt exce
    .
    p tion to this is the case whe n the value
    of the solubility product of the insoluble salt is very small examples , .

    of which we have seen in certain sul phides



    When heated to 2 1 3 ortho phos phoric acid gives o ff water ,


    forming mainl y the pyro acid but also a little meta acid through -

    out the react ion The pyro acid on the other hand is converted
    .
    -

    b y further heating into the meta acid -


    .

    With silver nitrate ortho phos phates give a y e l l o w pr e c ipi


    tate of silver phos phate A g3 PO 4 soluble i n nitric acid and ammo
    , ,

    nia I n the case of a primary or secondary phos phate the pr e


    .
    ,

    c ipit at io n is not com plete since nitric acid is liberated in the ,

    reaction

    N a2 HPO 4 + 3 A g N 0 3 = A g3 PO 4 + 2 N aN 0 3 + HN 0 3 ,

    o r, expressed in ions

    HPO
    3 Ag A g3 P0 4 + H
    i

    )
    4 C .

    If however an excess of sodium acetate is added the pre c ipi


    , , ,

    "
    t at io n is practically com plete .

    The reason for this is obvious By the addition of acetate t h e .

    acetic anions O 2B 3 0 2 are forced to combine with the H ions fo r


    '

    acetic acid is only very slightly ionized and its ionization is more ,

    over considerably lessened by the excess o i sodi u m acetate ? The


    ,

    result is that in the equilibrium HPO 4 + 3 A g 2 A g3 P04 + H


    '

    the H ions are removed The inverse reaction is then no longer


    .
    216 I N O R GA N I C C HE M I S TR Y 1 46 .

    p ossible ,
    and the direct reaction must t herefore become com
    p l et e ,
    or in other words all the phos phoric ,
    acid is p reci p itate d
    as silver phos phate .

    I t was stated above that the alkali salts of phos phoric aci d
    are soluble in water These aqueous solutions differ markedly
    .

    in reaction The solution of a primary salt KH2 PO 4 is acid


    .
    , , ,

    that of a secondary salt feebly alkaline and that of a tertiary ,

    s alt strongly alkaline The cause of this variation mus t be more


    fully explained .

    The acid reaction of a salt such as K H2PO 4 must be attributed


    to the fact that its anion H2 PO 4 ( analogous to the an i on

    ,

    is ca pable of s plitting u p into the ions H and HPO 4 the former '

    p roducing the acid reaction The feebly alkaline .reaction of a

    salt like K 2HPO 4 is accounted for by hydrolysis Such


    a salt is extensively ionized in dilute solution into 2 K and HPO 4 '

    However while H3 PO 4 is rather highly dissociated (into H and


    ,
    '

    H2PO 4 is but slightly ionized into H and HPO 4


    '


    In this case H2 PO 4 beh aves as a weak acid Hence if there is

    .
    ,

    a large pro p ortion of HPO 4 ions in a solution they will tend ,

    to unite with H ions because the system


    '

    is only in equilibrium when the right hand side pre ponderates -

    The necessary H ions are supplied by the water which is Spli t


    '

    u p to a very slight extent into H and O H



    Bu t when the H
    '

    .

    ions unite with HPO 4 ions we have a surplus of O H ions in


    the solution and the latter takes on an alkaline reaction E ntirely .

    analogous is the ex planation of the strongly alkaline reaction of


    the tertiary phos phates such as K3 PO 4 Their aqueous solutions
    , .

    contain the ions which have a still stronger tendency to


    unite with H ions than the HPO 4 ions The PO 4 ion there

    '

    .
    ,

    fore causes t h e presence o f an e v en larger pro portion of O H i ons


    ,

    ,

    not com pensated by H ions so that the result is a strongly alkaline


    '

    reaction .

    Phosphoric acid is preci pitated from an ammoniacal solution


    by a magnesium salt as white crystalline am m oniu m m agn esiu m
    p h o s pha t e ,
    N H 4 M g O 4 + 6 H 2O
    P A nother very characteristic test
    .

    for phos phoric acid is that in nitric acid solution a nely crystal
    line yellow preci pitate is produced by ammonium m olybdate
    ,
    ,

    es pecially on warming This preci pitate has approximately t h e


    .

    compo sition i e it is an amm o . .


    218 I N O R GA N I C C HE M I S TR Y . 1 48

    it volatilizes without breaking u p into water and p entoxide When .

    b o iled in aqueous solution it goes over into ortho phos phoric acid .

    It is very deliquescent ; use is made of this pro p erty o c casionally .

    M eta phos phoric acid is monobasic corres p onding to the formula ,

    HP0 3 I t s alkal i salts only are soluble in water


    . I n solution .

    the meta acid can be distinguished from the ortho and the pyro
    -

    ac ids by its ability to coagulate albumen and give white pre c ipi
    tates with chlorides of barium or calcium .

    The vap or of this substance at bright red heat consists chiey -

    o f H2 P2 0 6 molecules ( di meta phos phoric acid ) which are a pp arently


    -

    liable to undergo p artial disso ciation and even to lose a small


    quantity of water .

    There are sa lts of v ari o us a ci ds k nown whic h must be regarded as ,

    po l ym ers of m eta p hos p hor ic a ci d e g K s O e potass ium d,


    i m e t.a ph
    . o s ,
    -

    phate ; there e xi st a l so tr i tetra and he x a m eta phos phates i.e sa l ts -

    , .

    of t h e a ci ds H4P40 1 2 and ,

    Hypo ph o sph oric A c id,

    1 49 When sti ck s of phosphor u s are s u spended i n a sol ut i on of


    .

    s odi um a c etate i n su c h a way that onl y cm is e xposed abo ve .

    t h e l e ve l of t h e liqui d and the te m perat u re i s k ept between 6


    and the phosphor u s o xi diz e s sl owly and the difc u l t l y s olu b l e


    a ci d sodium sal t of hypo phosphor ic a ci d N a H2P 0 + 6 H20 soon , 2 2 6

    beg i ns to crystalliz e o u t I t c an be pur i ed by c rystalliz at i on fro m


    .

    a d ilute so lu t i on of acet i c a ci d I f th i s sal t i s d i sso lved i n


    .

    water and barium c hl or i de added a prec i pi tate of barium h ypo ph os ,

    p hate i s for m ed fro m,


    wh ic h an a qu eo u s so lu t i on of the free a ci d c an
    be O bta i ned by m eans O f dilu te s ulphuric a ci d Thi s c an be e v aporated .

    at 3 0 to a s i ru py cons i sten c y wi tho u t de c o m pos i t i on and when left



    ,

    in a va cuum y i e l ds c rysta l s of the a ci d


    ,
    A t an e le v ated te m perat ure .

    and i n the presence of a mi nera l a ci d phosphoro u s and phosphoric a ci ds


    are form ed Thi s behavi or j u st ies the c ons i derat i on of h ypo ph os
    .

    h ric ac i d as a mixed anhydr i de of the two l ast na m ed a ci ds :


    p o
    -

    OH HO OH OH
    O PO H HO P O PO H PO H
    |OH mo 0
    P h os p h o ric Ph o s p h o r o H y p ph p ho os o ric
    ac id . ac i d . a ci d .
    PHO SPH O R O Us A C I D .
    9

    Howe ver , i t has not ye t been poss i bl e to prepare t h e hypophosphoric


    a ci d by m el ting together the other two a ci ds .

    Fro m t h e determinat i on of the m o l ecul ar we i ght of t h e m ethyl ester


    it seem s probabl e that the formul a of t h e a ci d i s H PO an d not H P 0 z 3 4 2

    M e t a ph o s ph o r o u s A c i d, HPO z .

    1 50 Thi s c o m po u n d was d i s c ov ered by V AN DE R


    . ST A D T duri ng the
    s l ow o xi dat i on of phosphi ne u nder reduced press ure 1 3 7)

    PH3 02 = H2 + HP0 2 .

    The s i des of the v esse l be c o m e c o v ered wi th feather like c rystal s of HPO Z -

    These m e lt at a muc h h igher te m perat u re than t h e c rysta ls of phos


    h r o us a ci d and are c onv erted i nto the l atter by the a c t i on of wat er
    p o

    vapor .

    PHO SPHO R O US A C I D , H3 PO 3 .

    1 In 1 4 9 it was mentioned that this acid is formed by t h e


    51 .

    slow oxidation of ph O Sph O I u S in moist air I t is more easily pre



    .

    p ared by d ecom p osing p hos phorus trichloride with water :

    P013 3 H 2 0 = H3 P0 3 3 HC l .

    The hydrochloric acid can be ex pelled by eva porating at 1 80

    and the phosphorous acid crystallizes out on cooling .

    The melting p oint of phos phorous acid is


    -
    I t is a very
    hygrosco pic substance Heating decomp oses it into phospho ric
    a cid and phos phine It has a strong reducing action being itself
    .
    ,

    o xidized t o phosphoric acid The oxygen of the air acts on it very


    .

    slowly I t precipitates the metals from solutions of gold chloride


    .
    ,

    mercuric chloride silver nitrate etc A characteristic reaction is


    , ,
    .

    the reduction of sulphur dioxide to sulphur which takes place at ,

    O rdinary tem peratures when solutions of the two substances are


    ,

    m i xed .

    I n Spite of its thr ee hydrogen atoms phos phorous acid acts as ,

    a dibas ic acid A s we have already observed the ionizatio n of


    .
    ,

    p olybasic acids sometimes a ffects only one If ion at rst the othe r s ,

    being split o ff with increasing di fculty A ccording to O ST WA L D .


    it may be supp osed that ionization beyond 2 11 and HPO 3 is in

    th is case so difcult that the acid seems to be only dibasic T h e .

    p hos p hites are not oxidized by the air but they yield t o the action
    ,
    of
    2 20 IN O R G A N I C C H E M IS TR Y . 1 52


    o xidizing agents the y liberate the prec ious metals fro m

    ; e .
    g .

    their salts as do es also th e aci d itself Heating breaks them u p


    , .

    into hydrogen pyro phos ph ates and phos phide The double , .

    phos phites give p reci p it ates with b aryta or lime water -


    .

    Hypo ph osph oro u s A c i d, E 3 P0 2 .

    1 52 . Sa lt s
    th i s aci d are produc e d
    of b y h e at ing ph o sph or u s w ith c au st ic
    so da ,
    l imew ater or b aryt a w ater -

    3 B a ( O H) 2 + 8 P 6 H 20 3 B a ( H 2P0 2) 2 + 2 PH 3 .

    It c an be set fre e fro m th e e


    ul ph uric acid ; t h e que o u o lut ion s sa lt s by s a s s

    i c o n c e trat e d at 80 9 0 an d the n c oo l e d tro n gl y w he re u pon t h e


    cid

    s n s , a

    cry t alliz e out M elt i g p i nt


    s s O n b i g h e at d at 1 3 0 1 4 0
    . n -
    o , e n e

    t he cid plit u p i n to ph phorou ci d a d ph o ph i n e ; t a ome w h at


    a s s os s a n s a s

    h igh e r t e mp erat ure t h e l atte r a ci d yi e l d ph o ph i n e an d ph o phoric ci d s s s a .

    Th e e qu at i on are : s

    Hypo ph o sph oro u s a ci d is a ve ry s trong re duci n g ag e n t G ol d s ilver -


    .
    ,

    an d m er cu ry ar e pre ci p i t ated fro m s o l ut i o ns o f th e i r s al ts b y t h e f ee a ci d r

    as w e ll as it s s alts Sulph ur d io xi de is re duc e d to s ulph ur at ord i n ary t e m


    .

    t u e s I n t h e s e re a c t i ons t h e a ci d i t s e l f is c o n v ert e d i n t o p h o s p h or ic
    p e r a r .

    a ci d I t is di st i n gui she d fro m ph o s ph o rou s a ci d b y it s b e h avi o r t o w ar ds


    .

    coppe r s ulph ate s olut io n ; w h e n it is w arme d w ith t h e l atte r a re d pr e c ipi ,

    t ate o f c oppe r h ydri de C q is forme d Hypopho s ph oro u s a ci d is mono


    , g, .

    b as ic .

    C om po un ds of Ph o sph or us an d Su ph url .

    53 1 i o u s c o.m pVar
    o u n d f t h i o t a e k o w n ; a l l of t h em s e o s s r r n ar

    o b tai n e d b y w armi g t h e t w o e l eme t t g eth er A s t h e r c ti n in n s o . ea o s

    very vig u w ith y llow ph o ph oru t h e e d f m i u u lly mpl y d


    or o s e s s, r or s s a e o e .

    Th e c ompo u d P 8 w h ic h i f e vic in o g
    n 2 ic ch emi t y i ye ll w
    5,
    s o s r e r an s r ,
    s a o

    cry t alli e u b t c m lti g at 2 7 4 27 6


    s n s s an d b ili g at
    e, e O be i g
    n
    0 -
    o
    an o n n n

    w a m d w ith w t r i t y i l d p h p h r ic
    r e a e ci d d ulph urette d h ydr g e s os o a an s o en .

    P S n it e w ith 3 m l e c l
    2 5 u
    s f K S t f rm lp h ph Sph t K PS i e a
    o u es o z o o a su O O a e, 3 4, . .

    p h p h
    os t e w h e o
    a x yg i e p l c e dosb y l p h u r en s r a su .

    S ver l c mp u d c t i i g
    e a o h lo g i add it i n t ph ph u a d
    o n s on a n n a a en n o o os or s n

    s ul ph u k w r g FSC l
    ar e Th i p h p h
    no n, e l p h h l id
    . . b p 3 . s os o ru s su oc or e c an e re

    p ar e d b y tre a t i n g ph o ph oru s p e n t chl ori d w ith h ydr g e s ul p h i d a m et h o d a e o n s e,


    2 22 IN O R GA N I C C HEM I S TR Y 1 55

    A rseno pyrite yields arse n ic on mere heating the latter sublim ing , .

    A rsenolite is reduced with carbon

    2A 8 2 0 3 60 AS 6 00 .

    Physica l Pr oper ties an d A l l otr opic C on dition s


    The conditi on
    in which arsenic usually o ccurs is the crystalline I t then has a .

    steel gray color and a s pecic gravity of


    -
    at 1 4 and is a goo d

    conductor of electricity It sublimes under ordinary pressur e


    .

    without melting ; under increased pressure however it melts at , ,

    By sublima t ion in a curren t of hydrogen a second crystal


    l iz e d form can be obtained together with a black modication ,

    which according to R E T G E R s is also crystallized A n amorpho u s .

    modication results from the de com p osition of hydrogen arseni de


    by heat the arsenic a ppearing as a dark brown dep osit on the si des
    ,

    of the glass Finally there is a yellow modication which is formed


    .

    when arsenic va p or is c ondensed in a dark ro o m b y liquid air .

    This yellow arsenic is very sensitive to light ; even at the tem


    r e of liquid air
    at which it is stable in the dark
    p e r a t u

    it is co nverted into the black modicatio n by the light of a


    Welsb ach burner It is a remarkable fact that a solu t ion of t h e
    .

    yellow modication in chlorine is much more stable towar d


    light and heat th an is the pure substance Such solutions are .

    obtained in c oncentrations u p to wh e n they are coole d


    y ellow arsenic crystalliz es out The relatio n between y ellow and
    .

    black arsenic is very analogous to that between yellow and


    red phos phorus exce pt that in the case of arsenic the yellow
    ,

    form is much less stable A t an elevate d tem p erature .

    all the mo difications p ass over int o the ordinary crystallin e


    form .

    Va p or D en s ity .

    The lemon yellow v a por of arsenic has a
    -

    density of ( air = 1 at about


    ) which m akes the m olecular
    A t 1 6 00 1 7 00 the va por density is less by half

    weight 2 9 3 8 .

    ,

    being Since the atomic weight of arsenic is 7 5 its m olecule ,

    therefore contains four atoms at about 860 and two at

    C h em ica l Pr oper ties A rsenic is not affected by dry air at


    o rdinary tem p erat u res ; in m oist air it becomes covered with a
    coating of oxide A t 1 80 it burns with a bluish flame to the
    .

    oxide A s 4O G giving off a peculiar garlic like odor A t an elevated


    ,
    -
    .

    H Y DR O GE N A R S E N I DE .

    tem perature it combines with many elements dir ectly ; it unite s


    with c hl orine without the aid of heat producing scintill ations , .

    HY DR O G EN AR SENI DE . AR SIN E , A sHa .

    1 56 . Direct synthesis from the elements is not p ossible with


    this com pound I t is formed when almost any arsenic com pound
    .

    comes in contact with nascent hydrogen ( z i11 c + s u l ph u ric acid ) .

    When thus pre pared it contains considerable hydrogen however ,


    .

    Pure arsine is obtained by treating zin c arsenide or s odium arsenide


    with dilute sulphuric acid :

    A s ga 3 H2 80 4 = 2ASH3 3 ZII SO 4 .

    Phys ica l Pr op ert ies


    Hydrogen arsenide is a gas ; it l iq u e e s
    at but does n o t solidify as low as Sp g = 3 8 9 . . .

    I t must be handled with great care as it is very poison ,

    ous F ortunately its presence can be easily detected by its peculiar


    .
    ,

    disagreeable odor .

    C h em ica l Properties A m ine ca n be decom posed into its ele


    ments by heat If the gas is p assed through a hot glass tube
    .
    ,

    arsenic is de posited on the sides in the form of a metallic m irror .

    Induction s parks also decom pose it B y the latter means it can .

    be shown that the resulting volume of hydrogen is 1 5 times as


    large as that of the gas itself in accord with the formula A n
    ,
    .

    It is an endothermic compound ,

    As + 3H As H3 C al ,

    and has been made to explode by fulmin atin g mercury


    Hydrogen arsenide burns with a pale ame yield ing water and ,

    arsenious oxide A S2 0 3 if sufcien t air is present ; if such is not the


    , ,

    case or if the ame is cooled arse nic is de posited O n heating


    , ,
    .

    otassium or sodium in the gas an arsenide A s K 3 or A s N ag is


    p , , ,

    formed Hydrogen arsenide preci pitates the yellow com pound


    .

    AsA g3 3 A gN 0 3 from a very concentrated solution of silver ni trate :


    -

    A s H3 6 Ag N O 3 A s A g3 3 A g N O g .

    This is decom posed by the addition of water into arsenious aci d


    nitric acid and meta l lic s ilver the latter being de posited
    ,
    .
    4 I N O R GA N I C C HE M I S TR Y .
    l 1 56

    Thi s react i on is called G u T ZE I T s tes t I t i s u sua lly c arr i ed o u t in the



    .

    fo llowi ng way : A drop of 50% A gN O 3 so lu t i on i s pl a ced on a pi e c e of


    ,

    l te r paper and the m o ist spot i s he l d over a test t ube c ontai ning so me -

    zi n c d ilu te s ul ph uric a ci d and the s ubstan ce to be tested for arsenic


    , .

    A plug of c otton i s inserted near the t o p to prote c t the paper fro m be i ng


    Spattered by t h e e fferv es ci ng so lu t i on I f arsen ic i s present the spot .
    ,

    be c o m es ye ll ow and t urns b l a ck when m o i stened with water


    , .

    A r in e If
    f
    C om pos ition arsine is passed over hot co pper
    o s .

    o xide wa t er and co pper arsenide are formed The ratio of


    ,
    .

    hydrogen to arsenic in ars ine is determined from this reac tion .

    For 1 p art (by weight ) of hydrogen parts of arsenic are


    obtained The molecular weight of the com pound as found fr o m
    .
    ,

    the s pecic gr avity (see above) is since the atomic weight o f ,

    arsenic is 7 5 the formula of arsine must b e A n


    '

    , .

    De t e c t ion of A rsen ic .

    1 The m aj ority of arsenic c o m po u nds are very poisonous Severa l


    57 . .

    of the m are of pra c t ica l u se and hen c e are on the m arket e g wh i te ,


    . .

    arsen ic O 3 (rat po i son)


    ,
    orpim ent A szS3 ; Sc hwe infurt green or , ,

    c o pper arseni e Poi son i ngs wi th these s ubstan ces happen o cc as i on


    .

    a lly So m e arsenic c o m po u nds be c a use of the i r pretty green c o l or


    .
    , ,

    are st ill u sed tho ug h muc h less than form erly i n dye ing tapestr i es
    , , ,

    p ort i eres a n d t h e like


    ,
    R oo m s i n w h ic h these are hung u s u ally con
    .

    ta i n part icles of arsenic a l m atter whic h are i nj uri o u s to the health , .

    F urther a c erta i n s pe cies of m o uld pen icil liu m brevicau l e whic h i s


    , , ,

    som et im es fo und i n s uch ta pestri es has t h e power of generat ing v o l atile


    ,

    and v ery po i sono u s arsenic c o m po unds Th e c hemi st i s therefore qui te .

    fre quent ly c all ed u pon to analyz e a given sam ple (of dyed m ater i al s
    or the like or the c ontents of a sto m a ch) for arsenic Fo r th i s pu r
    , .

    p ose a m ethod has been de vi sed wh ic h enab l es h im to dete c t w i th c er


    ta i nty e xtre m e ly sm a ll a m o unts of arsenic It i nv o lves t h e fo ll owing .

    o perat i ons : The or ganic s ubstan c e i n qu est i on i s at fi rst d i s i ntegrated


    as we ll as poss i ble u su a lly by di gest i on Wi th hydro c hl oric a ci d on the
    ,

    water bath a li tt le pota ss ium c h l orate be i ng added fro m t im e to t im e


    , .

    Thu s the arsen ic c o m po u nd i s o xi diz ed to arsen ic a ci d Wh en the .

    chl or i ne has been e xpelled by warming and the liqui d has been ltered ,

    hydrogen s ul phi de i s passed i n for so m e t im e at a te m perat ure of abo u t


    80 to pre ci pi tate the arsen ic as s ul ph i de Th e s ul ph i de i s then d i s

    .

    so lv ed i n n i tric a ci d ( i n c a se t h e pre sen c e of ant im ony i s s u spe c ted i t


    must rs t be rem o ved) ; thi s solu t i on i s ev aporated to dryness to ge t
    r i d of t h e ex c ess of a ci d t h e dry res i du e i s di sso lved i n w ater and thi s
    , ,
    6 IN O R GA N IC C HE M I S TR Y .
    l 1 57

    the liq ui d to be tested for arseni c The least tra c e of the latter reveals .

    i tse lf by a characteri st ic garlic li ke odor caused by the evo lut i on of -

    arsenica l gases .

    C om po un ds of Ar s enic with the Hal o gen s .

    1 58 Three arseni c halogen c om p ounds of the ty p e A s X5 are


    .
    -

    known ; vi z the p entachloride A sC l 5 the p enta io dide A s I 5


    .
    , , ,
    -

    , ,

    and the p e n t a u o ride A s F5 A side fro m these only com p ounds


    ,
    .

    of the ty p e A s X3 are known .

    A r s e n i c t ri c h l o ri de , A SC l g can be obtained by direct synthesis


    ,

    or by the action of hydrochloric acid on white arsenic The latter .

    way is analogous to the formation of metal chlorides from the oxid e


    and hydrochloric acid This com pound is a colorless oily liquid
    .


    having a s pecic gravity of )
    ( dZ I t freezes at 1 8 and

    .

    bo ils at I t is extremely p oisonous When exposed to t h e .

    air it throws o ff dense white fumes With a little water it form s .

    an oxychloride A s( O H) g C l ; with much water hydrochloric acid


    ,

    and arsenious oxide I n this latter system a rise of tem perature


    .

    results in partial r e formation ofthe trichloride which is volatil e


    -

    with the water va por T h e fOll o w m g equilibrium seems to ex1st :


    '

    A8 20 3 GHC l Q A SC l g 3 H2 0 .

    O xyg e n C o m po u n ds of A rs enic .

    Two such com pounds are known : A SQ O g , ars en iou s oxide, an d


    AszO 5 , a r s en ic ox ide .

    AR SENI O US O XI DE, A s20 3 .

    1 59 . A rseniousanhydride ( commonly called arse nic or



    white arsenic ) is found in nature I t is formed by the com .

    b u s t io n of arsenic in air or oxygen and by the oxidation of arsenic


    with dilute nitric acid I t is manufactured commercially by .

    roasting arsenical ores ; the oxide volatilizes and is con densed in


    brick walled chambers where it collects as a white powder
    -

    ( arsenic meal I t is rened. by sublimation from iron cylinders .

    Phy ical
    s P r op er ti e s A rsenious oxide is an odorless solid tha t ,

    d oes not melt under ordinary pressure but sublimes Under , .

    higher pressure it is possibl e to melt it A t 800 its vap or density .



    1 59 3 A R SE N I O US O XI DE . 227

    is 1 98 which makes the molecular fo rmula A S4O G .

    A bove this tem perature dissociation begins and at 1 800 the va por

    '

    density corresponds to the formula A s 2 O g By the ebulliosco pic .

    metho d ( elevation of the boiling point) the molecular formula has


    -

    been found to b e AS AO G at 2 05 also ( in bo iling nitrobenzene)



    .

    Var iou s M odication s A rsenious oxide is known in a vitreous


    .

    form as well as in crystals of the regular and mon o c linic systems .

    The v i treous m o di c at i on i s produ c ed when the c o m pound i s s ub


    I im ed or heated to the s ub lim at i on po i nt Sp g
    -
    . A fter st and
    . .

    i ng for so me t ime at ord inary te m perat ures thi s for m be c om es w hi te


    ,

    like por ce la i n be c ause of c onvers i on i nto i som etric crystals Th e l atter .

    for m i s better obta i ned by di sso lvi ng the vi treo u s m odic at i on i n water
    or hydro c hl or ic a ci d and lett i ng i t c rysta lliz e out Du ri ng t h e c rystal .

    l iz at io n the s trang e pheno m enon of brig ht lumi nes c en c e is obser v ed ,

    which is c au sed by the brea ki ng of t h e crys t al s Thi s pheno m enon .


    ,

    whi c h i s al s o n ot ic ed in other c rystalliz at i ons is c all ed tribol u m i n es


    ,

    c en c e . T h e tran sform at i on of t h e a m orpho u s i nto t h e re gul a r v ari ety


    i s a cc om pan ied by the e v olu t i on of heat Th e m ono cli n ic
    form is obtai ned by c ond uc ti ng the c rys t allizat i on abo ve 200 ins te ad

    of at ord i nary tem perat u res I f the l owe r hal f of a sea l ed gl ass t ube
    .

    c ontai ning arsen i o u s oxide be heated above i t will b e fo und after


    c ooling that t h e l ower heated part c ont ai ns vi treo us t h e mi ddl e m ono ,

    cli ni c and the upper o c tahedral arsen i o u s o xi de


    , ,
    .

    Si nce the transfor m at i on of a m orpho u s i nto c rysta lliz ed arsen i o u s o xi de


    takes pl a c e e v en at ordinary te m perat ures (rapi dly at and wi th
    the evo lu t i on of heat the octahedral for m i s to be re garded as t h e stable
    ,

    one at ord i nary te m perat ures ; the glassy form i s only ab le to e xi st


    at these te m perat u res be c a u se the ve l o ci ty of transform at i on i s then
    ,

    very s m all A cc ordi ng to the abo ve i f o c tahedra l arsen i o u s o xi de i s


    .
    ,

    grad u ally warm ed we have rst a transform at i on i nto m ono clinic and
    ,

    then another i nto a m orpho u s arseni o u s o xi de Th e trans i t i on t e m .

    e rat u re s have not yet been deter mi ned


    p .

    C hem ica l Pr operties A rsenious


    oxide is easily reduced to
    arsenic ; for exam ple by heating with charcoal or nascent hydrogen
    ,
    .

    It is also easily o xidized to arsenic oxide and is therefore useful as


    a reducingagent Th is oxidation can be brought about by chlorine
    .
    ,

    bromine ( bromine water) iodine solution potassium perman


    -

    , ,

    g an at e strong nitric acid etc I t is slightly soluble in water ; the


    , ,
    .

    solution h as a salty metallic taste and a weak acid reaction I n .

    acids it dissolves much more easily because it acts towards them ,

    as a basic oxide I t was stated above


    . 1 58) that a solution of
    22 8 I N O R GA N I C C HEM I S TR Y . 1 59

    the oxide in hy d rochloric acid gives off arsenious ct ride White .

    arsenic is a rank p oison ; freshl y precipitated ferric h y dr oxide


    serves as an an t ido t ei
    AR SENI O O XI DE , (A SZO Q x .

    1 This comp ound cannot be prep ared like the


    60 .

    ing phos phorus com pound by burning arsenic in the


    oxidation goes no farther than to arsenio u s oxide .

    oxide can only be pre pared by heating arsenic acid

    2 H3 As O 4 3 Hg O As zO 5 .

    This arsenic anhydride is a white glassy substance that dis ,

    solves in water slowly going over into arsenic acid By heating


    ,
    .

    with carbon it is easily reduced to arsenic A t an elevated tem .

    e at e it breaks u into oxygen and arsenious oxide I t s m olec


    p r u r p .

    ular weight is no t known ; the formula A s zO 5 is siIn pl y empir ical .

    O xy ac i ds of A r sen i c .

    Two of these are known : a rs en iou s a cid E g A sO 3 ( onl y in ,

    aqueous solution and salts ) and ar s en ic acid H3 As O 4 , .

    A R SEN I O US A C I D , H3 A sO 3 .

    1 61
    This acid exists in the aqueous solution of the anhydride
    . .

    It still rema ins to be discovered however which hydrate H 3 AS O 3


    , , , ,

    HA s or some other is present ,O n eva poration the anhydride


    .

    and not the acid se parates out This acid forms three classes of
    .

    salts according as one two or three of its hydrogen atoms are


    , , ,

    re placed by metals ; it is therefore tribasic C ertain salts are



    .

    known which are derived from a m eta ars en iou s a cid HA s -

    ,
    .

    The salts of the alkalies are soluble in water ; those of the other
    metals are not but dissolve easily in acids however A neutral
    , ,
    .

    arsenite solution gives a yellow precipitate of silver ar seni te ,

    A g3 A s O g with sil ver nitrate


    ,
    .

    The so lut i on of the free a ci d is eas il y ox i diz ed to arsenic acid by


    iodine so lu t i on
    H3 As O 3 I2 11 2 0 H3 As O 4 2HI .

    Suc h a so l ut i on can therefore al so be e m pl oyed for the titration of iodine


    93 )
    23 0 I N O R GA N I C C HE M I S TR Y . 1 63

    AR SENI O TR I SUL PHI DE, A szsg .

    Ar s e nic is pr eci pitatedfrom the acid s oluti o n of a rs e nious


    o xide by sul phuretted hydrogen as sul phide ; in this r es pect t oo

    it behaves as a heavy metal I n the above r eaction arsenic tri


    .

    sul phide is de p osited as an amorphous yellow pow de r A pure .

    solution of arsenious acid gives n o preci pitate with sulphurette d .

    hydrogen but sim ply a yellow liquid


    ,
    A rs e m c trisulphide
    o ccurs in nature as or pim en t having a laminate d c rystal
    line structure ; it owes its name to its beautiful golden lustre .

    By fusing articial arsenic trisulphide a product is obtained wh ich


    is very similar t o the n atural orpiment but has a lower speci c ,

    gravity instead of C ommercially t h e trisulphide is


    re
    p p ared by fus ing white arsenic with sul phur ; the p roduct still
    contains the oxide h owever and is therefore poisonous A rse ni c
    , ,
    .

    trisulphide is ins oluble in water and in acids .

    AR SENI O PEN TA SUL PHI DE, As,s, .

    A fter sul phuretted hydrogen has been led into a warm a c idu
    lated solution of arsenic acid for some time arsenic is pre c ipi ,

    t at e d as an amor phous yellow p owder of the co mp osition A s 2 S5 .

    The latter is also obtained by fusing arsenic trisul phide with the
    required amount of sul phur I n the absence of air it can be
    .

    sublimed without decomp osition I t is insoluble in water and in


    .

    acids .

    SUL PHO SA L T S O F A R SEN I C


    -
    .

    1 64
    The trisul phide and the p entasul phide of arsenic dissolv e
    .

    easily in alkali sulphides forming salts of su l pho acids :


    ,
    -

    A s zs3 i
    3 K2 8 2 K3 A S S3 ;
    Po t . sul ph
    ar se n i t e .

    A 8 2 S5 3 K 2S 2 K 3 A S S4 .

    Po t . su l ph
    ar se n a t e .

    The formation of these sul pho salts can be regarded as analo-

    go us t o that of an oxy salt from a basic oxide and an acid anh v


    -

    dride , e .
    g
    BaO + SO g = Ba SO 4 .
    A N TI M O N Y . 23 1

    The tris ul phi d e an d ntasulphide are t herefo re t o be c on


    the pe

    s ide re d as su l pho a n hydrides of t hose sul ph o a cids


    - -
    .

    The s u l ph ars e n at e s can also be obtained f rom arse ni c t ri


    s ulphid e wi t h t h e aid o f an alkali polysulphide :

    A S2 8 3 K 2S3 2 K A8 8 3 .

    Po t . s ul ph o
    m et a -
    a rs e n at e .

    This reacti o n can b e explained b y supposing th at t h e arse nic


    trisulp hide is conve rted int o the pentasulphide b y the excess
    o f sulp hur j us t as the t rioxide is oxidized to the pentoxide
    ,
    .

    They are als o produced b y treating an arsenat e with hy dro


    g e n s ul phid e

    Th e s u l ph ars e n at e s s u lph ars e nit e s


    of t h e al kalies dis
    an d

    s olve e as ily in wate r an d can b e obtained in the c rystalline fo rm

    from the solution ; those o f t h e o the r metals are insoluble Th e .

    free sul pho acids are unknown O n the addition o f an acid t o


    -
    .

    the s olution of a sulpho salt t h e libe rated sulpho acid b reak s up


    -

    ,
    -

    int o hyd r ogen s ulphide an d a rse ni c tri or pentas ul phide .

    AN TIM O NY .

    1 65 An t im o ny
    . ccurs in natur e in stibnit e Sb 2S3 as w ell as
    o , ,

    in many less c ommon mi nerals Sti b ni t e w as known to t h e


    .

    anci e nts . In Japan it is foun d in mag nicent large crystals .

    A nt imony w as frequently em ployed by the alchemis ts BA S I L I U S .

    V A L EN T I NU S in the latter p art of the fteenth c entury described


    its extraction from stibnite in a monogra ph entitled The tri

    u m ph al c ar of A ntimonium .

    The element is at present ob tained from s tibnit e b y t w o


    p ro cesses I n
    . one the mineral is roasted being thus transformed ,

    into antim onious oxide This o xide is then reduce d wi t h char co al


    .

    t o m et alli c antim ony :

    1 .

    11 . 2s o 3 + 3 c = 4 Sb + 3 C O z .

    Th e o th e r method is t o fuse the mineral with iro n




    S3 l 3 Fe = 2 8b 3 Fe S
    s .
    32 I N O R GA N I C C HE M I S TR Y . 1 65

    The crud e antimony thus obtained usually still con t ains arsenic ,

    lead sulphur e t c I t can be rened by fusing with a li t t le sal t =


    , , .

    p etre the,
    im p urities being oxidized .

    P y ica
    h l P A ntimony is silvery white an d has a
    s r op r ti s
    e e -

    high metallic lustre and a laminat e crystalline structure (rhombo -

    h e dral ) ; as a result of the latter it is very brittle and can be easily


    p ulveri z ed S p .
    g
    = 6 7 1 68 6
    . M
    . elt ing p oint boiling
    .

    '
    -

    p oint ,
    M E N s C H I N G and V M E Y E R s u c c e e de d in d e t e r m in .

    ing the va por density at i e slight l y below the boiling po int. .


    -

    and found that the molecule unlike that of phosphorus or arseni c , ,

    consists of less than four atoms .

    L ik e arsen ic antim ony has a bl a ck and a ye ll ow m od ic at i on ; t he


    l atter i s obtained by passin g air i nto liqui d st ibi ne c oo led to It ,

    is e ven l ess stabl e than t h e yell ow arsen ic .


    C hem ica l Pr oper ties A t ordinary tem p eratures the element is
    not affected by the air ; when heated it burns with a bluish white ,
    -

    ame to the trioxide I t combines with the halogens directly


    .
    ,

    p roducing scint illat io ns I t is dissolved by hydrochlori c

    acid although very slowly with the evolution of hydrogen thu s


    , , ,

    asserting its metallic character A qua regia dissolves it readily . .

    U s An timony is a constituent of various alloys T h e most


    '

    s e .
    .


    irn por t an t of these is typ e metal from which printer s ty pe is -

    made I t s a pproximate com postion is lead


    . antimony
    and tin
    HY DR O G EN AN TIM O NI DE , STIBIN E, SbH3 .

    1 66 Stibine
    is formed when nascen t hydrogen acts o n a solu
    .

    ble antimony com pound I t is bes t pre pared by treating an allo y


    .

    of one part of antimony and two parts of magnesium with dilut e


    hydrochloric acid The product consists princi pally of hydrogen
    .
    ,

    but contains 1 0 1 4 % Sb H3
    I f this gas mixture is p assed through
    .

    a Utube and the whole is plunged in liquid air stibine con ,

    denses to a White solid mass that soon melts after the tube is ,

    removed from the liquid air It va porizes to a relatively stabl e


    .

    gas The least trace of oxygen however causes some antimony


    .
    , ,

    to be de posited .

    I f an electric s park is p assed through stibine gas it ex plodes ,

    antimony is set free and the volume of hydrogen liberated is foun d


    to be 1 5 times that of the stibine which is in accord w ith t h e ,

    formula Sb H3 I t is also decomposed rapidly by heating t h e


    .

    containing vessel above


    34 IN O R GA N I C C H E M I S TR Y . 1 67 A

    d ecom poses it forming difc u l t l y soluble o x y c h l o r ides


    ,
    The .

    com position of the precipitate de pends on the amount and the


    tem perature of the water used in the decom p osition There is .

    evidence of the existence of the com pounds Sb O C l and


    Sb 4 O 5 C l z = 2 Sb O C l s o g ) b 0 l) h of which crystalli z e
    -

    , ,
    -

    The pr e .

    c ipit at e d o x y c h l o r ide s on being re eatedly boiled with water e v e n t u


    p
    ally lose all their chlorine and go over into the trioxide Sh 2 o 3 ,
    .

    Powder of A lgar oth once used in medicine is obtained by the


    , ,

    decom p osition of antimony trichloride with water and has nearly


    the same formula as the second of the abovementioned oxy
    chlorides .

    An tim o n y pe n t ac hl o ri de , Sb C l 5 is pre pared by heating anti,

    mony in a current of chlorine or treating fused trichloride with



    chlorine ; I t is a yellow fuming ill smelling liquid which crys
    , , ,

    t all iz es at When heated it d issociates into the trichloride


    and chlorine It unites with water forming SbC l 5 HzO and
    .
    ,
    -

    SbC l 5 4 HzO
    o
    Hot water decom poses it into h ydgpc h l o r ic an d
    .

    p yroantimonic acids .

    O xygen Cem poun ds of A n tim on y .

    1 68 .Thr ee are known : a n tim on y trioxide Sb 20 3 antim on y , ,

    t etr oxide s O 4 and a n tim on y pen tgf


    , ,
    r ide Sb 2 0 5 ,
    .

    A n tim o n y t rio x i de o ccurs as a mineral s enarm on tit e.


    I t can , .

    be obtained by bur ning antimony in the air as well as by the ,

    oxidation of antimony with dilute nitric acid I t is dimorph ic .


    ,

    o ccurri ng in both regular and rhombic crystals .


    I t is ya light yellow crystalline p owder alm ost insoluble in ,

    water I t volatilizes at
    . the va p or density at this tem
    p e r a t u re corres p onds to the formula Sb 4 0 6 I t is insoluble in .

    sulphuric and nitric acids but easily soluble in hydrochloric and


    tartaric acids and in alkalies O nbeing heated in the air it turns .

    to the tetroxide .

    The corresp onding hydroxide is Sb ( O H) 3 This hydrate sepa .

    rates o u t when tartar emetic ( see below ) is decom p osed with


    d ilute sul phuric acid I t gives u p one molecule of water readily
    .

    and passes over into the hydroxide Sb O O H m eta a n tim on iou s a cid ,
    -
    .

    The latter is more easily obtained by treating a solution of t h e


    trichloride with soda s olution :
    A N TI M O N Y PE N TO X I D E A N D A N TI M O N I C A C ID . 23 5

    2 Sb C l 3 3 N a 2 00 3 HgO 2 Sb O O H GN a C I 3 00 2 .

    It a ppears as a white precip itate which is c onverted into an ,

    t im o n ic oxide by b oiling with water This meta antimonious .

    acid is dissolved b y alkalies forming salts of the acid O n e of


    -

    , .

    them which has been obtained crystallized is the sodium meta


    antimonite N aSb O z + 3 HzO The latter is d if c u l t l y soluble in
    , .

    water and decomp oses o n concentration of its solution


    , .

    O n the other hand antimony hydroxide dis p lays basic pro per
    ,

    ties b y uniting with acids to form salts There are salts known of .

    Sb ( O H) 3 as well as of Sb O O H
    , E xam ples of the form er kind
    -
    .

    are the crystallized a n tim on y s u l pha te Sb 2 ( SO 4 ) 3 and the n itra te , , ,

    Sb (N O g) 3 In analogy with other trivalent metals double salts


    .

    are known e g KSb ( SO 4) 2 A s to the salts derived from Sb O O H


    ,
    . . .
    o

    we may look up on the group Sb O as taking the place of a uni


    valent m etal Thus Sb O O H may be com pared with K O H For
    .
    -
    .

    this reason the group ( Sb O ) has been given the n ame an tim on yl ;
    o n e of its salts is a n tim on yl s u l phat e ( Sb O ) 2 SO 4 The m ost ,
    .

    familiar a n timonyl c o m p ound is tar ta r em etic p otassium antimonyl ,

    ta rtrate,

    which is em ploye d in medicine . Se e O R G C H E M . . 1 92 .

    A N TI M O NY PEN TO XI DE A N D A N TIM O N I C A C I D
    '

    An tim o n i c i d, Hn O 4 is obtained by warming antimony


    ac ,

    with concentrated nitri c acid and als o by decom posing the penta
    chloride with water It is a white p owder almost inso l uble in
    .
    ,

    water and nit ric acid ; nevertheless when moist it turns litmus , ,

    a
    p p er red O n
    . heating salt p etre w ith p owdered anti m ony the
    p otassium sal t of m e ta a n t im o n ic -
    acid K Sb O g is formed in an, ,

    ex plosive reaction When this is boiled with wate r it dissolves


    .
    ,

    producing m o n o p o ta ss i u m o r t h oa n tim o niat e K H s O 4 ; on fusing ,

    with potash pota s siu m pyr oa ntim on ia te K 4s O 7 is formed w hich , , ,

    dissolves in wate r giving 2KO H and K 2H28b 20 7 4 6HQ O In t h e


    , .

    case of antim ony as in that of phos phorus we meet with three kinds
    , ,

    of acids belonging t o t h e h ighest st age of oxidation : their formul ae


    corres p ond t o those of t h e analogous phospho rus c ompounds .
    23 6 IN O R G A N I C C H E M IS TR Y .
    1 68

    An tim on y pen to xi de , s O 5 (molecula r weigh t unknown) can ,

    b e obtaine d by heating antimonic acid at I t is a yellow


    amorphous powde r soluble in hydrochloric acid If heated
    , .

    s tron gly it gives u p


    p a r t of its o x yge n an d g oe s o ve r int o an ti
    m o n y t e t r o xide , s O 4 a white p owde r that tu rns yellow on
    ,

    heating but resumes its original c olo r on cooling This tet ro xide .

    c an b e r egarded as a n tim on yl m eta a n tim on ia t e SbO 3 Sb O - -


    .
    ,

    Su l ph u r C o m po u n ds of An ti m o n y .

    1 69 . t ri s u l ph i de , Sb 2S3 is found in natu re


    An tim o n y ,

    I t can be made by leading hydrogen sul phide into a hydrochlori c


    acid solution of the t ri chloride fr om which it is de pos ited as an
    ,

    amorphous red powde r I t can b e m elte d; o n c o oling it c rystal


    .

    l izes and takes on the a ppea r ance of stibnite .

    An tim o n y pen t a s u lphi de , Sb 2 S5 is preci pitate d when hydrogen


    ,

    s ul phide is passed into the acidied solution of antimonic acid .

    It is more easily obtained by the decom position of sodi um sul ph


    a ntimoniate with dilute s ul phuric acid It forms an amorphous .

    o range red p owde r which Splits u p in t o sul phur and the trisul phide
    -

    o n being strongly heated I t is insoluble in dilute acids ; boiling


    .

    h ot concentrated hydro chloric acid dissolves it forming antimony ,

    t richloride hydrogen sul phide and sul phur


    ,
    I n aque ous solutions .

    o f alkalies and their sul phides it dissolves easily with the form ation

    o f s u l ph an t im o n iat e s M 3 Sb S4 ,
    The best kno w n of these is s odiu m
    N a3 Sb S4 + 9HzO

    s u l pha n tim on ia t e , SC H L I PPE S It can
    b e obtained b y boiling antimony trisulphide with sul phur and
    caustic soda solutio n I t crystallizes in large colorless tetrahedrons
    .
    ,

    is easily soluble in water ( 1 part by weight in parts water at


    and reacts alkaline I t is decom posed by acids de positing
    .
    ,

    p entasul p hide ; even carbonic acid causes this hence the crystals ,

    b ecome cove red with a yellowish red coating of pentasulphide afte r-

    having stood some time in the ai r The fre e sulphantimoni c aci d .

    is not known .

    BI SM UTH .

    1 This elemen t b elongs undoubtedly among the metals s o


    70 .
    ,

    far as its physical character is concerned ; its chemical pro pertie s


    also class it with them in almost every res p ect inasmuch as it s ,

    o xides are mainly b asic in their behavior .


    O xygen C o m po u n ds .

    1 7 2 . Thre e oxides are known : B iO , 13 12 0 3 , and Bl 0 2 .

    i
    B s m ut h ou s o xid BiO is obta i ned by add ing an a lk ali ne stannou
    e, ,
    s

    chl ori de so lu t i on to a so lu ti on of bi s mu th chl or i de I t i s de pos i ted .

    as a dark brown pre ci pi tate of B iO When heated i n the a i r i t s m o l ders


    -
    .

    like t inder It i s do ubtf ul w hether thi s pre ci pi tate i s a hom o geneo u s


    .

    s ubstan c e or a m i xt ure of Bi O wi th ne ly d ivi ded b i s mu th z 3


    .

    B i sm uth t ri oxi de , Bl 2 0 3 is the mos t familiar oxide of this ele ,

    m ent I t has strictly basic pro perties


    . In order to pre pare it we .

    can heat the nitrate or carbo n ate or we can preci pitate the hydroxide
    from the solution of a bismuth salt by means of a base and hea t
    the pre cipitate I f a boiling solution of a b ismuth salt is treate d
    .

    with caustic potash the trio xid e se parates out in glistening needles
    ,

    of microsco pic d ime nsions L ike the corres ponding oxides of .

    arsenic an d antimony it is dimo rphic ,


    .

    B i sm u t h i xi d
    d o e, BiO ,, has been li ttl e studi ed ; i t i s a reddish yell ow -

    p owder .

    B i sm u t h pe n t oxi de Bi O appears as a reddish brown powder whic h


    , z s,
    -

    , .

    i s v ery unstabl e and ev o lves o x ygen on heating as i t also does when ,

    warm ed w i th s ulphu ric a ci d Hydro c hl oric a ci d does not c onv ert i t .

    i nto the c orresponding penta c hl ori de BiC l b u t produ c es the tric hl ori de , s,

    BiC l an d free c hl or i ne
    , .

    Hy dr oxi de s an d Salt s .

    1 73 . B i sm u th h y dr oxi de , Bi( O H) 3 , is
    obtained by p reci pitating
    a bismuth sal t with an alkali I t is an amor phous white powder .
    ,

    insoluble in potassium hydroxide or ammonia A t 1 00 it goes .


    over into the com pound BiO O H with the loss of a molecule of -

    water B oth of these hydroxides are wholly basic in character


    .
    .

    The salts derived from B i( O H) 3 are called neutral those from ,

    BiO O H basic
    -
    .

    The n eu tra l n itr ate B i( N O g ) 3 i s obtained by dissolving bis


    , ,

    muth in nitric acid I t crystallizes with ve molecules of water


    .

    in large translucent triclinic prisms I t is deliquescent The . .

    addition of much water converts it into the basic n itra tes several ,

    of which are known By treating the neutral nitrate with abou t.

    2 0 parts of boiling water a product is obtained whose com position


    is not perfectly constant for different pre parations but corres ponds ,

    nearly t o the formula or 2 BiO N O g


    175 ] S UIWM A R Y O F TH E N I TR O G E N G R O UP . 23 9


    + Bi( N 0 3 ) 3 This is the b i s m u th s u bn itr at e , which

    is used in medicine .

    B i sm u th su l ph at e B i2 ( SO 4 ) 3 is obtained as an amor phous


    , ,

    white substanc e when the metal is heated with concentrated sul


    p h u r ic acid With water it
    . forms a basic sul phate B i2 ( O H) 4 SO 4 , .

    Su l ph u r C o m po u n ds .

    1 74 t ris u l ph i de is found in nature


    . B i s m u th 1 7 0) ar t ic iall v
    it can be pre pared by heating bismuth with sulphur or by leadi ng
    hydrogen sulphide into the aqueous solu t ion of a bismuth salt .

    In the latter case it comes down as an amor phous black powder


    tha t is easily soluble in warm dilu t e nitric acid I t is insoluble .

    in alkalies and their sul phides hence forms no sul pho salts Whe n ,
    -
    .

    heated wi t h an alkali sul phide solu t ion to 2 00 it takes on a crys

    t al lin e form simil ar to that of the natural mineral .

    S UM M A R Y O F T HE N I T R O G E N G R O UP .

    1 75 . L ike the halogens and the elements of the oxygen grou p ,

    th e elements j ust discussed v iz nitrogen phos phorus arsenic ,


    .
    , , ,

    antimony and bismuth also form a natural grou p Their family , .

    relation shows itself even in the formula types of their com pounds .

    The hydrogen com pounds have the ty pe R H3 ( lacking with bis


    muth ) the halogen com pounds R X3 and R X5 ( the latter also lack
    ,

    ing with bi smuth ) the oxygen com pounds R 2 0 3 and R 2 0 5 I n


    , .

    other words the elements of t his group are trivalent or pen t iv al e n t


    , .

    We nd here j ust as in the grou ps previously studied that as the


    , , ,

    atomic weight increases a gradual c h ange occurs in the physical ,

    ro
    p p erties This is shown by. the following small table :

    A to mic w igh t e . 31 0 .

    Spe cic gravity . 5 7


    .

    ( Wa t e r 1) li q ui d
    M lti g po int 8 00
    0
    e n -
    . + 44 4 ca .

    Bo ili n g po int

    -
    1 94 4 27 8
    Co l o r col o rl ess ye llo
    w or re d gr y a

    In
    the chemical pro perties also regular variations are to be , ,

    observed all of which can be summed u p in the general statemen t


    ,
    40 I N O R GA N I C C H E M I S TR Y . 175


    that the metallo id character g ives w ay to the metallic c haracter

    as the a t omic weight increases N itrogen forms either indifferen t


    .

    or acid forming oxides only ; so does phos phorus ; arsenic o n the


    -

    contrary dis plays a very feebly basic charac ter in arsenious oxide ;
    ,

    since this oxide forms the trichloride with hydrochloric acid the ,

    trichloride reac t ing inversely with water however and breaking , ,

    u p into hydrochloric acid and arsenious oxide In antimony .

    trioxide this basic character is a little stronger ; some salts and


    double salts of it with acids are known The corres ponding chlo .

    ride does no t su ffer an immediate hydrolytic dissoc iation with


    water but o x yc h l o ride s are formed which require a great deal
    , ,

    of water to convert them entirely into the trioxide While the .

    highest oxides of a rsenic and ant imony have s t ric tly acid pr op
    e r t ies with b ismuth the acidic nature has practically d isa pp eared ;
    ,

    the oxide B i2 0 3 has exclusively basic pro perties and the higher
    oxide B l 2 0 5 ac t s like a p eroxide giving o ff oxygen readily ( it
    ,

    generates chlorine with hydrochloric acid ) an d going over into


    the lower oxide B izO g B ismuth trichloride B iC 13 gives the oxy
    .
    , ,

    chloride BiO C l with water and this is not decom posed by an


    , ,

    excess of water .

    I n the hydrogen com pounds too the gradual cha n ge of the


    , ,

    ro
    p p erties is very a pp arent C onsider the
    . stability for exam le
    p :
    ammonia requires a very high tem perature for decom posi t ion ;
    p hos p hine and arsine a much lower tem p erature ; stibine is unstable
    at ordinary tem peratures when it comes in contact with oxygen ,

    and the hydrogen com pound of bismuth is so uns t able that the
    conditions for its formation and existence have not y e t been
    ascertainabl e A similar change is noticeable in their ability
    . ,

    to form XH4 ions in aqueous solutions ; it is stro n g in ammonia


    much weaker in phos phine and wholly absent in arsine and


    stibine .

    I n the sul phur com pounds a progressive c h ange of color is


    observed P2 S5 is bright yello w A s 2 S5 dee p yellow Sb 2 S5 r e d
    .
    , ,

    and Bis black The rst three are sul pho anhydrides of sul pho
    .
    -

    acids bismuth sul phide is not however thus displaying , ,

    again the more basic nature of bismu t h .


    24 2 IN OR GA N I C C H E IWIS TR Y .
    i 1 7 6f7
    I

    diameter His method consists essentially in dissolving carbo n


    .

    in molten iron at a high tem perature and then cooling it rapidly .

    FI G . 39.
    A RT IFICIA L D I A M O ND S ( M A G N IFI ED ) .

    This is accom plished as follows : I ro n is brought in c ontact wi t h


    pure carbon ( sugar charcoal ) in the electric furnace at a high t e m
    p e r a t u re A fter the iron has become saturated with c arbon at
    .

    about the fu sed mass i s suddenly cooled by pouring it into


    a hole drilled in a co pper block which is ke pt cold by water and , ,

    at once covering the cavi t y with an iron sto pper When the Iron
    ,
    .

    is all cold it is dissolved away by acids leaving the carbon whic h ,

    did not combine with t h e iron T h is residual carbon consists .

    p artly of small diamonds which are identical with


    ,
    the natural
    diam ond in har d ness crystal form etc Fig 3 9 presents an
    , ,
    . .

    enlarged v iew of some articial s pecime n s ; they dis play the same ,

    ro
    p p erties as the rough natural diamonds p articularly the rounded ,

    edges and angles and the striations .

    The formation Of the diamond by this m ethod h as been ex plained


    by BA K H U I S R O O ZE B OO M as follows : I n all probability the transition
    of diamond into gra phite i s endothermic For this r e as o n diam o n d .

    is the more stable form at lower tem peratures graphite at higher ,

    ones in analogy to the rhombic and m ono clinic modications of


    ,

    sul phur Bu t w h il e t h e velocity of transformation of mono clinic


    .
    ,

    sul phur is fairly great at low tem peratures and the monoclinic
    sulphur can thus exist only for a shor t time below its transition
    point the transition velo city of gra phite into diamond is practically
    ,

    zero for tem peratures below C arbon that has crystallized


    from m olten iron in t he form of gra phite cannot therefore pass ove r , ,

    int o diamond The ra pid cooling of the molten ir on however ,


    .
    ,
    A LLO TR O PI C FO R M S O F C A R B ON .
    24 3

    has the effect of bringing the carbon into the region of temperature
    in which diamond is the stable modication ; it can therefore
    s e parate in this form from its solution .

    The e l e c tri c furna c e that M O I SS A N u sed for these and num erous
    other e xperim ents i s very s im pl e i n c onstr uc t i on It c onsi sts of two .

    bl o cks of u nsl aked lime that t t i ght ly together I n the l ower b l oc k .

    FI G . 40.
    M o I S S AN s E

    L E C T R IC FURNA CE (C R o s s -
    S E C T I oN ) .

    there i s a trough i n wh ich the carbon termi nal s are l ai d Th e upper .

    bl o ck i s s li ght ly ho ll owed out on i ts l ower s i de so as to re e c t the heat


    rays on to the cr ucib le F i g 4 0 shows a c ross se c t i on of an e le c tric
    . .
    -

    f urna c e Fig 4 1 a pic t u re of the s am e a pparatu s i n o perat i on


    ,
    . .

    The te m peratures obtai ned i n the e le c tric f u rnace are as fo ll ows

    C urrent of 3 0 am peres and 5 5 v o lts wi th a stea m engine of 4HP


    -
    2 250
    ( f ( f ( l ( K ( t ( l ( l 0
    45 8 2500

    450 70 50 3 000

    FI G 41 Mo I S SA N FURNA CE IN O PERA T IO N (A FT ER M O I SSAN )



    .
    .
    s . .
    4 I N O R GA N I C C HE M I S TR Y . 176

    The last nam ed tem perat u re can howe ver only be m aintained for a
    -

    brief per i od as the uns l aked lim e soon m e l ts and ows like water A t
    , .
    '

    2 500 the lim e beco m es c rystalli ne i n stru c t u re after a few mi nutes



    .

    ( 5) G r aphi t e is also crystallized carbon Unlike diamond it is .


    ,

    very sof t and o paque and a go od co n ductor of heat and electricity .

    Sp g = 2 09
    . . . A s was stated above gra phite can be pre ,

    p ared articially by the crystallization of carbon from molten iron


    and by heating diamond strongly There are various kin ds of .

    gra phite I f gra phite is treated with a mixture Of perfectly dr y


    .

    p otassium chlorate and very concentrated nitric acid it t u r n s to a ,

    yellow crystallized substance containing hydrogen an d oxygen in ,

    addi t ion to carbon and called gra phitic a cid This subs t ance is
    ,
    .

    peculiar in that it de com p oses ex plosively on heating and yields a


    large volume of extremely ne amorphous carbon G raphite is .

    used in th e manufacture of lea d pencils crucibles electro des , , ,

    p olishes etc , .

    ( )
    0 A m o r p h o u s C a rb o n This is obtained in the purest state
    .

    by charring sugar The resulting m ass is boiled with acids to


    . .

    remove the mineral m atter and nally heated re d hot in a curr ent -

    of chlorine for quite a while to re m ove all the hydrogen It can .

    als o be pre pared from soot A m or phous carbon is o paque black


    .
    ,

    an d infusible A t the highest tem perature that M O I SSAN could


    .

    r each with his furnace by em ploying a current of 2000 am peres


    and 80 volts ( obtained with a 3 00 horse power engine ) it was barel y -

    p ossible to make carbon sublime The sublimate . was gra p hite .

    A mor phous carbon has a s pecic gravity of


    Various sorts of amorphous carbon are known They are .

    p robably di fferent allotro p ic m odications or mixtures of such


    ,
    .

    Ga s ca r bon and c ok e are obtained as resid u es in the dry dis t il l a c

    tion of coal They conduct heat and electricity Wood char coa l
    . .

    is very porous and can condense large quantities of gases in it s


    p ores e g ,
    9 0
    . t.imes its o w n volum e of ammo nia ( see also
    When warmed or when the pressure is reduced these gases all ,

    esc a p e again B on e bl ack is obtained b y heating b ones away


    .
    -

    from air ; the resulting black mass is treated with hydro chloric
    acid t o remove the phos phates and carb onates p resent I t has .

    the p ower of absorbing coloring matter and certain salts e g lead


    -

    ,
    . .

    salts from liquids The charcoal obtained from the dry distilla
    ,
    .

    ti on of sugar is n o ted for its p eculiar lustre These di fferent .


    246 IN O R G A N I C C HE M ISTR Y . 177

    Peat and the various coal s owe the i r ori gi n to the sa m e geo l ogi cal
    p ro c ess , the s l ow de c ay of pl ant r e m a i ns i n the absen c e of air
    -
    Peat i s .

    th e yo u ngest form at i on and anthra ci te c oa l the o l dest Du ri ng thi s .

    trans i t i on c arbon d i o xi de and m ethane O H4 are g iven o ff and the res i due
    , ,

    be c o m es r i cher i n c arbon and poorer i n hydro gen and o x ygen than the
    c orrespondin g c hief c onst i t u ent of pl ant t i ssues ce llul ose The follow , .

    ing tabl e shows thi s :

    C ar b on. Hy d rog e n . O xygen .

    Ce llul o se
    Pe at
    Bro w n o ac l .

    C ann e oalc l .

    ci coal
    A n th r a t e

    The pl ants of wh i ch these for m ations ori ginally c ons i sted are di fferent .

    Peat a ppe ars fro m i ts str uc t u re to have c o m e c h i e y fro m swa m py


    growths m osses and t h e like ; mi nera l c oa l fro m e x ti nct plants gi gant ic
    , .

    horsetail s (e qui seta) l e pido de n dra and s igil l ariae


    ,
    .

    M ol e c u l ar an d A to m i c W e i gh t of C ar b o n Ch em i c al Pr o e rt ie s
    .
    p .

    1 The c arb o n molecule p robably co ntains a large number of


    78 .

    atoms It has no t yet b een p ossible to determine how large this


    .

    number is I t is su pp osed th at gra phite has a larger number of


    .

    ato ms t o the molecule than amor phous c arbon and diamond more ,

    than gra phite since gra phite and diamo nd are less easily attac ke d
    ,

    by chemic al re agents and b ec au se they are denser .

    A determination of the vapor density of carbon is of course


    out of the question The measureme t of the melting point
    n .

    de pression that carbon produces in iron is also im practicable ;


    however it is known that even a small percentage of carbon causes
    ,

    a considerable lowering of the melting point of iro n (see -

    It can be shown in the following way however that the n umber , ,

    of atoms in the carbon molecule must be very great By the i


    .

    oxidation of amor phous carbon with p otassium p ermanganate


    m el litic a cid is formed which contains 1 2 carbon atoms to the
    ,

    molecule This makes it quite probable that the carbon mole


    .

    cule contains at least 1 2 atoms for in the oxidation of organic ,

    substances the products almost always contain either a smaller


    or the same n umber of carbon atoms to the molecule For the .
    M O L E C UL A R A N D A T O M I C WE I G H T O F C A R BO N .
    24 7

    following reason it is however to be supposed that the number


    , ,

    of atoms in the carbon molecule is much greater than 1 2 When .

    m ar sh ga s -
    H
    C 4 is p assed through a red ho t tube ethyl en e O 2 H 4
    , , , , ,

    is formed among other things I f this is then treated in the same .

    way acetyl en e C 2 H2 is obtained and from this again ben zen e


    , , , , ,

    C 6 H6 O n conducting benzene va por thro u gh a glowing tube


    .
    ,

    n aphtha l en e C 1 0H8 pyr en e C 1 6 H1 0 etc


    ,
    are formed If either
    , , ,
    .
    ,
    .

    of the latter is heated still higher (in the absence of air ) carbon
    is deposite d We thus see that as the tem peratur e rises the num
    .

    ber of carbon atoms in the molecule steadily increases The .

    nal pro duct of these o perations carbon w ill therefore probably , ,

    contain a considerably larger number of atoms in its molecule


    than na phthalene or pyr ene .

    C arbon can unite directly with many elements A t or dinary .

    tem peratures it comb in es with uorine only M O I SSAN intro .

    du c e d lam pblack into uorine gas and the carbon commenc ed ,

    to glow ; when uorine was present in excess car bon tetrau oride ,

    C F4 was formed
    ,
    .

    H y d r o g e n combines with carbon directly to form ac e t y


    -

    lene and a small quantity of marsh gas when an electric arc is -

    p assed between two carbons in an atmos phere of hydrogen O f .

    all t h e many com pounds consisting of only carbon and h ydrogen


    these are the only ones which can be obtained by d irect synthesis .

    Under analogous conditions carbon unites with c h l o r i n e t o


    .

    form perchloroethane 0 2 016 an d hexachloroben zene C 6 C 16 , , ,


    .

    O x y g e n u nites with carbon at an elevated tem p eratur e to


    form carbon monoxide C O or carbon dioxide C O z according as , , , ,

    carbon or oxygen is in excess I f sul phur v a por is passed over .

    red hot coals carbon disul phide C S2 is produced


    -

    , , ,
    .

    The elements of the n i t r o g e n g r o u p N P As Sb and , , , .


    ,

    Bi do not combine with carbon directly


    , S i l i c o n and car .

    bon unite at the tem perature of the electric furnace to form C Si ,

    ca r boru n du m which is so hard that it can be used as a


    , pow d er for
    polishing glass and precious stones .

    M O I S S AN also found that many metals are able to c ombine


    with carb o n at a very high tem p erature forming ca r bides This , .

    was previously known to be true of iron and certain o ther


    metals .
    IN O R G A N I C C HE M I S TR Y 179
    48 .

    The d i fferen c e i n the behavi or of these c arbi des towards water i s


    interest ing Iron . carbi de i s u naffected by i t ; c alcium c arbi de gives
    a c etyl ene C 2H2 ; ,
    alumin iu m c arbi de yi e lds m ethane ; other c arb i des
    g ive mix tures of the two hydro c arbons ; u ran ium carbi de produc e s
    m ethane and a l so liq u i d and soli d hydro c arbons .

    79 1 The . a t om ic w eight of ca r bo n has been determined with


    great accuracy by DUMA S and ST AS The aver ages for t h e .

    di fferent series of ex p eriments each of which sh owe d littl e ,

    va riation were as follows :


    ,

    R a t i o b y w e i g h t o f c a r b o n t o o x y ge n i n c a r b o n di
    oxide from the combustion of
    N at u ra l graph i te 2 999 4 8 0000
    A rt ici a l
    Di a m ond

    The ratio of carbon to oxygen in carbon dioxide is thus ve ry


    cl ose to A s the Specic gravity of carbon dioxide points t o
    a m olecula r weight of 4 4 for this gas it must contain according , ,

    to this ratio p arts by weigh


    ,
    t of carbon and 3 2 p arts of
    ox y gen The formula is therefore O s
    . I nasmuch as n o carbon .

    com p ound is known whose m olecular weight includes less than 1 2


    parts of carb on we have C 0 2 as the formula
    , ; hence the atomic
    weigh t of carbon must be for O = 1 6 .

    C o m po u n ds with Hy dr o gen .

    1 80 . and hydrogen form a v ery large num b er of com


    C arbon
    p ounds ( hyd roca r bon s ) which are m ore fully discussed
    ,
    in organic
    chemistry Two of them will b e treate d here briey
    .
    .

    M e th an e , also called m a rs h gas and r e da m p is the only hydro


    - -

    carbon with j us t one atom o i carbon I t o ccurs in nat u re in .

    volcanic gases ; moreover it gushes out of the groun d in the n eigh


    ,

    b o rh o od of t h e oil wells at Baku and various places in A merica



    -



    It is an im p ortant constitu ent of n atural gas I t owes t h e .


    name marsh gas to the fact that it arises from swam ps es pecially
    -


    when the decaying vegetation at the bottom is stirred u p I t
    is called re dam p b ecause it o c curs in c oal beds
    -

    fro m
    .

    which it esc ap es when they are broken u p I t forms a violently


    '

    ex plosive mixture with air which is frequently the cause of mine ,

    ex plosions F or its modes of formation and its physic al and chem


    .

    ical pro perties reference should b e had to O R G C H EM 29 . .


    , .
    2 50 IN O R GA N I C C HE M I S TR Y .

    l 1 82

    carbon O n passing steam over red hot coals a mixture of hydrogen


    .
    -

    a n d carbon m onoxide is produced :

    Thi s mix t u re goes by the nam e of I t i s us ed on a l arge


    w ater gas -
    .

    s ca l e for heat i ng and li ght i ng es pe ci ally in A m eric a Fo r t h e l atter


    , .

    p pu r ose i t i s c har g ed w i th t h e v a p or of hydro c arbons r ic h i n c arbon ,

    s i n c e it s o w n am e i s not lumi no u s Th e u s e of t h e i n c andes c ent gas


    .

    light 29 1 ) m akes th i s c arb urett ing unne cessary Water g as c o n .


    -

    tai ni ng 5 0% of c arbon m ono x i de i s very po i s ono u s ( O R G C H E M . .

    C arbonmonoxide is also formed by the redu ction of carbo n


    d ioxide with red ho t carbon : -

    C + CO z = 2 C C .

    This reaction is limited by the reverse one an d we have here a


    case of balanced action expressed by .

    C + CO z 2 2C O .

    In view of the caloric e ffec t of the reaction ,

    2 00 C 00 2 9
    3 00 C al .
    ,


    an elevation of temperature must according to LE C HA T ELI E R S ,

    r ule increase the amount of carbon monoxide ; a de pression


    o f tem p erature the O pposite E x perience h as Shown this to be
    ,
    .

    actually the case A s the tem perature rises the quantity of c arbon
    .


    monoxide increases ra pidly and at 1 000 there is still a very small
    amount of dioxi de A t on the other hand practically all
    .
    ,

    the carbon monoxide is changed into carbon dioxide and carbon .

    This resul t is sur prising because the same chan ge should also
    ,

    o ccur at lower tem peratures ; nevertheless carbon monox ide seems ,

    p erfectly stable at ordinary tem p eratures even as high as ,

    The cause of this phenomenon must as in analogous cases be , ,

    sought in the very great retardation of the velocity of the reaction


    2 C O > C O z + C when the tem perature s inks
    O n usi n g certa in .

    catalyzers e g nely divided nickel the velocity of the reaction


    ,
    . .
    ,

    2 C O > C O z + C becomes measurable as low as


    These measurements have shown that the decomp osition of


    c arbon monoxide into carbon dioxide an d carbon is not a b im ol e c u

    l ar reaction as would be ex pec ted from the above equation b u t


    , ,
    C A R BO N M O N O X ID E . 25 1

    a unimolecular one To ex plain this it may be suggested tha t


    .

    the decom position takes place in two stages : I C O = C + O ; .

    I I
    . CO + O = CO z I f we assume that the second stage has an
    .

    innite velocity it is only the rst that is really measured i e a


    , , . .

    unimolecular reaction .

    The reduction of salts of carbonic acid also furnishes a m ethod -

    of pre paring carbon monoxide I f chalk ( C aC O g) or magnesit e


    .

    ( M gCO g ) is heated with zinc dust p ure carbon monoxide is formed,:

    C aC 0 3 Zn C aO Zn O CO .

    Physica l Pr operties C arbon


    monoxide is a colorless odorles s ,

    g as of a s p ecic gravity of I t is hard to condense ,

    its critical tem perature being and its critical pressure


    atmos pheres I t boils at.
    1 9 0 and solidies at

    It
    is onl y slightly soluble in water .

    1 83 .C h em ica l Pr oper ties C arbon monoxide b urns with a


    characteristi c blue ame to c arb o n dioxide I t can unite with .

    chlorine directly to form ph osgen e 0 0 0 12 and also with sul phur , ,

    ( at an elevated tem p erature ) to form c a r bo n o r g/ p


    s u l h ide C O S; ,

    b oth com p ounds are gaseous A gain it unites directly with.

    nickel and iron giving the co m p ounds N i(C O ) 4 and Fe (C O ) 5


    ,

    2 1 4 and
    O n accoun t of its tendency to combine with oxygen it displays ,

    strong reducing power es pecially at high tem peratures


    ,
    Thus .

    metallic oxides like F6 2 0 3 C u O etc are easily converted into the


    , , ,
    .
    ,

    metals when hot Some com po unds are reduced by carbon mon
    .

    oxide even at ordinary tem peratures Palladium is precip itated .

    from an aqueous so hit io n of p alladious chloride and an ammoniacal


    silver solution ( pre pared by dissolving silver oxide in ammonium
    hydroxide to the point of satura tion) is turned black by the gas
    on account of formation of the metal Bo th of these reactio n s serv e .

    for the detection of carbon monoxide .

    A n ammoniacal cu prous chloride solution absorbs the g as


    because of the formation of a com p ound C u 2C 12 C O l 2 HzO -

    , ,

    which can be isolated in the crystalline state but decomp oses again
    very readily .

    The c om p os ition of carb on m onoxide can be determined by


    ex ploding a mixture of the gas with oxygen I t is then found that .

    2 vols CO unite with 1 vol 0 2 t o form 2 vols C 0 2


    .
    . This togethe r . .

    with the va p or de n sity establis h es the for mula as C O .


    2 52 IN O R G A N I C C H E M I S TR Y .
    l 1 83

    '

    C AR BO N DI O XI DE , C AR BO NI C A C I D AN HY DR I DE, co,

    1 84
    This com p ound o ccurs not only by itself but also in com
    .

    bination I t is a regular constitue n t of the air


    . many
    m ineral waters contain the free gas ; in some places of the e arth

    ( in the D og s G rotto at N a ples and the famous Poison V alley in
    Java ) it comes u p out of the ground and it is also found in volcanic
    exhalations The most mi n erals and rocks contain num erous
    .

    extremely small cavities partly lled with liquid carbon dio xide
    ,
    .

    C ombined it occurs in large quantity in the carbonates of lime


    ,

    an d magnesia

    C arbon dioxide results from the c omb u s tion of carbon in an


    e xcess of oxygen and als o from the direct dec om position of m any
    '

    Salts of carbonic acid (car bon a t es ) b y h e at :


    2 N 3 H0 0 3 = N3 2C O 3 + H 2 O i 00 2 , 03 00 3

    00 2 .

    d
    So iu m b i
    c ar b o n at e .

    M oreover , it is formed when a carbo n ate is decom posed by an


    a cid :

    the action of o x yg en at high tem peratures all carbon com


    By
    pounds are burned with the for m ation of carbon d ioxide I t is .

    also produced by the action of carbon on oxygen co m pounds e g ,


    . .

    by heating powdered charcoal with an excess of co pper oxide ;


    nally also by the interaction of carb on com p ounds and oxygen
    com pounds This latter action is the basis of the general method
    .

    for determining the pro p ortion of carbon i n organic substances ,

    they are heated together with co pper oxide and the c arbon dioxide
    formed is absorbed i n a weighed amount of caustic potash .

    C arbon dioxide at ordinary tem peratures


    Physica l Pr oper ties .

    and pressures is a gas with a somewhat pungent odor and taste .

    Sp g =
    . 1 52 9 . I t is thus ab out half again as heavy as
    .

    air so that in those places where it comes out of the earth as in


    , ,

    the Dog s G rotto at N a ples it stays in a layer close to the ground
    ,

    and a dog for instance is s u ffocated while a man can breathe


    , ,

    with comfort C arbon dioxide is easily co n de n sed becom ing li q uid


    .

    ,

    at 0 u n der 3 5 atm os pheres press u re I t s critical tem perat u re is .

    and its critical pressure


    ( liquid carbonic acid
    atm L iquid carbon dioxid e
    is man u factured in gre at q u an t it ie s an d
    .
    4 I N O R GA N I C C HE M I S T R Y .

    liberated from its salts by almos t e v ery other acid By adding .

    hydrochloric acid to a carbonate H ions are introduced into the


    '

    liquid and they unite with the C O 3 ions to form integral H2 C O g


    molecules These however break u p largely into water and


    .
    , ,

    carbon dioxide the latter of which can o nl y remam in solution


    ,

    u p to a certain amount at a constant pressure so that all in excess ,

    of this passes out A s a result the concentration of the H2 C 0 3


    .

    molecules cannot exceed a denite and in this case low limit , .

    Since however the ionization of these molecules is very weak


    , , ,

    in reality all of the carbonate is decom posed by the strong acid


    73 )
    The neutral carbonates of the alkalies are soluble in water ,

    giving an alkaline reaction as a result of partial hydrolysis ,

    The acid H2 C O g is a weak acid al t hough its salts e g K 2 C O g


    , , , ,
    . .
    ,

    are strong electrolytes ; A Solution of such a salt therefore con , ,



    tains a large number of C 0 3 ions par t of which must unite with ,

    the H ions of the water in order to establish the equilibrium b e


    '

    tween carbonic acid and its ions The result of this is that other .

    molecules of water mus t be Split u p I nto io n s in order to com


    p ensate the loss of H ions This leaves in the liquid a certai


    . n

    number of O H ions which are no t balanced by an equal number



    ,

    of H ions The liquid therefore acquires an alkaline reaction


    '

    . .

    The carbonates of the other metals are insoluble in water ;


    however the acid carbonates are mostly soluble C alcium carbo
    ,
    .

    nate e g dissolves in water containing carbonic acid The solu


    ,
    . .
    , .

    tions of such acid carbonates give o ff carbon dioxide on merel y


    boiling however and the neutral carbonates are preci pitated
    , , .

    In the solid state also the acid carbonates give o ff carbonic aci d
    gas very readily on warming .

    C om pos ition of C ar bon Dioxide I n connection with what w as


    stated in 1 7 9 it is an im portant fact that no change of volum e
    occurs when carbon burns in an excess of oxygen :
    C +O2 = CO 2 .

    1 v ol . l v ol .

    When a v ery c on c entrated so lu t i on of p otass ium c arbonate i s el e c


    t rol y z e d w i th hi gh cu rrent de n s i ty at 3 0 po t a s s i u m pe r c ar b o n at e

    ,

    K C O i s form ed at t h e anode
    z z G, I n a qu eo u s so lu t i on i t set s free i od i ne
    .

    fro m K I so lu t i on at on c e whic h serv es to di sti ngui sh i t fro m H O s i n c e


    , Z Z,

    a dilu te so l ut i on of t h e l atter liberates i odi ne only v ery s l owl y .


    O THE R C A R B O N C O M PO UN DS . 2 55

    O th e r C arb o n C o m po u n ds

    .

    1 85 . C y an o gen , (O N ) 2 ,
    can be pre p ared by heating mercuric
    cyanide Hg (C N ) 2 or by treating a solution of p otassium cyanide
    , ,

    with co pp er sul phate solution I t is p ossible that rst cu pric .

    cyanide is formed and that this at o nce breaks u p i n t o cu p rous


    cyanide and cyanogen :
    4 KC N i
    2 K2 SO 4 0 11 2 (C N ) 2 (C N ) 2 .

    C yanogen
    has a penetrating o do r Wh en liqueed it boils at .

    I t is unaffe cted b y high tem peratures I t dissolves in .

    water b ut the s olutio n de p osits amor pho us brown akes after a


    ,

    whi l e I t burns with a pur p le t inge d ame a ccording to th e


    .
    -

    e quatio n

    C2N 2 20 2 2C 0 2 J
    r N2 .

    The reaction h owever is not trimolecular the rst stage b eing


    , , ,


    C zN z l O z 2C O + N 2
    '

    r:
    .

    ie
    . . a bimolecular p ro cess .

    Th i s o ve d b y D I X O N b y dete rmi n i n g t h e velo city o f pro pag ati n


    w as p r o

    o f t h e e xpl o s io n o f mixt ure s o f c yan o g e n a n d o xyg e n W he n e xp l o s ive .

    g as mixture s are i n tr o duc e d i n to a lo n g tu b e an d th e ir e xp l o s io n s t ar t e d


    at o n e e n d ( b y an e l e c tr ic s p ark fo r e x am p l e ) a ame re s ul ts w h ic h is
    , ,

    prop ag at e d thro ugh t h e tu b e w ith a de n it e an d m e as ur a b l e ve l o city .

    B ER T H E L O T c a ll e d th i s s e l f pro p ag at i n g ame t h e exp lo s io n w a r e


    -
    .

    DI X O N ig n ite d a m ixtu r e o f 1 v o l cyan o g e n an d 1 v o l o xyg e n o b t a i n in g


    . .
    ,

    afte r t h e e x pl o s i o n c arb o n mon o xi de an d n itroge n ; t h e ve l o city o f t h e


    e xpl o s i o n w ave w as fo u n d to b e 2 7 2 8 m p e r s e c The re u pon h e m ix e d 1 v o l
    . . .

    cy an oge n w ith 2 vol s oxyge n in o n e in st an c e an d w ith 1 v o l oxyge n an d


    . .

    1 v o l o f an i n d i ffe re n t g as in an othe r i n st an c e ; in b o th c as e s t h e ve lo city


    .

    o f t h e e x p l o s i o n w av e w as n e arly t h e s ame viz 23 2 1 m an d 23 9 8 m pe r


    ,
    . . .

    se c . I t is p l a i n th e re fo r e th at t h e s e c o n d v o lume o f o xyg e n i n u e n c e d
    , ,

    t h e e x pl o s i o n w ave in t h e s ame w a a s t h e i n d i ffe r e n t g as viz as a dilu e n t


    y ,
    .

    Th e c o n clu s i o n m ay b e d r aw n th at in t h e e x pl o s i o n w ave its e l f o n ly c ar b o n


    mon o xide an d n itroge n are forme d e ve n in t h e pre se n ce o f an e xc e s s o f
    ,

    oxyge n Ho w e ve r s in c e t h e tub e c o n ta in s o n ly c a b o n d io xi de an d n itro g e n


    .
    ,
    r

    afte r t h e c o m b u st i o n it must b e as sume d th at t h e c o mb ustio n o f c arb o n


    ,

    mo n o xide to c arbo n dioxide is a se c o n dary pr o c e s s .


    2 56 I N O R GA N I C C HE M IS TR Y . 1 85

    Hy dr o gen
    y an i de , HC N (pru s sic a cid) is im po rt ant in inor
    c ,

    g a n ic chemistry because of the numerous com plex salts which it


    forms Those of the alkalies are soluble in water and crystalliz e
    .

    beautifully ; see 3 08 The salts of the alkaline earths and


    .

    mercuric cyanide are also soluble in water the other salts in ,

    s oluble .

    1 am e is produce d b y the b u rning of a gas ; s olids lik e


    86 A .
    ,

    i r on carb o n etc b urn withou t a ame If a ame is obse rve d


    , ,
    .
    ,
    .

    d u ring t h e b ur ning of coal a can d le or t h e l ik e , it is du e ,

    FI G . 43 .
    R E V ER S E FLA M E . FI G . 44 . PO T A SS I U M C H L O RA T E FLAME .

    to the fact that at tha t high tem perature gaseous dec om position
    products are formed which b urn If a gas burns
    , in the air it

    is .
    ,

    calle d a combustible gas and the oxygen of the air is called the s u p
    p orter of the com b u stion These ex pressions in common. use are

    only relative term s ; it is possible to lig ht the oxygen and have i t


    burn with a ame in a gas which is ordinarily called combustibl e .

    This phenomenon is illustrated in a way by the r ever s e am e .

    Thi s can be eas il y obtained with the aid of the apparatus of Fig 4 3 . .

    A lam p ch im ney i s t ted wi th a two ho l e cor k at its l ower end


    -
    Through
    -
    .
    2 58 IN O R G A N I C C HE M I S TR Y .
    m 1 88
    1

    pr essur e i
    , t s ame is st r ongly luminous incan d es c e n t gases . O the r ,

    such as the va p ors of certain metals can rende r a ame lum inous ,

    even at ordinary pressure im parting to it a de ni te color C olored


    , .

    ames of this sor t give a l i n e s pectrum p


    A gas am e whose light is due to incandescent p articles of car
    -

    bo n is made non lu m inous by mixing the gas with air before the
    ,
    -

    co m bus t ion This is the princi ple of the B UNS EN burner ( Fig
    . .

    which is used in all laboratories and quite extensively also with som e ,

    variation or other in heating and cooking a pparatuses (gas stov es )


    , .

    The Buns en b urner cons i sts of a base in


    which i s a tube for supplying the gas which ,

    escapes fro m a narrow ori fi ce at a Here .

    it mixes w i th air that enters thro ugh the


    l ateral ho l es in c the pro portion of ai r being
    ,

    regul ated by the c o ll ar b Thi s m i x ture .

    burns with a colorl ess ame when ignited


    at the t o p of c .

    The O pi nion was or 1g1 nal l y held that the


    loss of l umi nos ity of the a m e is d u e to
    the oxygen of the a i r t h e l atter caus ing the
    ,

    co m pl ete co mb ustion of the c arbon partic l es .

    As has S ince been shown howe ver the , ,

    d il ut i on of the burning gas w i th ni trogen al so


    has a part i n i t : i f illumi nat i ng gas i s m i xed -

    with two or three t im es as much nitrogen ,

    the form er burns wi th a co l orle ss a m e .


    FI G . 45 .
    B UN S EN BURNER .

    With the aid o f a wire gauze a burning gas mixture can be


    co oled so l o w tha t the c ombustion cannot pro pagate itself thro u gh
    the gau z e ; in o ther words the ame does n o t ge t thro u gh the
    ,

    gau z e (Fig . I f gas is allowed to ow o ut of a BUN SEN burner


    and a wire gauze is held across the curren t a shor t distance from
    the orice the gas can be lit above the gauze withou t the ame
    ,

    Springing back to the b urner .

    I t w as by experi ments such as these that DAV Y was l ed to discover


    As Fig 4 7 shows th i s cons i sts of an o il l am p

    h is m in er s s afety l amp -

    . .
    ,
    -

    the a m e of whic h is surro unde d by a wi re c ag e A co mb u st ibl e g as .

    mixt ure m ay c at ch re i ns i de of the l antern bu t the re c annot pass ,

    t hro u gh the ga uz e to the o u t s i de .


    1 88 TH E FL A M E . 25 9

    1 88The tem peratu re of the am e is much lower than we migh t


    .

    su ppose Since when hy d rogen burns in oxygen


    .
    ,
    k g calories , .
    -

    ar e pro d uce d by every 1 8 g of the mixture and the s pecic heat of


    .
    ,

    FI G 4 6 E FF E C T
    . . or A WI R E G AU ZE ON A F LA M E .

    t am
    s e is this amount of heat ough t t o r ais e the 18 g s t eam
    . to

    a t emperatur e of In r eality the t em peratur e


    of t he am e d oes cee d not This d ifferenc e be tween
    ex

    c alculatio n an d observation is d ue t o t he fac t tha t on accoun t

    o f dissociation only a p artial combination of h y

    d rogen an d oxyge n takes place in any part of


    the ame The tem perature of 6600 coul d indee d
    .

    b e obtaine d at any point if the gases unite d ther e ,

    com pl e tely and instantaneously ; b u t this is im


    p ossible for above 1 3 00
    ,
    the formation of the com

    p ound is checked b y the O pposite process the dis ,

    s ociatio n of steam Therefor e what o ccurs mus t


    .

    b e this : oxygen an d hy d rogen when brought to ,

    gether at the a perture combine and effec t a certain ,

    rise of tem perature ; in the same measure as t h e


    system in equ ilibrium (hydrogen oxygen steam) , ,

    Fm 4 7 .

    .Ma m a s cools o fresh portions of the gases unite

    ,
    Their .

    SA F E TY L A M P

    combustion cannot therefore take place at any


    '

    p articular p oin t b u t must be g r adual throughout the whole extent


    o f the ame and at any one p oint the tem perature cannot ex

    c ee d a certain l imit which is determine d by the degr ee of dissocia


    ,

    t ion of the combustion pro d uct .


    2 60 IN O R G A N I C C HE M I S TR Y .

    1 89 . Zones o f a lu min ou s am e . Le t us take a candle am e fo r


    -

    e xam pl e . In the c e n t r a l zone ( 1 in the diagram Fig 4 8) .

    FI G . 48 .
    Z O NE S L U M I N O U S FL A M E .

    there is no comb ustion The stearin o f t h e candle is her e c on


    .

    ver t ed b y t h e heat of the ame into volatile combustible products .

    I n a large candle this can be proved in the manner shown in Fig .

    48 .
    The narro w tube conducts o ff the inammable gases and they
    can be lit at the outer end .

    The hollowness of a ame can be demonstrated in various ways ;


    in a B unsen burner for instance by placin g a match head in t h e
    , ,
    -

    center where it does no t ignite or by holding a thin platinum wire


    , ,

    across a ame ; the wire only g l ows a t the edges of the ame .

    The dark central zone of the ame is next surrounded by t h e


    l u m i n o u s zone Here the volatilized hydrocarbon is dec o m
    p osed with the se p aration of ca rbon because the air su pply is ,

    in su ic ien t for com plete combustion These carbon particle s .

    becom e incandescent and so make the ame lumin ous Finally .

    there is the b l u e o u t e r zone in which the glowing particles


    of carbon are burned by direc t contac t with the air I t radiates .

    very little ligh t .

    The a m o u nt of so li d carbon in a am e whi c h is raised to in can de s


    cen c e and hence giv es li ght is very s m all as the fo ll owing calcul ati on ,

    s ho w s The s ubstances i n burn ing illumi nat ing gas w h ich break u p
    .
    -

    wi th the li berat i on of carbon are ch i e y ben z ene and ethyl ene The .

    for mer m akes u p abo u t 1 the l at t er abo u t 4 pe r c ent by volum e of


    , ,

    the gas I f we assum e t hat the ben z ene i s com pl etel y bro ken u p and
    .
    2 62 IN O R G A N I C C H E M I S TR Y .
    M 1 90

    t he ai r t o a ve ry high temperature burning t o silica I t unites ,


    .

    with uorin e at ordinary temperatures the c o mbustion being ,

    marked by a glow ; c ombination with chlorine takes place on gently


    warmi n g A t an elevated temperature Silicon combi n es with ni tro
    .

    gen and some metals ; these s il icides have been pre pared main ly
    by M O I SSAN in his electric furnace .

    I t is in differen t towards sul phuric n itric and h ydroch l oric ,

    acids Hy dro u o ric acid dissolves it however with the evolution of


    .
    , ,

    hydrogen Hydrogen chloride gas reacts with it at a high t e m


    .

    pe r a t u r e forming
    ,
    sil icon tetrachloride an d silico chloroform I t -
    .

    dissolves in a hot solution of sodium or p otassium hy d roxide pro ,

    du c ing hydrogen and a silicate :

    Si 2 KO H H2 0 K2Sl O 3 2 H2 .

    Hy dr o g e n Sil i c i de , SiH4 .

    1 This gas is obtained by adding freshly prepare d magn esium


    91 .

    silicide to hydrochloric acid The magn esium silicide is pre pared


    .

    by he ating sand with an excess of magn esium powder or better by ,

    fusing 4 0 parts of anhydrous magnesium chloride with a mixture


    o f 3 5 p a rts of so d ium u o s il ic at e 1 0 of sodium chloride and 2 0 of
    ,

    sodium The hydrogen silicide so obtained is mixed with hydro


    .

    gen A purer product results from heating an organic d erivative


    .

    o f Silicon tri ethyl s il ico fo rm at e :


    ,
    -

    4 SiH 3 Si(0 02 m) , 8111 4 .

    Hy d rogen s ilici d e or silicon tetrahydri d e is a g as which


    , , ,


    b ecomes liquid at 1 u n der a pressure of 1 00 atmos pheres I t has

    .

    a disagreeable odor I t takes re in the air ; each bubble that


    .

    esca pes from the ge n erat or forms a cloudy ring of hydrated silica .

    If however the hydrogen silicide is perfectly pure it does no t


    , ,
    ,

    ig n ite Sp ontaneously in the air at ordinary temperatures except


    under re d uced p ressure The s p ontaneous ignition in the air


    .

    is caused by the p resence of small quantities of other c om poun d s ,

    p rob ably also c om p ose d of silicon and hydrogen We have .

    therefore in this case phenomena similar to those in t he case of


    hydrogen phos phide Heat de co mposes the hydrogen
    silicide readily into Si an d 2 H2 I t burns in a chlorine a t mos phere
    .

    and is d ecom p osed by an alkali solution acc ording to the equation :


    SiH4 2 KO H H2 O 4 H2
    1 K 2 Sl O g .
    1 92 ] HA L O GE N C O M PO UN DS O F S I L I C O N . 2 63

    S ili i s form ed by the de c o m posi ti on of m agnes ium


    co e t h an e ,
    -
    SizHG,
    s ilici de by hydro c hl oric a ci d I t i s a gas wh ic h c an b e l ique ed be l ow
    .
    ,

    Halo ge n C o m po u n ds of Si l i c o n .

    1 9 2 . Sili c o n
    t e tr ac h lori de SiC l 4 is pre pa red by heating Silicon , ,

    in a current of chlorine at 3 00 3 I t is a colorless liquid with

    the s pecic gravity at 0 and the boiling p oint It


    -

    is instantly decom p osed b y water forming hydrochloric acid an d ,

    hydrated silica .

    Sl ii -

    m SiC l H i s obtained together w i th a l arge qu ant i ty


    c o c h l or o fo r , s , ,

    of s ilic on tetra c hl ori de o n heating s ilic on i n a current of hydro c hl ori c


    ,

    a ci d gas Fro m this mix t u re i t i s se parated by fra c t i ona l d i st ill a


    t i on I t i s a co l orl ess strongl y s m elli ng c o m pound whi c h f um es i n
    .
    ,

    t h e a i r bo il s at
    , and i s deco m posed by water .

    By the a c t i on of dar k e l e c tric a l d i s c harges o n a mixture of dry


    hydrogen an d s ilic o c hl oroform v apors c hl ori ne s ilic on c o m po unds are
    -
    -

    form ed of the order Si C 1 + e g p erchlorO s ilico ethan e Si C l e t c


    n 2n 2, . .
    ,
    - -

    , z e, .

    Sili c o n t e t r a u o r ide , SiF4 ,


    can be obtained by warming 3
    mixture of sand and calcium uoride with concentrated sul phuric
    acid :

    2 03 F2 J
    r 810 2 i H2 80 4 2
    Sl F4 2 03 80 4 2 H2 0 .

    It is a colorless gas with a very pungent an d suff o cating o dor ;


    it condenses under 9 at m p ressure or by cooling t o When .

    p erfectly dry it does not attack


    ,
    glass .

    Silicon uoride is also forme d by the action of hydrogen uoride


    o n silicates ; the Silica is rst set free from them and then attacked

    in the way j ust des cribed G lass etching 5 3 ) de pends on this .


    -

    action .

    By the re peated treatm ent of s ilic ates with hydro u s h ydro u o r .

    ac i d all the s ilici c a ci d i s driven o ff as s ilic on u or i de Th e bases whic h .

    were i n c o mb i nat i on wi th the s ilicic a ci d are left behi nd i n t h e form


    of uori des They c an be transfor med i nto s ulphates by warmi ng
    .

    wi th s ul phuric a ci d and the n c onverted i nto a for m s ui tabl e for an al ysis .

    We have here a v ery u seful m eans of determi ni ng the m eta ls present in


    t h e s ilic ates .

    Wate r d ecom poses silicon uoride as follows

    3 SiF4 3 H2 O H2 S10 3 2 H2 SiF6 .


    4 IN O R GA N I C C HE M I S TR Y .
    M 1 92

    Th e c o mpound HzSiFe is called h ydro u o silicic acid ; it is


    known only in aqueous solution I f the latter is concentrated by .

    e vap oration silicon t et ra u o ride escapes but hydrogen uorid e


    ,

    stays in solution When the concentration corres ponds to


    .

    H2 SIF6 the vap or contains 2 HF to I SiF4 ; but dilute solutions


    yield a vapor which contains much more hydrogen uoride I f, .

    therefore a concentrated solution of h ydro u osilicic acid is par


    ,

    t iall y eva porated the residual liquid is able to dissolve silica becaus e
    ,

    o f the presence of free hydrouoric acid O n the other hand .


    ,

    a d ilute solution after partial evaporation leaves a residu e fro m


    , , ,

    which silicic acid is dep osited because the excess of silicon tetra
    ,

    uoride which it contains is decomp osed by water according t o


    the above equation .

    The deco m pos i t i on of s ilicon u oride by water i s usually de m on


    st r at e d in the fo ll ow i ng way : The c o m po u nd i s enerated i n the
    g pr e
    scri bed m anner i n a as k ( Fig whereupon i t i s condu cted through
    .

    FI G . 49 .
    PREPARA T I O N OF HY DR O FL U O S ILICIC A CI D .

    a doubly bent gl ass t ube i nto a cyli ndric a l j ar co n ta i ni ng a l i ttle


    -

    cury (into which the tube o pens) and on t o p of th i s so m e water Every .

    b ubbl e of gas that ri ses fro m the m erc u ry into the water generates in
    the l atter a c l o u d of s ilicic a ci d If the gl ass tube o pened direct ly in
    .

    water it woul d soon be c o m e sto pped u p beca u se of thi s decom posi ti on


    , .
    2 66 I N O R GA N I C C H E M I S TR Y .
    m 193 _

    into col d wate r at once without cracking They are atta cked only .

    by metallic oxi d es an d at a high tem perature R e cently it ha s .

    become possible to utilize fuse d (vitreous) quart z for the manu


    fa cture of chemical a pparatus It is interesting that quart z .

    vessels are trans parent to ultraviolet rays which is n o t the case ,

    with glass vessels .

    C hem ica l Propert ies Es peciall y in t h e c rystallized condition


    .

    silica is very l ittle acted up on by acids except hydrouoric acid


    Fused alkalies d iss olve it form i ng alkali silicates It can , .

    be reduced by carbon in the electric furnace carborundum 1 7 8) ,

    being formed I t is also reduced by heating with magnesi um


    .

    Sili c i c A c i ds .

    1 94 When a soluti on of potassium or s o d ium silica t e (water


    .

    gkt ss ) is treated with hydrochloric acid a very voluminous gelat , ,

    in ou s mass se parates out ; this consists of hydrous silicic acid co r


    res ponding to t h e general formula SiO zaq A fter being washed .

    with water and dried in the air it is a ne white amorphous p owde r


    of the a pproximate comp osition Hg SiO g Freshly precipi t ated .

    silicic acid is slightly soluble in water b ut more s o in dilute hyd r o ,

    chloric acid I f therefore wat er glass is introduced into an excess of


    , ,
    -

    hydrochloric acid the silicic acid stays in solution ; it can b e sepa


    ,

    rated from the sodium chloride simultaneously formed b y t h e fol ,

    lowing pro cess :


    The solution is pu t into a piec e of parchmen t t ubing which ,

    is tied at both ends and the whole submerged in pure water t h e


    , ,

    latter being frequently renewed It is found that the salt go es .

    through the parchment b u t that the silicic acid does not T his
    ,
    .

    p rocess is call ed di aly s i s and any arrangement for carrying it out is


    known as a dia lyzer G RAHAM found that crystallizable substances
    .

    in solution ( crys ta ll oids) are able to p ass through such a membrane ,

    while other substances which he called coll oids are not In t h e


    , ,
    .

    latter class are glue gums gelatine albumen in Short many


    , , , ,

    amorphous substances occurring in the animal and vegetabl e


    kingdoms .

    T he silicic ac id whic h se par ates fro m t he collo idal solution


    d ries in the air t o a white amorp hous p owder still containing a ,
    S I LI C I C A C I DS . 67

    go od deal of w ater however The water c an be Slowly extracte d


    ,
    .

    in a sul phuric ac id desicc ator .

    Since silicon tetrachloride is changed to silicic acid by water ,

    j ust like phos phorus pentachloride to phosphori c acid we


    can c onsider the com p ound as the basis from which the remaining
    silicic acids are derived The latte r can in general b e r epresented
    .

    by the formula m S (O H) 4 n HzO


    i .

    The se polys i l ici c ac i ds themselves have not been isolated but ,

    many of thei r salts and doub le salts are known which occur as -

    minerals in na t ure .

    The silicates of potassium and so d ium are soluble in water those ,

    o f the other metals insoluble as are also most of the double si l icates ,

    o f the alkalies .

    In t heso il hydrous s ilic ates are found whose bases are usu al ly lim e
    and alum ina In c onta c t wi th alkali sal ts these u nderg o a do ubl e de com
    .

    pos i t i on an inso l ubl e potass i u m alumi n i um s ili cate for e x am pl e be i ng


    , , ,

    form ed together wi th c hl ori de of c al c ium whi ch is ta ken o ff by the under ,

    g o u nd water
    r This pheno m enon is sai d to be caused by the a bsorptive
    .

    p ow er of the soi l ; it pl ays an i m portant r bl e i n the determ ination of soil


    values It is this that ho l ds ba ck the potash an inval uabl e nutrient
    .
    , ,

    whic h is f urnished to the so i l in the for m of potassium sal ts and wo uld


    otherwi se be quickl y washed o ff by the ra i n because of i ts so lubi lity .


    The so l ubl e phosphates are absorbed by the so il i n the sam e
    way Th i s i s m a inl y to be as c ribed to the lime they c onta i n wi th wh ic h
    .
    ,

    i n so l ubl e tr i or d ic alcium pho sphate i s form ed ; to so m e ex tent th i s ah


    sorpt i on m ay be caused al so by bas i c lim e s ili cates .

    l
    Si ic o n C om po u n ds of O t h er El em ent s .

    9 5 Si icon
    1 . l su l ph i de ,
    SiS z,
    is pro d uc e d w h en c rb on di ulph ide vapor
    a s

    is l e d o er a v mix t ur e of c c l
    h ar o a a n d ilic t e d h t I t f m l n g
    s a a r ea . or s o ,

    s ilken n ee dl w h ic h
    es, ar e b ro ke n up b y w ate r i n to SiO aq an d h ydro g e n 2

    s ul ph i de .

    Sil i c o n n it ride ,
    SizN a, a white amorph ou s u b st n c e e pl t fro m t h es a , r s s

    h e t i g o f s ilic on
    a n in an at m o ph ere o f n i tro g en
    s ( Fo r metal s ilici de s f. c .
    I N O R GA N I C C HE M I S TR Y .
    196 .

    C O LL O I D S .

    1 9 6 In silic ic a c id we h aVe be c ome acquainted with a sub


    .

    stanc e th at occ urs in a s pe ci al form v iz as a c olloid A co n ,


    .
    ,
    .

    s ide r able number of such sub stanc es is now known and the ,

    stu d y of them h as latterly been so a ctive and pr ol ic that a


    br ief reca p itul ation of the princi p al re sults is t t ing a t this p o int .

    G RAHAM discovered that in a queous solution a number of


    substances p rinci pally a mo rphous materials such as the glues
    , , ,

    albumen and dextrin have a very small p ower of diffusion


    , ,

    quite contrary to most salts A c cordingly he distinguished


    .

    between c o ll o ids and c rystall o i ds Subsequent investigations


    .

    served to increase greatly the number of c olloids i e sub stan ces ,


    . .
    ,

    of small diff usibility G radually the vie w develo ped that the
    .

    colloidal condition is not something p eculia r to ce rtain c om


    p o unds but
    ,
    that all sorts of substances even the crystall oids
    , ,

    can b e obtained colloidal by suitabl e treatment Hen ce the .

    c olloidal st at e is n o w regarded a s a general p ro perty of matte r .

    Just aS w e have substances in the solid liquid and gaseous states


    '

    , ,

    so we can also transform them into the c olloidal state .

    The question that arises rst is : Ho w may this conditio n


    b e b rought about ? The following methods serve the purp ose :
    I n the rst place colloids may be p re pared by sim ply dis
    ,

    solving certain substan ces such as glue in water


    , ,
    .

    Secondly they are formed in many cases instead of p re


    ,

    c ipit at e s when no ions are p resent Fo r exam ple if hydrogen .


    ,

    sul phide is passed into a solution of arsenic trioxide there results , ,

    instead of a p recip itate of A s 2 S3 a yello w liquid containing the


    ,

    arsenic sul phide in colloidal solution Ho weve r if the a rsenic .


    ,

    trioxide solution is rst a cidied with a little hydro chlo ric a cid
    ( a highly ioni z ed sub stance ) the A s
    , 2 S3 se parates out a s a yellow
    p reci p itate .A gain we
    ,
    may take mercuric cyanide a c om p ound ,

    that is hardly ionized at all in a queous so l ution If a solution .

    of it is treated with hydrogen s ul phide which is also a very feebly ,

    ionized substance the mercuric sul phide that is form ed is


    ,

    r etained in c ollo idal solution ; yet the usual p recip itate can b e
    ,

    o btained by a d d ing p reviously a small amount of a strong mineral

    a ci d
    .
    270 I N O R GA N I C C HE M I S TR Y .
    1 96 .

    a h y dr o s ol ( or in case alcohol is the solvent an a l c os ol ) and the


    , ,

    gelatinized mass a h ydro gel .

    When the solve nt water is extra cted fro m a reversible colloid


    by eva p oration at a l o w tem perature a hydrogel is at rst formed ,

    which still contains a great deal of water This water is partially .

    lost on ex p osure to the air M ore ra pidly in a desiccator and.


    ,
    ~

    its va p or tension does not differ perce ptibly fro m that of p ure
    water When however a certain stage of dehydration is rea che d
    .
    , ,

    the va p or tension begins to diminish I f water is a dded to the


    . .

    hydrogel before this stage is rea ched a hydrogel is again obtaine d ,

    with the same p ro perties as originally The p ro ce ss of s o l .

    and g e l fo rmation is thus a reversible one


    -
    .

    O ther interesting p ro perties are attached to hydrosols .

    C rystalloid salts for exam ple diffuse in them e ven in the con
    , , ,


    gealed mass almost as easily as in water If a p iece of j ellied .
    ,

    agar agar is immersed for some time in a dark blue am monia cal
    -


    solution of a co pp er salt the agar agar becomes s t ain e d t h ro u gh
    '

    out its entire mass C olloids on the contrary do not diffuse


    .
    , ,
    .

    This can b e shown by a colloidal solution of Prussian blue which ,


    does not p enetrate at all into the agar agar a s ab ove The ,
    .

    ele ctrical conductance to o is p ract ically the same fo r a gel


    , ,

    c ontaining c rystalloid salts in solution as f o r an a que ous solu


    tion of the same salts at like concentration .

    O f t entimes large a mounts of c rystalloid salts can be ad ded to


    a reversible hydrosol without the formation of gel This is very .

    di fferent with the second class of colloids the ir r e ve rsi b l e c olloids , ,

    for they are in many cases very sensitive to additions of salts .

    When the salt is adde d the irreversible hydrosol begins to a pp ea r


    cloudy and a p reci pitate is fo rmed which cannot be reconverted
    ,

    o ffhand into hydrosol .

    I rreversible hydrosols can be p re pared in the various ways


    already mentioned They com prise the c olloidal metals sul
    .
    ,

    p h id e s hydrated
    ,
    oxides etc M ost of them are mobile
    ,
    liquids
    .
    ,

    in contrast to many reversible colloids such as glue ,


    .

    The quantity of an electrolyte that is j ust sufcient to pre


    '

    c ipit at e an irreversible hydrosol is connected with the vale nce

    of the electro l yte the quantity decreasing ra pidly with in


    ,

    creasing valence The A Sz Sg hydrosol is j ust coagulate d by


    .
    C O LLO IDS .

    71 mill e quivalents of N a Cl
    -

    p e r liter ,
    of M gC l z and
    Of Al C l g .

    C e rtain irreversible colloids are ca pable of mutuall y p re


    c ipit at in g each other ; others are not The hydrosols of ferric .

    oxide and arsenious sul p hi d e give a preci pitate when mixed ,

    but the hydrosols of gold and arsenious sul phide mix without
    p reci p itation These
    .
    p henomena have been shown to be connected
    with the behavio r of the substances toward the electric current .

    If a solution is introduced into a Utub e su pplied with electrodes


    at the u pper ends and a strong current ( say 1 1 0 volts ) is passed
    through it the colloid is seen to se pa rate out and wander either
    ,

    to the ano de o r to the cathode A t one of the two ele ctro des an
    .

    aqueous layer a ppears which is entirely free from coll oid and is
    ,

    se parated sharply from the hydrosol This convective trans .

    ference or e l e c tri ca l e n dos m os e is by no means to be confuse d


    , ,

    with the ionic migration in electrolytes For while in the elec .


    ,

    t ro l yt e s there is an electrical O pp osition between the disso cia


    tion p ro ducts of the dissolved substance the electrical o pp osi ,

    tion exists in this case between the colloid and the solvent .

    I n general mutual p reci pitatio n is only p ossible with c olloi d s


    ,

    whose electrical charges are o pposite with respect to that of a


    common solvent .

    The coll oidal state must b e regarded as a very ne divi


    sion o r distribution of one substance in another This follows
    , ,
    .

    from the great analogy which exists between sus pensions


    clay and water ) and c olloids B oth can be se parated out
    .

    b y centrifuging and b oth dis play the TY NDA LL effect This .

    e ffe ct may be des cribed as fol l ows : When a beam of light


    p asses through a b ody of air that is
    invisible t ransversely ; the gas is o ptically a vacuum
    free from dust

    it is
    Bu t .
    ,

    so soon as dust pa rticles enter the air the path of the beam can ,

    be f ollowed through the dis persion of the light by the particles .

    O ptically va cuous liquids and o ptically va cuous solutions of


    c rystalloid salts can also be pre pared Bu t if a beam of light is
    .

    p assed through a hydrosol the p ath of the beam can be seen .

    The hydrosol is therefore not an o ptical vacuu m ; it must con


    tain oating particles b ut these are s o s mall that they can no t be
    ,

    seen even with the best microsc o pes .


    27 2 I NO R GA N I C C HE M I S TR Y . 1 96

    H ow ever SIE D E N T O PF and Z SI G M O ND Y have succee d ed in


    ,

    rendering these s u b m 1 c r o s c o p i c particles visible with an


    a pparatus that they call the u l tr am icr os c op e I n it the hydrosol .

    is illuminated transversely so that the luminous rays do not blind


    the eye of the observer The submicros co p ic particles bend (dif
    .
    i

    fra ct ) the light rays in all direction s so t hat w ith sufciently


    inten se illumination the light effect p roduced b y ea ch individual


    p article comes within the range of microsco p ic visib ility and can
    b e se parately observe d without however revealing it s form .

    Sus p ension s resemble c oll oids further in that they exhibit


    electrical endosmose and can b e preci pitated by the addition of
    ele ctrolytes .

    When a liquid is distribute d through another in exceedingly


    mall dro p s we have an e m u lsio n The most familiar exam ple is
    .

    milk an emulsion of butter fat There is reason for a ssuming


    ,
    . .

    that many reversible col l oids are extremely ne emulsions ; for


    instan ce an emulsion like a gelatine solution cannot be coag
    , , ,

    u l a t e d by the addition of an electrolyte .

    The knowledge that in the colloidal state we have to do with


    a very ne distribution of one substance in another has led to the
    introduction of a new set of terms The substance distributed
    .

    as a colloid is now generally s poken of as the dis p ers e p ha s e ,

    distributed in the disp er sion m ediu m Further the words dis


    p er s oids and em u l s oids are re placing the word colloids
    .

    It was formerly thought that a sharp distinction mus t be


    d rawn between colloids and real solutions G RA H AM s poke of .

    two diff erent worlds of matter I n contrast to the true solu


    .

    tions colloids exhibit pra ctically n o diffusion no va p or p ressure ,

    lowering no b oiling p oint elevation or free z ing p oint de pre s


    ,
    -

    sion in short no osmotic p henomena The researches of recent


    , ,
    .

    years have however shown that essential differences do not


    , ,

    really exist To begin with we have c ome u pon many cases


    .
    ,

    of transition between colloidal an d real solutions Furthermore .


    ,

    it was p reviously observed by L O B R Y DE B RU Y N that salt solu


    tions can be se parated by centrifugal force into p o rtions of unlike
    c oncentration M ore im p ortant still
    . the investigations of ,

    E I N ST E I N PERR I N
    ,
    SV ED B E R G and others have shown that
    ,

    colloids j ust like t rue solutions are subj ect t o the o smotic laws
    , ,
    .
    27 A IN O R G A N I C C H E M I S TR Y .

    G erm an ium x
    dio ide , G e O z, is p r o d uc e d b y h eat in g t he corre p di g s on n

    h ydro xide or b y r t i g t h l m t it ul ph i d o b y
    , o as n e e e en or s s e r tr t i g i t w ith
    ea n

    n i tric cid I t i w h ite p w de r o f a pe cic g avity f


    a . s a at 1 8 a d o s r o

    n

    i u
    s na ffe c te d b y h e t a .

    G erm an ium dis ul ph id G S s p at a w h it pr ci p it te w h e n e, e z, e ar es as e e a

    h yd ge
    ro ul ph i d i p e d i to t h e lut i
    n s f g e rm
    e ium d i xi de i
    s as s n so on o an o n
    str on g hydr ch l ric ci d I m i t i it d c mp s givi g ff h yd g n
    o o a .
    '
    n o s a r e o o se ,
    n o ro e

    sulph id I t di o lve in lk lie s an d alk li sulph i de s t o fo m l ph o lt


    e . ss s a a a r su -
    sa s .

    Fo g erm an ium cf al o
    r 218 . s .

    TIN .

    1 98 This metal is not very widely distribute d on the earth ; in


    .

    some plac es however it is found in quite large quantities The


    , , .

    p rinci p al tin mines of E uro p e are those in C ornwall ; e ven the


    Ph oe nicians obtain ed tin there The most irn po r t an t present locali .

    ties are on the group of islands lying east of Sumatra ( B anca Bil ,

    liton Sin k O p
    ,
    There the metal occurs in the form of t in
    ,

    stone ( cass iter ite SHO 2 ) ; it is foun d in quadratic crystal s which


    , ,

    are usually colored brown or black by a small amount of iron I n .

    order to extract t h emetal the ore is at rst roasted to eliminat e , ,

    any sul phur or arsenic it may contain and then reduce d with car ,

    bon The tin thus obtained is rened by liquation i e by fusin g


    .
    , . .

    again at a low tem perature and pouring it o from the less fusibl e
    alloy of tin with iron and arsenic I t is then melted once mor e .

    and stirred with a wooden pole (branch of a tree) whereby t h e ,

    oxide still r ema ining is re d uc ed The Banc a t in is nearly chemic .

    ally pure .

    Phys ical Properties Tin is a silve ry white metal melting at -

    and volatilizing between 1 4 5 0 and S = 7 293



    p g . . .

    at It has a crys t alline structure which can b e made vis ib l e


    b y moistening with hydrochloric ac i d whereupon peculiar fros t ,

    like etch g u res are p roduced on the surface ( tin moir e ) When t in
    - -
    .

    is bent a characteristic crackling sound ( cry of tin ) is heard which


    , ,

    is probably caused by the grating of the crystal faces on each other .

    Tin is very malleable and ductil e ; it can be beaten into very thin
    leaves ( tin foil ) at the ordin ary temperature and at 1 00 it can be
    -

    drawn out into wire A t a very low tem perature and in contac t .

    with an alcoholic pink sal t solution t in passes s pontaneously


    -

    into another modication gray tin which has a lower s pecic gravity , , ,
    TI N ,
    27 5

    A bove 2 0

    this form changes back to white tin If the l atter .

    is brough t in contac t wi t h gray tin at ordinary tem peratures


    it tur ns very slow l y into gray tin falling to owder
    p , ,

    called the tin



    probably because of the increase in volume ( this phenomenon is
    I f it is not in contact with the gray
    modication the transformation does not take place at all at
    ,

    ord inary temperatures or at least not for centuries Evidently , .

    there is a transition poin t of the two forms at and we are


    forced to the odd conclusion that exce pt on warm summer days , ,

    tin is in the me t astable condition .

    The reaso n why tin even in c ontact w ith gr ay m odicatio n ,


    ,

    passes so slowly into that form at ord inary tem peratures is tha t
    the velocity of transformation is small in the neighborhood of t he
    transition point ; it is accelerated on moving away from that point .

    When the tem perature sinks this acceleration is counteracted ,

    however by the retardation tha t all reactions un dergo by a lower


    ,

    ing of tem perature I n many cases therefore there must be a


    .
    , ,

    maximum of the velocity of transformation such as we have here ,

    at below that tem perature the transformation again becomes


    slower .

    O rd in ary t in c y t lliz e i t h e t etr go n l sy te m I n addit io n t o t h e


    r s a s n a a s .

    gray modic at ion th re i l o a th ird o n e t h e rh omb ic modic t ion Th e


    e s a s , a .

    tr it i n po i t t e t ag o n al a h o m b ic i about
    an s o n r r s

    Th i p i t w a de te rmi d in a u iqu e w ay n me ly b y me a uri g t h e


    s o n s ne n ,
    a ,
    s n

    velo city f w f t h e m t l u n d r h igh pre ure F th i purp


    o o o e a the e ss . or s o se

    s o li d m e t l w a pl c d i a cyli n d r h vi g
    as a e h l e i t h e b ott m
    n d t hee a n a o n o , an

    qu an t ity f m etal w m a ur d th t w f c d t u der c n t t pr


    o as e s e a as or e ou n o s an es

    s ure in t h e u n i t f t im I n g er l t h i qu t i ty i n c e e r p i dly w ith


    o e . en a ,
    s an r as s a

    i i g t mp ture b t w ith t in it w f u d t dimi i h c o ider b ly w h e n


    r s n e e ra ,
    u as o n o n s ns a

    t h e t m p e r tur r c h d a b o u t
    e a e ea T h i m a y b e t ak n
    e pr f th at s e as a oo

    t h e m t al h s an th r (th i rd) mo dic at io o b r i ttl e th at



    e a o e A t 2 00 t i i n . n s s

    it an b e e a ily p l veriz e d
    c s u .

    C hem ica l Pr oper ties


    Tin is una ffec ted by the air at ordin ary
    .

    temperatures ; if heated strongly it burns with an intense white ,

    light to tin oxide Sn O z Hydrochloric acid dissolves it formin g


    ,
    .
    ,

    stannous chloride and hydrogen I t is also attacked by nitric acid .

    A boiling solution of caustic soda or potash converts it


    into a stannic acid salt ( S t a n n a t e ) with the evolution of h ydro e

    Sn 2 KO H H2O K zsn 0 3 2 H2 .
    I N O R GA N I C C H E M I S TR Y .

    In t h e presenc e o f weak aci d s ( acetic acid ) an d alkalies it is very


    stable .

    1 99 . Us es .
    -
    On
    account of its permanence tin is used as a pro
    t e c t iv e covering for metals which are attacked by the air and t h e

    above named agencies M any kitchen utensils are tinned
    -
    . Shee t .

    iron is covered with a layer of tin to protec t it from rusting ,

    and is then known as tin pl ate or sheet tin This is done by simply ,
    -
    .

    dipping the shee t iron which has b een cleane d by hydrochlori c


    ,

    or sul phuric acid in molten tin ,


    .

    Many all oys of tin are in use Solder consists of tin and lea d
    .

    ( in the ratio or or and is harder than E ither of its


    com ponents b u t more easily fusible The alloys of c o p p e r and .

    t i n a re called bron zes; their com position varies according to t h e


    p pur ose they serve A t p resent
    . the bronzes usually contain a
    little lead and zinc as well Bronze is hard and tough can b e .
    ,

    easily worked and fuses to a mobile liquid hence it is p articularly ,

    suitable for casting G u n m etal contains 90% co pper and 1 0% tin ;


    .

    bel l m eta l 202 5 % tin the rest being co pper


    ,
    Phos phor br onze is .

    re
    p p ared by fusin g co pper with tin phos phide The result
    ing mass is remarkably homogeneous and contains
    hos horus and 1 5
    p p 5 % tin I t s great hardness and rmness render
    .

    i p
    t es ecially valuable for certain p arts of machines ( axle bearings
    ) .

    Sil ic on br on ze contains silicon in place of phos phorus is very har d ,

    and conducts electricity well hence it is used for making telephon e


    ,

    wire Tin amalgam forms the metallic coating of mirrors


    .
    .

    C o m po u n ds of Tin .

    Tin forms t wo sets of com p ounds ; they corres po nd t o t h e


    o xygen com p ounds s tan n ou s oxide Sn O
    , and s tan n ic oxide SnO z , , , .

    STA NN O US C O M PO UN D S .

    2 00 . St an n o u s ch lo ri de , Sn C l z , is pre pared by dissolving t in in


    hydrochloric acid :
    SH 2HC l ZSD C l Q H2 .

    It crystallizes with t wo m olecules of water wh ich are given o ff at ,

    I t is very readily soluble in water ( 1 part in


    ,. at ordina ry
    t em peratures ) A nhydrous stannous chloride is white and trans
    .

    p arent ; it melts at 250 and b oils at



    A little above t h e
    278 IN O R G A N I C C HE M I S TR Y . 2 oo_ ,

    Tin take s u p t w o m o r e positive charges b u t thi s n ec ess itates that ,

    the two C l atoms become ions ; they thus r equire two negative
    charges ; but when these are form ed two positive charges are o b
    t ain e d at the same time However the Sn "".

    and C l ions unite ,

    to form stannic chloride Sn C l 4 which is a very weak electrolyte


    , ,

    ( f
    c .

    the pre paration of chlorine hydrochlo ric acid is


    In ,
    xidi
    o ze d
    b y manganese dioxide :
    M n o2 4 11 01 M n oi2 2 11 2 0 012 ,

    Mn 0 2 4H 4 Cl M IT 2 C l l 2 H2 O
    O lg ;
    ' ,

    the p ositive charge of the four H ions is thus trans fe rr ed h al f t o


    '

    , , '

    the manganese and the rest serving to discharge two chlorine ions ,

    i e t o equalize their negative charges


    . . .

    V arious dou bl e sa l ts of stannous chloride are known e g ,


    . .

    St an n o u s h ydr oxi de , Sn ( O H) 2
    is preci pitated when a s olut i on
    o f stannous chloride is treated with soda

    Sn 012 + N 5 20 0 3 + H20 Sn (O H) 2 + 2 N a01 + C O z .

    This hyd r oxide is insoluble in amm o nia but soluble in alkalies ; ,

    when the latter solution is boiled tin is de p osi t e d an d alkali stan ,

    n ate e g
    ,
    K zSn O g formed
    . . The h ydroxide is also soluble in
    ,
    .

    a cids thus dis playing a b asic as well as an acidic nature


    ,
    Such .

    com p ounds a r e able to give hydroxyl ions on t he



    o n e hand and hydrogen ions ( Sn O z + 2H ) o n the o the r
    '

    They
    _
    .

    ar e termed am ph o t e ri c c o m p o u n ds .

    St an n o u s oxi de is obtained by heati n g the hydroxid e in a cur


    r ent o f carb on dioxide ; it is a dark brown powder which takes -

    re in t h e air bur n ing to sta n n ic o xide Sn O z


    .

    , ,
    .

    sal ts of stannous o x ide than the above m entioned stann ous


    O ther -

    chl ori de are al so known The sul phate for instan c e is obtained by dis
    .
    , ,

    so lvi ng the hydro xide or the metal in d ilute sulphuri c acid It form s a .

    basic salt readily .

    i de , Sn S is preci pitate d as an am orphou s b rown


    St an n o u s su l ph ,

    po wd e r when hydrogen sul ph ide is p assed into the solution of stan


    n ous s alts It is insoluble in p otassium sul phide K Q S but i t
    .
    , ,
    S TA N N I C C O M PO UN DS .
    27 9

    d issolve s t o form a ul p S
    when brought in c on tac t
    ho stannate
    with the p o l y s ulphide of ammonium or potassium Ks (x = 2 ,

    811 8 K 2 S2 K 2 SIIS3 .

    St ann ous s ul phide can also be pre pared by fusing tin with sul

    phur I
    . t t hen forms a bluish gray crystalline mass -
    .

    STA NNI C C O M PO UN D S .

    201 St an n ic c hl o ri de , Sn C l 4 , was pre pa r ed as early as 1 605 I t


    . .

    was named s piritu s fu m a n s L ibavii , after its discovere r I t is .

    o btained by the action of chlorine on tin or stannous chloride .

    Stan nic chlori de is a liqui d which fumes strongly in the air ; it


    b oils at an d has a s pecic gravity of at When
    br ough t in contact w ith a little water or o n taking u p moisture
    from the air it goes ove r into a semi s olid crystallized mass
    ,
    -

    , ,

    Sn C l 4 3 HQ O the s o called
    -
    ,
    t in bu tter A fresh solution of stannic
    -

    chloride is a very poo r conductor of electricity Howeve r the con .


    ,

    du c t iv it y increases slowly at ordinary faster a t higher tem pera , ,

    t ures ; afte r several days it reaches a m aximum In the case of


    -
    .

    more d ilute s olutions this m ax im iim is much high e r These facts .

    can b e explained by assum ing that stannic chlo ride is b ut feebly


    ioniz e d an d that it r eacts wi t h water in the following way ;
    Sn C l 4 + 4 HzO Sn (O H) 4 + 411 01;

    in othe r wo rds that it un d ergoes hy dr olytic dissociation I t is


    , .

    the liberated hydrochlo ric acid that causes the conductivity .

    The solution contains tin hydroxide ia the colloidal state The


    '

    wate r has thus s pli t u p the stannic chloride into a basic hyd r oxide
    an d an acid .

    Stannic chlo ride forms well crystallized d ouble salt s with t h e -

    alkali chlorides e g Sn C l 4 2 KC 1 and Sn C l 4 2 N H4 C 1 The latte r


    ,
    . .
    - -
    .

    is known as pink s a l t (b ecause of its color ) and is use d as a mor


    dant in dyeing Tin tetrachloride also unites with t h e chlo rides of
    .

    the metalloid s t o form crystallized substances e g SnC l 4 PC 15 ; ,


    . .
    -

    Su C l 4 PO C 13 Sn C l 4 SC l 4 e t c
    -
    I t combines with hydrochloric acid
    -
    ,
    .
    ,

    fo rm ing a leafy c ry stalline mas s Hg SnC l GHzO which melts at


    -

    ,
    -
    ,

    Tin u o ride , SnF4 , itself is n ot kno wn b u t there is a c om pound , ,

    KZSnFG which corres ponds to potass ium uo s ilic ate ; the sa lts of hydro
    ,
    -

    u o t an n ic ac i d are isom orpho u s w i th t h e an al o g o u s s il ic on c om pound s


    s
    .
    2 80 I N O R GA N I C C H E M I S TR Y .
    1 2 01

    o xi de , Sn O z can b e pre p ared synthetically b y heatin g


    Stan n i c ,

    tin in air I t is an amorphous white p o wder insoluble in acids and al


    .
    ,

    kalies ; the latter however dissolve it w h e n f


    , ,

    s p o n din gto Sn 0 2 have only very weakly b asic p ro perties ; here t h e


    acidic p ro perties are p rominent The normal hydroxide Sn ( O H) 4 .
    , ,

    is unknown but there is a hydroxide of the em p iric al com p osi


    ,

    tio n HQ O ) corres p onding to c arb onic acid , ,

    H2 C 0 3 . Strangely enough this exists in two modications which ,

    di ffer from each other b oth chemically and physically ; they are
    c alled stannic and metastannic acids .

    The s tan n i c a c i d is precip itated when ammonia is added to an


    aqueous solution o f st ann ic chloride or hydro chloric acid to a po t as
    '

    sium stannate solution This preci p itate reacts acid when moist
    .

    and is soluble in c oncentrated hydro chloric and nitric acids as well ,

    as in alkalies I t grad u ally changes into metastannic acid


    . .

    M etas tan n i c a c i d is generally p re p ared by treating tin with


    strong nitric acid ; it is then formed in a vigorous reaction as a
    dense whit e p owder M etastannic acid is insoluble in sodium
    .

    hydroxide but nevertheless unites with it to form sodium m e t ast an


    ,

    nate this is dissolved by water although with di fculty but is in s ol u , ,

    ble in the caustic so da solution When boiled with hydro chlori c .

    acid metastannic acid goes over into a chloride which is insolubl e


    , ,

    in the concentrated acid but soluble in water This solution does .

    not contain the ordinary tin chloride but another one me t a t i n , ,


    -

    h l o r i d e having however the same com p osition Sn C l 4 I t is


    , , , , .

    distinguished from the ordinary stannic chloride by giving a yellow


    coloration with stannous chloride solution ; the solution of the ordi
    n ary chloride does not do this till after some tim e during which ,

    the m e t a ch l o ride is formed in it .

    Stannic acid and the corres p onding chloride thus p as s over int o
    the meta com pounds s p ontaneously ; on the other hand m e t ast an
    -

    nic acid c an be converted into the ordinary tin com p ounds b y b o il


    ing it for some time or fusing it with a caustic alkali .

    i
    Th e d ffer en c e b e tw een stann ic an d m etas tann ic acids w as po i nted o ut by
    BER ZE LI U S as e rl y as t h e b e gin n i n g o f t h e n ine t eenth c entury
    a Th ey ar e .

    b oth co ll o i ds T h e s al ts o f m e t as tannic a ci d h v e in gen e ral a very c o m


    . a

    plic at e d c om p o s i t i o n s im il ar to t h e p o l y silic at e s
    , fo r w h ich re as o n
    m t as tann ic a ci d is regarde d as a p o lym er o f t h e ordin ary stannic acid i e
    e ,
    . .
    ,

    th at it s mol ecul e is rep resen ted by (11 8 0 0 stan nic aci d i ts elf b e in g H Sn og
    2 11 1 1 3, z .
    28 2 IN O R G A N I C C H E M I S TR Y . 2 03

    Phys ical Properties L ead is a sof t ductile metal of a bluish


    color O n exposure to the air
    . it loses its lustre rapidly becoming ,

    c oated with a very thin layer of ox ide I t has a s pecic gravity of .

    melts at and b oils at


    C h emica l Prop er ties The thin coating formed by the oxide o n

    the brillian t surface of the metal protects the lead from further
    attack by the air If however it is prepared in a very nely
    .
    , ,

    d ivided state e g by heating lead tartrate or citrate in the absence


    ,
    . .
    ,

    of air it takes re in the air even a t ordinary tem p eratures ( O ther


    , .

    metals can be reduced in a similar way to a ne state of division ,

    whereupon they ignite s pontaneously in the air A substance .

    which exhibits this phenomenon is called a p y r o p h o r u s


    When lead is melted it becomes coated with red oxide of lead ;
    ,

    by constantly removing the latter the lead can be entirely oxidi z ed ,


    .

    A com pact mass is unaffected by sulphuric or hydrochloric acid ,

    b ut when nely divided it reacts to form the c orres ponding salts


    , , .

    N itric ac id easily dissolves it to form the nitrate A cetic acid .

    a n d various veget able acids attack it ; Since all lead salts are very

    p
    _
    io s o n o u s and very serious effects resul t from chronic p oisoning
    with insignicant but succ essive amounts it is n o t admissible to ,

    u s e tin containing lead in tin plating vessels for use in the kitchen
    -
    .

    Zinc and iron preci pitate the metal from solutions A piec e of .

    z inc becomes covered with a dendritic crystall ine mass lead


    tree This reaction can be expressed by :
    Zn + Pb
    "

    ie .
    zinc is changed into the ionic condition and the lead ions are
    .
    ,

    discharged How it comes about that one metal thus assumes the
    .

    electri c al charge of another may be explained by a hy pothesis of


    N ERN ST His supposition is that every metal on coming in con
    .

    tac t with water or a solution tends to send positive ions into it .

    This emission of ions continues until the p ositive cha rge acquired by
    the solution and the negative charge created on the metal balance
    by their mutual attraction the tension ( called the el ectrol ytic
    s olu tion ten s ion ) with which the ions are driven into the solution
    -
    .

    This tension differs considerably for different metals ; fo r zinc it


    is much greater than for lead When therefore a strip of zinc .
    , ,

    is dipped in a lead solution it forces zinc ions into the solution an d


    the zinc thus becomes much more negatively charged than woul d
    O X I D E S O F L EA D .
    283

    a piece of lead by the emission of lead ions The lead ions ar e .

    therefore at t r ac t e d b y the zinc and d ischarged i e lead is pre cipi ,


    . .

    t at e d from the solution Th is process sto ps only when all the


    .

    lead of the solution has been re placed by zinc .

    Distilled water from which the air has been entirely removed
    ,

    by boiling has no e ffec t on lead but the simultaneous action of air


    , ,

    and water produce lead h ydroxide which is somewha t soluble in ,

    water This hydroxide is converted into insoluble basic carbonate


    .

    by carbonic acid .

    Fro m a hygi enic standpo int these pro perties of l ead are of vast im por
    tan c e be c au se dr i nki ng water i s a lm ost universally c ondu c ted thro ugh

    -

    ppi es m ade of l ead or m ater i a l c onta i n i ng l ead ( co m p o The


    absorpt i on of l ead fro m s uc h pi pes by water and t h e c ont i nu at i on of
    the pro c ess depends i n a l arge m eas u re on the proport i on of sal t i n the
    water As a r ule the l ess of sal ts i t c ontains the m ore lead i t takes
    .
    , ,

    up .R ai n water wh i ch i s a lmost ent i re l y free fro m so li d m atter b u t


    -

    , ,

    contai ns o xygen c arbon di o xi de and tra c es of a mm on i a is therefore


    , , , ,

    m ost likely to d isso lve l ead The l ead eave tro ughs e t c wh ich were .
    -

    ,
    .
    ,

    on c e e xtens ive ly u sed sho ul d therefore b e re j e c ted i n c ase t h e rai n


    , , , ,

    water i s u sed for dri nki ng We ll Water u s u ally c onta i ns a ci d c alcium


    .
    -

    c arbonate and gyps um ; as a res ul t t h e lead pi pes soon be c o m e coated ,

    wi th an i nso lubl e l ayer of l ead s ul phate and bas ic carbonate (as well
    .

    as c alcium c arbonate ) so that after a whil e the lead c an no l onger be


    ,

    absorbed by t h e water .

    L ead is used for many


    ur
    p p oses not only in the elemental con ,

    dition but also in the form of alloys ( see


    ,

    O xi de s of L e ad .

    2 04 . The following oxides of lead are known : Ph 2 o Pb O , ,

    Pb 2 0 3 , Pb 3 0 4 , Pb O z .

    L ea d o x i de , Bb O , is the only o n e of these oxides with basic pro p


    e rt ie s .It is formed by direct synthesis from its elements
    I t is fusible and c ongeals again to a red d ish yellow mass called
    ,
    -

    l itha rg e By carefully heating lead lead hydroxide o r lead nitrate


    .
    , ,

    the oxide is obtained a s an amor phous brown p owder (m a s sic ot) .

    It is somewhat soluble in water forming the hy d roxi d e It d is ,


    .

    solves in caustic potash and cry stallizes out in rhombic p risms on


    ,

    cooling .
    2 84 IN O RG AN I C C H E M I S TR Y .

    L ea d h ydr oxi de , Pb ( O H) 2 , is formed by pre cip itating a lea d

    so lution w ith an alkali I t is am photeric sin ce it is solubl e


    .
    ,

    in caustic al k alies ; amm o nia however d oes n o t d issolve it , ,


    .

    O n b ein g warmed to 1 4 5 it gives u p water an d turns t o

    o xide It is somewhat sol uble in water im pa rtin g to the latte r


    .
    ,

    an alkali n e rea ction an d absorb s carb on d ioxi d e from t h e


    ,

    a1 r .

    Min iu m , or red l e ad, Pb 3 0 4 ,


    is prepared by heating lead oxid e
    o r white lead in the air for quite a wh ile at 3 00 B ecaus e
    o f its pleasing red color it is used as a p igment in painting .

    G e n tle heating makes the colo r a brighter red at rst ; stronger


    heating turns it violet and nally black ; on cooling however , ,

    the original color returns By treating it with dilute nitric acid


    .
    ,

    lead nitrate and lead peroxide are formed henc e minium may b e ,

    r egar ded as 2 Pb O Pb O z -
    .

    L e ad per o xide Pb O z is obtained in the way j ust stated ; mor e


    , ,

    easily however by p assing chlorine into an al kal ine lead solutio n


    , ,

    o r add ing a hy ochlorite to a lead salt thus


    p ,

    2 Pb C 12 C a(O Cl) 2 2 H2 O 2 Pb O z C aC l z 4 HC 1 .

    Milk of lime then added to neutralize the free acid


    is .

    L ead peroxide is an amor phous dark bro w n powder It has t h e -


    .

    p ro p erty c ommon to most


    , p eroxides of givi n g u p oxygen easily
    , .

    A t an elevated tem perature it Splits u p into lead oxide and oxygen .

    O n warming it with sul p huric acid lead sul phate and oxygen are
    -
    ,

    formed ; on warming with hydrochloric acid lead chloride and ,

    c hlorine are produced .

    L ead peroxide like the oxides C 0 2 and Sn O g has the characte r


    , ,

    o f an acid anhydride ; it is soluble in hot concentrated p otassium .

    hydroxide and this solution on cooling de posits crystals of the com


    , ,

    p osition K Q Pb 0 3 + 3 H 2 O ( which are thus entirely analogous in com ~

    p osition to p otassium stannate ) .


    This p l u m ba t e is easily decom p ose d
    by water into potassium hydroxide and lead p eroxide If we regar d .

    lead p eroxide as an acid anhydride minium can be considered as ,

    the lead salt of the normal plumbic acid Pb (O H) 4 i e Pb 2 Pb O 4 , ,


    . .

    .

    Th is idea is conrmed by the following method of formation : I f a


    solution of lead oxide in potassium hydroxide is added to a solutio n
    o f the plumbate K 2 Pb 0 3 a yellow substance is precip itate d having
    ,
    236 IN O R G A N I C C HE M I S TR Y . 2 06

    Le ad trachl oride Pb C 1 i s form ed when a so l uti on of l ead d ic hl ori de


    te , 4,

    i n strong hydro c hl oric a ci d c ool ed by ic e i s sat urated wi th c hl ori ne


    , , .

    Fro m th i s liqui d a mm on i u m c hl or i de pre ci p i tates a l e m onye ll ow c rys


    t all in e s ubstan c e 2 N H C l Pb C 1
    , 4 havi ng a c o m posi ti on anal ogous to
    -
    4,

    p i n k sa l t
    -

    A nal ogo u s doub l e sal ts of Pb C l are al so form ed w i th t h e alk ali


    4

    m etals such as p otass i um and r ub i dium (s Pb C l ) I f one of these


    , .

    do ub l e sal ts i s treated wi th ic e c o l d c on c entrated sulphuric a ci d l ead


    -

    tetrachl ori de gradua ll y separates o u t as a hea vy yell ow oil (sp g . .

    whic h i s stab l e at a l ow te m perat u re and c rystalliz es at A t as


    hi gh a te m perat ure as roo m te m perat ure and m ore rapi dl y o n war mi ng , ,

    i t brea ks u p i nto l ead d ichl ori de an d c hl orine .

    O th er L ead Sal ts .

    206 . L e adit rate , Pb ( N 0 3 ) 2 is obtained by dissolving lead in


    n ,

    dilute nitric acid I t is colorless crystallizes isometric and is


    .
    ,

    soluble in 8 parts of water Heating decom poses it .

    Several basic lead nitrates are known


    L e ad su lph at e , Pb SO 4 is prac tically insoluble in water and can
    ,

    therefore be obta in ed by preci pitating a lead solution with dilute


    sulphuric acid or a soluble sul phate It occurs as a mineral in .
    _
    i

    crystallized form under the name of angl esite; it is isomor phous


    with the sul phate of barium barite L ead sul phate is soluble in
    ,
    .

    concentrated sul phuric acid ; hence the crude acid which is con
    c e n t r at e d in lead p ans 1 86 3 ) contains lead sul phate ; this is
    ,

    p reci p itated on diluting the acid with water I t is dissolved by .

    c onc entrated alkalies



    I gnition on charc o al reduc es it t o sul phide
    .


    L ead disu l ph at e , plumbic sul ph ate Pb (SO 4 ) 2 se parates fro m , ,
    .

    the acid around the anode when sul phuric acid of s p ecic
    gravity is electroly zed between lead electrodes It has n ot been .

    obtained quite free from lead sul phate I t is a white granular sub .

    stance of stro n g oxidi z ing p ro pert ies Water de com po ses it readily .

    int o sul phuric acid and lead peroxide I t is iso meric with l e ad .

    p e r su l ph at e , Ps O g a salt,
    of the dibasic p ersul p huric acid .

    L ead c arb o n at e , Pb C O g is de p osited when a solution of the


    ,

    nitrate is treated with ammonium carbonate White l ead a basic .


    ,

    carbonate is used extensively as a p igment However it soon


    ,
    .
    ,

    turns black if any hydrogen sul phide ( from drainage p i pes etc )
    , ,
    .

    comes in contac t with it ; moreover it is inj urious to the health , ,

    because it comes o ff of the p ainted walls in the form of dust and


    S UM M A R Y O F THE C A R B O N G R O UP . 2 87

    gets into the lungs Wh ite lead is particularly valuable for its .

    cov erin g pow er , i e the p ainted surface a ppears p erfectly white


    -
    . .

    when covered with only a very thin layer of the pigment ; it is


    much greater than that of o ther white pigments such as white zinc ,

    and barite which are frequently substituted for white lead becaus e
    ,

    they are harmless .

    The m an u f a c t u r e o f w h i t e l e a d i s st ill c arri ed on e xten


    -

    siv e l y after the Dut c h m ethod Thi s c ons i sts i n pl a ci ng ro lls or


    bu ckl es of lead pl ate into j ars c ontai ni ng a li ttl e a c et ic a ci d The
    -
    .

    vesse l s are l oose ly c o v ered wi th a l eaden li d and b uried i n a heap of


    horse m anu re Th e heat generated by the de c ayi ng m anure c auses
    -
    .

    a part of the a c et ic a ci d to e v aporate and converts t h e lead i nto bas i c


    lead a c etate The l atter i s then transformed to whi te l ead by t h e c ar
    .

    b o n d i o xi de gi ven o ff fro m the de c ay i ng heap Af ter abo u t ve or .

    s ix wee ks the pl ates are alm ost ent i re ly changed to whi te l ead Th i s .

    is then gro u nd m o i st washed o u t (to re m ove any a cetate ) and dried ,

    where u pon i t i s sent to the m ar ket .

    L e ad
    l ph i de , Pb S is black and comes down amorphous when
    su ,

    hydrogen Sul phide is passed into a lead solution A liquid con .

    taining only traces of lead is colored brown by sul phuretted h y


    drogen ; this is a very delicate means of testing for lead Strong .

    nitric acid oxidizes it readily to lead sulphate .

    SUM M A R Y O F THE CA R BO N G R O UP .

    The elements carbon s il icon germ an iu m tin and lead


    207 .
    , , ,

    fo rm a n atural group as may be seen from a com parison of thei r ,

    physical and chemical pro p erties I n the following table the .

    most im portant p h y s i c a l co n stants are summarized ; here ,

    as in other natural groups the gradual change of these constants ,

    with the rise of the atomic weight is very evident

    A tomic w ight e . 207 1 0


    Spe cic g ravi ty . 11 39
    Me lti n g p int-
    o . 23 3
    3 27

    Bo ili g po int
    n -
    . ab o ve 3 000
    circ a 1 500

    1 52 5

    28 8 IN O R G A N I C C HE M I S TR Y .
    m 207
    With re spect to t h e c h e mi c a l pro pe rties we n ote in t h e
    '

    first place that all th ese elem en t s h ave the same com p ound ty pes -

    MX2 and MX4 ; in other words t h at they are b i or quadri valent ,


    -

    this is even true of lead ( Pb O z Pb C l 4 which does not t , ,

    into the table of physical pro perties with its boiling an d m elt ing
    points M oreover there is to be n o ted in ge n eral a transiti on
    .
    ,

    from metalloid to m e t allic character as is plainly Shown by t h e ,

    following facts :
    1 O nly carb on and Silicon are known to form hydrogen com
    .

    p ounds ( o f an indi fferent nature ) .

    2 O f the oxygen com p ounds of the M O ty pe that of carbon is


    .
    ,

    indifferent and the others ( no su ch com pound of silicon is known )


    grow m ore b as ic in character as the atomic weight increases lea d ,

    hydroxide having rather strongly alkaline pro perties .

    3 The oxygen com p ounds R O 2 however are decidedly acidic


    .
    , , ,

    in character in the cases of carbon and silicon and also in the cas e
    of germanium while in that of lead the salts of the acid Hs O 3
    ,

    are immediately de com p osed by water so that here the acid pro per ,
    ~

    ties appear much weakened .

    4 A s to the halogen com p ounds those of carbon (C X4 ) are


    .
    ,


    unaffected by cold water perha ps be cause of their insolub ility
    in it ; the o ther halogen com p ounds MX4 are decom posed by , ,

    water .

    L ead i n so m e of i ts, phys ic a l


    and che mic al pro pert i es does not dis ,

    pl ay the g radat i on wh ic h i s ord i nar il y m e t w i th in t h e e l e m ents of a

    gro u p Th l S pheno menon i s qui te often observed i n e l e m ents of very


    .

    high ato mic we i ght I n the ni trogen group we saw it in the case of
    .

    b i smu th .

    M ETH O DS O F DETER M I N I N G A T O M I C W EI G HT S .

    2 08 . So
    far only one method of determi n ing the atom i c weigh t
    has been m entio n ed This consists in investigating as large
    as p ossible a number of gaseous com p ounds of the element as t o
    their va por densi t y and em pirical com p osition and then calc u lating
    how m any grams of the element are contained in a mole of
    the various com pounds The smallest gure thus found is taken
    .

    as the atomic weight A lthough this method is quite general


    .
    ,
    El em ent. Sp H
    . . At . Wt . P r o du c t .

    L iqui d .

    Sp H
    . . at 2 57 pro

    Boron . 0 2 54 11 0 . A m rph o us
    o Sp H
    . . . at 40
    prod .

    C arb on
    m o rp h ou s
    r
    a

    1d i am on d Abo ve 9 00

    Sp H = 0 4 5
    . . .

    pro d .

    So d ium
    M ag e s
    '

    A lumi n ium
    Silic on . C rys ta lliz e d . Sp H . . ab oy
    prod
    0
    2 00 5 . .

    Ph osph orus . l
    Y e l ow . Sp H o f re d P
    . .

    pro d .

    ul ur
    S ph . R h o m b ic .

    Po tassium
    Ca lcium
    c ium
    S and .

    C h romium .

    M ang n es e a

    I ron

    Zinc
    G llium
    a
    G ermani um .

    A rs n ic
    e
    Sel e n iu m .

    Bro mine
    Zirconium .

    M olyb d num e
    R u th n ium e .

    R h o d ium .

    P ll dium
    a a .

    C ad mium .

    Tin
    im
    A n t on y .

    Tellu ium
    r .

    i
    Io d n e .

    um
    L an th an .

    ium
    C er
    u g
    T n s te n .

    Osmium

    G ol d o o o o o o o

    Th a llium .

    L e ad
    i mu
    Bs th
    um
    Th o ri
    C a ium
    r n
    2 09 ] M E TH O D S O F D E TE R JI I N I N G A TO M I C WE I G H TS .

    the result thus o b taine d is only a p p r o x i m a t e l y


    O f course
    c orrect for the p roduct
    ,
    is not strictly constant The metho d .

    is however reliable enough to determine what multi ple of th e


    , ,

    equivalent weight 2 2) the e x a c t value of which c an be foun d


    by analysis is the atomic weight
    ,
    .

    209 2 C losely c onnected with th e law j ust enunciated is tha t


    . .

    o f N E UM A N N which has been more carefully investigated by R E G


    ,
    c

    N AU L T and K O PP This law says that in s olid com pou n ds each


    .

    el em en t ha s a con s ta n t a tom ic hea t, which var ies bu t l ittl e tha t


    f rom

    of the fr ee el em en t The molecul ar heat is therefore equal to t h e


    .

    sum of the atomic heats I f the molecular heat of so l id com .

    p ounds i s d ivided by the number of atom s the quotient must be ,

    about I n reality this quotient proved to be : for b romine


    compounds R Br for R Br g ,
    for iodine comp ounds R I
    , ,

    R 12 ,
    The law of N EUMANN l ikew ise holds for many elements
    whose s pecic heat in the solid state has not been susce ptible of
    measurement thus e g for chlorine compounds : for R C l com
    ,
    . .

    p ounds the quotient referr ed to was for R 0 12 for certain ,

    double chlorides For other elements like oxygen the


    , , ,

    ato m ic heat found from the molecular heat of the com pounds is
    constant but it is about
    ,
    instead of about The same is
    true of hydrogen whose mean atomic heat in soli d com pounds
    ,

    is These gures were found by determ in in g the molecular


    heat of various oxygen or hydrogen compoun d s and subtracting
    from it the known atomic heats of the other elements If the .

    atomic heat thus obtained is divided by the atomic weight w e ,

    have the s pecic heat of the element in its compounds .

    The way in which the law of N EUMANN can be applied t o


    atomic weight determinations is illustrated by the following
    exam ple

    The proble m i s to deter mi ne the ato mi c we i ght of c alcium wi th the


    he l p of the Spe ci c heat of s ul phate of lim e C aSO 4 whic h a m ounts t o , ,

    ac c ord i ng to R EG NAU L T .

    A nalys i s has show n that anhydro u s c a lcium s ul phate c onta i ns


    c alcium , s ul phu r a n d o xygen Si n c e s ul phates c ontain the
    , .

    S0 gI O Up i n c o mb i nat i on w i th a m eta l i t fo ll ows fro m t h e abo ve


    4

    analys i s that there mu st b e asso ci ated wi th thi s gro up 4 0 parts b y


    w ei ght of c a l c ium T h e ne x t qu est i on i s whether 4 0 i s reall y t h e
    .
    ,
    .

    2 92 I N O R GA N I C C H E M I S TR Y .
    209

    ato mic wei ght of c alcium or a mul ti pl e or s ub mul ti pl e of the ato mi c


    we i ght .

    N o w t h e m o l e cul ar wei ght of c alcium s ul phate mu st b e 4 0 + 3 2 + 4 X 1 6


    = 1 3 6 no m atter whether 4 0 i s t h e re l at iv e we i ght of one or of m ore
    ,

    than one c alcium ato m The m o l e cul ar heat i s therefore 1 3 6


    .

    The ato mic heat of s ulph u r i n c o m po unds is about and that of o xygen
    ab o u t c onse qu ently t h e m ol e cul ar heat of t h e S0 grou p in i ts so li d 4

    c o m pounds i s Fo r the ato mic heat of c al c ium w e


    ha v e t h e re m a i n der ,

    I t therefore fo ll ows that the formul a of c a lcium s ul phate mu st be


    C a SO whi c h m eans that 4 0 i s the ato mic wei ght of c alcium ; for i f the
    4, ,

    ato mic wei gh t were a mul ti pl e or s ub mul ti pl e of thi s n umber we sho ul d ,

    hav e fo und for the ato mic heat of t h e m etal a n umber muc h farther
    fro m the a verage ato mi c heat of the el em ents than ,

    The value of t h e atomic weight calculate d from N E UM A N N s

    law therefore serves merely t o decide what mul ti ple o f the e q u iv a


    lent weight must be taken ; for this pu rpose the num b e r so o b taine d
    is su fciently accurate .

    2 10 3 Th e l aw of M it sc h erl ic h
    . . The crys ta l form of com
    .

    p o u n ds h a vi n g a n a l og o u s ch em ica l c o m p o s ition is the s am e : or in ,

    o ther words com pou n ds of an a lo gous


    ,
    chem ica l com pos ition ar e

    is om or phou s The compoun ds KCI KI KBr e g are , , ,


    . .

    analogous in com position ; they all c rystalliz e in cub es HzK PO 4 .


    ,

    H2 KA SO 4 H2 (N H4 ) P0 4 also have an analog ous c o m position an d


    ,

    all crystallize in the tetragonal system The anal og ous c om poun ds


    .

    KC IO 4 an d KM n O 4 both crystallize rhombic .

    If two com pounds have been prov ed to b e isomo rphous it is ,

    v er y probable that their com position is analogous whereu pon ,

    the at omi c wei gh t is readily foun d L et u s for e xam ple tak e


    .
    , ,

    the case of manganese suppos ing its a t omic weigh t t o be unk n own ;
    ,

    now p otassium permanganate is isomo rphous with po t assium per


    chlorat e which latter is known t o hav e t h e formula KCIO 4
    , .

    An alys is h as shown the formula of po t assium perm anganate to b e


    KM n O 4 a: bein g unknown fo r 3 9 par t s (b y weigh t ) of po tassium
    x , ,

    ( 1 atom ) a r e c o m b in e d w it h 64 p a rt s of oxygen ( 4 a tom s ) an d 55

    p arts of manganese ( 3: a t oms ) From . its isomor p hism with K C l O4


    it follows tha t it s formula mus t be K Mn O 4 ( i e x = 1 ) hence 55 . .
    ,

    is the atomic weight of manganese ,


    .
    29 4 IN O R G A N I C C H E M I S TR Y . 21 1

    l ast de c ade ato mic w e igh t d te min at io s h ave b e n c a ie d


    In t h e e r n e rr

    out o n a c l e f much g te r r m t b y M O R L E Y R IC H ARD S G U YE


    s a o re a e ne en , ,

    an d oth ers d t h e ccu cy f t h v lu


    an h b n e xt d d a th d cimal ra o e a es as ee en e an o er e

    p l c e a o th a t
    , w sn t a f w f t h t mic w e igh t a e t b li h e d w ith
    no o e o e a o s re s a s

    c ert a in ty to w i th i a f w u it i t h e th ird d cim l p l c e


    n e n s n e a a .

    I n de termi n i g t mic w igh t e ith r pur ly c h e mic l o r ph y ic


    n a o e s e e a s o

    ch emic l m t h m y b e e mpl y d
    a e B th h ve b e n g e tly pe rf c te d
    oas a o e . o a e r a e

    in th e e l atte r in ve t ig t i s a d th ey w ill n o w b e de c r i b d in a fe w p ara


    s s a on n s e

    gr aph s .

    ure ly ch emic al me th o d th ere a e f ur conditi n s w hich


    A s fo r t h e p s, r o o

    a e e
    r n t i l to a n
    sse ccu te d t rmi t i
    a f n at mic w e igh t : ( ) A
    a ra e e na on o a o a

    s ui t b l e a u b t c e mu t b fou d w h ich n b pre p r d p f ctly pure


    s s an s e n ca e a e er e .

    ( b) Th i c mpo u d mu t c o t i in dditi o to t h e l m nt u d r tu dy
    s o n s n a n a n e e e n e s

    only e l m t o f accu t ly k w n tomic w igh t ( ) Th e val c e f t h e


    e en s ra e no a e . 0 en o

    e lem t i th i c o mpou n d mu t b e w e ll d e d I t i n t permi ib le


    en s n s s e n . s o ss ,

    fo e x m pl
    r th t t h e s ub ta n c b e a mixtu e f t w t g
    a e, a f o xi d t ion
    s e r o o s a es o a .

    ( d) Th e c ompou n d e l e c t e d mu t b e ad pt d to n e x c t s ly i or e l e s a e a a an a s s, s

    it s ex ac t yn th i from t h e w igh d l m e t mu t b e p
    s es s ib l e e e e e n s s o ss .

    N otw ith t d i g t h e implici ty a d l gi t im c y o f t h


    s an n d m d i t is
    s n e a e se e an s

    often di fficul t to ti fy the m Th e pre p arat i n f a c o mp und in t h e pure


    sa s . o o o

    s t ate is am n g t h e m t d ifcult o f oper tio


    o if b y p ur ity w e m an t h e
    os a ns, e

    re duc t io f t h e impu it i to a
    n o p rt o f t h e w h ol r It w esf me rly a e . as or

    b li e ve d th at th i c oul d b e e dit y a cc o mpli h d b y r c ry t lliz t io


    e s bu t r a s e e s a a n,

    n w w e k o w th t
    o v y ub t c e th t e p r te out in a o li d ph se h s
    n a e er s s an a s a a s s a a

    a t e nde cy to r t i n u po it urface or i it i t ri r a p art f t h e oth e r


    e a n n s s n s n e o o

    s u b s t an c e c o t i e d i t h e ph e o u t f w h ic h t h lid e p a t d Al l '

    n a n n as o e so s ra e .

    pre ci p it t s cry t l from qu u s lut i


    a e or c t i n w t r th t i ot
    s a s a eo so on s on a a e a s n

    i c h e mic l c o mb i at i o n
    n a Ev t h e pl d i d gli t i g i lv r c ry t l th at
    n . en s en s en n s e s a s

    a e r b t i n e d i t h e e l e c tro l y i
    O a nf a ilv it te luti d e pp re t
    s s o
    n l y s er n ra so o n an ar a a

    pe rfe ct ly d y an d pu c o tain n o t on ly w ate r b t ilv r n itr te


    r re n w e ll u s e a as .

    Silve r c h l ori de pr ci p i t t e d f o m , olut io f dium c h l i d b y s ilver


    e a r a s n o so or e

    n i trate m ay h ve i clu d d t c e s of N C l A g N O
    a n N NO ve afte r a
    e ra a or a n
    , , 3 3, e

    th orough w h i g P t iu m c h lorate th ough m uch l


    as n . o lubl e th n
    as s , ess so a

    p ot a ium c h l i d
    ss co t i n e ve rth el e
    or e, f t h l tt
    n ft r re pe ate d
    a ns ss o e a er a e

    re c yst lliz t io
    r a O e o f t h e m o t t o u b l e o me o u r c e
    a ns . n of ro in al l s r s s s er r

    qu ntit at ive e e ch i t h e u n u p cte d pr e n ce f h ygr cop ic lly


    a r s ar es s s s e es o os a

    h e l d w at e r i c e i t i o t at all e
    , s n y to d t c t b y c h e mic l t t
    s n d c u es as e e a e s s an a s

    n o e t i al ch ge in t h e e xte rn al app ar n c e o f t h e su b stance c t aining


    ssen an e a on

    it .

    Th e a aly i f a su b t an c e re o lve s i t lf in mo t c a e i to a e parat i on


    n s s o s s se s s s n s

    o f it s c o mpo e n t i t h e form f oth r c om pound a d w e igh ing o f t h e


    n s n o e s n s

    l tte r Fo e xampl i ord to d t rmi t h e ilve r co te n t o f s ilve r


    a . r e, n er e e ne s n

    n itrate t h e m t al i t h row n do w a ilver ch l o i de a d t h e l atte r i w e igh e d


    e s n s s r n s ,

    w h ere u pon t h e qu t ity of ilve r c n b e c lcul ate d fro m t h e kn o w ilve r


    an s a a n s

    c ont e n t o f t h e ch loride Th e anal yst ge n erally n ds it al o ne cessary t o . s

    c ve rt
    on c mp u d i t
    on e oth qu t i t t iv ly T h m d i
    o n n o t iga
    an o er an a e . e o e rn n ve s
    D E TE R M I N A TI O N O F E Q UI VA LE N T WE I G H TS . 2 95

    t ion s of a tomic w e igh ts h ave al s o t augh t u s th at th i s is O fte n a ve ry d i fcult


    l m m n g o the r s o u rc e s o f e rro r in t h i s c o n n e c t i o n a r e t h e s o lu
    p r o b e A. o
    b il it y o f t h e s o c all e d
    in s o lu b le s u b st an c e s an d t h e s o lu b ility o f gl ass
    -

    .

    I t h as l o n g b ee n kn o w n t h at s u b s t an c e s like s ilve r c h l o r i de b ar ium s u l ,

    p h a t e , e t c a r e n
    . o t
    ,
    s tr ic t l y i n s o lu b l e ; b u t th e ir s o lu b ili t
    y h as r s t re c e ive d
    t t n t i o n in c o n n e c t i o n w i th t h e re c e n t a t o mic w e ig h t de te rmi n at i o n s
    p ro p e r a e .

    I n w orki n g w ith gl as s v e s s e l s i t is imp o ss i b l e to a vo i d s ilicic a ci d a s a n


    impu r i ty R e c o gn i t i o n o f th i s fa c t h as l e d to t h e u s e o f v e s e l s o f qu a rt z
    . s

    o r b e tter s t ill O f p l at in um w h ich h as pro ve d to b e a n imp o rt an t re n e m e n t


    , , ,

    of method .

    2 1 2 Ph y s ic o c h e mic a l m e th o d s h a v e fo u n d a pp lic at i o n in t h e d e te rmi n a t i o n


    .
    -

    o f t h e v o lum e w e igh t of g as e s O n e of t h e mo st fruitful o f m o de rn ph y s ic al


    .

    c o n c e p t s is th at o f t h e i de a l g a s w h o se e xp an s ion at c o n st an t p r e s s u e o r
    , r

    r s s u re i n c re as e at c o n s t a n t v o lum e b oth h ave a c o e fci e n t fo r a t e mp e ra


    p e

    ture ch ange o f o n e de gree o f e xactl y 1 / M o re ove r t h e i de al g as ,

    is in s t r ic t a cc ord w i th B o Y L E s l aw A gram mol e cul e o f s uc h a g as a t



    .

    6 an d 7 60 mm Hg pre ss ure w oul d o ccu p y a v o lume o f 1 Ho w e ve r



    . .
    ,

    t h e a c t u al g ase s a re more c ompre s s i b l e an d e x p an s i b l e th an t h e i de al g a s ;


    h ydro g en an d h e li u m ar e t h e only O n e s that ar e l e s s c om pre ss i b l e Fo r th i s .

    re ason 1 o f a n a c tu al g as at 0 an d 7 6 0 mm Hg c o n ta i n s a li ttl e

    . .

    more than o n e g ram mo l e cule I f w e l e t 1 + /l re pre se n t t h e n umb e r o f


    .

    g ram mo le cul e s o f an a ctu al g as w h ich are containe d in l t h e mo le cul ar .


    ,

    w e ight o f t h e g as b e c o me s

    where G is t h e w e igh t of a lite r


    nder norm al c on dit ions Th e
    of t h e g as u .

    e st ab li sh ment o f t h e ato mic w e ight o f a g as th u s re so lv e s i t s e l f i n to t h e

    a ccurate de t e rmi n at i o n o f t h e m agn i t u de s G a n d I Th e me th o ds fo r .

    a s c e rt a ini n g t h e e x a c t w e igh t o f a give n v olume o f a g a s h ave u nde rgo n e

    import an t impro ve me nts in r e c e n t ye ars Th e agre e ment o f t h e value s .

    fo u n d b y t h e di ffe re n t inve st ig ators is w ith in Wh il e forme rly


    t h e g ase s w e re w e igh e d in h ug e glo b e s so me c o n t ai n in g as much as 2 1 l , .
    ,

    l ate r i n ve stig ators h ave be en ab le to reduc e thi s volume to b et w e e n o n e lite r


    a n d h al f a lit e r or e ve n l e s s N e ve rthe le s s t h e c o n c orda n c e b e tw e e n t h e
    , .

    variou s se rie s o f de termin ati o n s w as impro ve d b e c aus e t h e corre ctio n s fo r ,

    t h e s m all glo b e s w e re much l e s s A n add it ion al c o rre c t i o n w as ap pli e d


    .

    fo r t h e c ont r ac t i on o f a gl o b e o n e v acu at i o n du e t o t h e e x t e r n a l pre s s ure ,

    o f t h e atmo s ph e re re duci n g t h e v olume s ligh tl y ; t h e b u o yan c y e ffe c t o f t h e

    a ir is s o me w h at l e s s fo r an e v a cu at e d glo b e th an fo r o n e l l e d w i th g as .

    I n o rde r to re mo ve c omp l ete ly t h e l aye r o f air th at h as b e e n c o n de ns e d


    o n t h e i n n e r s u rfa c e o f t h e gl o b e it is n e ce s s ary t o e vacu ate t h e l atter
    ,

    re pe ate dly to as l o w a v acuum a s poss ib l e an d t o ll i t w ith t h e g as w ho se


    de n s ity is t o b e de termi n e d gre at c are be i n g t aken me anw hile t o e xclu de
    ,
    .

    t he a ir .

    F urthermore , the p uricat ion of t he gase s to be w e igh e d is much be tte r


    29 6 IN O R GA N I C C HEM I S TR Y . 21 2

    ac complish ed by rst liquefying th em an d th en removing t h e impurit ies


    b y f ct i ra l d i t ill t io n at a l o w te mperatu re
    on a s a .

    Th d t rmi e ti f t h q u t it y I c
    e e b
    na cc mpli h d i f u diffe t
    on o e an an e a o s e n o r re n

    w y a Wh ich a f u n d d c b d i t h l g r ph y ic m u l
    s, re o I t h ul des ri e n e ar e s s an a s . s o

    be n t d h w v o e th t th y h v o t y t tt i d t h x ct
    , o e e r, a th t e a e n e a a ne e e a n e ss a

    ch ct iz t h m th d f d t mi i g G I t h c
    ar a er es e ef th l o ily
    s o e er n n . n e ase s o e e s s e as

    c d
    on d ge n se li k H N O d C l h w ve r v ry ccur te d t mi at i
    ase s , e , , , an , o e , e a a e er n on s

    h v a l dy b m d
    e a re a ee n a e .

    Fr m exp
    o im t l t dpo i t th e ph y ic o ch mic l m th o d h ve
    an er en a s an n es s -
    e a e s a

    a d cid d up e i ity ov r t h e pu ly ch mic l m th d in th t l j jysic a


    e e s r or e re e a e o s a p
    7

    me u m t as re l y a e c a ri d t ft r t h g h a b
    en s on b t i n d pure
    r r e ou a e e as s een o a -

    . .

    All t h e u c t i t i th t
    n i v lv d in ch mic l t
    er a n f m ti
    es s a e t h us
    a ar e n o e e a r an s o r a on r

    a v i de d ;
    o a d u p n s uc h t n f m tio e v e ry p ur ly c h e mic al de t e rm i
    o r an s o r a ns e

    n at ion f ato mic w e igh t is b a e d


    o an s

    T HE PE R I O DI C SY ST E M O F T HE E L E M E N T S .

    3 studying
    2 1 the
    . elements Inwhich we h ave considered so far ,

    w e have found that they can be arranged into grou ps of elements


    a c cording to their valence the elements of each g rou p sh ow ing ,

    great similarity in t h e ty p es of their co m p ounds The ph y sical .

    and chemical p ro perties of th e elements of such a grou p are


    foun d to change p rogressively as the atomic weight increases .

    The questio n now arises whether all elements can be thus arrange d
    into grou p s ; the re ply is a frmative .

    cour e f t h e l t c e n tury th re w as n l ack o f atte mpt to a r n ge


    In t h e s o as e o s r a

    t h e l m t i to g u p
    e e en s f imil r e l e m t n DO E N R c ll d
    ro tte s o s a en s . BE R E I E a e a n

    ti on to a s impl e r l tion b tw e n t h t mic w igh t f ki dre d l me tse a e e e a o e s o n e e n

    a s arly e 1817 n d in 1 8 29 h e pr
    as e te d t h e do c tr i n e
    , a f t i d i e he es n o r a s, . .

    s h o w d th t th ere
    e d i ff t grou p
    a f th ree e l e m nt e c h w h ich h ave
    are e re n s o e s a ,

    a g t imil rity amo g th e m lve s d a co t t differe n c e in t h at mic


    re a s a n se an n s an e o

    w igh t
    e g Cl B I; C
    s, e .S B . tc I n t h y r 1 86 5 t h e l w f o t es
    ,
    r, a, r, a, e . e ea a o c av

    w as p po d b y N E W L AND S h e h vin g d i c ove r d th t if t h e e l e me ts


    ro se , a s e a , n

    a re arr ge d ccordi g to i cre i g t mic w igh t ft r an in terv al f


    an a n n as n a o e , a e o

    se ve l me t a l me t f ll w w h ich h p opert ie a l ogou s t o tho e


    n e e n s n e e n o o s as r s na s

    o f th r t i t h r t ighth ft n th e t c are s imil ar I n 1 86 9


    e s ,
    . e . e s , e ,
    ee ,
    .
    , .

    M N D E FF a d L O T H AR M E Y ER lm t imult eo u s ly re ach ed c o n
    e lu i
    E

    w h ich
    s on s
    EL E

    e c o m pre h e de d b y t h e t e rm
    n

    pe ri dic syste m
    ar

    n
    a os s an

    o .

    If we arrange t h e elements ac cording to increasing atomi c


    weight thus : ,

    H 1
    L1 7 Be 13 11 0 12 N 14 0 16 F 19
    N a 23 M g 24 A1 2 7 1 . Si s 32
    29 8 IN O R G A N I C C H E M I S TR Y . 213 .

    tion from metal to metalloi d an d a continuous d ecrease in Specic


    g ravity B u t more ; if we pu t this last row under the rst two
    .

    H 1
    Li 7 Be 9 1 . B 11 0 12 N 14 0 16 E 19
    Na Mg A1 Si P s 01
    Ag Cd 1 1 2 4 . In 1 1 5 Sn Sb Te I

    it is apparent that the elements in the same vertical columns


    b elong to a grou p This has been . demonstrated for the last fou r
    columns in preceding chap ters ; it will be proved for the o thers
    later on .

    I n the ligh t of these facts we are le d to the conclusion that ,

    the physica l a n d chem ica l pr oper ties of the el em en ts ar e fu n ction s of


    t heir a tom ic w eights; and when we consider the series begin ning
    with lithium and sodium and note that in each instance after a , ,

    difference of about 1 6 there follows another element with corre


    ,

    Spo n din g pro p erties we are led to the su pposition that these
    ,

    p pro erties are p er iodic functio ns of the atomic weights .

    By a f unct i on we understand in genera l a dependent re l ation between


    t wo or m ore m agnit u des of su c h a sort that when one c hanges the
    ,

    other does lik ewi se In the e quations y = a t x ; y = ax ; y = x etc


    .
    ,

    z
    ",
    ,

    .
    ,

    y i s a f u n c t i on of a A pe r i o dictf u.n c t i on re qui res that the Sam e va lu e


    appear for one m agni t u de i n regul ar interv als as the other m agni t u de
    steadily i n creases An e xam pl e of this ki nd i s presented by the gonio
    .

    m etric fun c t i ons as y = s i n 35 e t c for e v ery t im e 3: i n c reases by 2


    , ,
    .
    , y 7r
    ,

    c o m es to hav e the sa m e va lu e again .

    If we desire to substantia t e the conclusion j ust stated we Shall ,

    have to investigate rst the length of each period in other words , ,

    determine how many elements intervene in the table according to ,

    increasing atomic weight between two with an alogous pro perties .

    It has already be en shown that fo r the elements as far as chlo


    rine a period always includes s e v e n elements A fter chlorine
    , .

    comes potassium which thus falls into the colum n unde r


    sodium The following elements
    .
    ,

    K 39 2 . C a 40 1 . Sc 44 1 . Ti 4 8 . 1 V 5I 2. C r 52 1
    . Mn 55 0, .

    corres pon d very well with the p receding series ,

    N a 23 1 . Mg 24 4 . Al 2 7 1 . Si 2 8 4 . P3 1 0 . S3 2 I
    .
    THE PE R I O D I C S YS TEM OF THE E L E M E N TS . 299

    at least so far as the valence and the form of the compound are
    concern ed (A l g and Se gO g TiO z and SiO z K zC rO 4 and K 2 SO 4 , , ,

    K M n O 4 and K C l O 4 ) although the Similarity of these elements in


    ,

    o ther res p ects is not very marked .

    The elements following manganese vi z Fe Co ,


    .

    Ni however do not t in at all under K C a Sc ; but if we


    , , ,

    p ass these by there follows another series of seven elements which ,

    corres ponds to the one beginn ing with p otassium

    Cu Zn C a 70 Ge As Se B r 80 0 . .

    We therefore reach the conclusion that after the rst t w o pe rio ds ,


    ~

    of seven elements ending with chlorine must come one of seventeen


    elements ( two of seven each and three elements placed at the side) , ,

    if the elements in the same vertical column are to corres pond in


    their pro perties .

    This l arge per iod of seventeen elements can therefore b e , ,

    arranged under the preceding s ma l l p er iod of seven elements in


    the following way :
    SM ALL P E R I O D .

    N a23 1 Mg 24 4 Al 2 7 1
    . . . Si28 4 PSI G
    . .

    L AR G E PE R I O D .

    K3 9 2
    . C a4 0 1 . Sc 4 4 1 . Ti4 8 1 V5 I 2
    . . Cr 52 1 . M n 55 0 Fe 55 9
    . .

    N i58 7 . C u 63 6 .
    ~

    Zn 6 5 4 G a 7 0. G a 7 2 5 A s 7 5 0 Se 7 9 2
    . . Br 80 0
    . .

    Inorder to arrange in periods the elements whose atomic weights


    exceed eighty it is again n ecessary to assume large periods and
    , , ,

    moreover to l e ave several places vacant I n this manner w e


    , .

    arrive at the s cheme known as M E N DE L EE FE S table (see p



    .

    As to the pos i t i on
    of hydrogen in th i s t abl e opin io n s are d ivi ded .

    ME N DE L EE FF pl a c ed th i s e l e m ent in t h e rst g i b u p above lit hium ; i ts ,

    che mic a l pro pert i es indic ate wi tho u t do ubt that i t be l ongs wi th these
    metal s O n the other hand O R M E M A SSO N has presented argum ents
    .
    ,

    for pl a cing i t at the head of group VII as is done in this table These , .

    argum ents are as fo ll ows


    ( 1 ) The m o l e cul e of hydrogen conta ins two ato m s as does a hal ogen ,

    m o le cul e wh il e the m o l e cul e of an alk al i m eta l c ons i sts of o n e ato m


    , .

    ( 2) Th e very l ow bo ili n g po i nt of hydro g en i nd ic ates a Simil ar i ty to


    -

    t h e hal o g ens ; m oreover the bo ili ng po i nts of the alk ali m etals fa ll wi th -
    3 00 I N O R GAN IC C H EM I S TR Y . 21 3 :

    increasing ato mi c we i ght ( 3 ) Th e di fferen c e between the ato m ic


    .

    we i ghts of t h e e l e m ents of a horiz onta l ser i es i s on the av erage 3 By , ,


    .

    pl a ci ng hydro g en in g ro u p VII i t d i ffers by 3 fro m the ne x t e l e m en t ,

    he lium ; b u t it i s then also l n g ood agree ment wi th uori ne for the ,

    mean difference in ato mi c wei ght between t h e s uccess ive e lements of a


    c o lum n is 1 6 The d i fference F H = 1 8 while L i H = 6 i e there i s no
    .
    -

    ,
    -

    ,
    . .
    ,

    a na l ogy i n the l atter c ase (4 ) L i qui d and so li d hydrogen have no m etalli c


    .

    p ro pert i es ( 5). T h e m ost im p ortant arg um ent for pl a ci ng hydrogen


    in the rst gro up i s based on i ts r e l at i on to the a ci ds whic h may be ,

    r eg arded as sal ts of hydrogen Bu t i n org anic c o m po u nds c h l ori ne


    .

    s ubs tan c e .

    c a n re pl a c e hydrogen w i tho u t essent i a ll y a l teri ng the nat ure of t h e

    Thi s organic arg um ent th us o ffsets the i norgani c

    one based on the anal ogy of a ci ds and sal ts


    ,
    .

    A s to the e l e m ent s di s c o v ered i n the at m os phere Si n c e 1 89 4 v iz , .


    ,

    h el iu m (at w t .n eon a rg on (4 0
    . kr yp ton and xen on
    it i s cl ear that they for m a nat u ra l gro u p for thei r pro pert ies displ ay ,

    g reat ana l ogy ( see S in c e they are not ab l e to for m c o m p o u nds


    wi th other e l e ments they c an be regarded as n u l liv al e n t I n that c ase
    ,
    .

    the ir gro up c o ul d nd a pl a c e after the e i ghth or before the rst, gro u p ,

    ( c o m pare t h e tabl e pag e ,


    formi ng a br i dge or transi t i on , ,

    fro m t h e strongest e l e c tro ne gat ive to the stron gest e le c tro pos i t iv e
    -

    ,
    -

    e l e m ents However i t mu st b e noted that arg on w i th an ato mic we i ght


    .
    ,

    of 40 pre c edes potass ium w i th an ato mic we i ght of 3 9 A s m ay b e seen .

    fro m Pl ate I the i r ato mic vo lum es t into L O T H AR M EYER S curve


    ,

    Very well .

    G rou p VII I as has b een said owes its origi n to the setting
    , ,

    at the Side of the elements included in it for by this means the ,


    corres p onding elem ent s of grou ps IV I I could be brought under


    e ach other I t will thus be of im p ortance to the syst em if the
    .
    ,

    n in e elements of this gr ou p dis play so much analogy to each o the r

    that the grouping of them together a ppears actually j ustied N ow .

    this is really the c ase as is seen from t h e following study of their


    ,

    p pro erties
    1 A l l these elements are of a gray color and dif cu l t l y fusi
    .

    b le ; in d eed osmium is one of the hardest of all metals to fuse


    ,

    iridium melts at wrought iron at etc The .

    melting point of iron is higher than that of c obalt and the latte r
    -

    higher than that of nickel A similar fall of this constant is found


    .

    with ruthe nium rhodium an d palladium and als o with o smium


    , , ,

    iridium and platinum .

    2 Thei r atomic volume s are small in c om parison with tho se


    .
    02 I N O RGA N I C C H EM I S TR Y . 21 3

    of the neighb oring elem e nts The atomic volume of molybdenum .

    is that of ruthenium rhodium and palladium ab out 9 ; that of


    ,

    s ilver that of cad mium


    3 They display in a marked degr e e t h e ability to let hydrogen
    .

    pass thr ough at red heat or to condense it on the ms elves at or


    -

    din ary tem peratures The former pro perty is especially developed
    .

    m 1r o n and platinum the latter in palladium ,


    .

    4 It is only with these metals that we nd R 0 4 com pounds in


    .
    ,

    o ther wor d s they are the o nl y ones which can be o c t iv al e n t


    ,
    The .

    c om pound s O SO 4 and R u O 4 for exam ple are known and also those, , ,

    with carb on monoxide as N i( C O ) 4 and Fe (C O ) 4 We nd here


    ,
    .

    a general tendency to form com p ounds with carbon monoxide ,

    e g Pt C 12 3 C C
    . . In this last com pound platinum can also be con
    -
    .

    s ide r e d o c t iv al e n t .

    5They form stable and in most cases well crystallizing


    .
    , ,
    -

    d ouble salts with potassium cyanide I ron ruthenium an d .


    , ,

    o smium give com p ounds of the typ e K4 R (C N ) 6 ; cobalt rhodium , ,

    an d iridium form K3 R (C N ) 6 while the elements of the last column , ,

    n ickel p alladium
    ,
    and p latinum give
    ,
    K-
    2 R ( C N ) 4 double salts , .

    6 They all form colored salts : those of cobalt are red or blue ;
    .

    the nickel salts are green ; all the rest are of v ar1 ou s sha d es of
    b rown .

    7 They all p ossess the ability to condense on thems elves


    .

    o ther gases than hydrogen in larger or smaller amounts ; es p ecially

    is this t rue of the platinum metals Platinum and palladium .

    ab sorb carbon monoxide greedily .

    L et us now examine the seven other grou p s ( vertical col


    u m n s ) more closely If we b ear in mind what was stated with
    .

    r eference to the large periods it is apparent that not all the ele ,

    ments in such a g rou p display perfect chemical analogy Such .

    analogy is foun d however when we compare with each othe r


    , ,

    o nly those elements that belong to the even or the odd rows of

    the large periods The s imila rity of the elements of these di visions
    .

    is seen in the case of the large periods from the following facts :
    , ,

    1 O nl y the elements of the odd r ows give hy d rogen o r alkyl


    .

    com poun d s .

    2 I n the even r ows the basic pro perties of the hydroxi d es ar e


    .

    p ro m i nent in the o dd ,
    rows the acidic ro
    p p erties .

    In general it may be sai d that passing from left to right in t h e ,


    THE PER I O DI C S YS TEM OF THE ELEM EN TS .
    3 03

    t able , we meet rst those that fo rm the strongest bases and then
    gradually those that give acids The latter pro perty is most .

    marked in the halogens since they even form strong acids on


    ,

    combin ation with hydrogen .

    A Similar change is observe d in going from the t op to the bottom


    of the system A s the atomic weight increases the metallic (base
    .
    ,

    forming) natur e of the elements in each group becomes more


    p redominant .

    2 14 The periodic system of the elements is of value in four


    .

    d ifferent res pects


    1 I n constructin g a system of the elements
    . .

    2 I n ascertaining the atomic weights of elements whose e q u iv a


    .

    lent weights only could be determined .

    3 I n foretell ing the pro perties of elements as yet un discovere d


    . .

    4 I n conrming or correcting atomic weights


    . .

    L et us look at these various applications in some detail

    t h e Pe r io di c L aw in C o n st ru c tin g
    '

    Th e Us e of a Syst em of the
    El em e n t s .

    2 1 .a careful com parison of the elements M E N DEL EE FF


    5 After
    reached the following important conclu sion : The en tire character of
    an elem en t , disp la yed in its phys ica l a s wel l a s in its chem ic al
    as

    p p
    ro er t ie s ,
    is det erm in ed by the pos ition whic h it occu pies in the sys
    t em and pa r tic ufla r l y j by the a t o m i c
    o u r a d acen t el em en ts , the
    a n a l o g u e s I f an element is in an even se ries the elements in
    .
    ,

    the adj oining even series are its atomic analogues ; the same is tru e
    of the odd rows From this it follows that when the pro pe rt ies of
    .
    ,

    an element are exactly known its place in the system can b e ,

    assigned A cou ple of illustrations will make this clea r


    . .

    The element b e r y l l i u m p ossesses marke d analogy t o alumin


    ium on the one hand and magnesium on the othe r ; therefore it
    was a much discussed question whether its oxide Should be given
    the formula B e O or B 6 2 0 3 Since acc o rding to analysis .
    , ,

    p arts B e combine with 1 6 pa rts O the atomic weight would be ,

    in the former case in the latter With the atomic


    weight the element would stand between n itrogen an d oxygen ;
    as nitrogen and the elements of the sul phu r gr ou p as well yiel d

    o nl y acid forming oxides beryllium ox id e woul d have t o be an


    -

    , ,

    a cid anhyd ride too w hi ch is n ot the case it bein g a basic oxide


    , ,
    .
    3 04 I N O R GA N I C C H E M IS TR Y . 215

    Thus beryllium would not t in the sys tem with that atomic weight .

    If however it has the atomic weight


    , ,
    it falls in the horizontal
    s e ri es between the strongly basic lit hium an d the weakly acidic

    boron an d over magnesium with which it shows real analogy , .

    This is indee d its t place i e its properties are those which must
    ,
    . .

    belong to an element in this position (see table ) Farther the .


    ,

    pro perties of beryllium are to those of lithium as the pro p erties


    of boron are to those of beryllium o r in the form of a pr O por t ion :
    , ,

    Be zLi : : B : Be Just as lithium forms a more strongly basic oxide


    .

    than beryllium so the basic character of beryllium oxide is stro n ge r


    ,

    than that of boron oxide ; again beryllium chloride is more vola ,

    tile than lithium chloride boron chloride more volatile than


    ,

    beryllium chloride .

    We also have the relation Be zMg : : Li : N a : : B zAl for beryllium ,

    o xide is less basic than magnesium oxide lithium oxide than ,

    sodium oxide boron oxide than aluminium oxide Beryl lium


    ,
    .

    uoride dissolves in water magnesium uoride does no t ; simi


    ,

    l arl y boron uoride but no t aluminium uoride is soluble in water


    , , .

    Finally we have B e zA l : : Li zM g : : B zSi The hydroxides of .

    beryllium and aluminium are very similar to each other ; they are
    gelatinous and sol u b le in alkalies B o th metals are scarcely acted
    .

    u pgn by nitric aci d and both dissolve in alkalies with the evolution

    of hydrogen Their chlorides must be pre pared in the same way


    .

    from the oxides (b y heating with charcoal in a current of chlorine ) .

    L ikewise lithium and magnesium are analogous in certain res pects ;


    the carbonate an d the phos phate of lithium l ike t he corresponding ,

    salts of magnesium are very difc u l t l y soluble which is ingmark ed


    , ,

    contrast with the o ther me tals of the lithium grou p B oron and .

    sil icon both form v ery refractory oxides and salts ; their uo rin e
    compounds are decom posed by water in a Similar manner etc ,
    .

    The e v iden c e in a cc ordan c e with which berylli u m was ass i gned its
    p resent p os i t i on in the syste m was s u bse q uent l y c on r m ed d i re c t l y
    by the determi nat i on of the v apor dens i ty of the c hl ori de whic h l ed ,

    to the formul a Be C lz The v apor densi ty of t h e beryllium c o m po u nd


    .

    of an organic s ubstance (a cetyl acetone ) also led to as the ato mi c


    we ight of beryllium .

    ASa second example let u s take thal lium This element dis .

    pl ays analogy with the alkali metals and also with alu m inium as ,
    3 06 IN O R GA N I C C HEM IS TR Y . 21 6

    the same way as we have Shown it for the oxides R 2 0 and R C it can ,

    also be demo n strated that indium could not be located in the table
    with an oxide I n O z I n g O 5 I n O g etc There remains thus no
    , , ,
    .
    , ,

    o ther possibility than to give the oxide the formula I n g O g and the
    element an atomic weight of 1 1 5 .

    L et us now see whether the pro perties of the element an d its


    com p ounds conform to this lo cation Two of its atomic analogues .

    for this p osition are cadmium and tin The oxides of both are easily .

    reduced ; th is is true also of indium oxide I f now we conside r .


    , ,

    the metals
    A g , C d, I n , Sn , Sb (7 t h series) ,

    we notice rst that the melting p oint of Silver lies highe r than that
    -

    o f cadmium ; l ikewise antimony melts highe r than tin :

    Ag > Cd ; Sn < Sb .

    If in d ium ts in this series it must therefore h av e the lowes t


    , , ,

    melting point o f these ve metals This is actually the case ; its


    -
    .

    melting poin t is
    -
    I n the color of the metals there is a further
    analogy ; silver cadm ium and tin are white and so is indium As
    , , .

    to the s pecic gravity cadmium has the s pecic g ravity


    , Silver

    the difference is thus The d ifference of the s pecic


    gravities of t in and antimony is o n the contrary small , , ,

    I f indium stands between these two pairs o f


    elements its s pecic gravity shoul d be smaller than the mean b e
    tween ca d mium and t in i e ,
    . In reality i ts
    .

    s pec ic gravity is
    The position of the metal requir es tha t its oxi d e b e feeb ly b asic ,

    weaker even than the oxides of cadmium an d thallium (T12 0 3 ) ,

    Since cadmium is at the left and thall ium farther down in the system

    on the other hand it must be more strongly basic than


    ,

    the oxides of aluminium and t in This condition also is fullled .


    ,

    as the following sets forth : the oxides of alum inium and tin b e ,

    cause o i their slightly acid nature dissolve in alk alies forming de


    , ,

    nite com pounds with the latter The oxi d es of cadmium and .

    thallium however are insoluble in alkalies ; they are dis tinctly


    , ,

    b asic I ndium s es quioxide is solub le in alkalies b u t forms n o


    .
    ,

    d enite compound with them .

    Finally there is also the con d uct of in d ium salts towar d hydro
    ,

    gen sul phide which su pports the plac ing of the elemen t between
    ca d mium an d tin for indium als o is , p reci p itated by hy d roge n

    Sulp hide from acid solutio ns .

    Pr e di ctio n t h e Pr o per t ies


    of El em en ts ye t Un dis c ov ere d
    of .

    2 17 When M E N DE L EE FF constructed his table t h e elements


    .
    ,

    gallium and germanium ( fth series ) were still unknown From .

    the pro perties of the atomic analogues he venture d however at that


    time to predict the pro perties of these elements ; thirteen years
    later WI N KL ER discovered an element with the atomic weight 7 2

    ( M E N DE L EE FF had termed such an one ekasilicon the disc overe r
    n amed it g er m a n iu m ) I ndee d there p roved t o be a very close .

    agreement between the actual p ro pe rties a nd those p re dicted as ,

    the following summary evidences

    P r o p e r t ie s o f e k a s il ic on p di t d
    re c e by P r o p e r t ie s of g e r m a n iu m dis c o v e re d by
    M E N D E L EE F F W I N KL E R .

    1 . Th e to mic w e ig h t mus t b e t h e
    a 1 . At .

    me an o f t h e four atomic an a
    l og nes Si, Sn , Zn , Se , i e .

    = 7 2 85
    l ) . .

    2 Th e Spe cic gravity (de duce d as Sp . g . at


    i ium b o ve ) must b e 5 5
    fo r nd a . .

    3 . Th e ato mic v o lume must l i b e e 3 . At .

    tw ee n th ose o f Silicon ( 1 3 ) an d
    t in b t b e onl y a tri eu
    ab o ve 1 3 .

    4 . Sinc it b e l ong in an Odd s ri s i t


    e s e e ,
    4 . A lky1 c ompounds w e re ob taine d .

    mus t b b l to fo m lkyl m
    e a e r a co G e ( C , H5 ) 4 b o ils at 1 60 an d it s

    pounds Ju dgi n g fro m a al gi e n S e c i c g ravi ty is a li ttl e l ess


    p
    . o s,
    t h e b iling p i t o f E S ( C H )
    o -
    o n 2 5 4
    must b e it s s p cic gravi ty e

    5 . Th e aci d pro p rt i s f E SO mus te e o 2


    5 . G eO 2 l ack s ntir ly t h b as ic p o p
    e e e r
    be s trong e r th n th se o f Sn O a o , . ert i s w h ich
    e fo u n d to a lim
    a re
    it e d xt n t in S O
    e e n , .

    6 Th e sp e cic gravity o f E 8 0 is 6 Th e s pe cic g ravi ty o f G O is e


    2 2
    . .

    at

    7 . Sn i ce t he o x i de s
    indium n d of a 7 . il
    G e O 2 is e as y re d e d to t h e e ta) uc m
    rs enic a
    a as il y r d uc e d
    re th i se e ,
    by h eat n w th i g
    ar b o n o r in i c
    mus t als b e t ue o f E8 0 o r 2 . hy dro en g .

    8 . E S b c a use f it s a n l gy w ith
    S 2, e o a o 8 . i lv
    G e S2 d ss o es read y in N H4SH il .

    Sn S w ill p o b ab ly b s lu b l e n
    ,, r e o i
    N H SH .

    9 E s Cl i s
    . u d liq i
    b o s b e o w 1 00

    ,
    . il l G e Cl 6 is liqui d , b oil s at an d

    (
    s n e ti c
    h e b o n o nt o f SiC l is
    p 4
    ili g i h as a s pe cic g ravit y o f
    5 7 a n d t h at o f an d
    h as a s pe ra cic g vi
    ty o f 1 9 . .

    1 0 K,Sn F6 b e n i gm
    o r e re a d y s o b e il lu l K2 SiF, is al m o s t i n s o lub le
    K, G e F6 di ss o lves m 3 4 p art s o f
    . .

    in Wate r th a n K2 SiFe t h e s o ,
    lu
    bil it y o f K, ES E6 s t a so b e mu l bo ili g w t r
    n a e .

    greate r th an th at o f K zSt .
    3 08 I N O R G AN I C C HEM IS TR Y 21 8

    Use of t h e Pe rio dic Syst em in C o rr e c tin g A t o mi c W eigh ts .

    2 1 8 In
    the grou p of the platinum metals the atomic weight s
    .

    were prev iousl y determined by B ER ZE L I U S and F REM Y to be as


    follo ws : O s = 1 99 Pt 1 9 8 I r 1 9 7 I n this order the metals n amed
    , , .

    do no t however t into the system for osmium Shou l d be t h e


    , , ,

    rs t of the three on account of its analogy with iron and ruthe nium ,

    i e it should have the smal l est atomic weight of the three


    . .
    On .

    the o ther hand platinum which is more a k in to palladium ough t


    , , ,

    to h a ve the highest atomic weight A painstaking investigation .

    by SEU B ERT Showed that in reality osmium has the atomic weigh t
    1 9 1 iridium
    ,
    an d platinum which order is in harmony
    V ith the system .

    2 1 9 G r aphi c r e pr ese t ti o
    . n a n The fact that an arrangement .

    of the elements according to increasing atomic weight also make s


    the gradual change of the phy sical properties apparent can b e
    seen most clearly from a gra phic re presentation ( as pro p osed by
    L O T HAR M E Y ER ) in which the atomic weights are the abscissas
    ,

    a n d the atomic volumes the ordinates ( s e e Plate I at end of book ) .

    The rst thing we notice in the curve is the regular rise an d


    fall of atomic volumes A t the beginning of each period t h e .

    atomic volume is at a maximum ; it reaches a m inimum half way


    through the period (in the large periods at grou p VII I ) and then
    incre ases again I n the descen ding portions ar e the ductile on
    .
    ,

    the ascending the brittle elements O n the ascending portions ,


    .

    an d at the maxima are further the gaseous an d the easil y fusibl e


    , ,

    elements ; on the d e scending and at the minima the dif c u l t l y


    and very difc u l t l y fusible O n the descending portions are t h e .


    electro p ositive on the ascending the electro negative elements -
    .
    , ,

    The pe riodici t y of the elements thus becomes very evident .

    220 . Th e di s c o ve ry of t h e pe ri o dic s yste m o n ce m o re th rust i nto t h e


    fore grou n d of i nte re t s one of t he olde s t o f q ue st i o n s viz t h at c o n ce rn i ng
    , .
    ,

    t he u nity o f m a tte r .

    Th e trikin g c onne ct ion b e tw e e n al l t h e pro pe rt i e s o f t h e e le me n ts an d


    s

    t h e i r ato mic w e igh ts l e ads u n avo i dab ly to t h e ass umpt ion o f a pri mor dia l
    o r gr o u n d su bstanc e As to t h e nat ure o f th i s s u b s tan c e n o e vi de n c e is at
    .

    pre s ent ob t ai n ab le PR O U T in 1 8 1 5 re g ar de d h ydro gen as suc h a s u b


    .
    , ,

    st an c e He o b se rved th at t h e (th en acc e pte d ) ato mic w e igh t s o i m an y


    .

    e l e me n ts b as e d o n h ydroge n as u n ity are w h o l e numbe rs


    ,
    L ate r ve ry
    , .
    ,

    a ccurate ato mi c w e igh t de terminat i ons part icul arly th ose o f ST A S w h ic h , ,


    3 10 I N O R G A N IC C H E M IS TR Y . 2 22

    LI THI UM AN D SO DI UM .

    L ith i u m .

    222. This m etal is not fo und free in nat u re ; in c o mbination how ever , ,

    it is very wi de ly di str ib u ted a l tho ug h a lways i n sm all am o unts Many


    , .

    m in e ral w at e rs c onta i n i t
    ~
    I t o ccurs c h i e y i n the s ilic ate l epidolite or
    .
    ,

    l ithia m ica a lso as the phosphate in tr iphylite an d i n c o m pany wi th a lu


    -

    mi n ium Sod ium and u orine i n am bl ygon ite Finally li thium i s m e t


    , ,
    .
    ,

    wi th i n the ashes of c erta i n pl ants s uch as toba cc o i ndic at i ng that it i s


    , ,

    a lso c ontained i n the so il W i th the a i d of the Spectroscope it c an be


    .

    dete c ted i n very m any mi nera ls .

    L i th i u m c an be obta i ned fro m l e pido li te by the fo ll owing very s im pl e

    p ro c ess : Th e mi nera l i s f u sed and then poured i nto c o l d water where u on


    p ,

    it be c o m es v ery br i tt l e and i ts s ilic ates are bro u ght into s uch a c ond it i on
    that they c an be de c o m posed by hydro chl or ic a ci d The ne ly powdered .

    m ass is boi l ed w ith hydro chl oric ac i d and the m etal s C a A l Mg et c , , , .


    ,

    p re ci p i tated by soda fro m the res ul t i ng so lu t i on ( after l ter i ng o ff the


    s ilic a) li th i u m and the other alk a li m eta l s re m ai n ing in solu t i on By
    , .

    evaporat i on a sal t mix t ure i s obta i ned fro m wh ic h the li th ium c hl or i de


    c a n be iso l ated by e x tra c t i on with a lc oho l the inso l ub l e c hl orides of
    ,

    s odi um an d potass ium re m a i n i ng beh i nd .

    Metallic li th ium is pre pared by e l e c tro lys i s of the f u sed c hl oride o r a


    c once n trated solution of th i s sal t i n pyrid i n e N ext to sol id hydrogen .
    ,

    it is the lightest of all soli d s ubstan c es i ts spe c ic g rav it y be i ng onl y , h

    so that i t oats on c oal o il I t i s Silvery whi te b u t tarn ishes very


    -
    .
    -
    ,

    rapidl y in m o i st air Me l t i ng point . W hen heated i n the ai r i t


    -

    burn s with an intense wh i te light to the oxide ; at ord in ary tem perat ures
    it is not so readily oxi d iz ed as sodi um and potass ium It de c o m poses .

    water with the e v o lu t i on of hydrogen the heat generated is suf c ient : ,

    h owever to m e l t the m etal


    ,
    .

    Lit h iu m o xide Li20 and h ydr o xi de LiO H


    , ,
    The form er is O btai ned
    ,
    .

    by heating the nitrate strongl y It d isso lves i n water Sl owly formi ng


    .
    ,

    the hydr o xide The l atter i s a wh ite c rystalline s ubstan c e Simil ar


    .
    , ,

    to c aust i c soda ; it d isso lves i n water produ cing a strongl y alk aline ,

    so lut i on .

    Li t h ium c hl o ride LiC l c rystalliz es anhydro u s i n regul ar o ctahedra ;


    , ,

    bel ow 0 i t takes u p two m o l e cul es of water of c rystalliz at i on however



    .

    I t di sso lves very eas il y in water and de liqu es c es in m o i st ai r .

    Lit h iu m c arb o n at e L izC O 3 unlike the c arbonates of the other a lka li es


    , , ,

    is dif cu l t l y s o lubl e i n water ( 1 00 parts of water at 1 3 t ak e Up

    p art ) ; hen c e i t c an b e pre ci pi tated fro m the c on c entrated so l ut i on o f

    t h e chl or i de by amm on ium c arbonate .


    LI THI UM AN D S O DI UM .
    3 11

    Li t h iu m ph o sph at e , Li3 P0 4 , is lik w i e very p ri gly oluble in w t er


    e s s a n s a

    ( 1 p art in 253 9 part s o f w ate r ) , alth o ugh t h ph ph t s f t he th e r


    e os a e o o

    a lkalie s are free y l s o lub le . Th e form at i o n o f th i s alt e rve s a te t fo r s s as s

    lith ium .

    Th e lithiu m p s c on i s t
    e c tr u m
    s s of t wo re d b ands , o ne of wh ich in p ar
    t ic u l ar is e asy to re c o gn iz e .

    So di um .

    22 3 . Sodium
    oc curs in nature in enormous q u an t it ie s an d is

    very widely di ffused I t is a constituent of c ountless silicates .

    and as a resul t of rock decay gets into the soil whence it enters
    , , ,

    the plants and nally reaches the animal organism The nitrate .

    is known as C hil i s a l tpetr e the chloride as r ock sa l t Or hal it e the , ,


    -

    carbonate as s oda; the cr yol it e (ice s t one ) of G reenland is a s odium -

    aluminiu m uoride C ommon salt N aC l constitutes the main .


    , ,

    p ar t of the saline matter in sea water C ertain bodies of wate r -


    .

    such as the Dea d Se a of Palestine and the G reat Salt L ake in ,

    N ort h A merica are almos t saturated soluti ons of common salt


    , .

    The m e t a l was rst obtained by DA VY in 1 807 by the elec


    t r ol ys is of molten sodium hydroxide G A Y L U SS A C and T H ENARD .
    -

    got i t by hea t ing sodium hydroxide with powdered iron to whit e


    heat The rs t named method is the o n e now generally em ploye d
    .

    for its commercial manufacture inasmuch as ele ctric po wer can ,

    be obtained quite chea ply .

    Fo r th i s purpo se s o dium h ydro xi de is h eat e d a little ab o ve it s m e lt i n g


    po i n t . Th e s o dium forme d at t h e c atho de is ke pt a w ay fro m t h e a n o de
    b y a n iro n n e t A t t h e an o de hydroxyl gro u ps ar e li b e rat e d w h ich y i e l d
    .
    ,

    w ate r a n d o xyg e n Th e l att e r e s c ape s b u t t h e w at e r di s s o lve s in th e mo lt e n


    .

    mas s an d come s in c ontac t w ith t h e sodium at t h e c ath o de c aus in g h alf ,

    o f i t to b e ch ang e d b ack t o s o dium h ydro xi de w h il e h ydrog e n i s e vo lve d , .

    A S a re s ul t t h e m aximu m y i e l d o f me t al fo r a give n qu an t ity o f e l e ctricity


    is o n ly If t h e te m perature g e ts too h igh duri n g t h e e l e c t rol ys is ,

    s o d ium d i s s o lve s in t h e mo lt e n m ass an d is o xi d iz e d at t h e an o de .

    Sodium is silvery white melts at 9 5 6 and boils at -

    turning at the latter tem perature t o a c olorless va p or A t .

    ordinary tem peratures it is ver y soft SO that it can be readily ,

    cut with a knife It can also be easily pressed through a small


    .

    hole c oming out in the form of wire


    ,
    Sp g at . . .

    Sodium l ike t h e oth e alk ali m t l ( Li K R b C s ) di solve s in liquid


    ,
    r e a s , , , ,
    s

    amm on i If
    a e o f th
    . e m t l
    on i i t duc d i t liqui d mm n i
    es e a sth s n ro e n o a o a, e

    b igh t s u rfac
    r f t h m e t l b e c om e t a n h d w i th
    e o e n i n d ig o b lue c o l o
    a s r
    i
    s e a -
    r,

    w h ich s oon t urn to a pre tty m t a llic e d


    s Th e m e tal the n li q u e e s and e r .

    form s a b ronz e c ol ore d soluti on w hi c h is dee p b lue at greate r diluti on


    -

    ,
    If .
    3 12 IN O R GA N I C C HE M I S TR Y .
    j 2 23

    ure o f t h e ammon i a ove r t h e s oluti on is dimini sh ed o t h e t em


    t h e p r es s r

    rai se d t h e s oluti on gives o ff amm on i an d deposi ts c opper ed


    p e r at u r e ,
    a -
    r ,

    c ry st lli n m sse s W h en th ere is n o lon ge liqui d soluti on th e s masses


    a e a . r a e

    al s o l o s
    e amm oni an d t h
    a m e tal is left b ehind in t h e c rystallin form
    e e .

    R U FF h a s de m on strate d th at w e do n o t h ave h ere c se f c omp un ds a a o o

    b e in g form e d b e tw e en t h e m e t l a n d t h e mm o i b t th at t h ac opp r ed a n a, u e e -
    r

    m asse s a e mixture s f m etal an d satur ted liqui d luti on ; f t h oluti on


    r o a so or e s

    c an b e pre s se d o ut l ea vi g a c om p c t p i c e o f m t l
    ,
    n a e e a .

    The molecule of sodium c ontains only one atom as is p roved ,

    by the de pression of the free z ing p o int of its solution in tin A -


    .

    great many metals have this same p ro perty .

    I n moist air the b right surfa ce of a freshl y cut piece tarnishes


    ra pidly but in air that has been dried with p hos p horus pentoxide
    ,

    it kee ps its metallic lustre for days Sodium can b e heated in the .

    air to melting an d e ven still higher withou t catch in g re It .

    ignites only when heated strongly whereu pon it burns with a very ,

    bright yellow ligh t ( es pecially in an atmos phere o f oxygen) Wit h .

    water it generates hydrogen sodium hydroxide be ing als o formed ,


    .

    If it is held rmly in one place during this process ( e g by laying . .

    it on a piece of l t er pa per oating on water or u pon ice ) t h e


    -

    , ,

    hydrogen takes r e because of the localization of the heat produc


    tion .

    Sodium nds extensive u s e in the laboratory and in the arts .

    Because of its stro n g reducing power it is often u s ed to obtain -

    the elements from their oxides ; magnesium and aluminium wer e


    form erly O btained thus I n organic chemistry it is also frequently .

    e m ployed for various pur poses .

    O XI DE S A N D HYDR O XI DE S O F SO DI UM .

    224 burning sodium in dry oxygen a mixture of two oxides


    . On ,

    N az O and N a g O z results Sodi u m o xi de , N ag O is obtained


    ,
    .
    ,

    p ure by the p a rtial and Slow oxidation of sodium with oxygen


    under redu ced pressure and removal of the excess of metal by
    distillation in a va cuum The oxide dissolves Slightly in the .

    metal and after d istilling o ff the latter the oxi d e is left in the
    crystalline fo rm I t is white ; it dissolves in water fo rming
    .
    ,

    sodium hydroxide N aO H and giving o ff much heat , ,


    .

    The pe ro x i de N a O is ob taine d by heating sodi um in a


    , g z,

    current of o xygen till no more o xygen is absorbe d Wi th 8 m ols . .


    3 14 IN O R GA N I C C HE M I S TR Y . 2 24

    p an ie d in an increasing measure by an unintended decom p osition


    of water O n this account the chloride electrolysis cannot be
    .

    c arried to com pleti on ; in practice the pro cess is inte rru pted
    as soon as the alkali hydroxide concentration gets u p to
    The caustic c athode liquid is then re placed by fresh brine and the
    former is evap orated in vacuum p ans to a concentration of
    whereu pon the undeco m p osed chloride se p arates out and is
    returned to the electrolytic cell .

    The diaphragm pro cess most favorably known in A m erica is


    the T O WN S END p rocess .Th e c om p artment c onta ining the
    ( gra phite ) an odes o c cu p ies the c enter of the c ell and on each side
    i ; a diap hragm of t h in asbest os The catho des of woven wire
    .
    , ,

    est closely against the outside of the dia phra gm and the c athode
    c om p artment is lled w ith warm oil that is kept in lively cir
    ,

    culation b y the escaping hydrogen The freshly formed c austic


    .

    liquor t rickles down the side of the catho de and is drawn o ff


    from beneath the O il The constant removal of the hydroxide
    .

    enables the electrolysis to be carried practically to c om pletion


    a n d the yield a pp roaches the theoretical A high current d ensity
    .

    is em p loyed .

    The C A S T NER pro cess is the most extensively used O f the


    amalgamation ty pe I t s cell is divided into three com p artments
    .
    ,

    the two outside ones containing brine and the carbo n anodes ,

    while the middle one contains the caustic liquor A layer of .

    mercury c overs the botto m of the whole cell I n the brine com .

    a rt m e n t s the mercury acts as c athode taking u p the sodium to


    p ,

    form amalgam . The amalgamated mercury is transferred to


    the middle com p artment wh ere it is dec omp osed by water to
    form sodium hydroxide This caustic solution is drawn o ff and
    .

    fresh water introduced at a regulated rate O n eva po ration a .

    ve ry pure sodium hydroxide results The efciency of the p ro c


    .

    e s s is enhan ced by conserving the electrical energy liberated in

    the decom p ositi on of the amalgam .

    I n one suc cessful bell process the anode consists of some


    carbon su pp o rted in a bell which is sus pended in the brine
    and has an exit tube at the t o p for pi ping o ff the chlorine .

    The cathode is a cylindrical piece of sheet iron encircling the


    bell .

    For critical dis cu ss ro n s of the relative merits of these and


    SA L TS O F S O DI UM .
    3 15

    com petitive pro cesses the reader must refer to the technical
    j ournals or the most recent works on industrial chemistry .

    The hydroxide is obtained by evap oration whereu pon it is ,

    generally cast into sticks for the market I t is radiate crys .


    -

    t all in e and very hygrosco pic I t dissolves in water with t h e .

    evolution of considerable heat Sodium hydroxide is a ve ry .

    strong base ; it is used in the arts for numerous purposes amon g ,

    ot hers the manufacture of so ap .

    SALTS O F SO DI UM .

    22 5Th e so dium salts are of great industrial im portance


    .

    many of them are p re p ared in enormous quantities The starting .

    p oint for their manufacture is usually c ommon salt .

    So di u m c h lori de , N aC l com m on sa l t is found in large masses


    , ,

    as r ock sa l t e g at Stassfurt and R eichenh all and in G alicia wher e


    -

    ,
    . .
    ,

    it is dug out by miners F arther large amounts are obtaine d .


    , ,

    from sea water and the water of salt wells Three metho ds are .

    em ployed t o remove salt I n sufciently warm c ountries (e g


    '

    . . .

    M editerranean c oast central N ew Y ork State ) the brine is le d


    into at basins of very large surfac e area
    ,

    or sal t
    I n these the water is remove d by solar eva p oratio n
    and th e salt crystalliz es out An y gy psum that may b e presen t .

    se parates ou t rst whereu p o n the brine p asses to further basins


    ,

    and yields pure salt L ater on the other salts s e parate out ;
    .
    ,

    thes e are s ometimes worke d u p c ommercially In c ountries .

    with a c old climate (e g o n t h e Shores of the White Se a) t h e


    . .

    water is allowed to freez e i n at b asins The ice th at forms .

    is free fro m sal t so t h a t t h e r emainin g liqui d is mo re c on


    c e n t r at e d .

    In c ountries of t h e t e m pe ra t e z o ne the sea w ater is con


    c e n t r at e d by letting i t e vapo r at e s po ntaneously fro m a
    greatly enlarge d su rfac e This is done b y the graduatio n
    .

    p ro
    in a
    cess
    ( Fig
    ric k
    B undles
    . of fagots are p iled u

    ab o ve which a trough with s mall outlet holes


    ,
    p t ogethe r
    -

    runs from end to end The brine is pum ped u p into t h e


    .

    trough and tri c kles down fro m along t h e e ntire length o f


    the latter u p on the brush ; in this way the surface of t h e
    salt solution is greatly enlarged and the ev ap orati o n is made
    3 16 IN O R G A N I C C HE M I S TR Y . 22 5

    much more ra pi d . A very c on centrate d b rine ows out at the


    bottom .

    Th e
    ( salt
    salt is obtain ed from this concentrated solution by boiling
    C ommon salt is almost equally soluble in ho t
    and cold water hence it does not crystallize out on cooling but fal l s
    ,

    o u t at the same rate as the saturated brine eva orates even whil e
    p ,

    FI G 5 0 G RADUA T I O N PR O C E SS
    . .
    .

    boiling hot The salt obtained from the rst crystallization is of


    .

    course impure containing small amounts of magnesium salts


    , ,

    which render it h yg ro s c O pic I n order t o purify it it is redissolve d


    .
    ,

    in water and again preci pitated by eva p oratio n .

    C hemicall y pure sodium chloride is ob tained by p assing hydro


    chloric acid gas into a saturated solution of the salt or treatin g the
    sol u tion with the concentrated acid The sodium chloride is
    .

    de posited be cause it is less soluble in hydrochloric acid than in


    water
    C ommon salt crystallizes in cubes ; when t h e s olution eva porates
    18 IN O R G AN I C C H EM I S TR Y . 225 g
    ~

    an d anhy d rous sal t ; below 3 3 the hydrous salt N azSO 4 1 0HzO ,


    ,
    -
    .

    is again formed The system N azSO 4 1 0H2 0 2 N aZSO 4 + 1 011 2 0


    .
    -

    thus has a transition point at This is conrmed by the fact



    that the solubility of G lauber s salt in water sudde nl y changes at

    3 3 from a rapid increase with r ising temp erature to a Slow de
    crease .

    This salt like the p receding one fo rms su persaturate d solutions


    , ,

    easily The solution saturated at 3 3 can be cooled down to room


    .

    temperature without any de position if care is taken to exclude


    eve n the tiniest crystal of the salt .


    Wh en a crystal of G lauber s salt is ex posed to the air it el oresces ,

    i e it gives off water vapor and becomes O paque like chalk


    . .
    ,
    This ,
    .

    is evidently d ue to the fact that the va por tension of its water of


    crystallization is gr eater throughout than that of the water vapo r
    in the air I nversely we say that a salt deliqu es ces when it takes
    .
    ,

    u p water va por from the air as a result of the vap or tension of


    ,

    its saturated solution b eing l e ss than the mean tension of the wate r
    va p or in the atmos phere I t is found that a perfectly s o und crystal
    .

    of N 3 2 80 4 1 0H2 0 do es not e fo res ce but that when e foresc en ce


    has begun at any p oint it Spreads over the crystal The phase rule .

    gives a satisfactory ex planation of this phenomenon We have .

    in the G lauber s salt two substances N ag SO 4 and H2 0 , in the cas e



    ,

    of a perfectly bright crystal ex posed to th e air we h ave only t w o .

    p hases N a z S O 4,
    1 0H 2 0 and H 2
    -
    0 ( moistur e of the air ) A ccordi n g .

    to the equation F + P = S + 2 7 1 ) we still have in this system


    two degrees of freedom i e the pressure of the water vapor and
    ,
    . .
    ,

    the temperature can both be selected arbitrarily (within ce rtain


    limits ) I f however some dehyd rated salt is present the numbe r
    .
    , , ,

    of phases is three ; then there is only one degree of freedom or ,


    ,

    in other words every temperature has only one corres ponding


    ,

    p ressure an d inve r sely every p ressure only one corres p on din g


    tem perature A c cordingly it is o nly p ermissible t o speak of t h e
    .

    well de n e d va p or tension of a salt with water of crystalliz atio n


    -

    when a seco nd solid phase is tacitly admitted t o b e present : for


    then only is the number of degrees of freedo m r e d uc e d to o ne .

    G laub e r s salt is used in medicine ; in t h e a rt s i t is e m ploy e d


    c hiey in the manufacture of so da .

    So di u m n itr at e , N a N 0 3 c alled C hil i s a l tp etr e b ec aus e of its


    ,

    extensive o c currence in C hili crystallizes in rho mb ohed r ons and ,


    SA L TS O F SO DI UM . 3 19

    melts at It is somewhat hygrosco pic L arge quantities of .

    it are used in fertilizing an d also in the p re p aration of nitric acid


    and p otash salt p etre .

    So di u m n it rit e , N aN O z is obtained by heating the nitrate t h e


    , ,

    addition of a reducing agent such as lead or iron aiding the process


    -

    It is very soluble in water and is consumed in large quantities in


    the aniline dye industry
    -
    .

    So di u m ph os ph at e s ( See . Trisodium phos phate ,

    N ag PO 4 1 2 Hg O is Split u p in aqueous solution chiey into


    -

    sodium hydroxide and the secondary salt for the solution reacts ,


    strongly alkaline and absorbs carbonic acid from the air The

    ordin ary sodium phos phate is the d i s 0 d i u m p h o s p h a t e
    .

    N azHPO 4 1 2 H Q O
    -
    . I t se parates from its aqueous solution at
    ordinary temp eratures in large crystals which soon effl oresce 1 00 .

    p a rts H g O d issolve p arts of the salt at 2 0 and parts at


    The solution is feebly alkaline By leading in carbonic aci d .

    gas a liquid of am photeric reaction (cf 2 2 4) is obtained which .


    ,

    turn s blue litmus red as well as red litmus blue M o n o S o d i u m .

    p h o s p h a t e N a H z P O 4 H 2 0 reacts
    -
    acid ,
    I t is converte d .

    by heat into the meta phos phate .

    2 26
    . So di u m c a rb o n ate , N a2 C 0 3 1 0H2 0 ( s oda s o l soda ) is -
    , , ,

    next to the chloride t h e m o s t im p ortant so dium salt and it is


    ,

    manufactured on an enormous scale I t occ urs in nature in E gypt .


    ,

    in Am erica (Wyoming ) on the C as pian Sea an d elsewhere ; t h e


    , ,

    ashes of many marine plants contain it .

    Th e m an ufac tu re of s oda is carrie d o n mainly b y t wo d ifferen t


    methods :
    ( )
    1 T h e L E B L AN C s o d a p r o c e s s .

    This pro cess c onsists of three p arts I n the rst place common .

    salt is warmed with strong sul phuri c acid ( chamber acid) ;


    hydro chloric acid and sodium sulphate salt c ake are formed .

    I n the second p a rt of the pro cess sodium sul phate is heated with
    coal and limestone The third section of the p ro cess consis ts
    .

    in lixiviating the mass last obtained black ash with water -

    whereby sodium c arbonate is dissolved out The latter is then .

    O btained from this solution by crystallization .

    A fter the black ash has been leached out as far as p racticable ,

    it is c ast aside as tank waste The m ost valuable constituent
    .

    of the latter is c alcium sul phide ; it is conserved by treating the


    3 20 I N O R GA N I C CHE M I S TR Y . 22 6 .

    waste with water and carb on dioxide to form hydrogen sulphide ,

    which is then oxidi z ed to sul phur and the latter to sul phuric
    acid The pro cess in its entirety is thus re presented by t h e
    .

    fo ll o wing equations :

    2 N aC l Hg SO 4 N ag SO 4 l 2 HC l ;
    =

    N ag SO 4 + 2 C
    b
    2 00 2 N ag S ;

    N ag S C aC 0 3 C aS N a zC O 3 ;

    C02 Hg O C aS C aC 0 3 Hg S ;

    HQ S j2 0 2

    HQ SO 4 ;
    or summed
    , up

    2 N aC l C02 Hg O 2 HC l N ag C O g .

    The pro c ess i s noted for i ts hig h e f ci en c y s i n c e al l the b y produc ts


    ,
    -

    are wor ked u p N ev erthel ess thi s pro c ess wh ic h for a l ong peri od of
    .
    , ,

    years p ra c t ic ally c ontro ll ed t h e i ndu stria l m ar k et i s n ow a lm o st who lly ,

    s u p ers eded by t h e other o n e an d a fe w years m ore w ill probab ly s ee i ts


    enti re abandon m ent .

    ( )
    2 The ammonia -
    soda p rocess o f S O L V A Y .

    This p ro cess which originally presented numerous technical


    ,

    difculties is now so p erfected that about ninety v e p e r cent


    ,
    -

    of the total soda productio n is by the SO LV A Y pro cess The .

    chemist ry of the SO LV A Y pro cess is very sim ple A mmonia .

    and carbon dioxide are led alternately into a cold concentrated


    salt solution under pressure The following reaction then takes
    .

    p lace :

    N aC l ( N H 4 ) H C 0 3 N a HC O g N H 4Cl .

    The acid sodium c arbonate bicarbonate so formed se p a


    rates out inasmuch as it is very dif c u l t l y soluble in the col d
    ,

    concentrated ammonium chloride solution It is broken u p on .


    ,

    heating int o soda and carbon dioxide the latter of which is


    , ,

    c arried back to be used over The ammonium chloride solutio n .

    is distilled with lime whereby ammonia is recovered


    ,
    .

    The p rocess as a whole may be re presented by the following


    e quations :
    3 22 I N O R GA N I C C HE M I S TR Y . 22 6

    A cid o di u m car b o n ate , N aHC og (bicarbonate of soda) is


    s ,

    obtained as a primary product in the SO LVA Y process I t dis .


    solves in 1 0 1 1 p arts of water at room tem perature and reacts
    alkaline O n being gently w armed it breaks u p into carb on
    .

    dioxide water and soda ; this dec omp osition occurs even on warm
    ,

    ing the aqu eous solution and when a current of air is p assed ,

    through the c oncentrated solution at ordinary temperatur es c ar


    b on dioxide escapes I t is use d extensively in baking p owders
    .
    -

    and is the sa l er a tu s of c ommerce .

    So di u m sili c a t e (sodium water glass ) is pre p are d among oth er -

    ,

    ways by fusing sand with G lauber s salt and charc oal This
    ,
    .

    yields a vitreous mass which is dissolved by b oiling water The


    ,
    .

    c oncentrated solution has the c onsistency of glue I t nds use as .

    a xative in c alic o printing as well as for im pregnat ing in am ,

    mable text iles l ike theater dec orations etc ; it is also used for ,
    .

    lling Soaps .

    The su lph ide s of sodium c orresp ond to those of p otassium an d


    are pre p ared in the same way ( see
    '
    So diu m bo rat e z cf B orax .

    PO TA SSIUM .

    22 7 . C om p ounds
    of p otassium occur in nature very extensively
    but not in such large quantities as those of sodium Potassium .

    exists prin cip ally in the silicates es pecially felds p ar and mic a , .

    Up on the dec ay of these minerals it is c arried into the soil and


    thence into the plants to which p otassium c om p ounds are indis
    ,

    p ensable P otassium
    . salts are also found in sea water The -
    .

    largest source of them however is the Stassfurt ,


    A brau m ,


    s alts mainly double salts of p otassium and magnesium ,

    such as car na l l ite MgC l z K C l 6 HQ O k ain ite MgSO 4 K Cl 3 HzO


    ,
    - -

    , ,
    - -

    et c
    . Th e la r g e amounts o f p otassi u m in th e felds p ars makes its
    r ecovery fro m them a very enticing p roblem .

    Th e m e t a ] was rst obtained by D A VY by th e electrolysis o f


    molten causti c p otash O n e of t h e commercial metho ds is t o
    .

    ignite a mixture of c arb onate of p otash and p owdere d charc oal


    (p referably ch arred acid p otassium tartrate ) The extractio n of .

    t he meta l is thus analogous to th at of s o d ium ; in the p re p aratio n ,

    o f p otassium however p ota s s iu m car bon yl C a( O K ) 6 may b e


    , , , ,
    O X Y GEN
    O

    C O IlI PO UN D S O F PO TA SS I UM . 3 23

    formed under certain c ircumstances a substance which acquires ,

    explosive pro p erties on exp osure to the air .

    Potassium has a s ilvery white metallic lustre and is almost as-

    sof t as wax at ordinary tem peratures Sp g = 0 87 5 at It . . . .

    melts at and b oil s at ab out forming a green vap or The .

    m irror like surfac e of the metal immediately becomes dull in the


    -

    air ; when heated in the air it burns with an intense violet light .

    Water is dec om p osed by it with great vigor the heat evolved


    '

    being sufcient to ignite the esca ping hydrogen and drive the
    p iece of p otassium around on the water .

    O xygen C o m po u n ds o f Pot as s i u m .

    22 8 . o x i de K Q O is formed by oxidi z ing p o t as


    Pot a ssi u m , ,

    sium by the metho d described in 224 I t is a white substance .


    ,

    which unites with water to form the hydroxide with the evolution
    of much heat .

    Pot as si u m pe r o x i de K O z is pro d uced together with the mon


    , ,

    oxide o n burning p otassium in the air I t is dark yellow I n c on . .

    tact with water it yields p otassium hydroxide hydrogen peroxide ,

    an d free oxygen .

    Pot ass i u m h ydr o x i de , K O H results from the action of p o t as ,

    si u m on water and is generally pre pared in the same manner as


    sodium h ydroxide viz by treating p otassium carb onate solution
    ,
    .
    ,

    with milk of lime C a ( O H) 2 I t c an also be obtained by heating


    ,
    .

    salt petre with p owdered c o pper ( forming C o pper oxide and p o t as


    Sium oxide ) and adding water ; the c o pper oxide can be remove d
    ,

    by ltration The hydroxide usually c omes on the market in


    .

    sticks .

    The c ommercial pro d uct c austic p otash is O btain e d chiey


    b y the rst method and usually c ontains a little sulphate chl oride , ,

    etc besides the c arb onate whic h is gradually formed by the action
    .
    ,

    of atmospheric carb on dioxide It can be p uried by treating with .

    strong alc ohol which dissolves o nl y the hydroxide ; after ltering


    , ,

    the alc oholic solution is evap orated in a silver dish C aus tic soda .

    is also puried in this way .

    Potassium hydroxide is one of the strongest bases In the soli d .

    state it greedily absorbs water and carb on dioxide from the air and
    nall y deliquesces to a c oncentrated solution of p otassium carbonate ,

    w hile sodium hydroxide under these c on d itions turns to a soli d


    3 24 I N O R GA N I C C HE M I S T R Y . 22 8

    white mass of soda For this reason c austic p otash is a much more
    .

    suitable absorptive agent for carb on dioxide in analyses than c austic


    soda for the use of the latter might easily cause a sto pping u p of
    ,

    the app aratus .

    C austic p otash is used es p ecially in the manufacture of soft


    soaps .

    Pot as si u m Salt s .

    9
    22 . r
    Po t as s i um
    lo i de ,chK C l occurs ,
    at S tassfurt in the min
    eral s yl vite I t crystalli z es in cubes and melts at
    . I t is easily
    volatilized at elevated temperatures 1 00 p arts Hg O dissolve .

    p arts K C l at 5 7 p arts at L ike its sodium analogue ,

    p otassium chloride is p reci p itated from its saturated solution by


    hydrochloric acid I t unites with man y salts to form double salts
    . .

    Pot assi u m b r o m i de , K Br is im p ortant thera peutically


    ,
    I t is .

    re
    p p ared by mix ing bromine with a p otassium hydroxide solution ,

    the bromide and bromate being formed ; the bromate is reduced


    by heating the salty product with p owdered charcoal Potas sium .

    b romide crystallizes in cubes and dissolves readily in water .

    Potass i u m i o dide K I also of medicinal value c an b e pre par e d


    , , ,

    like the bromide an d also in the following manner : I odin e and


    iron lings are m ixed together under water whereup on a solu ,

    tion of the c omp ound Fe gI g is formed ; on treating this with a


    p otash solutio n the oxide F e 3 0 4 is p reci p itated c arb on dioxide,

    escap es and p otassium iodide is left in solution ; the sal t is then


    obtained by ltration an d evaporation I t crystallizes in cubes .

    and is very soluble in water : 1 p art Hg O dissolves p arts


    KI at O n ex p osure to light or the air the crystals gradually
    turn yellow because of the se p aration of iodine .

    It was remarked in 4 o that iodine though only slightly ,

    soluble in water d issolves to a much greater exten t when the


    ,

    water c ontains p otassium iodide This is due to the formation .

    of 1 3
    '
    ions in the latter c ase Th at the io dine has entered i nt o
    .

    c ombination may be concluded in the rs t place from the fact


    that t h e additio n of i odine to an aqueous solution of p otassium
    iodid e does not c ause a further de p ression of t h e fre e zing p oint ; -

    the number of molecules is thus unch anged or i n other words , , ,

    io dine has co mbine d with p otassium iodide : in t h e second place ,

    from the fact that c arb o n disul phide takes u p nearly all t he iodine
    from an aqueous solution of the latter when it is shaken with t h e
    solution but o nly a small pr o p ortio n when the same o peration is
    ,
    3 26 I N O R G A N I C C HE M I S TR Y . 22 9

    at the anode oxidizes the sodium chloride to chlorate N aC l O g ,


    .

    The latter is converted into the p otassium chlorate by treatment


    with p otassium chloride The advanta ge of this method is that
    .

    sodium chlorate is much more soluble and does not retard the
    electrolytic pro cess by se p arating from the solution as does ,

    p otassium chlorate .

    Potassium chlorate is a well crystallized salt which is used for


    -

    the pre p aration of oxygen furthermore it is used in the ,

    manufacture of matches and reworks and also medic inally as a ,

    r emedy for sore throat O n being heated it gives up oxygen


    .
    ,

    p art of the salt being at the same time c onverted into p ot a ssi u m
    pe r c h lo r ate , K C l O a .

    Th e l ast nam ed sal t i s difc u l t l y so lub le i n water I t i s so metim es


    -
    .

    fo und i n c r u de C hili sal tpetre renderi ng the l atter un t for use i n


    ,

    fert ilizi ng v ari o u s cul t iv ated pl ants .

    Pot ass i u m su l ph at e , K zSO 4 is obtaine d by the action of sul


    ,

    p h u r ic acid on p otassium chloride I t cryst a.llizes in beautiful ,

    lustrous rhombic pr iSm S and dissolves with some difculty in c old


    water ( 1 p art in 1 0 p arts E g O at room tem p erature ) I t is used .

    p rinci p ally for the p re p aration of p otash acc o r ding to the L E

    B L AN C method . A c i d pot as s i um su l ph at e , K E SO 4 is very soluble ,

    in water ; it melts at losing water and going over into po t as


    s i u m py r o su l ph at e , K 2 S2 0 7 . The latter breaks u p into p otassium
    sul phate and sul phur trioxide on heating .

    Potas si u m n it ra t e , KN 0 3 is widely distribute d in nature


    , ,

    although usually foun d only in small amounts for it is forme d


    wherever n it r og en e ou s organic bodies decay in c ontact with po t as
    sium c om p ounds This is the basis of an articial metho d of
    .

    p pre aring salt p etre ,


    which method was formerly much used .

    A nother process of manufacture de p ends on the double de c om


    p osition of C hili salt p etre with p otassium chloride which is obtaine d ,

    in large quantities at Stassfurt :

    KC l N aN 0 3 KN 0 3 N aC l .

    For this purpose hot saturated solutions of the two salts are brought
    -

    together A s sodium chloride is much l e s s s ol u b l e than saltpetre


    '

    .
    PO TA SSI UM S A L TS . 3 27

    at the tem perature of b oil ing water it is the rst to crystallize ,

    out on evap oration but when the solution is c ooled the saltpetre
    ,

    c omes out rst for it is much less soluble than sodium chloride
    ,

    in c old water .

    Potash salt p etre crystalliz es in anhy d rous pris ms either rh o m ,

    b oh e dr al or rhombic acc ording to the tem p erature I n the neigh .

    b orh oo d of the melt ing p oint the former is the stable variety
    -

    at ordinary tem peratures the latter The location of the transi .

    tion p oint of the two forms has not yet been determined 1 00 .

    p arts H g O dissolve p arts K N 0 3 at 2 4 7 at I t melts


    at farther heating breaks it u p into p otassium nitrite and
    oxygen I t has a c ool ing taste
    . .

    23 0 P o t a S h salt petre is c onsumed in large quantities in the


    .

    manufacture of gu n powder This is a m ixture of sul phur charc oal


    .
    ,

    and p otash salt petre the p ro p ortions varying in d ifferent c ountries


    , ,

    but be ing in mos t c ases 7 5 % KN O 3 1 0% S and 1 5 % charc oal , .

    23 1 Pot ass i um pho sph ate s


    .
    The three p otassium salts of
    p hos p horic acid are kno w n They are very . soluble in water .

    Pot a ssi u m c a r b o n ate c og p ota h


    ,
    s
    This salt was formerly
    , .

    o btained solely from wood ashes these being soaked in water and ,

    the straine d liquor evap orated A t present it is manufactured .

    e xtensively from
    p otassium chloride after the L E B L AN C p rocess .

    A nother source of p otash is the molasses of the beet sugar fac -

    t ories that c ontain s the p otassium salts in which the sugar beet is
    ,
    -

    rich .

    At the N e u st assfurt salt mi ne i t i s m ade fro m potassi um c hl or i de


    by a patented pro c ess as fo ll ows : M agnes ium c arbonate M gC O 3 3 HzO ,
    o

    is s uspended i n a so lu t i on of potass ium chl ori de an d carbon di o xi de ,

    i s l e d in where u pon the fo ll ow i ng rea ct i on takes pla c e :


    ,

    3 M goo, su p 2K 01 + coz = M g o1, 2Mg co, K HC O ,

    Th e potass ium m agnes ium c arbonate separates o u t and i s bro ken u p


    by heat i ng to a te m perat ure not e xc eedi ng 80 i nto m agnes ium c ar

    bonate and potash Th e form er sal t i s aga i n obta i ned wi th three m o le


    .

    cules of water of crystalliz at i on which form i s the only one s ui ted for
    ,

    t h e abo v e rea c t i on .

    Potassium carbonate is a white p owder , which deliquesces


    in the air and is v ery soluble in water p arts K 2 C O g in 1 p art
    28 I N O R GA N I C C HE M IS T R Y . 23 1

    H2 0 at the solut ion has a strong alkaline reac tion The salt .

    melts at I t is used in the prep aration of soft soaps and har d


    glass (p otash glass ) -
    .

    Pot ass i um sili c ate , p otassium water glass is formed when san d-

    is fused with p otash Different salts of this sort are described


    . .

    They dissolve in water form ing a thick mucilaginous mass which


    , ,

    on drying turns to a vitreous and nally op aque product ,


    :

    ,
    .

    Potassium water glass is used for t h e same p urp oses as s odium


    -

    water glass-
    .

    Sul phide s of Pot assium .

    Po t assiu m m o n o su l ph i de , K zS, is p re pa re d b y reducing


    po tassium sul phate with cha r c o al I t d iss olves in water very
    .

    r ead ily an d c rystallizes out with ve m olecules of wate r .

    It absorb s o xygen from the air going over into the thio ,

    sul phate a n d hy droxide :

    2KgS Hg O 20 2 K 2 S2 0 3 l 2 K O H .

    A cidsreact with it li b erating hydrogen sul p hide


    ,
    .

    Pot assiu m h ydr o su l ph i de , K SH is obtaine d by saturating, a

    caustic p otash solution with hydrogen sul p hide

    KO H H2 S K SH Hg O .

    It is very soluble in water the solution reactin g alkaline ; on


    ,

    evap oration in vacu o the solution de p osits crystals of the c om


    p osition 2 K SH + H 2 0 With p otassium hydroxide
    . it forms t he
    monosul phide i

    KSH KO H K2 8 11 2 0 .

    Po ass um
    t i h
    po ly l p i de s
    su When
    a solution of potassium mon o
    sul phide is obtain the c omp ounds K 2 S3
    boiled with sul phur , we ,

    K zS4 K zS5
    ,
    A m ixture of these substances is also obtained by
    .


    fusing p otash with sul phur ; besides these it c onta ins the sul phate
    and the thiosul phate and is called hepar su lphu ris ( liver of sul
    hur because of its liver
    brown c olor These olysul hides are
    p p p .
    0 IN O R GA N I C C H E M I S TR Y . 23 2

    o ff . u b i d i u m has a s ilvery l ustre m el t s at


    R and has a spe cic ,

    gravity of at Th e m etal o xi d iz es v ery rap i d ly i n the a i r or


    i n o xygen forming dark brown c rystal s of t h e p ero xide R b O O n
    , , z .

    be in g heated in c urrent of hydrogen i t y ie lds the hydro xi de an d free


    o xygen :
    2R b 0 2 + 2 H2 2E b 0 H + H 2 0 O .

    R ub i d ium
    o xi de when prepared i n t h e sam e way as N a O i s obtained
    , z ,

    as transparent p al e ye ll ow c rystal s wh ic h t urn go l den yell ow o n heat ing


    ,

    but l ose th i s c o l or agai n on c oo ling .

    Th e h v dro x ide i s a v ery strong base ; it s sa l ts Show muc h Simil ari ty


    to t h e anal ogo u s p otass ium c o mp o u nds ; they a re in se veral i nstan c es
    l ess so lubl e e g R b alum R b per c hl orate
    ,
    . .
    ,
    et c ,
    -
    .

    0 an s i u m i s a s ilvery wh i te m eta l ; sp g m pt
    -

    b pt . . .
    -
    . .
    -
    .

    I t soon ta k es re on e x pos u re to t h e a ir Th e o xi de 0 8 0 .
    , 2 ,

    obtained i n t h e sam e way as t h e other alkali o xi des i s c rystalliz e d an d ,

    is oran ge c o l ored at roo m te m perat u re b u t a lm ost b l a ck at


    -

    The sal ts of c aesium are v ery Similar to those of r ub id ium ; som e of the m
    .

    are ev en l es s so lub l e an d are therefore u sed for t h e preparat i on of


    ,

    p u re c aes ium c o m p u n ds
    q Th i s i s p art icul ar l y tr u e of
    . the p l at i n um
    do ub le sal t already m ent i oned and t h e c aes ium a lum an d the a cid
    -

    tartrate .

    R ub i di um bro mi de and i od i de and e v en m ore so the c orres pondi ng ,

    co m po unds of caes i um hav e the pro perty of c o mb i ni ng w i th two ato m s


    ,

    of bro mine and i odine formi ng ye ll ow or brown c rysta lli ne co m pounds


    , ,

    e g C SI3 ; these m etal s c an th u s be tr i va l ent


    . .
    .

    SUM MA R Y O F T HE G R O UP O F A L K AL I M ETAL S .

    3 The gradual
    23 change of
    .
    the p hysical p ro p erties of these
    metals with increasing atomic weight is made pla in by the follow
    ing table :

    A tomic w igh t e
    Sp ecic g vity ra 0 59 . 0 97 1 52 1 85
    M l ti g p i n t

    e n -
    o 1 80 0 97 6 38 5 26 27
    B ili g p oi n t

    670

    o n -

    < 1 400 87 7 696


    A t mic v olum e
    o
    A M M O N I UM S A L TS .
    33 1

    The Specic gravity increases with th e atomic weight as does ,

    also the atomic volume ; on the other hand there is a fall in t he ,

    melting and b oil ing p oints -


    .

    From a chemical stand p oint we notice in the rst place the , ,

    same general ty p e in the c om p ounds showing that all these ele ,

    ments are univalent The hydroxides all have the formula R O H


    .
    ,

    the halogen c om p ounds R X et c The salts of them all even ,


    .
    ,

    the c arb onates and phos phates are soluble in water ( although in ,

    d ifferent degrees ) the carb onates with basic reaction The metals
    , .

    all oxidize very readily in the air .

    O n the other hand we cannot overlook the fact that the metals
    ,

    p otassium rubidium
    ,
    and c aesium which are very similar to each ,

    other di ffer from sodium and lithium in many res pects The last
    , .

    named metal as we shall see in the sequel displays analogy


    , ,

    with magnesium in several im p ortant p oints thus di ffering from ,

    the metals of its own group A Slight divergence in the behavior .

    of the r st members of a grou p from that of the rest is found to


    characterize alm ost all of the grou ps We may recall carb on fo r .
    ,

    instance the rst member of the fourth grou p which differs dis
    , ,

    t in c t l y from s ilic on and the rest in the ability of its atoms to unite
    with each other ; also uorine with its soluble Silver c ompoun d .

    St ill other exam ples of this sort will be met with later .

    Sodium di ff ers from the sub grou p K R b C s in the solubil ity -

    , , , ,

    o f its salts The sodium salts are almost all readily soluble in
    .

    water ; this is true even of the platinum double salt N at C l the -

    , ,

    acid sodium tartrate and others Soda crystals e f or es c e while .


    ,

    p otash deliquesces in the air The Sp ectra of sodium on the one


    .
    ,

    hand and the other alkali metals on the other are entir ely dis
    , , ,

    s imilar .

    Am m o n i u m Sal t s .

    2 In the description of ammonia


    34 . 1 1 2) it was alrea d y
    O bserved that it c ombines with acids direct l y forming salts Which ,

    are very similar to those of p otassium and in which the group , ,

    N H4 the a mm on iu m grou p is assumed to exist


    , I n c onnection
    , .

    with the alkali group a descrip tion of a few amm onium salts may .

    nd a place .

    The aqueous solution of am monia must because of its electrical ,

    co nductivity and its alkaline reaction c ontain N H; and O H ions


    ,
    332 IN O R G A N I C C H E M I S TR Y .
    [1 23 4 4

    an d henc e also undisso ciate d molecules of ammonium hydroxide ,

    N H4 0 H While solutions of the alkalies K O H N a O H etc


    .
    , , ,
    .
    ,

    c onduct the electric current very well this is not the c ase with an ,

    a mmonia solution ; it is a p o or co nductor A normal solution .

    c ontai ns o nly 5 % of ionized N H4 O H molecules while a solutio n ,

    O f p otassium hydroxid e of t h e sam e c o nc e nt ration is 9 1 %


    ionized .

    An aqueous solution of ammonia may be presumed to c ontain


    ( 1 ) free ammonia N H 3 ; ( )
    2 hydrates,
    of ammonia N H g n aq ; ( 3 ) ,
    -
    .

    ammonium hydroxide N H4 0 H ; (4 ) t h e ions N H ; and O H


    ,

    The .

    existence of these hydra t es in addition to free ammonia reveals


    itself in the b ehavior of ammonia solutions on being shaken with
    A cc ording to B ERTHE L O T S law ( O R G C HEM 25)

    c hl oroform . . .
    ,

    t he distribution ratio of the ammonia between the two solvents


    should be c onstant Bu t this is not the case
    . Therefore j ust .
    ,

    as the deviations from H ENR Y S law lead us to c onclude that a


    d is solved gas exists in a Spec ial c ondition so we c an apply a simi ,

    lar explanation to the exce ptions to the B ERT H E L O T law ; for


    H ENR Y S law is real l y the ex pression of the distribution ratio of

    a gas between a liquid and a vacuum while the other law has to ,

    d eal with the dis tribution ratio between two liquids .

    Since in the case of ammonia this deviation is observed only


    when one of the two liquids is water we are obliged to c onclude ,

    that there is a c ombination of the ammonia with the water The .

    r eason for assuming the existence of hydrates instead of amm o


    nium hydroxide N H4 O H is a double one We have on the
    , ,
    .
    ,

    one hand the analogy between the behavior of a m monia and


    ,

    amines and on the other the entirely abnormal behavior of the


    , ,

    organic quaternary ammonium bases For while the aqueous .


    ,

    solutions of primary sec ondary and tertiary amines are weak


    ,

    electrolytes as is the case with ammonia the solution of a quater


    , ,

    n ary base o u the c ontrary c onducts electricity as well as a solu


    , ,

    tion of p otassium or sodium hydroxide We may thus c onclude .

    that if ammonium hydroxide N H4 O H c ould reach the same , ,

    c oncentration in solution as a quaternary base it wo ul d display


    j ust as great a c onductivity as the latter Unl ike the quaternary .

    b ase however it breaks u p principally into ammonia N H3 and


    , , , ,

    water for the quaternary base cannot be thus dec omp osed
    ,
    .

    That an aqueous a m monia solution really c ontains at least


    334 IN O R GA N I C C HE M IS TR Y . 23 4 ,

    s imila rly dr i e d amm onia gas and hydro chl o ric ac id gas do n ot
    uni t e t o form ammonium chlori d e Traces of wa t e r t hu s
    p ro duce a marked catalytical ac celerati o n b oth ,
    of the formatio n

    and of the de com position o f ammo nium chlori de We have here .

    an illustratio n o f t he general r ule th at when one p art of t h e


    system in a r e v ers i b le reaction is ac celerate d by a catalyzer t h e
    o ther must be likewise affected The pro of of this rule lies in
    .

    the im p ossibility of the c ontrary being true sinc e that w o ul d ,

    n ecessitate a change in the e quilibrium ( see

    I n m a ny othe r c as e s i t is al s o o b s e rve d th at trac e s o f w at e r h ave a


    c on s i derab le i n ue n c e o n t h e ve l o city o f ch e mic al re a ction s Th e foll o w .

    in g e xamp l e s m ay b e ci te d : ( 1 ) Pho s ph oru s th at ordi n ar il y t ake s r e


    ,

    in m o i s t a ir at a littl e ab ove roo m te m pe rature c an b e h e ate d in o xyg e n


    ,

    to 1 50 w ith out ign ition provi de d t h e oxyge n h as b e e n c are fully dri e d b y



    ,

    p h o s p h oru s p e n to xi d e .
    ( 2 ) C ar b o n m ono xi d e b urn s i n mo is t oxygen muc h
    more e as ily th an in dry oxy ge n ( 3 ) Ve ry c are fully drie d de ton at in g
    .

    a s c an b e h e at e d in a t u b e to re d he at w i th o u t e x pl o d i n g
    g
    -
    .

    Am m o n i u m su lph at e , ( N H4 ) Q SO 4 crystalliz es in large rh o m b ic


    ,

    p r isms and dissolves very readily in water O n b oiling the a que


    .

    ous solution some ammonia esca pes acid sul ph ate being forme d , .

    I t s solu t io n in 3 0% h y dro gen p e roxi de yi e l ds o n ev aporat i on c rystal s


    of t h e co mpo s it ion Wh e n the s e are h e ate d under re
    du c e d pre s s ure a h igh pe r c ent h yd ro ge n pe ro xi de dist il s o ff .

    (
    A m m o n iu m n itr at e N H4 N 0 3 deliquesces in the air ; when
    , ,

    heated it b r eaks u p into water and nitr ous oxide This


    s al t is known in three crystallized modications the transition ,

    p oints 7 0 ) of which have been determined .

    Am m o n i u m ph o sph ate s . The tertiary salt is


    ,

    d ep osited in crystallin e form on mixin g c oncentrated solutions of


    p hos p horic acid and ammonia It
    . cannot be dried however for , ,

    it then loses amm onia and goes over into the secondary phos phate ,

    ( N H 4 ) 2 H P O 4 O n
    . b oiling the solution the salt again yields ammo
    n ia and is transformed into the primary phos phate .

    The best known of these salts is the s o di u m am m o ni um ph o s


    p h a te ,
    N a N H 4 H P O 4 4 H-
    2 0 ,
    m i cr ocos m ic s al t I t forms
    . large
    tra nsp arent crystals O n being heated it melts loses water and
    .
    ,

    ammonia and passes over into a vitreous substance sodium meta


    , ,

    p hos p hate ,
    N a P 03 .

    Am m o n i u m c arb o n at e was formerly obtain e d by the dry distil


    lation of nitrogenous organic substances such as hair nails , , ,

    leather etc hence the name
    , .
    ,
    salt of hartshorn which still ,
    SA L T SO L UTI O N S .
    335

    c l ings t o it At pr esen t h ow e v er it is ma d e b y dry d is t illing a


    .
    , ,

    mixture of calcium c arb onate and ammonium chloride or sul ph ate .

    The p ro duct is a mixture ( molecule for molecule ) of acid salt ,

    N H4 H0 0 3 and ammonium carb amate N Hz C O z N H4 ( this


    , ,
    - -

    lat t er being t he neutr al salt minus 1 H2 0 ) From its c omp osition .


    ,

    H2 0 it takes the name am mo n iu m s esgu icar bo n a te


    -
    , ,

    O n p assin g a mm o ni a gas into a c oncentrated aqueous solution of it


    the neutral salt (N H4 ) 2 00 3 se parates out as a crystalline p owder ;
    , ,

    it smells strongly of ammonia and p asses slowly over into the acid
    salt N H4H00 3 a white odorless p owder which is scarcely soluble
    , , ,

    in water This acid salt is also formed directly from the sesqui
    .

    c arb onate as the latter gives o ff carb on d ioxide and ammonia in


    ,

    the air (hence the o d or of ammonia) an d goes over into the rst
    named salt .

    Am m o n i u m sul ph i de is extensively use d in analysis A


    s olution of amm onium hy d rosul phide ( or sul phydrate ) N H4 SH , ,

    is ob taine d by satur ating aqueous amm onia with hydrogen sul phi d e ;
    it is a c olorless liquid which soon turns yellow because of the for
    ,

    mation of am mo nium p olysul phides The oxygen of the air oxidi z es .

    p art of the hydrogen sul p hide and thus sets free sul p hur which ,

    c ombines with ammonium hydrosul phide to form p olysul phides .

    These p olysul phides are also obtained by d is solvin g sul phur in a


    solution of ammonium hy d ros ul phi d e .

    mi xi ng vo l s H gas and vol H gas at 1 8 a whi te crystal


    O ZS
    n 2 N 3 1 . .

    line m ass i s obtai ned whic h de c o m poses at ordi nary te m peratures i nto
    ,

    N H SH and N H
    4 The c o m po und N H SH separates o u t c rystal li ne
    ,. 4

    when hydrogen s ul phi de is passed i nto alc oho li c a mm oni a As l ow as .

    4 5 it is co m plete ly di ssoc i ated i nto e q ual vo l u m es of N H3 and HZS



    .

    SA LT SO L UT I O N S .

    2 35 . Eve ry
    solid substance is soluble in every liqui d ; howeve r ,

    the pro portion which dissolves c an vary all the way from zero to
    innity I f only an innitesimal amount of the solid goes into
    .

    solution we say ord inarily that the substance is insoluble in the


    ,

    liquid ; there can be no doubt however that if our means of inv e s , , ,

    t ig at io n were sufciently irn pr o v e d and large enough quantities of


    liquid were taken the solub ility woul d be perce ptible
    ,
    This has .


    already been demonstrated in many cases of so calle d insolubl e
    substances E ven when we conne our attention to
    aqueous soluti o ns of salts (includ ing acids an d bases ) we nd t h e
    336 IN O R G A N I C C HE M I S TR Y . 23 5

    same innite di ff erence in solubility that is observed between sub


    stances in general Substances such as sand barium sul phate
    .

    silver iodide etc are insoluble ,


    oth ers like sul phuric
    .
    ,
    ,

    acid are able to dissolve in any give n amount of wate r


    ,
    .

    Wi th regard to the so lub ili ty of sal ts the foll owing pra c t ic al rul es are
    worth re m e mbering : P o t a s s i u m s o d i u m and a m m o n i u m ,

    s a l t s are so lub l e N orm al n i t r a t e s c h l o r a t e s and a c e ,

    t a t e s are so lu b l e N orm a l c h l o r i d e S are so lub l e (e xc ep t A gC l ,

    n C l ,,
    and N or m a l s u l p h a t e s are so lub l e (e xc ep t those

    of Ba Sr C a an d Pb ) H y d r o x i ( 1 e s are i nso lub l e (e xc ept those


    , , ,
    .

    of the alk ali es and alkaline earths) N orm al c a r b o n a t e s p h o S ,

    p h a t e S and s
    ,
    u l p h i d e s are i nso lu b l e ( e xc e pt those of t h e a lk a
    lies) B a s i c s a l t s are insolubl e A c i d s a l t s are so lub le i f

    t h e a ci d i t sel f i s so lub l e .

    The solubility i e the maximum relative amount of salt tha t


    ,
    . .

    c an go in to solution is a fu nction of the temp erat ur e and the


    ,

    p ressure I n the great maj ority of cases the solub ility increases
    .

    with the tem perature I f the temperature is plotted on the axis .

    of absc issas and the amount of salt which dissolves in one hundre d
    p arts of water is p lotted on the o rdinate axis a s o l u bility cu rve ,

    is obtained ( Fig 52) which shows at a glance the variation of the


    .

    l
    i

    solubility with t h e t em per at u r e .

    For some salts e g p otassium nitrate the solubility increases


    ,
    . .
    ,

    very rap idly with the temperature ; for sodium chloride it remain s
    p ractically constan t I n certain cases such as those
    . of c alcium ,

    hydroxide and c alcium sul phate (within certain limits of tem p era
    ture ) the solubility decreases with rising temperature These .

    p h enomena are c onnected as has already be en ex p lained with , ,

    the heat of s o lu tion i e with the caloric e ffec t which acc omp anies
    ,
    . .

    the p rocess of solution and in the manner expressed by VA N T


    ,
    I

    HO FF s principle of mobile equilibrium



    I n fact salt p etre ,

    for instance whose solubility increases very rapidly with the


    ,

    tem p erature ( see Fig 52 ) dissol ves in water with a c onsiderabl e.

    absorp tion of heat .

    2 36 . Th eter m heat
    f has v ario u s m eani ngs o We are obliged
    s ol u tion .

    to di sti ngui sh between ( 1 ) the c al oric effe c t of di sso lvi ng a sal t i n a very '

    l arge am o unt of water ; ( 2) the c a l or ic e ffe c t of d i sso lvi ng a sal t i n an


    alm ost sat urated so lu t i on ; an d (3 ) the total heat of so lut i on i e the ,
    . .

    who le c al oric e ffe c t of disso lvi ng a sal t i n water u ntil the so lut i on i s
    sat ur ated A S a rule these three m agni tudes will hav e di ss imilar
    .
    338 C HE M IS TR Y
    '

    IN O R G A N I C .
    23 s

    c ussed i t was beli eved t hat there were e xc ept i ons to the
    , pr i n ci p l e but
    ,

    cl oser i nvest igat i o n h as p ro ved t h e c ontr ry a .

    In some cases the solub ility of a salt at rst increases gradual ly


    with rising tem perature and then steadil y decreases so that the ,

    solubility curve has a maximum (cf Fig I n full agr eement . .

    with V A N T H O FF S principle the heat of solution is negative in


    the ascending p ortion of the curve zero at the maximum and ,

    p ositive in the d escending p ortion I n the case of y


    g p sum .

    C aSO 4 2 H2 0 for instance the maximum was found to lie at


    -

    , ,

    about 3 8 an d at that p o int the heat of solution was actually



    p roved to be at 1 4 it is abov e

    + 02 4 .

    The e ffect of pressure on the solub ility


    is at the most very s l ight but it is in e ntir e ,

    acc o rd with the principle of L E C HAT E L I ER .

    A mmonium chloride for instance dis solves , ,

    with expansion ; therefore its solubil ity lessens


    FI G 53 . .

    with in creasing pressure ( 1 % for an increas e


    of 1 6 0 C opp er sul phate which d issolves with c ontraction
    , ,

    has its solubility in creased by an increase of 6 0 atm pressure . .

    23 7 I t was formerly thought that the terms


    . solvent an d
    d issolved substance solute Should be ke p t distinct How .

    ever it has since develo ped that there is no essential d ifferenc e


    ,

    between the c omp onents of a solution and that aqueous solutions


    are therefore better dened as liquid c omplexes one of whose ,


    c omp onents is water than as water in which substances are
    ,
    0

    dissolved .

    The interchangeability of the terms solvent and solute


    is evidenced rst of all by the phenomena attending the c ooling
    of salt solutions L et u s c onsider for in s t an c e a nearly saturated
    .
    -

    , ,
    f

    solution of p otassium chloride at a denite temperature We have .

    in it two substances ( K C l and H2 0 ) and two phases g ) hence ,

    two degrees o f freedom We will supp ose that the s ol u t ibn 1s then
    .

    c ooled ; p otass i um chloride crystalli z es out forthwith and as thr e e ,

    p hases ar e t h en
    p

    resent the system bec omes univariant
    ,
    We recall
    that ch anges in the quantity of any phase have no e ffect on such
    a system ; therefore if more sal t is introduced into the system
    ,

    the c oncentrations of saturated solutio n and vapor are una ffecte d .


    SA L T SO L UTI O N S .
    339

    This is none the less true when water is added or the vap or
    volume increased so l ong as the three phases remain
    , .

    O n c ool ing still farther more p otassium chloride is gra d ually


    ,

    dep osited until a p oint is reached below w hi ch the entire liquid


    c o n g e al s t o a mixture of salt and ice This p oin t is known as the
    .

    c ryo h y dr i c , or e u t e c ti c , p oin t There are now four phases salt


    .
    ,
    ,

    ice solution an d va por hence the system has become nonvariant


    ,

    , .

    Th e o pini on was form erly hel d that at thi s po int a chemical com
    p o u nd between the sa l t and water ( a c ryohydrate c a

    m e i nto e xi st
    en c e That i t i s o nl y a m atter of mixt ures c an be seen in the c ase of
    .

    c o l ored sa l ts for i nstan c e w i th a mic ros c ope ; m oreo v er the


    ,

    co m pos i t i on of these so c alled hydrates m ay di ffer in c ase the s o l idi


    -

    c at i on tak es pl a c e u nder a d i fferent press ure .

    we start with a d ilute p otassium chloride solution as another


    If
    e xam ple and c ool it we have ice formed at a denite te mp eratur e
    , ,

    and a univariant system established ice being the th ird phase ,

    r equired B elow this p oint the s ol u tion can be r egarded as s atu rated
    .

    in r es pect to ice j ust as it c oul d be c o ns idered saturated in


    ,

    r espect to the salt in the previous case ; for an increase of t h e


    s olid phase ( ice ) does not now cause a dis placement of the
    e quilibrium 7 1 ) any more than the addition of the solid ( salt )
    d id in the previous instance The addition of p otassium chloride
    .

    c auses p art of the ice to go into solution (i e melt) ; for the . .

    dissolving of more salt increases the c oncentratio n of the solution .

    Therefore if the tem p erature is kept c onstant ice must melt in


    , ,

    o rder to restore the solution to its previous c oncentration It is .

    therefore perfectly analogous to the addition of wat er to a satu


    r ated p otassium chloride solution in c ontact with the solid salt ,

    in which c ase also the solid phase goes into solution I f the tem .

    r at u r e r ises mo r e ice dissolves ; if it falls more crystall izes out


    p e , ,

    j ust as with rising tem peratur e more p otassium chloride goes int o
    solution ap d with sinking tem perature more crystalli z es out O n
    . .

    farther c OOl in g more and more ice wil l be de posited until in this ,

    c ase also the cryohydric p oint is reached below w hi ch the whol e


    , ,

    system solidies to a mixture of salt an d ice The analogy is .

    therefore c omplete .

    The cryohydric p oint is acc ording to this view the poin t of


    , ,

    intersection of two curves viz : the solubility c urves of salt an d


    ,
    .

    of ice in the salt solution .


    3 40 I N O R GA N I C C HE M I S TR Y .
    23 7 .

    An other argument against the assumption of any essential


    d i ff erence between solvent and solute is found in the behavior of
    the solutio ns of certain hydrous salts e g C aC l z 6H2 0 A satu ,
    . .
    -
    .

    r ated solution of C aC l z in water at 3 02 has exactly the com

    osition C aC l z 6 H2 0 A t this tem p erature therefore the hydrate


    p
    -
    .
    , ,

    melts to a homogeneous liquid I f e i t h e r H2 0 or C a C l 2 is


    .

    a dded ther e is a depos ition of C a C l 2 6 H2 O on c ool ing for the ad di



    -

    , ,

    tio nof either c auses a de pression of the p oint of solidication (fr ee z


    ingp oint ) of C aC l z 6H2 0 I n the rs t case this hydrate is in
    -
    .

    equilibrium with a liquid which c ontain s more water than t h e


    hydrate does and which is therefore called an aqueous so l ution
    in the ordinary sense I n the sec ond it is in equil ibrium with a
    .

    liquid which c ontains more C aC l z than C aC l z 6 H2 0 and must -

    therefore be regarded as a solution in C aC l z .

    O n examinin g the solubility curves of various salts ( cf Fig 52 ) . .

    it is found tha t they are in general regular ; however in one of the ,

    curves (sodium sul phate ) a sudden change of direction is noticed .

    This is often observed with salts that c ontain water of c r ys t all iz a


    tion Taking sodium sul phate as an exam ple the p henomenon may
    .
    ,

    be explained thus : I t has already been remarked 22 5) that this


    salt has a transition p oint at the temperatur e of N a2 S0 4 1 0H2 0
    being transformed into N a2 S0 4 and 1 011 2 0 Up to therefore ; ,

    we have the hydrous salt as the solid phase ; ab ove this temp erature
    the anhydrous s al t This change must necessarily involve a sudden
    .

    bend of the solubility curve B elo w 3 3 the curve re presents the


    .

    solu b ility of N a2 S0 4 1 0H2 0 ab ove 3 3 that of N a2 S0 4


    -
    ,

    We .

    c an therefore also r egard the poin t of in ection of the cu r ve ( a t


    as t he p oin t of in ter s ection of the cu rv es for N a zSO 4 I OH2 0 a n d -

    N a zSO 4 I n sodium sul phate the Special case a ppears where the sol
    .

    u b il it y of the anhydr o us salt decreases with rising tem p erature an d

    hence the solubili t y curve falls as the temp erature rises above
    I n the light of the ab ove the solubil ity of a substanc e which
    has a transition p oint is the same for b oth mod ication s at this
    p oint .This m u st always be the case ; it can be demon s trated in the

    same way as in 7 0 where it was Shown that the vap or pressures


    ,

    become equal at the transition p oint I ndeed the same gure can .

    be employed if it is borne in mind tha t the solub ility of a


    ,

    met astable modication is always greater t han that of the stable


    modication at one and the same tem perature I nvers ely more .
    ,

    over we have here a means of de t ermining the transition p oint


    , .
    3 42 I N O R GA N I C C H EM I S TR Y .

    curve must again bend here and in such a way that a t t h e p o i n t


    B the solubility curve of the salt with m + n mols H2 0 is stee per .

    than that of the salt with m mols no matter what the form of .
    ,

    the curves K B and B C may be This is readily understood by .

    a c ourse of reasoning entirely analogous to that given for the


    transiti o n of ice to water or of rhombic to monoclinic sul phur
    Finally at C we have a sec ond transition p oint from sal t
    with m mols Hg O to anhydrous salt so that the solubil ity curve
    .
    ,

    there Shows one more bend W h e r e the curve C D ends de pends


    .

    on circumstances I n many c ases e g that of Silver nitrate it ends


    .
    ,
    . .
    ,

    at the melting p oint of the anhydrous sal t ( c oncentration of the


    -

    I n other instances the anhydrous salt c an form


    a sec ond ( fused ) liquid layer under the saturated solution Finally .
    ,

    mention may also be made of the c ase of c o pp er sul phate which at ,

    a given tem p erature loses its water of crystallization in c ontact with


    its saturated solution and from that p oint o n Shows a decrease in .

    solubility with rising temperature which nally ends in ahn ost ,

    total insolub ility .

    I f we draw a line 701 702 through K p arallel to the ordinate axis ,

    the gure is divided by this line and A K B C D into the following


    r egions : T o the right of the solub ility curve is the region of the
    unsaturated solutions A K k z is that of the superfused l B C D
    , ,

    that of the supersaturated solutions To the left of k l k z o nl y


    ,
    .

    ice solid salt c an exist under ordinary pressures .

    A solubility curve such as that represented in Fig 5 4 c an


    , .
    , ,

    on the other hand be used to detect the ex istence of c omp o u nds


    ,

    b e tween the sal t and the water From the cryohydric p oin t .

    u pward every bend in the solubility curve shows that a salt with
    a d ifferent amount of water of crystalliz ation has been formed .

    Ea c h branch of the curve thus re presents a se p arate salt i e a ,


    . .

    d iff erent solid phase The c omposition of these solid phases is


    .

    by no means always self evident Such is however the case when


    -

    .
    , ,

    the phase fuses without altering its c om p osition o r what amounts , ,

    to the s ame thing when it can exist in equilibrium with a liqui d


    ,

    p has e of the same c om p osition This does not often


    . occur with
    salts in aqueous solution b u t an example of it was seen above in
    ,

    t h e cas e of C aC IZ GHg O '


    The ins pection of the solub ility curve
    .

    o r melt i ng p oint curve is then esp ecially valuable for the d isc ove ry
    -

    o f c om p ounds I n order to understand this let us rst examine


    .

    a sy stem of two substances A and B which do n ot c ombine Fig


    , , . .
    SA L T SO L UTI O N S .
    3 43

    5 5, re p resents the melt i g p oint curve that one o b t ain s on t h e


    n -

    addition of increasing amounts of B to A A t r st the meltin g .

    p oint sinks until the eutectic p oint E is reached A long AE A .

    alone sep arates out of the fused mass on free z ing A t E however .
    , ,

    B also se parates out I f more of B is now added the melting


    .

    p oint rises ; we obtain the curve E B which termi n ates in the ,

    melting p oint of pur e B A long EB o nl y B sep arates out of the


    -
    .

    fused mass .

    FI G 55 . .
    FI G 5 6
    . .

    Supp ose we now assum e that A and B for m a c omp ound A B


    in the mo l ecular pro p ortions ( Fig O n the addition of .

    B to A AB is formed and dissolves in the excess of A This lowers .

    its meltin gp oint When a certain amount of B has been added


    .

    th is p oint is lowered to E 1 Here b oth A and A B sep ar ate out . .

    E 1 is the eutectic p oint for mixtures of A and A B I f more of .

    B is added the meltin g p oin t rises j ust as in the case where -

    there is no c omb ination between the c omp onents O nl y A B .

    now sep arates out of the fused mass The c ont inued additio n .

    of B however increases the amount of the c om p ound A B ; at


    , ,

    M free A has d isappeared and the mass c onsists wholly of p ure


    A B whose melting p oint is AI
    ,
    A t this p oint the meltin g tem
    -
    .
    -

    p e r at u r e reaches its maximum for the addition of either A or B ,

    lowers the melting p oint of the p ure c omp ound The further

    -
    .

    m
    u te ct ic p i t is mo r g r l th n o h ydric p i t cry
    Th e t e r e

    o n t he e en e a a o n ,


    l atte r t rm b i g u u ally trict d t qu us s luti
    e e n

    tu re an d cryo hydric mixture



    s

    a s imil
    E ut c t ic mix
    re s

    ly rel ate d
    e o a eo o

    re
    on s .

    ar
    e

    .
    I N O R GA N I C C HEM I S TR Y 23 7
    3 44 .

    c ourse of the curve is readily seen As more and more B is added .

    to A B the melting p oint sin k s


    A B n
    alone sep arating out u til ,
    ,

    the eutectic p oint E 2 is reached where both AB and B crystalliz e


    ,

    out and thereafter the melting p oint again rises along E QB t ill
    ,
    -

    it nally ends in the melting p oint of the pure substance B


    - .

    If more than one com ou n d is formed between A and B each


    p ,

    one will cause a m axim u m poin t in the curve i e each m a xim u m ,


    . .
    ,

    wil l corr es pond to a c om pou n d The following examples will serve


    .

    to make this clear


    1 The system S0 3 + H2 0
    .
    Here there are a num ber of h y
    .


    dr at es which are indicated by the melting p oint c urve ( Fig
    ,
    .

    FI G . 57 .

    mixtur e of 6 2 % SO 3 + 3 8 % Hg O has a freezing p oint of


    A -

    O n the addition of sulphur trioxide this p oint rises til l at the c om


    p osition S0 3 + 2 H 2 0 = H 2 S0 4 H2 0 it
    -
    reaches its rst maximum .

    A t this temp erature the whole mass solidies yielding crystals ,

    of the above c omp osition The further addition of sul phur tri
    .

    oxide has the same e ffect on the meltingpoint of the hydrate


    H2 S0 4 H2 0 as the o r din ary addition of a foreign substance to
    -

    a pure substanc e A t rst the meltingp oint falls ; that which


    .

    crystalli z es out is the hydrate H2 S0 4 H2 0 A t a com p osition -


    .

    of about 3 H2 0 + 2 S0 3 a eutectic p oint is reached The


    mass solidies at 3 5 to a m ixture of H2 S0 4 H2 0 and H2 SO 4

    -
    .

    C ontinued addition of sul phur trioxide causes a rise of the meltin g


    p oint till at + 1 0

    a second maximum is reached where the whole ,

    solidies to a homogeneous mass cons is ting of pure sul phuric ,


    3 46 I N O R GA N I C C HE M I S TR Y .

    fragment of N a2 S0 4 1 0H2 0 is sufcient to cause a su d den


    - c r y s t al l i u

    z a t io n of this salt .

    Sodium sul phate is only one of a large number of salts cap able
    o f forming solutions of this nature Sodium thiosulphate and many
    .

    of the nitrates are other goo d examples Such solutions are .

    called su pers atu rated They are perfectly stable ; neither rubbing
    .

    with a glass rod nor Shaking (which trea t ment ordinarily tends
    to induce crystalli z ation) causes the formation of c rys t al s prov ided ,
    \

    no trace of the solid salt comes in contact with the solution Such .

    a system which is u ns tabl e u nder on ly on e corul ition is called a


    , ,

    m e t ast ab l e syste m (Se e page .

    I f a su persaturated solution of sodium sul phate is cooled down


    below room temperature another hydrate crystallizes out vi z
    , ,
    .
    ,

    N a2 S0 4 7 H2 0 ; the resulting system is still metastable however


    , ,

    fo r contact with the slightest trace of N a2 S0 4 1 0H2 0 sufces to o

    convert it entirely i nto the stable system with the deposition of ,

    N 3 2 8 0 4 1 0H2 0 .

    The sm allest am ount of salt (crystal nuc leus) that is suf cie nt to
    d i st urb and thus c ause the di sappearan c e of a m etastab le syste m such ,

    as i s re presented by a s u persat urated so lut i on i s a quant i ty of abo u t


    .
    ,

    the order g, a cc ord.i ng to O S T WA L D The e xtre m e m i nu te ness


    .

    of thi s am o unt e xplains why a spontaneo us disappearan c e of the m eta


    stable c ondi t i on was formerly regarded as poss ible Inas muc h as very .

    sm all b i ts of c rystals are always oat i ng i n the ai r (espe ci all y in l abora


    tori es) i t i s u s ually only ne c essary to o pen a bottl e c ontai ni ng a s u per
    ,

    sat urated so lu ti on or to r ub the s i des w ith a g l ass rod (wh ic h always


    h a s crysta l fragm ents on its surface) in order to e x c i te c rystalliz at i on
    ,

    into t he stabl e syste m .

    2 38For the reasons stated in


    . 65 an d 66 it is assumed that
    acids bas es and salts in aq ueous solution are Sp lit u p into ions
    , .

    This dissociation can be more or less com plete according to the ,

    nature of the solute the temperature of the solution and its con
    ,

    centration E xamples of this have alre ady been mentioned here


    .

    an d there in the text ; hydrochloric and nitric acids in tenth normal -

    s olutions are almost com pletely dissociated carbonic and silicic ,

    a cids scarcely at all A mong the bases the hydroxides of o t as


    p
    .

    srum sodium and the alkaline earth metals are almost com pletely
    ,

    dissociated at this dilution A Similar difference is shown by


    .
    S A L T S O L UTI O N S . 3 47 .

    s alts ; those o f the al k al ies are practically com pletely ioniz ed whil e ,

    mercuric chloride is very Slightly so We shall return to this sub


    .

    j e c t more in detail in the discussion of the metals .

    The prin ci pl e that so lu t i ons c ontai ni n g e quiv alent am o unts of different


    e l e c tro lytes differ great ly in c onduc t iv i ty and hen c e in degree of i oniz at i on
    c an be de m onstrated in an e l e g ant m ann er with the a i d of an a arat u s
    pp
    devised by WHI TN E Y ( Fig .

    FI G . 59 .

    Four glass cylinders (3 cm d i am ) are tted ea c h w ith two hori z ontal


    . .

    pl at i num d i sks ( c o pper c an be u sed b u t i s less sat i sfa c tory) to serve as


    e le c trodes the uppe r ones be ing m o vable Ea c h l ower e le c trode i s
    ,
    .

    conne c ted w i th an i n c andes c ent lam p and the apparat us as a who l e


    with the termi nal s of a (preferably) alternat i ng 1 1 0 v o lt circ uit A fter -
    .

    p l a ci ng i n ea c h of the t u bes 1 2 0 cc di st illed water they are lled


    .

    wi th 5 cc of half e quivalent norm al hydro chl oric s ul phur ic m o n o ch l o


    .
    -

    , ,
    ~

    ra ce t ic and a c et ic a ci ds res pe c t ive l y . O n m a ki n g the d i stan c e between


    the electrodes alik e in all the c yli nders the l am p beneath the hydro
    ,

    c h l or ic a ci d i s fo u nd to gl ow br i ghtest Si n c e the res i stan c e of thi s so l u


    ,

    t i on i s t he l east The other l am ps fo ll ow i n bri ghtness i n the order


    .

    giv en abo v e . Th e e l e c trodes ar e ne x t adj u sted so that all t h e l am ps


    are e qually bright when i t is seen that whil e the e le c trodes i n the hydro;
    ,
    48 I N O R GA N I C C HE M I S TR Y .
    23 8

    chl or i c a ci d are farthest a part those in the acetic


    ,
    acid are a lm ost in

    c onta c t .

    I n order to Show that the alkali salts of these a ci ds u nh k e the ac i ds


    0 0

    t he m se lves hav e nearl y t h e sa m e c onduc t ivi t i es an d degrees of disso


    ,

    c iat io n t h e so lu t i ons are j ust ne u traliz ed w i th potass ium h ydr o x 1 de

    a n d the l a m p test re peated


    .
    Th e lam ps are e qu ally br i l li ant when
    .

    the e le c trodes are at appro ximate ly the same he i ght .

    2 39 . the solution
    In of an extensively ionized salt we should
    ex pect to nd the pro perties of the cation and the anion I t must .

    exhibit the sum of the pro perties of the two ions or to use other , ,

    words its pro perties mu st be a dditiv e with reference to those of


    ,

    b oth io ns This is actually the case both physically and chemically


    .
    ,
    .

    A s for the chemical pro perties we observe that solutions of differe n t


    ,

    salts of the same metal all give the same reactions ; from the solutions
    of all lead salts for instance hydrogen sul phide preci pitates black
    , ,

    lead s u l phide sul phuric acid whi t e lead s u l phate etc


    ,
    Similarly ,
    .

    the solutions of salts of the same acid are all cha racterized by the
    s ame reactions ; sul phates for exam ple by the p reci pitate they give
    , ,

    with barium chloride solution Al l this appears very strange .

    when we recall that the solid salts are markedly different from
    e ach other in their p ro perties but we are forced to j ust such a con
    ,

    c l us io n when we assume that the salts are ionized in solution .

    A mong the physical pro perties add itivity is very a pp arent in


    the color of salts of colored acids and bases O ST WA L D found that .

    all permanganates with a colorless base when pre pared in e q u iv a ,

    lent solutions give exactly the same absorption Spectrum


    ,

    Al l dilute C o pper solutions are blue I n the permanganates it is
    "
    .


    the anion Mn 0 4 in the co pper solutions the cation C u
    , which ,

    is to be regarded as the color carrier -


    .

    When the so lvent i s one i n whic h i oniz at i on does not occur the ,

    salts of the sam e base m ay differ wi de ly i n c o lor Fo r i nstan c e a so lu .


    ,

    t i on of c obalt ni trate in alc oho l i s purple that of t h e c hl ori de i s b lui sh


    ,

    v i ol et ; b u t i f both are pou red i nto an e xc ess of water the so lut i on ,

    be c o mes pi nk in ea c h c ase Another e xam ple i s fo und i n the alc oho li c


    .

    so lu t i ons of cu pric chl ori de and nitrate ; t h e form er i s dar k green the ,

    latter blue ; o n the addi ti on of water both be c o me blue .

    This additive nature manifests itself in various other physical


    p ro perties also Bu t since it cannot usually be Shown directl
    y
    .

    ,
    3 50 I N O R GA N I C C HE M I S TR Y . 23 9

    mole are mixed the same caloric e ffect will be observed This
    , ,
    .

    is found to be the case The o nl y change tha t takes


    plac e in the mixing is the formation of water from its ions
    Further the s o called l aw of t h erm o n eu tr ality which says tha t
    ,
    - -

    when two dilute salt solutions are mixed there is no caloric e ffect ,

    is a natural consequenc e ; for the ions of the two salts exist in


    t he free state both before and after the mixing .

    AC I DIM ETR Y A N D AL KA L I M ET R Y . TH E O R Y OF
    I N DI CA T O R S .

    2 40 The amount of acid or base present in a liquid can b e


    .

    determined most Simply by volumetric analysis Those parts


    of vol u metric analysis which com prise the methods us ed for this
    u
    p pr ose are known as a cidim etr y and a l k a l im etr y Su pp ose that .

    we wish to determine the amount of hydrochloric acid present in a


    given volume of liquid A known volume of this liquid ( 50 cc
    .
    .
    ,

    1 0 cc or less according to the supposed concentration ) is meas


    .
    , ,

    u re d out and sodiu mhydroxide solution of known concentration is

    Slowly added from a burette When the point has been found at .

    which the liquid becomes neutral it is easy to calculate the con ,

    centration of the acid from the n um be r of cubic centimeters of


    sodium hydroxide consum ed .

    E xamp l e . Determi ne t h e
    am o unt of nitri c a c id present in a li ter of a
    so lu t i on of thi s a ci d i f 1 0 cc are ne utraliz ed by . cc of a norm al alkal i .

    so lu ti on These . cc are e quivalent to the sam e number of cub ic c e n


    .

    t im e t e rs of norm al n i tr ic a ci d Therefore the 1 0 cc c ontai n


    . milli .

    gram m ole cules of ni tric a ci d or m g O n e liter m ust conta in .

    a hundred t imes as m u ch or g , .

    B efore we can determine the concentration of an acid or an


    alkali in this manner we must rs t possess an alkali or base solu
    ,

    tion of known concentration and further have a delicate means of


    detecting when the liquid is e xactly neutralized .

    1 Pr epara tion O f a n a cid a nd a n a lk al i O k n own con cen tra tion


    .

    f .

    This can be done in various ways O xalic acid C g H2 0 4 2 H2 0 .


    ,
    -

    succinic acid C 4 H6 0 4 or tartaric acid C 4 H6 0 6 can be used as the


    , , , ,

    basis for all of these are crystallized solids and can be easily obtained
    ,

    in a state of sufcient purity ; hence the amount of acid dissolve d


    A C I D I M E TR Y A N D A L KA LI M E TR Y . 3 51

    can be ve ry accurately determined by previously weighing the


    substance on an analytical balance We thus weigh out 1 g equiv .
    .
    -

    al e n t g mol ) of one of these acids dissolve it in water and


    .
    -
    .
    ,

    dilute to exactly a liter Thereup on with the hel p of this normal


    .

    acid a normal alkali is pre pared ; a little more than 1 or or 11 5 ,


    etc gram equivalent of sodium hydroxide or potassium hydroxide
    .
    ,

    ( barium hydroxide is also very satisfactory ) is dissolved in water


    an d this solution is standardized according to the normal acid i e ,
    . .

    the concentration is determined by titration with normal acid and


    then diluted so that it is j ust normal .

    Sodi um carbonate c an a lso be u sed as a basis After be i ng rst .

    heated i n order to e xpe l all m o i st ure i t i s we ighed o u t and di sso lved i n


    water Thi s so lut i on is heated to bo ili ng and c o vered wi th a glass
    .

    p l ate w i th a ho l e i n i t thro u gh wh
    ,
    ic h the no zzl e of a b urette i s passed .

    The so lut i on of the a ci d whose c on c entrat i on i s to be determi ned is


    then all owed to o w from the b urette into the bo ili ng l i qui d t ill n e u
    t raliz at io n i s e ffe c ted C arbon d i oxi de escapes but the gl ass pl ate
    .

    ,

    p revents any l oss of the liqui d by S p u rt i ng .

    The standardizing c an al so be a cc o m pli shed by adding the a ci d .

    so lu t i on that i s to be standardiz ed to a mixed so l uti on of potass ium


    iodi de and potass ium i odate Hydri odi c and i odic a ci ds are set free
    .

    and they react at on c e i n the foll owing m anner

    5K I KI O 3 6HX = 5HI 11 1 0 3 exx 5m HI O 3 =3 H


    , o 61 .

    Thu s for e very e quivalent of a ci d one atom of iodine is se t free By .

    t i trat i ng wi th sodium thi os ul phate the am o unt of i odine liberat ed can


    be determi ned Thi s m ethod gives very a cc urate res ults
    . .

    2 . Det erm ina tion of the poin t at which th e l iqu id bec om es n eu tr a l .

    Since the point of neutralization of an acid b y a base or vice ver sa -

    '

    is not indicated by any visible phenomena a minute quantity of ,

    s ome substance is added whose color is altered by an excess of the

    neutralizing liquid Such substances are l itm u s (blue in alkaline


    .

    and red in acid solutions ) ph en ol phtha l ein (red in alkaline color


    , ,

    less in acid solutions ) m ethyl ora nge ( yellow in alkaline red in acid
    , ,

    solutions ) an d many others Therefore o n gradually adding an


    ,
    .
    ,

    alkaline acid
    SO 1u ti on to an solution in the presence of one of
    acid alkaline
    3 52 I N O R GA N I C C HE M I S TR Y . 2 4 04

    these substances a cha nge of c ol or will be noticed when the point o f


    neutralit y is j ust passed C oloring matters like the above are
    .
    -

    t ermed i n di c ators The change of color is due in many cases to a


    .

    transformation of the substance into a salt whose free acid is ve ry


    unstable and passes over almost immediately into an isomer hav
    ing a di fferent color from the free acid or the salt .

    241 From the stand point of the ionic theory the following
    .

    th e o ry of in di c ator s has been advanced : I f a couple of dro ps of


    the indicator are introduced into an acid solutio n the ionization ,

    of the indicator which is o n ly very Slight is reduced by the great


    , ,

    excess of acid to practically zero I f a base is then added the .


    ,

    H ions of the acid to be titrated are removed by the O H ions


    - -
    .

    However if the acid is very strong enough H ions remain in t h e


    , ,
    -

    liquid u p to the last to prevent anything like an extensive ioniz a


    tion of the coloring substance ; not until the rst excessive drop of
    -

    alkali is added do the anions of the coloring substance come into -

    existence the alkali com pound of the latter being strongly diss o
    ,

    c iat e d . Th e cha n ge of c ol or is th er efor e s harpl y den ed for it is ,

    due to this di fference in color of the non ionized molecule and the -

    anion O n the other hand if the acid is a weak one there w ill n o t
    .
    , ,

    be enough H ions present when the end of the titration is nearly


    -

    reached to prevent a Slight ionization of the coloring substance -


    .

    AS a result we Shall have in the solution not only the undissociated


    c oloring substance but its anio n s as well even before the titratio n
    -


    is com pleted in other words the cha nge of col or bec om es m or e
    , ,

    g r a du a l and hence the end reaction more indenite The e ffec t .

    will be the same if the alkali e m ployed contains carbonate In .

    that case n ear the end of the titration the solution will o nly contain
    carbonic acid which is very weak ; consequently the color change
    ,

    will not be sudden I t is for this reason t h at in titrating soda solu


    .

    tions (see 24 0) the carbonic acid must be expelled by boiling .

    I f a weak acid is to be titrated it is necessary according to t h e


    , ,

    above to select an indicator which is mu ch less ionized even tha n


    ,

    the acid itself and whose alkali salts are sufciently ionized t o
    produce a distinct change of color A very suitable one for this
    .

    purpose is phenol phthale in


    A cetic acid fo r exam ple can be s at


    .
    , ,
    ~

    1Sfact o ri l y t 1 t rat e d with it if a strong base is em ployed for t h e


    ,
    ,

    reasons set forth above O n the other han d in case a weak bas e
    .

    is to be titrated phenol phthale in is not so s atisfactory Am moni a


    '

    , .
    54 IN O R G A N I C C HE M I S TR Y . g 242 .

    silicates et c The Slag floats and can be run o The fusion


    , .
    .

    p rocess is re p eated until all the iron is eliminat ed The resul ting .

    mixture of impure c o pper sul phide and c o pp er oxide is called matte


    ( also r eg u l u s and c oa r s e m et a l ) B y re p eated
    . roastin g an d fus ing ,

    crude metallic c opper is obtained :

    2C u 2 0 (3q 6 0u S0 2 .

    Fin ally it is fus e d with c oal to reduce any c o ppe r oxi d e remainin g .

    R e f i n i n g The c opper thus obtained often c ontains s m all quant i t i es


    of other m etals Si nc e these im puri t ies l ower its conduc tivity a better
    .
    ,

    grade is de m anded for e lectric al purposes Crude c o pper i s now re ned


    .

    by an el ectrolytic process whic h yi elds chemic ally pure c op per If an .

    im pur e copper solu t i on i s ele ctrolyz ed i t i s poss ible under s ui tabl e c on


    ,

    dit io n s to pre ci pi tate pure c o pper i n a c o m pa c t m ass wh ile the im pur i ,


    ti es re mai n i n so lut i on or are depos ited as powder Fro m thi s powder .

    ( Sl im es a c onsi derable am o unt of go l d an d Silver i s obta ined


    The usual arrange m ent is to su spend pl ates ( anodes of cru de .

    coppe r and thi n sheets of pure co pper alternate ly i n a c opper vi tri o l


    solu t i on a ci died wi th sulphuric a ci d If the c ru de pl ates are then
    .

    conn e c ted with the pos i t ive po l e and the thi n Sheets with the negat ive
    po le of the dynam o current pur e c o pper i s depos i ted on the Sheets
    , ,

    wh ile an e qui valent am ount of the crude copper disso lves to take i ts
    p ace
    l .

    Phys ical Properties has a b right red c olor It is


    . C opper .

    r ather hard but very extensible and exible ; it can be drawn out
    into very ne wire and beaten into extremely thin Sheets imitation
    (
    gold leaf) which are green in trans m itted light Sp
    -

    , . .

    melting p oint 1 083 ; boilingp oint 0


    ,

    C hem ica l Proper ties I n dry air c o pp er is permanent at ordi


    .

    nary temperatures b u t in moist air it becomes c overed with a thin


    ,

    c oating of basic c o pper c arbonate which protects it from further


    ,

    rusting O n being heated in the air it turns to c o pper oxide C u O


    .

    , .

    It is readily attacked by nitric acid but not by dilute hydro


    chloric acid Sul phuric acid has no e ffect on it at ordinary tem
    .

    p e r at u r es but at higher temperatures a r eaction takes place in


    ,

    which sul phur dioxide is given o ff A mmonia and oxygen


    dissolve it to form a blue liquid ; co pper oxide ammonia C o pp er .

    is de p osited from solutions of its salts by iron magnesium an d ,

    o ther metals .
    C O M PO UN DS O F C O PPER .

    Us es and a ll oys nds extensive use in the arts b oth


    . C o pper ,

    as such and in alloys The well known yell ow b r a S S is an alloy -


    .

    o f 1 p art z inc and 2 p arts C o pp er and is harder than c o pper itself .

    G e r m a n s i l v e r c onsists of ab out 50% C u 2 5 % N i and , ,

    2 5 % Zn ; its electrical c onductivity is a ffected very little by changes


    of tem p erature which makes it valuable for resistance c oil s etc
    , , .

    For b r o n z e s see 1 99 .

    C o pp er is em ployed in large quantities in e l e c t r o t y p i n g


    A cast is r st c onstructed of plaster of Paris and made a conductor
    b y being c oated with graphite whereu p on it is suspended by the ,

    wire of a battery into a c o pper sul phate solution ; a plate of pure


    c o pper se rves as the anode I f the p otential d ifference at the .

    electrodes is pro perly regulated the c o pper is dep osited on the ,

    p laster cast in c om p act form so that all the detail s of the original
    ,

    are reproduced with the greatest delity .

    C o m po u n ds of C o ppe r .

    2 43 . C oppe r
    forms two sets of salts which are d erive d from t h e ,

    ox i d es C u zO cupr ou s oxide and C u O


    ,
    cu pr ic oxide , , .

    C UPR O US C O M PO UN D S .

    C u pr o u s
    o xi de , C u g O can be obtained from cupric salts in
    ,

    various ways e g by reducing them in alkaline solution with grape


    ,
    . .

    sugar hydroxylamine arse ni ous acid or the like I t forms a


    , , ,
    .

    reddish yellow crystalline p owder which is unaffected by the air


    -

    at ordina ry tem peratures When cu prous oxide is heated it .


    ,

    breaks u p into cu prous oxide and oxygen ; 2 C q _

    A t 1 02 5 the disso ciation tensio n of the cu p ric o xide reaches


    1 5 0 mm ; consequently at this tem p era


    . ture in the air it passes
    ov er com pletely into cu prous oxide Since the p artial pressure ,

    7 60
    of the oxygen of the a 1 r 1s -
    1 52 mm . C u prous ox i de di S
    5
    solves in ammonia ; this solution ra p idly turns blue because of
    the absorption of oxygen the cu prous oxide going over into ,

    cu pric oxide C u prous oxide is transformed by sul ph u ric aci d


    .

    into co pp er sul phate and co pp e r :

    C l lz o HQ SO 4 C U SO 4 + O H Hg O .
    3 56 IN O R G A N I C C HE M I S TR Y . 243 ,

    is p ossible that cu prous sul phate is rst formed


    It
    and that the cu prous ions of this solution are forthw i th
    changed into cu pric ions and non ionized co pper -

    Of the c u pro u s s alts the Sul phate and halides are known .

    011 2 012 C u z B r g and C u g l z are all


    , ,
    insoluble (cf their .

    sol ubility decreases with increasing atomic weight of the


    halogen .

    C u pr o u s c h lo ri de , C u zC l z ( the vapo r d e ns i t y in d cates this


    i

    doubled formul a) sep arates ou t when a solution of cupric chl o rid e


    ,

    is bo iled with co pper or when a mixe d solution of C o pper sulphat e


    ,

    and sodium chloride is saturated with sulphur dioxide gas and t h e


    resul ting liquid p oured into water It is a white crystalline sub.

    stance which must be kept under water for it absorbs oxygen


    , ,

    rapidl y when moist and turns green because of the formation of


    basic co pp er chloride, C u C l O H I t melts at 4 3 0 and distils at
    o
    .

    about I t is soluble in concentrated hydrochlori c acid an d


    in am monia These solutions are at rs t colorless but very soo n
    . .

    become blue because of the absorption of oxygen ( formation Of


    cu pric com pounds ) They also have the power of absorbing car
    .

    bon monoxide fo rming an unstable comp ound C u zC lz C C 2 H2 0


    , ,
    - -

    which crystallizes in colorless laminae Use is made of this pro p .

    e rt y in gas analysis .

    C u pr ou s io di de , C u n is formed when a solution of co e r


    ,
    pp
    sul phate 1 S treated wit h p otassium iodide half of the io d ine being ,

    liberated
    2Cu S0 4 + 4 KI = 2 K2 80 4 + C u2 1 2 + 1 2 .

    It may be supp osed that cu pric iodide is rst form ed an d tha t


    it then breaks u p into cuprous iodide and io dine or rathe r tha t t h e , , ,
    ions of cupric iodide interact thus :

    Cu + 2I ' = Cu I + I
    ,

    the cuprous io d i d e being un ionize d because ins olub l e .

    A cc ordi ng to O ST WAL D however an e quilibri um is form ed here


    , ,
    ,
    for tho ugh the cu pro u s i odi de 1 S b u t Slightly so lubl e t h e rea c tion does
    ,
    ,
    n o t c o m plete i tse l f an d so m e cu ric i ons st ill re m a i n in so lu t i on The
    p .
    3 58 I N O R GA N I C C H E M I S TR Y . 24 4

    C UPR I C C O M PO UN D S .

    2 44 . C u pri c
    o xide , C u O is a dense black p owde r o b taine d b y
    , , ,

    heating co pper in the presence of oxygen at a high temperature I t .

    can also be p re pared by heating the nitrate to redness or igniting


    the hydroxide or the carbonate When fin ely divided it occludes .

    o n its surface large amo unts of steam I t nds extensive use in .

    o rga ni c a nalysis .

    C u pri c h ydr oxi de , C u O n H2 0 se p arates out as a o c cu l en t


    '

    ~
    , ,

    voluminous blue preci pitate (hydrogel 1 95) when the solution ,

    of a C o pper sal t is treated with caustic potash or soda O n boiling .

    the liquid it turns black water being liberated an d cupri c oxide


    ,

    formed .

    C u pri c c h lo ri de , C u C 12 2 H2 0 is o b tained b y d issolving cupri c


    -

    o xide or carbonate in hydrochloric acid I t crystallizes in blue .

    rhombic needles whi ch however often appear green because of


    , , ,

    mother liquor adhering to them


    -
    I t is readily soluble in water
    .

    and alcohol Th e anhydrous salt is yellow ; the concentrated


    .

    aqueous solution is green ; the dilute solution is blue This differ .

    ence can be attributed to the breaking u p of the salt into its ions ,

    for all dilute C o pper solutions are blue no matter what the acid ,

    r ad ical is It therefore follows that the co pper ion imparts a blue


    .

    color to solutions The green color of a concentrated solution


    .

    seems most probably due to the formation of com plex ions ,



    such as ( C u C 13 )
    C u pri c b r o m i de is analogous to the chloride ; c u pr i c i o di de is
    un stable d ecomposing at once into iodine an d cuprous io dide
    ,

    C o ppe r lph ate , C u SO 4 5H2 0 , b lue vitriol , is the most familia r


    su -

    s alt of co pper I t is obtained as a b yproduct , chie fl y from gol d


    .

    an d Silver reneries an d is also manufactured b y d issolving


    ,

    co pper in sul phuric acid I t crystalli z es in large blue tricli nic


    .

    crystals which lose four molecules of water at


    , the fth
    is liberated at The anhydrous co pper sul phate is a white
    powder which absorb s water greedily turning blue again
    , At , .

    2 0 1 00 parts Hg O dissolve

    parts of the crystalli z ed sulphat e .

    B lue vitriol is employed in large quantities in electro lating etc


    p ,
    .
    S I L VE R . 3 59

    C oppe r nit a e , r t
    can c rystallize with three or Six
    C u (N 0 3 ) 2 ,
    molecules of water an d is dark blue .

    C o ppe r c arb o n ate The normal salt is unk nown but b as ic salts
    .
    ,

    have been pre pared .

    C o ppe r ar s e n it e , CUHAS O g is used as a pigment unde r the ,



    name of Scheel e s green Schweinfu r th gr een or Paris gr een is a
    .
    , ,

    d ouble comp oun d of co pper arsenite and co pper acetate Since .

    b oth are ve ry poisonous their use in dyeing textile fabrics wall , ,

    a
    p p er etc
    ,
    1 5 7 )
    . is being restricted .

    C o ppe r s u lph i de , C u S is fo rmed as a black preci pitate by pass


    ,

    ing hydrogen sul phide into a co pper solution When moist it .

    o xidizes slowly in the air to C o pp er sul phate O n being heate d .

    in a current of hy d rogen i t yields cuprous sul phid e C q an d , ,

    hydrogen sulphid e .

    C opper s al t s and amm on ia O n m m g a solution of ammo nia .

    wi t h a co pper salt a preci pitate of co pper hy d roxide is rst forme d


    , ,

    if not too much ammonia is use d ; this precipitate is dissolved by


    an excess of ammonia to a dark blue solution I f the latter is .

    e vap orate d or treated with alcohol ammoniacal com pounds c rys ,

    t al liz e out ; a ty pical one is C u SO 4 4 N H3 H2 0 which is trans - o

    formed into C u SO 4 2 N H3 on being heate d to -


    The aque ous
    s olutions of these substances are to be assumed to contain complex

    ions of co pper and ammonia Since they do not give some of t h e ,

    o rdinary co pp er reactions e g preci pitation with caustic potash


    ,
    . . .

    The fact that certain other reactions of co pper do however appear ,

    e g prec ipitation with hydrogen sul phide p roves that free C o pp e r


    . .
    ,

    io ns are still present in the liqu id although only t o a small extent ,


    .

    SI LVER .

    This metal o ccurs n ative; nuggets weighing 1 00 kilos are


    2 45 .

    n ot unknown The important silver ores are argen tite A n


    .
    , ,

    s tr om eyer ite C q An pyr,


    a rgyr it e 3 A g
    o
    2 S S b 2 S3,
    and s t ep ha n it e ,
    -
    , ,

    Ag 5 S4 Sb I t is also found in smaller amounts in cerargyr ite or


    .
    ,

    horn s il ver A gC l Traces of Silver compounds are known to exis t


    ,
    .

    in sea water M any lead ores e g galenite contain a small per


    -
    .
    ,
    . .
    ,

    c entage of Silver and in some cases it is extracted .

    The chief silverproducing countries are the United States


    ( C olorado and neighboring S tates ) M exico A ustralia and B olivia , ,
    .
    3 60 I N O R GA N I C C HEM I S TR Y . 24 5 .

    The presen t annu al world s production of Silv er is about


    troy ounces kg ) .

    S ilver is now generally obtained from its ores by the c ya n ide

    r oc ess I n this p rocess the pulverized ore is allowed to stand


    p .

    for some time in a weak solution of sodium cyanide .

    The Silver sul phide dissolves as the double cyanide according


    to the equation
    An 4 N aC N 2 A g N a (C N ) 2 N ag S .

    AS soon as a certain amount of Silver has gone into solution an ,

    equilibrium is formed because the N ag S tends to react back


    ,

    ward with the formation o f Silver sul phide This is avoided .

    by blowing air into the solution and thereby oxidizing the sodium
    ,

    sul phide M etallic Silver is also taken u p by the sodium cyanide


    .

    solution so is the chloride or horn silver The recovery ,


    .

    of the silver from the double cyanide solution is ac com plished by


    p reci p itation with z inc or by
    ,
    electrolytic de p osition .

    L ead ores usually contain some Silver I n t h e smelting of lea d .

    the silver all goes into the lead and is recovered from it in the

    following way : The argent iferous lead is fused and then c ooled
    Sl owly till it begins to c ongeal Jus t as pur e ice crystallizes out of
    .

    a d ilute salt solution on cooling so the lead sep arates out her e ,

    in crystals free from Silver These are removed and this process
    .


    c alled Pa t tin on i i g after its inventor
    s z n is ke pt u p til l the percent
    age o f sil ver reaches about Th is rich lead is then subj ected
    to the 0 u p e l l a t i o n process i e the lead is fused in a rever
    ,
    . .

    ber at ory furnace whose hearth c onsists of a p orous mass ( cu p el


    , ,

    or test ) The lead is oxidi z ed to the easil y fusible oxide Pb O


    .

    ( litharge ) which is p artly driven o ff by a blast from time to time


    through the channel provided for its escape and partly absorbed ,

    by the p orous material ( bone ash or clay and limes t one) o f the
    -

    cupel Towards the end of the process the l m of litharge remain


    .

    in g becomes s o thin that the silver beneath reects the light pr o ,

    du c in g a beautiful iridescence Here and there the lm breaks


    .
    ,

    disclosing the brilliant surface of the metal brightening of t h e


    silver) The Silver is nally left in the metallic state
    . .


    A nother method ( PAR K E S ) involves the princi ple of dis t ri
    b u t io n between two slightly miscible solvents ( O R G C HE M . .
    ,

    M olten z inc and lead are only slightly soluble in each


    other Silver is several hundred times more soluble in molten
    .
    3 62 I N O R GA N I C C HE M I S TR Y .
    2 45
    .

    p late a n d j ewel ry usually contain 7 5 or more p e r cen t o f silver ; t h e

    s ilve r coins of the Unite d States and continental countries c o ns is t

    o f 90% s ilver and 1 0% co pper ; the E nglish shillings ( sterling



    s il ver) contain Silve r The admixture of co ppe r mak es t he
    .

    metal hard er .

    C ons i d erable Silve r is cons ume d in Silvering obj ects of c o pper


    o r other metals (S i l v e r p l a t i n g ) A t p resent t.hi s is usually
    d one by electrolysis The obj ect to be plated is m a d e t he
    catho d e an d a silver plate the anode ; the b ath co ns ists of s ilver
    c yan i d e d is solve d in an excess of p otassium cyani d e .

    Th e m arket pric e of Silver o n a gol d bas is was alm ost c onstant fro m
    , ,

    1 6 50 to 1 8 7 0 the m ar ket rat i o of t h e two m eta l s at L ondon re m a i n ing


    ,

    v ery cl ose to b u t in t h e l ast few de c ades the valu e of Silver has


    de c reased rel at ively v ery greatly The reason for th i s shrin k age of
    .

    valu e i s to b e fo und not only in t h e c he mical impro v em ents i n the


    m etal lurgy of s ilver b ut muc h rather in the d is c o very of l arge dep os i ts
    ,

    of hi gh per c entage Silver ores espe ci ally i n the Western He mi sphere


    -

    , .

    I n 1 9 02 the rat i o w as Si n c e then i t has im pro v ed somewhat ,

    be ing in 1 9 1 1

    C o m po u n ds of Sil v e r .

    2 46 . The kn own oxides are : Ag4 O silver su boxide ( ve ry un ,

    s t ab le) ; A gg O s il ver oxide from whi ch the salts of Silver can b e


    , ,

    de rived ; and A gO s ilv er peroxide ( formed from silver and ozone )


    , .

    Silve r o xi de , A g Q O is d eposited as a dark brown amorphous


    ,

    p reci pitate when the solution of a Silver salt is treate d with caustic

    s oda or baryta water free from carbo ni c aci d It is somewhat sol .

    u ble in water mole pe r liter at the solution pro b


    ab ly contains the silv er hydr oxi de, for it reacts alkaline an d mus t

    therefore contain hydroxyl ions In its saturate d aqueous solu


    .

    tion 7 0% of the molecules are foun d to be ionize d Silver h ydrox .

    ide is thus not so strong a base as the alkalies but co ns iderably ,

    stronger than amm onia M oist Silver oxide (A g O H) absorbs ca r


    .

    bon dioxide from the air and the Silver salts react neutral while t h e ,

    salts of most of the other heavy metals give an acid reaction be


    cause of a sligh t hydrolytic dissociation in aqueous solution By .


    heati n g to 2 50 Silver oxide 1 s broken u p into its elements It is .

    reduced by hydrogen at as low a temperature at A rrim onia


    C O M PO UN D S O F S I L VE R .
    3

    wate r d issolves it rea dily b ecaus e of the fo rmation of a complex


    ion Ag (N H3 ) 2

    o
    ,

    Sil v e r c hl o r i de , A gC l is obtaine d by preci pitating a Silve r solu


    ,


    t i on with hydrochlori c aci d or a soluble chlorid e like so dium chl o
    ri d e ; it fo rms a characte ristic cur dy precipitate I t is al most .

    ins olub le in wate r 1 p art in ,


    Hg O a t

    When a Silver so lution is added very carefull y to a sodium chl oride


    solution ( or to another chl oride) a po int can be fo u nd when the liqui d
    ,

    g ives a c l oudiness ( due to A g C l ) wi th e i ther so l ut i on Th i s mu st be .

    attribute d to the fa c t that the liquid is saturated with silver chl or i de an d

    c onta ins no other s ilver sa l t nor any other c hl or i de I n View of the very
    .

    hi gh dilut i on of s uc h a s ilver chl ori de so l ut i on (see above) it m ay be


    ass um ed that the d i sso lved part i s co m plete ly i oni z ed I f Silver or .

    chl ori ne ions are now introdu ced into the liqui d the ioniz at i on of the ,

    s ilver ch l or i de i s d imi n i shed and A g C l m o l ec ul es are for m ed but these ,

    cannot re m ai n in so l ution Since the so l ution is already saturated with


    ,

    them .

    Silve r chlo rid e dissolves readily in ammo nia potass ium cyani de ,

    and so dium thiosul phate forming com plex ions


    ,
    .


    If a solution of Sil ver chlorid e an d ammo n ia is allow ed t o evap _

    o rate in the d ark at room tem perature S ilve r chlo ri d e c rys t alli zes
    ,

    ou t in nely d evelo pe d o ctahe d rons .

    Silv e r b r o m ide , A gB r is less soluble than the c hl o ri d e an d has


    ,

    a yellowish color It dissolves with difcul ty in amm onia bu t


    .

    e asily in thiosul phate Silv e r io di de , A gI is even less soluble than


    .
    ,

    Silver b romi d e at or d ina ry tem p eratures It is ins oluble in ammo


    .
    ~

    nia . It is yellow A t high temperatures these halides melt an d


    .

    on co o ling form a horny mass whi ch can be cut with the knife
    ,

    horn Silver cf
    -

    ,
    . Sil v e r u o ri de , A gF is much more solu ,

    b le in wate r than the three precedi ng halogen compounds .

    Potass i um s il v e r cyan i de , KA g (C N ) 2 obtained on a d ding pot as


    ,

    sium cyanide to a Silver solution dissolves rea dily in water and is

    "
    ,

    used in large quantities in electro plating -


    When a current passes
    .

    t hrough it potassi u m is deposite d (primarily) at the catho d e while


    , ,

    the anion Ag (C N ) 2 wande rs to the anode ; however, po tas sium pre
    cipit at es Silve r fro m potassium Silve r cyani d e ;
    "if

    - 2 KO N + Ag .
    64 I N O R GA N I C C HE M I S TR Y .
    M 246

    Thus Silve r is d eposite d on the catho d e while t h e anion Ag (C N ) 2

    t akes u p an atom of sil ve r at the silver ano d e to fo rm s ilve r cyanid e


    an d again unites with potassium cyanide to fo rm the d ouble salt ;

    if the ano d e is of platinum cyanogen gas is set free from the anion
    ,

    an d the ano d e becomes covere d with Silve r cyanid e ,

    which soon interru pts the current .

    All the S ilver salts p ar ticularly the chloride bromide and iodide
    , , ,

    are s e n s i t i v e to light i e they are decom p osed by light es pe


    ,
    . .
    ,

    c ial l y by the violet and ultra violet rays of the Sp ectrum ; as a result
    -

    the halogen p asses off and the c olor of the salt becomes r st viole t
    an d then b lack A b lackened pre paration of this sor t c an be re
    .

    whitened b y chlorine or bromine water The sensitiveness to light


    - -
    .

    d epends in large measure on the manner in which the Silver halide


    is precipitated .

    2 47 . Photogr a phy The pro perty of Silver chloride and sil v er


    .

    b romide j us t mentioned forms the basis of pho t ography The .

    p rocess is essentially as follows : A glass p late is c oated with a



    sensitive l m i e a thin layer of Silver chloride or bromide is
    ,
    . .

    S pread over it .Formerly this was usually prepared by the ph o


    t ogr aph er s thems elves from collodion (see O R G C HEM 23 1 ) . .
    ,

    w hich c ontained a halogen salt e g C dI z in solution A fter, . .


    , .

    the evaporation of the solvent a h alide c oating remained and by ,


    d i pping the plates so pre pared into a solution of s ilver nitrate ,


    t h e Silver halide was formed on them These were the wet .


    p lates :
    n o w they are almost entirely su erseded by the
    p dry
    p lates.

    The latter are prep ared c ommercially on a large scale They .

    c o ns ist of a lm of Silver bromide in gelatine (less frequently in


    collodion ) on a glass plate .

    A sensitive plate of this sort is place d in the hotogra hic


    p p

    t here

    apparatus which is essentially a cam era O bscu ra and the plate is
    ,

    ex posed to a light image which affects the Silver halide


    -

    ,
    ,

    chemically I t is very probable that by the action of the light a


    .

    subhalide is formed ; the liberated bromine enters into c ombination


    with the gelatine or t h e c ollodion and is therefore unable to trans

    the plate ; it must rst be develo ped


    form the sub h zu into halide A S ye t no pictur e c an be seen on .

    For the latter pur pose .

    the plate is immersed in a liq u id c ontaining a reducing substance .

    A typical develo per is a solution of ferrous oxalate in an excess


    of p o t ass 1 u m oxalate
    ; various other organic c om p ounds ( ami d o
    3 66 IN O R GA N I C C HE M I S TR Y . 24 7 .

    having co llected to form l arger o nes wh ic h render the m ass o pa que and
    ,

    therefore inc rease i ts absorpt ive power Th e ripened s ilv er bromide gel a .

    t ine i s then spread u p on the pl ates .

    2. T h e L aten t I m age W hen t h


    . e pl ates are e x p osed to li ght there i s
    form ed o n all pla c es that t h e li ght has affe c ted a p h o t o h al oid i e a

    , ,
    . .
    ,

    mixt ure of s ilver bro mide with s o m e ul tra mic ros c opic particles of Silver -
    .

    When A gBr i s e xposed to the li ght ordinarily ( apart fro m ge lati ne) free ,

    bro mine is form ed d u ring t h e e xposure ; i f a cl osed apparat u s i s used and


    i t i s afterward pl ac ed in t h e dark silver bro mide i s form ed agai n More
    , .

    o v er not all the s ilver bro mide i s de c o mposed but an e quilibri um i s


    , ,

    estab li shed

    A gBr< A g Br,

    which is displ aced farther to the ri ght the stronger the il lum ination , .

    Li ght thus plays the sam e ro le in thi s di ssoc i ati on as heat in other di s
    so ci at i ons If a gelat i ne pl ate i s used the latent i m age re m a i ns for
    .

    m onths u naltered be cause the free bromine is taken u p by the gelatine .

    3 Deve l oping
    .
    This process is e x plained by so m e as fo ll ows : By
    t he reduci ng a c t i on of the deve l o per Silver is i m m ed i ate l y s e t free fro m
    silver s ubbro mi de b u t not fro m Silver bro m ide notwi thstandi ng that ,

    the l atter is c apable o f be ing reduced The syste m Silver bro mi de plus
    .

    devel oper can be com pared to a su persaturated so luti on whi c h only ,

    depos i ts so li d sal t when i t c o mes in conta c t wi th a c rysta lli ne nu cleus of


    sal t (cf . The nucle i of m et all ic s il v er are furni shed by the s ilver
    separated out of the subbromi de The depos i tion of additi onal s ilver
    .

    m o l ecul es tak es place only upon those m o lec ul es already there and
    not on spots where there was no subbro mi de originally i e Silver is ,
    . .

    depos i ted onl y where the li ght acted on the plate A c cord ing to this .

    nucle us theory the deve loping process woul d be co m parab l e to the


    fo ll owing e xperim ent : If a fe w l etters are wr i tten on a gl ass l ate with
    p
    a piece of al um and the pl ate is laid in a s upersaturated so l ution of
    t his sal t the letters beco m e visibl e because a lum is de os i ted on them
    , , p .

    Silv e r l ph ate , A gg SO 4 is obtained by dissolving Silver in


    su ,

    hot concentrated sulphuric acid It is scarcely soluble in c ol d .

    water .

    Sil v e r n it r ate , A gN O g prepared by dissolvin g silver in n itric


    ,

    acid crystallizes isomorphous with saltpetre in beautiful rhombic


    ,

    c ry stals I t is very soluble in water ( 1 part in


    .

    p
    ar t a t room
    temperatur e) and melts at

    I n medicine it is frequently
    employed es pecially as a caustic ; it goes under the n ame of lunar
    ,

    caustic I ndelible i nk s are also pre pared from it
    .
    .
    G O LD . 3 67

    Si l v e r
    itrite , A gN O z is formed as a yellowish preci pitate on
    n ,

    mixing an aqu e ous alkali nitrite solution and silver n itrite ; it dis
    solves in b oiling water and c rystalliz es on c ooling in beaut iful
    needles .

    G O LD .

    2 48 This me t al generally occurs native b eing foun d in b e d s


    .
    ,

    o f quar t z and alluvial de p osits resulting from the decay of quartz

    r ocks Traces of gold have been detected in sea water I t occurs


    .
    -
    .

    in Hungary Transylvania the Ural and p articularly in A ustralia


    , , ,

    in Transvaal and in the western part of the United States and


    C anada R ecently large quantities have been disc overed in A laska
    .

    ( K londike region ) I n C olorado


    . c onsiderable gold is obtained from
    t ellurides (s yl v an ite ,

    I nasmuch as the amount of gold contained in a cubic meter of


    ore or rock in the most protable instances is only very s mall it ,

    becomes the task of metall urgy to extract it fr om pro portionately


    large quantities of rock .

    In the Transvaal this is acco m pl i shed as fo ll ows : The go l d oc curs


    there in so c a lled r eefs wh ich are vert ic a l veins in the quart z These
    -

    ,
    .

    reefs are se l do m m ore than one m eter thi ck b u t e x tend for miles east and ,

    west ; the i r de pth is unkno wn They are mi ned by bl ast ing with dyna
    .

    mite ; the l arge pieces are reduced to about the s iz e of an egg in a heavy
    iron apparatus and then sent to the stam ps that move in a l arge trough ,

    t hro u gh wh ic h pl enty of water is k e pt ru nning The water carri es o ff .

    the ne a uriferous slim e whi c h is m ade to ow over am algam ated copper


    ,

    p l ates that are so m ewhat in clined The g o l d i s reta ined. by the m er cu ry .

    A fter so m e t im e the pl ates are s c ra ped o ff and the m erc u ry re m oved by


    di st illat i on l eaving the go l d
    ,

    The e xtracted s li m e ( taili ngs .

    i s treated agai n for go l d for which ,

    p ur p ose the c yan i de process of SIEME N S i s e m pl oyed .

    By thi s process the ta ili ngs are a ll owed to stand for fro m one day to
    three w ee k s i n contact wi th a to p otass ium c yan i de so lu t i on .

    Under the i n uen c e of t h e o xygen of the air the go l d d i sso lves in it ,

    formi ng a do ubl e cyani de KA u ( C N ) 2 : ,

    2A u + 4 K C N 2HzO =
    O z 2KA U( C N ) 2 + 2K O H HZO z .

    Hydrogen peroxide i s al so for m ed and serves to bri ng f urther am o unts of


    go l d into so l ut i on :
    2A u + 4K O N HZO 2 2KA u ( C N ) z 2KO H .
    68 I N O R G A N I C C HE M IS TR Y .

    Fro mthis
    o l ut i on t h e g ol d i s obta i ned by e l o c t r ol y sis between stee l
    s

    anodes and l ead c athodes A t the anode Pru ssi an blue 3 08) i s form ed .
    ,

    whic h i s treated for potassium cyan i de ; t h e gol d is de pos i ted at the


    c a thode Thi s g o l d i s separated from t h e l e ad i t c ontai ns by
    cu pe ll at i on .

    [Part icul arl y in the Un i ted States two pro c esses ( ch l or i nat i on and
    cyani de) are in general u se for e x tra c t ing g ol d fro m its ores wi tho u t
    am al gamati on B oth pro c esses are espe ci ally applic able to l o w grade
    .
    -

    and s ul phuro u s ores e g the te lluri des of C o lorado I n the chl or in ation
    ,
    . . .

    r oc ess t h e ore i s c r u shed a n d roasted and then treated in revo lvi ng


    p
    barre ls wi th chl or ine prepared e i ther c he mic ally or e le c tro lyt ic all y
    , ,

    after which the gol d i s pre ci pi tated wi th hydrogen s ul phide and roasted .

    Th e cyanide pr oces s i s muc h Similar to that des c r i bed above for treat i ng
    the tailings bu t zi nc generally serv es as the pre ci pitant i nstead of e lec
    ,

    t ro l ys is .

    and hydra u lic m inin g n d a pplication in newly di s c o v ered


    Pl acer
    deposits b u t are muc h l ess c omm on than vein m ining For the present .

    status of t h e m etallurgy of gol d as well as other m etals the st u dent


    shoul d consult a mining annual TR ] .
    -
    .

    2 49 . Physical Pr oper ties


    When pure gold is reddish yellow , ,

    very soft ( much like lead ) and extremely malleable and ductile
    , .

    The thinnest gold leaf a ppears green in tra ns mitted light Sp -

    . .

    g . at It is a very good conductor of heat and elec


    t ricit y A t 1 063 it me l ts to a greenish liquid
    .
    0
    .

    C em ica l Pr operties
    h
    G old is the typical re presentative of t h e
    precious m etals ; it is not attacked by acids and is dissolved only
    by chlorine water aqua regia and potassium cyanide solution (see
    -

    above ) I t s com pou n ds are all very unstable ; on warmi n g they


    .

    decom pose leaving the metal , .

    Us es A bout one half the wo rld s pr o d uction of gold is used


    -

    for industrial p ur p oses For these purposes the pure m etal is too .

    soft h owever and must be alloyed with co pper or Silver The


    , , .

    pro portion of gold in the alloy is ordinarily expressed in car ats;


    the pure metal is 24 carats ; gold j ewelry etc usually 1 4 1 8 carats , .

    i e 24 parts of the all oy contain 1 4 1 8 arts of gold The gold


    p
    . .
    , .

    coins of the United States contain 1 part co pper to 9 parts gold ,


    those of En gland 1 part co pper to 1 1 parts gold
    -

    For purposes of gol d plating the same electroly t ic processes are


    e m ployed as for silver plating -

    .
    3 70 IN O R G A N I C C H E M I S TR Y .
    M 2 5o

    Splits up into its elemen t s O n b eing wa r m d wi t h wate . r yiel ds e it


    2A u and A UC l g .

    r o
    Au u s io i
    d de is fo rmed ( like cu pr ous io did e ) o n t r eat i ng a

    solution of the chloride with potassium iodide .

    The gold double cyanide K C N Au C N is prepare d b y dissolving , ,

    auric oxide l n potassium cya nide ; it is used l n gold plating -


    .

    Of the oxy salts o f a u r


    -
    ous o xid e o n l y a fe w d o u b l e s al t s ar e

    known .

    A u ri c C o m po u n ds .

    A u ric c hl o
    ,
    ri de can be obtained
    Au C l3 , b y d issol v ing g ol d in

    aqua regia or by the action of chlorine on t h e metal It fo rms a .

    dark red crystalline mass which deliqu esces ra pi dly O n t h e ,


    .

    eva poration of its solution it partially decom p oses int o chlo ri ne


    and aurous chlori d e By eva porating with hydrochlo ric acid long
    .

    yellow n eedles are obtained consisti n g of a com pound A u C 13 HC I ,


    -
    ,

    wh ich can be regarded as chl orau ric acid M any salts of this aci d .

    are known to exist e g K C i A u oig + 2 E zo and N H4 C l A u C lg i -


    - - -
    . .
    ,

    HgO as well as many chlor aurates of organic b ases


    , _
    These doub le -
    .

    s alts give the ordinary tests for gold hence this acid eithe r fo r ms ,

    n o com pl ex ion A u C l 4 or is very uns t able A ur ic chlo rid e is als o


    '
    .

    s oluble in alcohol and in ether .

    A u ri c o xi de , A u 2 0 3 can b e pr epare d b y pr eci pitati n g auri c


    ,

    chloride with magnesia The latter can be r emoved from the pre .

    c ipit at e with concentrated nitric acid the auric oxide remai n ing ,

    as a brown powder which breaks u p at 2 50 int o its elements


    ,

    .

    I f the preci pitate produced by magnesia is treated with dilut e


    nitric ac id a reddish yell ow powde r of the formula A u 0 3 H3 is
    ,
    -

    obtained which dis plays acid instead of b asic pro pe rties Salts
    , , , .

    of this au ri c ac i d are known which ar e derived from t h e com ,

    p ound A u ( O H ) 3
    H2 0 = Au O O H P otassium aurate for exam -
    .
    ,

    p l e
    ,
    has the formula K A q l 3 H 2 0 and crystallizes in yellow - -

    needles M any other salts are also k nown ; the above mentioned
    .
    -

    preci pitate with magnesia for exam ple can be looked u pon as t h e , ,

    magnesium salt of auric acid Mg (Aq ) 2 , .

    A u ri c s u lph i de , A u 2 S3 is preci pitate d fr om gol d solut ions b y ,

    hydrogen sul phide It is ve ry dark b rown and solubl e in am


    .

    m o niu m sul phide .

    G old is preci pita t ed from its solut ions in t h e m et all ic fo rm b y


    A UR I C C O M PO UN DS .
    371

    various reducing agents Ferrous sul phat e o xalic aci d .

    an d acetylene water serve very well for this pur p ose Hyd r oge n .

    kl
    peroxide preci pitates gold q u y in alka l ine solutio n
    ig .

    2 51 For m any c enturies the al chem is ts endeav ored to produ c e go l d


    .

    fro m the baser m etals I t i s needless t o say that the i r efforts were ne ver
    .

    rewarded The chan c es of thi s ho pe be ing realiz ed m ust at present be


    .

    regarded as very Sli ght Sin c e go l d i s an e le m ent Inas m uch however as


    ,
    .
    , ,

    o u r c on c e ption of an e l e m ent i s re l at iv e i e it depends on the . .

    e x tent of our m astery o ver natural for c es the i m poss ib ili ty of de com ,

    p os i ng g Ol d or synthesi z ing
    ~
    it from other e l e m ents 1S by no m eans ab so

    l u t e l y estab l ished ( Se e 2 66 .

    A l tho u gh we now ascribe to every metal xed un a l terable pro pert i es , ,

    it m i ght we ll have see m ed possib le to the a lc he mis ts with the i r m ore ,

    lim ited knowledge that the pro pert i es of the m etal s c oul d vary N one
    , .

    of the m etal s e xc e pt go l d oc cu r pure i n nat u re ; they h av e to be e x tracte d


    fro m o x ides or s ul ph i des whi ch fre q uent ly contai n various i m pur i ties

    , .

    The m etal s thus obta i ned had no de ni te pro pert i es ; distinction was
    m ade between various sorts of l ead co pper etc The m utab ili ty of , , .

    the m etal s m ay be said to have been the rst princ i pl e w h ich observation
    taught ; indeed when a pie c e of m etal is fused with sm all am o unts of
    ,

    various other subst ances its pro perti es ( c o l or et c ) re ally do change


    ,

    Moreov er at the t ime of the a lc he mi sts the present conce pt e lem ent
    ,
    ,
    .

    was not yet estab li shed ; thi s was rst i ntroduc ed by B O Y L E ( 1 62 7


    Before then the do c trine of A R I ST O T LE was v ery gen erall y acbe pt e d

    , ,

    a cc ord i ng to which all s ubstan c es are m ade u p of a i r e earth and ,


    r
    ,

    water I n order to produce go l d it therefore seem ed o nl y necessary to


    .

    de prive the baser m etal s of c ertain pro pert i es and substitute others ,As .

    to the m etals the m se lves the idea was prevalent in alchem istic cir cles
    that m er cury was the pri m ordial substance and that it h ad u ndergone
    vari o u s changes Before go l d c ould be m ade fro m it it m ust be m ade
    .

    refra c tory and of a ye ll o w c o l or N o t a fe w al che m ists were conv in c ed


    m oreover that the su cc ess of the great work
    ,
    .


    depended on t h e co Ope r
    ,

    ation of a higher power .

    SUMM A R Y O F THE G R O UP .

    2 52 . Th e
    metals C o pper Silver and gold form a b ri d ge from ,

    the difcul t l y fusible metals N i Pd Pt (G roup VI I I ) t o the , , , ,

    easily fusible Zn C d Hg ( G roup I I ) ; their melting points are


    , , ,
    -

    between those of the two grou ps The following brief table Si n .


    d

    m ariz es the physical constants of these metals as well as thos e of


    the related elements lithium and sodium : ,
    3 72 ,
    IN O R G A N I C C HE M I S TR Y .
    M 25 2

    10 5 19 3 3

    8 94
    .
    .

    1 08 3 961 1 06 3
    re d wh eit re d

    The analogy in the chemical pro perties is chiey apparent in


    the O u s compound s These have the ty pe R 2 0 for the oxygen
    -
    .

    compounds a n d R X for the halides The o us halides of C u A g


    .
    -
    ,

    and A u are all white an d insoluble in water ; they are isomorpho u s


    with sodium chloride .

    M oreover there are certain analogies in s olubili t y


    ,
    Li t hium .

    carbonate and hydroxide are less soluble in wa t er than the corre


    Spo n din g sodium com pounds ; co pper carbonate an d hydroxide
    are insoluble while the corres ponding Silver compounds dissolve
    ,

    to some extent The s u l phate of sodium ( third horizontal series )


    .

    crystalli z es preferably wi t h 1 0HzO that of co pper ( fth series )


    ,

    with 5H2 0 while Silver sul phate (seventh series ) is anhydrous


    , .

    The oxygen compounds exhibi t a gradual d ecrease in stability .

    LizO and N azO are una ffected by high temperatures but C u O is ,

    transformed into C u g O and the oxides of Silver and gold break u p


    ,

    even at comparatively low temperatures into their elemen t s .

    However it must be admitted tha t the analogy b etween thes e


    ,

    elements is not so great as in o t her groups Thei r di fference in .

    valence is especially striking and moreover there is li ttle simi


    , ,

    l arit y in the pro per t ies of the higher s t ages of oxi d a ti o n This is .

    one of the weak parts of the perio dic syste m .

    BE R YLL I UM AN D M A G N E SI UM .

    I . Be rylli um ( G lucinum ) .

    2 53
    This
    .
    is one of the rarer e l e m ents I t o cc urs in the mi neral beryl
    .

    ,
    A l 3 that v ar iety of beryl whi ch i s co l ored green
    by traces of a c hro mi um c o m pound i s the gem ca ll ed em erald or s m aragd , .

    C hrys oberyl has the co m pos i ti on B e O A


    l 3 -
    .

    Al m ost a ll the berylli um c o m o unds are m ade fro m beryl Thi s is


    p .

    d i si ntegrated by fusing wi th potass ium c arbonate The fused m ass after .


    ,

    coo li ng is treated wi th s ulphuri c a ci d to pre ci pi tate the s i l i ca M ost of


    ,
    .

    m
    the a lu i ni um i s then re m o ved by crysta lliz ati on i n the form of al u m ,
    3 74 IN O R GA N I C C HEM I S TR Y .
    m 2 54.

    II . M agn esiu m .

    2 54 . This element o ccu rs as carbonate silica te and chl o , ,

    ri d e in consi d erable quantities M agn esite is MgC O g dolomite . ,

    MgC a (C O g ) 2 A mong the silicates contai ning magnesium we have


    .

    ta l c and s oapston e HzMg3 8l 4 0 1 2 s erpen tin e (as bes tos ) H4 M g3 SizO g ;


    , ,

    m eerscha u m H4 Mn i3 0 1 0
    ,
    I t is found in smaller amounts in .

    many other silicates e g horn bl ende (as bestos) augite tou rm alin e
    ,
    . .
    , , .

    O ther sal t s foun d in nature are carna ll ite MgC l z KC l 6H2 0 kic ,
    - -

    s crite,
    MgSO 4 Hg O and kain ite MgSO 4 KC l 3 HzO (Stassfu rt
    -

    , ,
    - -

    A brau m s al ts ) Up on the weathering of the s ilicates the mag


    .

    n esiu m goes into the soil whence it is absorbe d by the plants ( t o


    which this elemen t is invaluable ) an d nally taken into the a n imal


    b ody .

    The m e t a l is manufactured on a large scale since it is ,

    e m ploye d for illumination in pho togra phy py r otechni cs etc on , ,


    .
    ,

    account of the intense light (ash l ight) produced b y its combustion -


    .

    A t present it is p re pared mainly by the electrolys is o f fuse d mag


    n esiu m chloride or ca rnallite in a cast steel crucible whi ch serves -

    as cathode ; gas carbon is used for the anode I t is also obtain e d .

    b y heating the double chloride MgCl g N aCl with sodium It is '


    .

    silvery white and has a high lustre Sp g


    -
    It is malleable . . .

    and ductile and comes on the marke t in t he form o f wire or rib b on


    as well as powder but the ribbon frequently contains zin c I t
    , .

    melts at 65 1 and boils at


    I t is quite permanent in the
    air Since it s o o n s becomes coated with a thin c ohesive lm of
    ,

    the oxide ; at an elevated temperature it burns to magnesia M gO ,


    .

    When it is heated red hot in a limited su pply of air a large p a rt


    -

    is converted into the nitrite M g gN z a yellowish green substance , ,


    -
    .

    B oiling water decom poses it slowly with the evolutio n of hydrogen .

    I t dissolves readily in acids but is una ffected by alkalies It is a .

    p owerful reducing agent reducing-

    silica for , exam le


    p ;
    moreover when ignited it burns in water va p or
    , , .

    M a gn esi u m oxi de , M g O m agn esia is the o nl y oxide of mag , ,

    n e s iu m known I t results from the combustion of the metal or


    .

    from heating the hydroxide or carbonate I t is a white ve ry .


    ,

    light powder which is em ployed in medicine under the name m ag


    ,

    n es ia u sta . With water it forms the hydroxide Mg ( O H) 2 .

    M a gn esium h ydro xi de M g ( O H) 2 is reci itated from solutions


    p p , ,

    of magnes i um salts by alkalies I t is slightly soluble in water and .


    M A GN E SI UM S A L TS . 3 75

    turns red litmus b lue ; however in an excess of alkali its ioniz ati o n
    is so diminished that it becomes practically insoluble It is a .

    weak base but is strong eno u gh to absorb carbon dioxide from


    ,

    the air It dissolves readily in an aqueous solution containing


    .

    ammonium salts A c cording to O ST W A L D this is to be ex plained


    .
    ,

    as follows : The solution of an ammonium salt contains a large


    quantity of N H4 ions When a substance is introduced into the
    -
    .

    s olution which gives o ff O H ions as does magnesium hydroxide


    -

    , , ,

    these N H4 ions unite with O H ions to form N H4 O H or rather


    - -

    N H3 + HQ O (cf As a result
    . of this reaction O H ions dis
    a ppe ar In order to restore the equilibrium between the undis
    .

    solved magnesium hydroxide and the solutio n more of this b y ,

    dro x ide must go in solution b u t again the freshly formed O H ions ,


    -

    are taken u p by the N H4 ions I f su fcien t of the latter are present


    -
    .
    ,

    this process will go on till all the magnesium hydroxide has entere d
    into solution I t now becomes clear why on the other hand the
    .
    , ,

    s olution of a magnesium sal t is not preci pitated by ammonia in


    the presence of a s u fcient quantity of ammonium salt .

    M A G N E SI UM SAL T S .

    2 . l o r i de , M gC l z crystallizes with six m ole


    5 5 M agn e si u m ch ,

    cules of water and is very hygrosco pic The deliquescence of .

    c ommon s alt is due t o the magnesium salt it usually contains .

    OH
    On eva p orating the aqueous solution the basic chloride M g
    Cl
    ,

    and hydro chloric acid are formed ; sea water cannot be used in -

    boilers because of the magnesium salt it contains for the hydro ,

    chloric acid set free attacks the iron M any double salts of mag .

    n e s iu m chloride are known .

    I t can be obtained anhydrous by heating the double chloride


    M gC l z N H4 C l 6 H2 0 when it forms a laminar crystalline mass
    - -

    ,
    -

    which melts at 7 08 and distils without dec om p osition at bright


    red heat .

    C a ref ulst u dy of t h e de c o mpos i t i on of m agn esI u m chl ori de by oxygen


    an d by stea m has shown that a rev ers ib l e rea c ti on i s i nvo lved i n ea c h
    c ase
    2 M gC l 2 O zz 2Mg O 2C l ; ; M gC l 2 + H zO r_ > Mg O + 2 HC l -

    form er rea c t i o n a r ise of te mperat ure d is pl a c es t h e e quili brium


    In t h e
    toward t h e ri ght al tho u gh bel o w 5 00 the v el o ci ty i s st ill v ery s mall
    ,

    .
    6 I N O R G A N I C C H E M I S TR Y . 25 5

    In t h e se c ond ro c ess t h c o m os i t i on of the g aseous e q u ili br ium mix


    p e p
    t ure at 7 00 has been fo

    u nd to be 9 0 % HC l 1 0 % E O z .

    i h t
    M agn e s um sul p a e , MgSO 4 7 2 H 0 E ps om s a l t n ds us e in -

    , ,

    medicine It is very soluble in water It loses 6 mols Hg O at


    .
    .
    .

    and the seventh above I n this res pect it behaves lik e


    othe r sul phates e g Zn SO 4 7 H2 0 Fe SO 4 7 H2 0 and those of
    ,
    . .
    -
    ,
    -
    ,

    nickel and cobalt which are moreover isomor phous with it A


    , , ,
    .

    further analogy between these sul phates a ppears in the fact that
    with sul phate of potassium or ammonium they form double salts of
    the same type K zSO 4 M gSO 4 6 H2 0 which are also isomo rphous
    ,
    - -

    ,
    .

    M agn e s i u m am m o n i u m ph osph ates MgN H4 PO 4 6 H2 0 serves ,


    -

    fo r the preci pitation of magnesium as well as of phos phoric acid .

    It is not wholly insoluble in water but does not dissolve in ,

    ammonia the reason for which is again to b e found in the re d u e


    ,

    tion of the ionization C om pletely analogous to this com poun d


    .

    is the corres ponding arsenate MgN H4As O 4 6HZO ,


    -
    .

    M agn esi um c ar b o n ate From solutions of magnesium salts .

    so d a preci pitates a b a s i c carbonate Mg ( O H) 2 4MgC O g 4 H2 0 ,


    - -
    .

    The carbon dioxide liberated holds part of the magnesium in solu


    tion as acid carbonate This precipitate is known as m agn esia .

    a l ba . The n e u t r a l carbonate can be prepare d f rom it by sus


    pending magnesia alba in water passing in carbon dioxide and ,

    allowing to stand ; in time the salt MgC O 3 3 H2 0 crystallizes out


    "
    -

    which is however readily Split u p hydrolytically by water form


    , , ,

    ing b asic carb onate again .

    C A L C IUM , STR O N TI UM AN D BAR IUM .

    I . C al c i u m .

    2 56
    This element is one of the ten princi pal constituents of
    .


    the earth s crust Particularly the o a r b o n a t e is found
    '

    in large quantities in nature l im eston e cal cite aragon it e m arbl e , , , ,

    and chalk all being forms of it


    , A n earthy d e posit Containing a .

    ce rtain amount of calcium carbonate is termed m a r l C alcium .

    silicates and es peciall y calcium double salts constitute the maj o r


    portion of the siliceous rocks There are also extensive beds of .

    calcium phos phate phosphorite apatite etc part icu l arl v in Spain
    , , , .
    ,
    .

    and Florida C alcium occu rs as sul phate in the form of


    gypsu m
    .

    and a labas ter Moreover in the animal kingdom large quantities


    .
    ,
    3 73 IN O R G A N I C C H E M I S TR Y . 25 7

    b eing heate d strongly with an


    '

    y hydrogen ame
    ox it-
    emits an
    intense white light I t absorbs water and carbon dioxide
    from the air ; as a result the chunks of lime which are hard and ,

    solid when they come from the kil n gradually crumble to ne ,

    p owder .

    ci
    C al u m hy d roxi de ,
    C a ( O H ) 2 ( Slake d lime ) i
    ,
    s obta i ned by
    slaking quick lime with water I t s formation is attended by
    -
    .

    the evolution of much heat I t is only s paringly soluble in water .

    ( forming l im e w a t er ) but
    -
    more soluble
    ,
    in c old water than in wa rm .

    The solubility is however su f cient to make the preci pitation of


    , ,

    this hydroxide by ammonium hydroxide imp ossible for the c on ,

    centration of the hydroxyl ions of the latter is too small together


    with that of the calcium ions presen t to reach the value of the
    solubility produc t of calcium hydroxide A t red heat it is recon .
    -

    verted in to the oxide .

    M or tar C alcium hydroxide is used in masonry For this .

    p pur ose quicklime is mixed with water and sand so as to form a


    thick paste called m o r t a r which is t hrown in between the
    ,

    stones A fter some time the m ass bec omes as hard as stone ; this
    .

    is due to the c onversion of the h ydroxide into the carbonate b v


    t h e action of the carbon dioxide of the air The sand makes the .

    m ass p orous so that the process of hardening extends inward ;


    ,

    t he older the wall the harder the mortar The formation of cal .

    c 1 u m si l ica te a ppears to play onl y a minor r ole in this p rocess .

    If the lim e c ontains more or less magnesia it is difcult t o


    slake ; it is therefore less adapted t o masonry purp oses an d is


    called p oor or lean in c ontrast with t he pure easily Slake d
    , , ,

    fat lime .

    C em en t contains besides lime


    , (50 6 0%

    princi pally silic a
    (c a . and alumina (ca I t is made by burning a mixtur e
    .

    of limestone clay and sand I n some places e g B r o hl t h al in


    , .
    ,
    . .


    the R hine region such a mixture occurs as tu ffstone which
    , ,

    yields cement directly on burning C emen t after being mixe d .

    with water sets very rmly in a short time ; this is due in all ,

    probability to the fact that on treating it with water calcium


    ,

    aluminate is dissolved and the solution slowly dep osits a hydrous


    aluminate which is much less soluble and causes the setting of
    ,

    the cement A t the same time insoluble calcium aluminium


    .

    s ilicates are formed .


    258 ] SA L TS O F C A L C I UM . 3 79

    C al ci u m pe roxi de , C aO z 8HQ O ,
    is de p osited when lime water - -

    is treated with hydrogen p eroxide solution I t gives u p oxygen .

    on heating .

    SALT S O F C A L C I UM .

    2 58 . l o ri de , C aC l z is obtained by dissolving the


    C al c i u m ch ,

    h ydroxide or carbonate in hydrochloric acid I t can crystalli z e .

    with various amounts of water The hydrate C aC 12 6 HQ O forms .


    -

    large crystals C alcium chloride is very h ygr O SC O pie and is there


    .

    fore frequently used to dry gases or to absorb water dissolv e d in


    organic liquids (ether c arbon disul phide I t melts at
    , ,

    It unites with ammonia to form C aC 12 8N H3 ; hence it cannot be


    i
    -

    u se d t o dr y t h is gas

    When c rystalliz ed c alcium c hl or i de is m i xed w ith i c e the tem perature


    fall s cons i derab ly e ven rea c hing ,
    Su c h a mix t ure i s c a lled a
    c oolin g ~
    or fr eezin g m ixt u r e an d i s often e m pl oyed for produci ng l ow
    -

    te m perat ures Bes i de s c alcium c hl ori de and ic e m any other s uc h


    .
    ,

    mix t u res are known ; the on e m ost fre qu entl y used i s that of c omm on
    sal t and ic e wi th whic h a te m perat ure of 2 1 c an b e obtai ned I ce
    ,

    .

    is not abso l u te ly ne c essary ; for instan c e i f so li d amm onium ni trate ,

    is added to i ts own we i ght of water a tem perat ure of can be ,

    p rod uc ed .

    I n order to understand why s uc h m i x t u res be c o m e so co l d we mu st


    re c all 23 7 Su ppose that ice i s i ntroduc ed i nto a sat u rated sal t so lu
    .

    t i on of so li d shl t be i ng present at the botto m so that t h e liqui d


    re m a i ns sat urated Th e syste m s olu tion ice i s n ot in a state of e qui
    .

    l ibrium at for the sal t so lu t i on has a free zing po i nt muc h l ower than -

    I t c annot therefore c ont i nu e i n thi s state b u t i f i t i s to be i n e quili br ium , ,

    w i th ic e as so li d phase the tem perat ure mu st s i nk an d thi s i s on l y


    , ,

    poss i b le as the ic e m el ts by whic h pro c ess heat i s c han ged i nto the ,

    latent c ondi t i on If eno ugh ice i s present i t c an by m el t ing c onti nu e


    .
    , , ,

    to wi thdra w free heat fro m t h e syste m t ill t h e c ryohydric po i nt i s


    rea c hed ; for only at or be l o w that po int can ice an d salt e xist perm a
    n e n t l y s i de by Si de I t fo ll ows therefore that t h e c ryohydric te m pera
    .
    , ,

    t ure i s t h e l owe st that ca n b e rea ched by the mixt ure I n 23 7 i t .

    was shown further that there is n o essenti al di fferen ce between the


    , ,

    two c o m ponents of a s o lut i on ; thi s i s al s o seen on c onsi deri ng c oo li ng


    m ix t ures c onta i ni ng n o ic e Fo r i nstan c e when amm on ium n i trate i s
    .
    ,

    added to water t h e so lu t i on has a free zi ng po int muc h l ower than 0


    ,
    -

    Here it i s t h e great absorpt i on of heat in d i ss o lvi ng t h e sal t that c au ses ,

    t h e fa ll of te m perat u re ne c essary to e s tab li sh t h e e quili br ium I f th i s .


    3 80 I N O R GA N I C C HEM I S TR Y .

    fa ll is to b e c ons i derabl e t h e so lub ili ty of t h e sal t must of c o urse be


    ,

    g reat I.n thi s c ase a l so the c ryohydr ic p o i nt is the l owest te m pera


    t ure that c an be rea ched by the mixt ure .

    C h l o ri de
    of lim e is a name given to a product o b taine d b y
    saturating Slaked lime with chlorine at ordinary temperatures .

    Just what compound is formed here is not yet denitely known


    although the matte r has been frequently inves t igate d There is .
    ,

    O Cl
    however much evidence in favor of the formula Ca < accord
    ,
    Cl
    ing to which it is a mixed salt of hydrochloric and hypochlo rous
    acids A t any rate this is more probable than the su pposition
    .

    that chloride of lime is a mixture of calcium hy pochlorite and


    calcium chloride for it is not possible to extract any chlo
    ride of calcium from it with alcohol although this sal t is very solu ,

    ble in alcohol and almost all the chlor ine is ex pelled by a current
    ,

    of carbon dioxide .

    C hloride of lime is employed in large quantities fo r bleach ing


    and disinfecting (bl ea chin g powder ) I t is an incoherent white -
    .

    p owder with the odor of chlorine ( on account of decom p osition


    by the carbon dioxide of the air ) When treated with hy d ro .

    chloric or other acids it yields chlorine

    O Cl
    Ca + 2 HC l C aC 12 E go + Cl2 ;
    Cl

    05
    8? H
    + 2 8 0 4
    = C aSO 4 + 11 2 0 + 012 .

    A so lu t i on of c hl or i de of lime when m 1 x e d wi th a cobal t sal t and


    ,

    warm ed ev o lves o xygen Thi s rea c t i on c an b e regarded as prim arily an


    , .

    o xi d ation of C 0 0 to C 0 20 t h e l atter then y i e l d i n g o xy en wi th c hl or i de


    , g
    of lim e an d forming C o O anew Th e c obalto us o xi de wo ul d thus a c t .

    as a c atalyz er .

    '

    C al ci u m fl u ori de , C 3 F2 ,occurs in nature as u or spar or u orite ,

    forming cubes which are often uorescent I t is insoluble in


    , .

    water I t fuses at red heat and is frequently employed as a ux


    .
    -

    in metallurgical processes I t can be obtained articially by treat


    .

    ing a solution of calcium chloride with sodium uoride N aF , .

    C al c i u m s u l ph i de , C aS is made by heating gy sum with char


    p ,

    coal O n treating the mass with water calcium hydrosul phide


    ,
    .

    C a ( SH) 2 is formed whose aqueous solution loses hydrogen sul


    , ,
    3 82 I N O R G A N I C C H E M I S TR Y .
    M 2 58

    tem perat ure Moreo ver t h e greater solub ili ty of the hal f hydrate as
    .
    -

    c om pared wi th that of the dihydrate i s an addi t i onal reason There i s ,


    .

    thus t h e sam e rel at i onshi p here as between t h e m etastabl e c rystal s


    N azSO 7 HzO an d t h e sal ts N azSO 1 0HQ O an d N aZSO e xc e pt that i n
    4
    -

    4
    -
    ,,

    thi s l atter c ase the transform at i on fro m m etastable to stabl e m o di


    c at i on takes pl a c e very easily o n to uching t h e he ptahydrate wi th a
    c rystal of t h e de c ahydrate while t he hal f hydrate of c alcium s ul phate
    ,
    -

    e ven in c onta c t wi th the dihydrate reta ins i ts i dent i ty i nde ni te ly ,


    .

    C al ci u m itr ate , C a (N O g ) 2 results from the decay of n it rog


    n ,

    eno n s organic substances in the presence of lim e I t crystallizes .

    with four molecules of water The anhydrous sal t deliquesces in .

    the air and dissolves rea dily in alcohol I t is converted into s alt .

    p etre by p otash or p otassium chloride


    The tertiary salt C a3 (PO 4 ) 2 is in solubl e
    C al c i um pho sph ate s , ,

    in water as is also the s econdary salt C a2 H2 (P0 4 32 The prim ary


    , , ,

    salt C aH4 ( PO 4 ) 2 however is readily soluble ; it is employed l n


    , , ,

    large quantities as an articial fertilizer u nder the name of super ,



    p hos phate .

    Thi s su perphosphate i s m anu fa c tured by thoroughly m ixing ground


    p ho s phor i te ( or bone m ea l ) in a c ast i ron mixer wi th chamber a ci d -

    a cc ordi ng to the pro port i ons of the e quat i on

    ca me ) ,
    2H28 0 4 2CaSO 4 .

    The m ass which i s at rst semi so li d soon be c o m es so li d s i n c e the


    ,
    -

    , ,

    c alcium sulphate that i s formed takes u p the water c ontai ned i n the
    chamber a ci d to form crystal s .

    When su perphosphate is mixed wi th soil t h e prim ary c alcium s ul phate


    goes i nto so lu t i on an d si n ce every so il c o n tains lim e i t i s forthwi th
    , ,

    re c onverted i n to i nso lubl e se c ondary or terti ary phos phate A ppar


    ently nothi ng has been gai ned toward m aki ng t h e phosphoric a ci d .


    so lubl e However t h e pho s phate i s now di ff u s ed w i de l y i n the so il
    .

    an d is therefore muc h m ore a cc e ss i bl e to the roots of the l ants than i f


    p
    the so il had been mixed wi th tert i ary phosphate on ly .

    2 59 . C al c i um ca rb o n ate
    is dimorphous o ccurring , C aCO g , ,

    rhombohedral as cal cite and rhombic as aragon ite When the ,

    solution of a calcium salt is treated with soda calcium carbonat e ,

    is at rst preci pitated in an amorphous very voluminous and mor e ,

    soluble form ; after a short time however it turns to a nely , ,

    crystalline powder I t is very Slightly soluble in water but more


    .

    ,
    S A L TS O F C A L C I UM . 3 83

    extensively so in water containing carboni c acid since the acid ,

    calcium carbonate is then formed The latter decom poses when .

    the solution is boiled carbon dioxide escaping and crystalline


    ,

    n eutral carbonate being de posited .

    Hardn es s of Wa t er A lmost every river or s pring water holds


    .
    -

    more or less lime i n solution The lime is present as sul phate or


    .

    as acid carbonate Such a water forms b u t little if any lather


    .
    , ,

    with soa p ; the fatty acids of the soa p form white insoluble salts
    with the lime so that water containing much lime is not g ood
    ,

    for washing Such a water is termed h a r (1 in contrast with a


    .

    water that is free or nearly free from lime which is called s o f t


    If the hardness is due to acid carbonate ( also called bicarbonate
    ,

    of lime ) it disa ppears on protracted boiling calci um carbonate
    , ,

    being preci pitated In such a case we Speak of t e m p o r a r y


    .

    hardnesS In metallic boilers and similar vessels the carbonate


    of lim e that is de posited adheres rmly to the Sides ( boiler ,

    If the hardness of a water is due to gy ps um which is ,

    o nly partially removed by b oil ing it is s poken of as


    p e r m a n e n t h a r d n e s s .

    When heated calcium carb onate b reaks u p into lime and


    ,

    carbon dioxide We have here a case of com plete heterogeneous


    .

    equilibrium for the su sb t an ces are C aO and C0 2 an d the


    p hases C a O C,
    a C 0 3 and C 0 2 This is con r med
    . by ex periments ,

    wh ich Sh o w t h at the concentration of the gaseous phase (the dis


    sociation tension ) at a denite tem perat u re is c onstant and there
    fo re inde pendent of the amount of each phase C om plete dec e m .

    p osition into lime and carbon dioxide can only occur therefore , ,

    when the gaseous phase is removed (as in lime burning 2 57 ) -

    or when its tension is ke pt below the dissociation tension On .

    the other hand if the tension of the carbon dioxide is greater


    ,

    th an the dissociation tension calcium carbonate cannot de c om ,


    p ose. U nder these circu m stances it is p ossible to fuse calcium


    carbonate ; on solidication it assu m es a
    crystalline structure and becomes m arbl e .

    I n the adj oining Fig m let A B re pre .

    sent the dissociation curve of calcium car


    bonate in a c o Or din at e system Pt O nly .

    along this cur v e are the three ph ases in


    FI G 6 0
    .
    equilibrium w ith each other ; under any
    other conditions one of the ph as es disa ppears
    3 84 I N O R G A N I C C HEM I S T R Y 2 59

    and we enter either the region of the phases C a O + CO z or that of



    C aC O g l C O Q .

    GLASS .

    2 60 . C al c i um is chiey im po rtant b ecaus e it is a c on


    silic at e

    s t it u e n t of almos t all so rts of glass .

    G l as s is a mixture of silicates of the alkalies with calcium silic ate


    or lead silicate The alkali silicates are soluble I n water amorphous
    . ,

    and easily fusible The calcium silicates however are ins oluble
    .
    , , ,

    very hard to fuse and frequently crystall ize d By fus ing bo t h .

    together an insoluble amorphous trans parent mass of mode rate


    .

    fus ibility is obtained which is glass It is pre pared b y fus ing a


    ,
    .

    m ixture of clean sand lime and soda in refracto ry cruci b l es


    ,
    .

    The pro pe rties of glass de pend primarily on t h e qualit y of t he


    materials and secondarily on the pro portions us ed By varying .

    these two conditions it is easy to obtain grades of glas s varying


    widely in fusibility hard ness lustre refractive powe r e t c The re
    , , , ,
    .

    are ve ry many diffe rent so rts in use Some of the mos t im port ant .

    are the following


    S o d a g l a s s (window glass ) is a s o d a lime silica t e

    I t is -
    .

    r eadily fusible and is used for most purposes of the househol d .

    P o t a s h g l a s s (cr own gl ass B ohem ia n glass) consists of a ,

    silicate of potassium and calcium It is ve ry difcul t to fuse an d .

    is therefore extensively us ed for chemical purposes ( com b us tio n


    tubes ,

    Le a d g l a s s (flin t gl ass ) is a silicate of potassium an d lea d .

    It is softer more easily fusible and highly refractive and takes on


    ,

    a beautiful lustre when polished It is therefore used fo r o ptic al


    ins truments and fancy glassware ( cut
    .


    Besides the substances mentioned many othe rs a r e use d in gl ass
    factories to im part particular pro perties to the glass Th e addi .

    tion of boric acid or the partial re placement of lead wi t h thall ium


    gives lead glass a still higher refractive index A n admixtur e of .

    alumina Al 2 0 3 prevents or hinde rs chemical utensils of glass fro m


    , ,

    becoming b rittle an d allows the re placement of part of the alkali


    by lime C ertain metallic oxides form c olored silicates and are
    .

    therefore mixed in with the furnace charge to color the glass


    ( cobalt blue ; chromium or co pper green ; uranium yellow
    , , ,

    g r c c n uorescent The addition of bone ash C a3 ( PO 4 ) 2


    ,
    -

    , ,
    6 IN O R GAN I C C H E M I S TR Y 26 0

    and the wholly solid states there is a continuous series of ,

    half liquid states A s it is thus im p ossible to nd a tem p erature


    -
    .

    limit to the a pplicability to glass of the laws of sol utions e g , . .

    the law of di ffusion it seems rational to consider the solid ,

    amorp hous state as liquid in contradistinction to the crystallin e ,

    state which latter is truly solid having very different p ro p erties


    , ,

    fro m liquids .

    S olid s ol u ti on This term was introduced by VAN T H O FF


    to a pply to a solid homogeneous mixture The best exam ple .

    is to be found in m ixed crys ta l s including isomorphous mixtures ,

    Thus for instance when a molten mixture of silver and


    , ,

    gold solidies the com p onents do not se p arate but solid ify
    , ,

    together in homogeneous crystals of the same com p osition as


    the melt (Se e Fig 6 8 III )
    . The term solid solution is
    .
    ,
    .

    applied to this and somewhat Similar solid mixtures be cause they ,

    exhibit some of the pro perties of liquid solutions e g in mis ,


    . .
    ,

    c ib il it y relation s hi p s G lass re p resents an amorp hous ty p e of


    .

    solid solution s of which the constituent silicates are the integral


    ,

    com p onents but as intimated in the preceding p aragra ph many


    , , ,

    are inclined to regard the amorphous solid solutions as pseudo


    sol id solutions i e really undercooled liquid solutions
    ,
    . .
    , .

    II . Stront i u m .

    2 61 This is one of the very widely di ffused elements C L AR K E


    .
    .

    showed that in most of the ro cks containing calcium this latter


    metal is accom p an i ed by small quantities of strontium and
    barium The princi pal strontium minerals are s tr on tia n it e
    .

    Sr C O g and cel es t ite SrSO 4


    , I t s com p ounds are very analogous
    , .

    to those of c alciu m .

    The m e t a l has been obtained by the electrolysis of fuse d


    strontium chloride I t s s p ecic gravity is I n its p ro p erties
    .

    it c orres p onds to calcium throughout


    '

    Stronti u m oxi de Sr O is formed on igniting the hydroxide o r, ,

    carbonate The tem perature required for the com plete disso cia
    .

    tion of the latter is higher than that for the corresp onding calcium
    com pound The hydroxi de Sr ( O H) 2 8 H2 0 is more soluble in
    .
    ,
    -

    water than calcium hydroxide The ch l ori de , SrC 12 6 H2 0 is . -

    hygrosc op ic li k e th at of c al cium I t is soluble in al c oh ol an d


    , .
    BA R I (M I .
    3 87

    c an with the ai d of the latte r be easily se parated from b arium


    , ,

    chloride which is insoluble in alc ohol Stro n ti u m s u lph ate is


    , .

    much less soluble than c alcium sulphate ; at 1 6 1 1 p art SrSO 4

    d issolves in 1 007 0 p arts Hg O (C aSO 4 1 par t in 54 3 at In a ,

    m ixture of alc ohol and water it dissol v es to an extremely small


    extent Strontiu m nitrate
    . is insoluble in alcohol ; ,

    this forms the b asis of se parating it from c alcium n i t rate which ,

    dissolves in alc o hol .

    Strontium s alts are used in p yrotechnics b eca us e of the beauti


    ful cri m s on c olor they im p ar t to a ame
    -

    II I . B a ri u m .

    2 62 This element o ccurs combined as barite o r heavy spar


    .
    , ,

    BaS O 4 and as w itherit e B aC O g in considerable quan t i t ies


    , In, , .

    re
    p p aring the other barium sal t s it is merely necessary to dissolve
    the latter mineral in the pro per aci d B ari t e howeve r mus t rs t .
    , ,

    be reduced by ignition with charcoal This can be accomplished .

    in the electric furnace

    (1) 4 13 5 s 0 4 + 40 = BaS + 3 B aSO 4 I


    4C C ; -

    ( )
    2

    The m e t a l is in this case also obtaine d b y t h e e lec trol ysis


    , ,

    of the fused chloride A nother metho d is to heat the oxide .

    with magnesium B arium dec om p oses water vigorously even


    .

    at ordinary tem peratures Sp . .

    B a ri u m oxi de , B aO is obtained by igniting the nitrate o r


    ,

    hydroxide at a high temperature I t unites very readily with .

    water to form the h ydr oxi de , B a (O H) 2 which is rather soluble in ,

    water (yielding baryta wa ter ) and crystalli z es from the h o t solu


    -

    t ion on cooling in pretty laminae which contain eight molecules o f ,

    wa ter .

    Bari u m pe r o x i de , B aO z forms on heating the oxi d e in a cu r ,


    ,

    r en t o i oxygen or air When it is introduced into dilute sul phuric


    .

    a cid
    ,
    barium s ul phate is preci pi t ated and hydrogen peroxide left
    in solution I f barytawater is again a d ded t he h ydrate B aO z 8H20
    .
    ,

    c ryst al li z es out .

    Barium c hl o ride , BaC 12 2 H2 0 is n o t hygros cO pic lik e t h e o

    c hlorides of s t rontiu m and calcium The n itrate crystallizes .

    a nhydro u s
    .
    3 88 I N O R G A N I C C HE M I S TR Y . 262

    Bar iu m l ph ate , B aSO 4 is characterize d b y an exceedingly


    su ,

    small solubility in water and acids ; at 1 8 4 1 part dissolves in

    par t s H g O I t is used as a ller and as a p igment unde r .

    a r i u m c ar b o n at e

    t h e name of p ermanent white or bl a n c xe B ,
    .

    yields carbon dioxide only at very high temperatures prolonge d ,

    hea t ing at 1 4 50 being require d for complete decomposi t ion



    .

    SUM M A R Y O F T HE G R O UP O F T HE A LK A L I N E E A R T HS .

    The following small table summari z es the physical p ro pe rties


    of the elements of this grou p

    0 0 0 0 0 0 0 0

    O O O O O O O O O O O O O O O O

    As to the Specic gravity we observe tha t only in t h e cas es of


    C a Sr and B a is a steady increase noticeable
    ,

    "
    I n res pect to the chemical pro per t ies it has already b ee n ,

    remarked that these elements act only as bivalen t ; all com pound s
    of the group therefore have the same formula type In the solu .

    b il it y of the sul phates a gradual decrease is to be o b serve d with


    rising atomic weight .

    Just as in the rst group three elements K R b Cs exhibi t a , , , .

    p articular kinshi p so here calcium strontium an d b arium are , ,

    closely related in their pro perties while the two other members of ,

    the group are unlike them in many res pects B eryllium displays .

    analogy with aluminium in cer tain points j us t as l ithi u m d oes


    with magnesium .
    3 90 I N O R GA N I C C HE M I S TR Y . 2 63

    is the ocular through which the Spectrum is seen Fo r furth er .

    inform ation textbooks on physics should be consulte d .

    I n order to examine the s pectra of m etals it is n e c e ssary t o


    convert the latter into the form of va por at a high tem pera t ure .

    There are di fferent ways of doing this O n e is to introduce salts .

    of the m etals into a c olorless ame by means of a platinum wire .

    The heat dissociates halogen salts and in the case of oxysalts


    converts them into oxides which are reduced to the metallic
    ,

    condition by the hot gases of the ame This m et h c d is very .

    s atisfactory for some ele m ents e g those of the alkali and alkaline
    ,
    . .

    ear t h grou ps when there is plenty of material I n other cases a


    ,
    .

    r u m of t his sort is n o t so good as a s a r k or an ar c s ec


    a m e s p ec t p p
    tr u m for with the latter it is possible to detec t with accuracy
    ,

    extremely small amounts of a substance O ther advantages of t h e .

    latter s pectra are their greater light intensity the greater con ,

    v e n ie n c e in execution and the like


    ,
    M oreover at the high tem
    .
    ,

    pe rat u re h ere prevailing most elements ex hibi t Spectra which


    canno t be obtained with the gas am e -
    .

    A s park s pectrum can be obtained in a very sim ple manne r ,

    thus : I nto the bottom of a little glass c u p


    (n Fig
    ,
    . ab out 1 5 mm wide is fuse d a platinum
    .

    wire which ends in a tube g containing mercury


    ,

    and is thus connected with the negative pole of an


    induction coil ; it is incased in a conical ca pillary
    tube x beyond which the wire proj ects about
    ,
    mm .

    A t the o pposite end is the positive electrode in the


    form of a platinum wire w hich with the e x ce p
    , ,

    tion of the short end d is fused into a glass tube


    ,
    '

    the latter is tted into the cork a If some of .

    the sal t solution is poured into the c u p about half


    way u p the negative electrode the liquid is drawn ,

    u p to the end of x by ca illarity and every s ark


    p p
    volatilizes a tiny portion . I n this way there is
    no loss of m aterial and the Sparks are very u ni
    form so that the observation oi the s pectrum can
    , FI G 6 2 . .

    be co n tinu ed at length .

    For the study of the s pectra of substances which are


    g a s e o u s at ordinary tem peratures the P L ii C K E R H I T T o R F -

    ( G E I SS LER ) t u b e s are u sed ( Fig The gases are sealed u p


    .

    I n them in a very dilute condition O n connecting one of these


    .
    S PE C T R O S C O P Y .
    3 91

    with the poles of an induction coil the whole tube is illuminated ,

    most intensely in the narrow p ortio n This p art is placed ver .

    ti cally in front o f the slit of the s p e ctros co pe .

    Some substances h av e the p ro perty of absorbing certain colors


    and trans mi t ting othe rs If the solution of such a sub s t ance is
    .

    placed before the sli t of a s pectros co p e and the light of a contin


    u o us Sp ectrum allowed to pass through it dark ban ds or lines are
    ,

    o bserved in the s pectrum A number of substances have very


    .

    characteristic ab s o rptio n s p ectra .

    2 64
    . The s pectrosc o pe is one of the mos t d elicate means we
    have of detecting many substances This is readily seen on c on .

    s ide rin g how sma l l an amount of the substance under examina

    tion is volatilize d b y the sparks We arrive at n umbers lik e .

    FI G . 63

    mg sodium for instance as the leas t amount tha t


    .
    , ,

    can be detected I t has thus been p ossible to disc over elements


    .

    which occur only in c om pany with large amounts of others an d


    would therefore have been very difcul t to nd in the ordinary
    way B UN S EN and K I R C H H O EE themselves found c aesium an d
    .

    r ubidium in this way in Durkheim mineral water In or d er t o .

    o btain these elements from it in the form of chlorides it w a s


    ,

    n ecessary to eva p orate kg water which yielde d . g of , .

    a mixture of the chlorides O ther very r are elements which were


    .

    d isc o v ered by s p ectrum analysis are thallium indium gallium , , ,

    y tterbium and scandium .

    The s p ectra of the elements di ffer greatly in a ppearance as ,

    may be seen at once fro m Table I I ( Frontis piece ) The numbers .

    indicate wave lengths of light ex pressed in hundredth microns


    5
    ( 1 0 C ertain metals such as so diu m,
    tha l lium and ,

    indium exhibit only 0 n e distinct line when their ame s pectra


    ,

    a r e examine d with a s p ectrosc o e like the one des cribed above


    p .

    I f a s p arking current or an electric arc is em ployed for the vola


    t il iz at io n of the substance and the s pectrosco p e is one giving
    strong dis persio n many more lines become visible I t is further
    , .

    found o n photogra phing s pectra that there are still more lines
    in the infra re d and ultra violet p ortions which are invisible
    - -

    t o the eye . Present day s pectrosco pic studies deal therefore


    -

    , ,

    a lmost exclusively with carefully re ared hotogra hs


    p p p p .
    3 92 I N O R G A N I C C H E M I S TR Y . 2 64

    The number of s pe ctral lines incr eases ra pidly as we p ro ceed


    t o elements of the highe r grou ps of t h e periodic system Whil e .

    lithium so dium and p otassium give 2 0 3 5 and 4 1 lines re


    , , , ,

    s pe c t iv el y
    ,
    the s pectrum of barium contains 1 6 3 lines and that .

    of iron more than 5000 lines .

    A mong these lines there are certain ones which in virtu e of ,

    their p osition ( color ) and intensity are s pecially characteristic


    ,

    of an element like that of the yellow line in the case of s o dium


    , ,

    the green line of thallium and the blue lines of indium For .

    ur
    p p oses of identication of such elements these p rominen t lines
    are generally observed directly i n the s p ectral a ppara t us .

    N itrogen is an exam ple of a substance that gives a band s p ec


    trum when it is examined in the manner descri bed in 2 63 .

    2 6 5 : Th e p osition of the s p ectrum lines was formerly indi

    c at e d numerically acc ording to an arbitrary scale N o w it is .

    ex pressed with the aid of the wave l e n gt h /l being taken as ,

    a unit and the unit being called the ANG ST R O M u n it after t h e


    physicist wh o intro duced it The wave length of the so dium
    -

    D1 line was found to be ex pressed by such units The .

    visible part of the s pectrum comprises the wave lengths of abou t



    7 500 4 000 AU . .

    '
    Thanks to the researches of R O W L AND M I C H E L S O N K A YS ER , ,

    and R UN G E and others the wave lengths of a very large numbe r


    , ,

    of s pectrum lines have been determined with great exactness ,

    s o that one is encouraged to attac k the questio n whether in t h e


    a pparently very p romiscuous distribution of lines in the s pectra
    there is such a thing as order .

    B A L MER was the rst to show that this is t h e cas e in t h e


    2
    m
    hydrogen s pectrum . Th e formula A= A 2
    where A is a '

    m 4
    constant ex presses the wave lengths A of the lines
    of the s pectrum of the element with very close a pproximation ,

    provided m is substituted by c onsecutive whole numbers begin


    ning with 3 .

    The s pectra of other elements have been examined for similar


    regularities chiey by R Y D B ERG and by K A Y S ER and R UN G E
    ,
    ,

    and it has been found that the regularities are in all of the cases
    more c om plex than for the hydrogen s pectrum I t would lea d .

    us to o far to enter u pon a discussion of these questions which ,


    3 94 IN O R G A N I C C HE M I S TR Y . 25 5 ~

    e ver they are lacking In their place we nd in the s p ectra of


    ,
    .

    l ead t in arsenic b ismuth an d others a c onstant di f


    f erenc e
    , , ,

    b etween the oscilla t io n frequencies of a c onsi d erable numbe r


    o f their lines .

    Su ch investigatio ns as thes e are p rom p te d by the notio n that


    a knowledge of th e laws which govern t h e distributio n of t h e

    Sp ectral lines of one and the same substanc e o n the one hand ,

    and the variation in the distributio n fro m substanc e to sub


    stance on the other hand would throw some light o n the nature ,

    and kinetic condition of the atoms .

    With the aid of spectrosco py it has been p ossible t o deter


    mine what elements are present in the heavenly b o dies IVh e n .

    light from the latter is passe d through a p rism line s p ectra are ,

    o btained and these lines corres p ond in p osition t o those of terres

    trial elements The com p osition o f sunlight has been es p ecially


    .

    t h e obj ect of a most extensive study The s pectrum of that b o dy .

    c ontains numerous b lack lines known as F R A U N H o F E R ,

    l in e s The theory of this phenomenon is ex plai ne d in O ptics .

    By com paring t h e F RAU NH O F ER l ines with t h e s p ectra of ter



    r es t r ial substances it has b e e n found that the sun s atmos pher e

    c ontains chiey F e N a M g C a C r N i B a C u Z n and H (t h e


    , , , , , , , ,

    latter in enormous quantity ) M oreover for 4 50 lines of the iron .


    ,

    s pectrum there are found to b e c orres p onding dark lines i n t h e



    sun s s pectr u m O n the other hand the s olar s pe ctrum dis plays
    .
    ,

    countless lines which are not yet i d entie d in terrestrial s pe c tr a .

    We ar e l e d t o p re s e th at um an y o f t h e m l m en ts to w h ich th e se l in e s
    e e

    are ill l
    du e w v l
    a s o b e r e e a e d on t h e e art h b
    y m o e c are ful re se rch e p ci lly
    r a , s e a
    wh w
    en c o id w h t a sm ll p t f t h
    e ns er rt h i k n own ( s fo otn ot
    a a ar o e ea s ee e,

    p . Th is p umpt i n h s b en t gly c m d b y t h dis v e y f


    re s o a e s r on on r e e co r
    '

    o
    h li m
    e u Th p i n ci p l li n f t h e l tte D r
    te rm e d b c au of
    a e o a e r, so e se
    a
    it s p ximity t t h d ou b l Dl i
    ro o
    ( D D ) f e d ium w
    a b
    e v d in t h e
    ne 1 2 o so s o ser e
    s pe c t f m n y x d t
    ra o s w ll
    a in t h t f t h s n b f re t h
    e s a rs a l m nt e as a o e u e o e e e e

    i t l f w i d t i d
    se as th rt h H lium w s th u di sc ov red in t h t rs
    en e on e ea . e a s e e s a
    b f e o re it w f u d n t h as th oIt in triki g f c t th t i t o ccur in
    o e e ar . s a s n a a s
    e xc di gly l g qu titi in t h x d t
    ee n ar e
    (an
    a cc d i g to
    es
    p
    c tr m e
    tr ic e e s ars or n s e o
    o b v ti ) w h il t h is pp ntly ly a v y sm all m ount f it o n t h
    se r a on s e e re a a re on er a o e
    ea rt h .
    THE UN I T Y O F M A T TE R
    ~

    2 66 . .
    3 95

    THE UN ITY O F M A TTER .

    The notion that all substances are derive d fr om a Single


    2 66 .

    original substance and that the variety that we observe in the


    material world is merely the result of a di fference in arrangement
    and form of the smallest p articles has long been prevalent E ven .

    the old G reek p hiloso phers had a fondness fo r it However the .


    ,

    rise of ex p erimental investigation was not very conduc ive to the


    idea B O YL E ( 1 6 2 6 1 6 9 1 ) introduced the conce p t el em en t in its
    .

    p resent form A c cording to this conce p t all substances are to b e


    .

    regarded as elements which with the means at our command


    .

    , ,
    ,

    c annot be further resolved into dissimilar com p onents The sub .

    sequent develo pment o f chemistry has shown that the number


    o f these elements is rather large .

    N otwith stan di ng that the i dea o f a p ri mordial subst ance l ac ke d


    substanti ati o n and w as mo re or less disc redited it was b y no ,

    me ans rej ected for we hav e b een ex pressly remi n d e d again an d


    ,

    a gai n th at t h e substances wh ich ch emistry regards as the sim pl e

    sub st anc es are o nly cl assed as el ements co nditionally ; th e p os


    s ibilit y always remains th at a s o c al led ele ment may b e foun d
    -

    cap able of division int o dissimil a r com ponents as has o f t en ao ,

    t u al l y b een t h e c ase .

    Imp ossibl e a s it w as to deny th e existence of a pri mor dial


    s ub st an ce th e resear ch es of the 1 8 th an d a large pa rt of thos e
    , ,

    o f t h e 1 9 th ce ntury b ro ught t o li ght nothing to supp o rt the idea


    , .

    N ot until the dis covery o f the Periodi c System di d t h e question


    agai n d emand seri ous att enti on This discovery w as the rst t o
    .

    su pply an ex perim ent al b asis for t he assum ptio n o f a primor dial


    s ub st a nce The s triking de pendence o f the pro perties o f
    th e elements o n th e p eriodic fun ctio ns o f thei r at om i c we i ghts ,

    which nds its ex p ression in this syst em le ads of itself t o the ,

    thought o f a fu n d ament al substan ce of whi ch the simple su b


    ,

    stan ces called el e me nts m ay b e said t o be p olymers incapabl e of ,

    r esolutio n by t h e me ans at our co mman d .

    A noth er argu ment for the divisibility of the elemental at oms


    is contribut ed b y s pec trosco py I n order to ex p lain the lin e
    .

    s pe ctra exhibi t ed by m any e l e m e n t s we as sum e that the m ov e


    ,

    me nts o f t h e ato ms give rise to li ght v ibratio ns of denite wav e


    3 96 IN O R G A N I C C HE M I S TR Y . 266

    len gth which are perceive d by us in the s pectral l ines Howeve r


    ,
    .
    ,

    sinc e th e s pe ctrum of a single element is extre mely com pli cated ,

    we sho uld have t o assume that the at oms engender ve ry c om plex


    moveme nts The simp lified hy pothesis was then o ffere d that it
    .

    is not the e ntire ato m but smaller p a ti cles o f whi ch the atoms r

    are com posed th at give rise by their vibratio ns t o the di fferent


    ,

    s pectral lines .

    The physi cal i nvestigati ons of the last decade have furnishe d
    subst anti al reasons for believing that th e chemi cal ato ms are no t
    i n re ality the ultimat e particles of matter but that th ey are divi
    sible i n to p articles ap proximately 2000 times smalle r than t h e
    hydro ge n atom These p articles carrying with them as they do
    .

    very strong el ectrical ch arges are called ele ctr ons


    We c annot
    ,
    ,
    .
    , ,

    in this b oo k do more th an i ndicate th e main observati ons an d


    inferences Th e h ypothes is of el ec tron s is the result o f the study
    .

    of c ath ode rays in co nnection with the belo w mentio ne d investiga -

    tions of radi o active elem e nts C ath ode rays are generated when
    -
    .

    the discharges of an induction c oil are s ent through a rareed gas ,

    It is assumed t h at fro m the catho de there are proj e cted p articles


    '

    with strong negative charges el ectr o n s , which are p ro pagated


    with a velo city of several thousand kil ometers p er sec o n d A c .

    c o rdin gl y the cath ode rays consist of a stream of these electrons


    , .

    M easurements of the mass o f an electron have Sho wn th at it is


    ab out m; of that of a hydrogen at om The ele ctro ns are t h e
    l
    .

    same what ever gas is c ontained in the a pp aratus an d whatever


    ,

    ele ctrodes are used so that we are e v ide n t l v dealing with a de co m


    ,

    p ositio n of the atoms int o their ultimate c om p onents .

    The anion s ac c o rdin g to the electro n theo ry c ons ist of a t o ms


    ,_ ,

    an d one or more electrons ; th e chlorine io n for e xam p le co n , ,

    sists of chl orine and an electron which latter is re presente d b y d ,

    The cati ons are formed from the ato ms b y t h e release o f one o r
    more ele ctro ns We may thus write .

    C l + d= C l '
    an d K

    Th e ionization o f potassium chlori d e i n wa t er c an be repres e nt ed


    by th e equation :
    K C l q = ( K d) q + a a

    C ert ain physicists presume


    to be able to go a s t e p furth e r .

    S ome very remarkable investigations of R O W L AND have sh own


    3 98 IN O R G A N I C C H E M I S TR Y .
    26 7

    The only means of control in the se p aration of these elements


    from the other com p ounds in uraninite after the removal of
    uranium was to measure the radio activity of the product o h
    t ain e d in each o p erati on This was ac com pl ished by measuring
    .

    the condu ctivity o f a layer of air that was ex p osed t o the rays .

    Thus afte r numero us ch e mi cal o perations th e ac tive subst an ce


    was c o nc entrated m o re an d more This method is com p arable .

    t o that em ploye d by BUN S EN and K I R C H H O FF l n isolating ru b id


    ium an d c aesiu m fro m th e Diir k h e im e r mineral water wh ere the ,

    Spectrosc o p e 2 3 2) indic ated the progress of th e conc entrati o n


    o f th ese ele ments However the measure ment of r adio a ctivity
    .
    ,
    -

    is many tho usand times more sensitive tha n a s pe ctrosc o p ic


    examination Were it not for this fact th e discovery o f the
    .
    ,

    radio active ele ments woul d h ave been imp ossible becaus e they
    -

    o ccur in su ch extremely small quantities For exam ple 2 000 kg .


    , .

    uraninite resi dues from J o ach im s t h al yiel d only about g .

    r adium chloride .

    R adiu m is th e b est known of these elements I t is t h e o nly .

    one that has been isolated and whose com p ounds have been
    p pre ared in the p ure state I t s s p ark s p ectrum
    . has three very
    bright lines in the blue and violet and accordingly the B unsen
    ame color is carmine I n its chemical behavior it shows close
    .

    analogy to barium ; it is se p arated from the latter element by


    fractional crystalliz ation of the bromides radium bromide ,

    being more dif cu l t l y soluble than the corres p onding b arium salt
    (this is true for all the res pective salts of the two elements ) .

    With the aid of the s pectrosco pe it can be determined whether


    the salt is entirely free from barium bromide .

    The atomic weight of the radium thus puried was found t o


    be which could not be raised by further fractional crystal
    l iz at io n With this atomic weight radium ts exactly into the
    .

    second grou p of the periodic system Al l radium salts are lumi .

    nous and excite a large number of substances such as barium ,

    p latinocyanide B a Pt (C N ) 4 uranyl sul phate p recious stones and


    , , , ,

    the like to p owerful uorescence I t similarly a ffe cts the dia


    , .

    mond G enuine diamonds can thus be distinguished from imi


    .

    t at io n s The radio activity of the pure bromide is about a million


    .
    -

    times that of uraninite .

    MM E C UR I E and DE B I E R N E suc ceeded in 1 9 1 0 in isolating the


    .
    R A D I O A C TI VE E L E M E N TS
    -
    .
    3 99

    element itself They electroly z ed a solution using a mercury


    .
    ,

    cath ode and obtained a radium amalgam from whic h the mer
    , ,

    cury was distilled o ff in a current of hydro gen R adium is a .

    white metal melting at


    ,
    E ven as l ow as this tem p erature
    it vol atil i z e s app re ciably I t is attac ked by the air and dec e m
    .

    p oses water vigorously .

    B esides uranium and thoriu m the most im portant radio


    ac tive elements are p olonium a ctinium ionium and radio
    , , ,

    thorium Polo n i u m is p reci p itated in a number of reactions
    .

    with bismuth ; by hydrogen sulp hide as well as when the b asic ,

    salts Of bismuth are p reci pitated by water ; stannous chloride


    p reci p itates it in the same way as mercury and tellurium It .

    i s also de p osited on a rod of silver or bismuth when one of these


    is immersed in a solution containing p olonium The radio .

    activity o f p oloni um is about a thousand fold as great as that of -

    radium From 1 5 tons of p itchblende MA R C K W A L D could only


    .

    obtain 3 mg p olonium salt still somewhat im pure ; so that p olo


    .
    ,

    nium also surp asses radium considerably in scarcity A cti ni u m .

    o c curs with the rare earth metals p articularly lanthanum and


    , ,

    c an be p artially though unsatisfactorily se p arated from them by


    , ,

    frac tion al crystalliz ation of the manganese double nitrate For .

    io n i u m see below ; for r a dioth ori u m see under thorium .

    The rays emitted by radium pre p arations are of three sorts


    and are distinguished as a and r rays Q uantitatively the -


    .

    rst are predominant A


    ll of them have the above mentioned
    .

    p pro erties in co mmon ; they differ however ,


    in their p enetrating ,

    p ower and in their behavior in the magnetic eld The a rays .


    -

    are not very p enetrating and are only slightly deected in a


    strong m agnetic eld A sheet of aluminium foil
    . mm thick .

    almost entirely sto ps their p assage M oreover they are com .

    p l e t e l y absorbed by a layer of air a few centimeters in thickness .

    The rays are strongly deected in a magnetic eld and consist


    -

    of rays of various but greater penetrating p ower ; some kinds


    of rays c an even p ass through an aluminium plate 1 cm thick . .

    The r rays are scarcely deected at all and go through obstrue


    -

    tions with ease several centimeters of lead being insufcient to


    ,

    sto p them ; they form only a small p art of the total radiation .

    The i nteresting thing is that these rays are analogous to those


    generated by electric discharges in highly rareed gases The .
    400 IN O R GA N I C C H E M I S TR Y . 26 6

    [
    ii
    -
    rays are to be regarded as cathode rays of great velo city .

    They consist of negative electrons which are p ro p agated with


    very great velo city some almost with the velo city of light
    ,

    km pe r From the deection which they undergo


    .

    in an electrical eld and a magnetic eld of known intensity their


    mass is calculated to be ( as in the case of the cathode rays )
    about 2 3 1 W of that of a hydrogen atom The velo city of these .

    electrons can also be calculated from the same data Their .


    enormous velo city ex plains the great penetrating p ower of rays .

    The a rays resemble a sort of radiation which is also obtained


    -

    by discharging electricity in a rareed gas viz the ca nal rays of ,


    .
    ,

    FI G . 64.
    E FFE C T or A M A G NE T IC FI E L D ON T HE a
    AND r
    -
    RA YS .

    G O L D ST E I N
    They behave as positively charged proj ectiles
    .

    hurled at a great velocity ( about 215 that of light) Their mass .

    is about equal to that of a hydrogen atom or much greater than ,


    the mass of the proj ectiles formed by the rays and the cathode -

    rays Their greater si z e and relatively small velo city explains


    .

    their slight penetrative power I n the light of the mor e recent


    .

    investigations they appear to consist of helium atoms bearing


    two positive charges each or more s pecically having lost two
    , , ,

    electrons The 7 rays are analogous to the X or R O EN T G EN rays


    .
    ~

    These pro ceed from a metal plate which is placed in the p ath of
    c athode rays ; they do not consist of a stream of electrically
    charged p a rticles but are regarded as a form of wave motion of
    ,

    the ether which originates when electrons are p roj ected with
    ,

    great velocity against a solid body .

    The manner of detecting the various sorts of rays follows


    402 IN O R G A N I C C HE M I S TR Y . 267 .

    chemical agencies are able t o alter emanation It is indifferent .

    to tem p erature variatio n between 1 80 and 500 is not absorbed


    by concentrated acids or alkalies and can be conducted without ,

    change over hot co pp er oxide I t has the p ro p erties of a gas of


    .

    the argon grou p R amsay has lately suc ceeded in p re p aring


    .

    radium emanation in somewhat larger quantities He calls this .

    element nito n I t is found to be a water clear liquid with a


    .
    -

    s p ecic gravity of about 5 and a boiling point of 6 2 under -


    atmospheric pressure I n glass vessels it is very highly u o re s


    .

    cent .

    E manation and induced radio activity must be considered -

    as intermediate stages in the complete disintegratio n of the


    radium atom into the above mentioned radiations How .

    ever other substances part of which have not been further


    , ,

    studied are formed Simultaneously O n e of them is pretty


    ,
    .

    well known vi z h e li u m
    ,
    . R AM SA Y and SO DD Y have demon
    ,
    . - 4

    s t r at e d that helium is formed in the sp ontaneous de c o m


    p osition of radium emanation The maximum quantity. of
    emanation that could be obtained from 50 mg radium bromide .

    was conducted by them with the hel p O f an oxygen current into


    a U tube cooled by liquid air and the U tube was then evacuated
    -
    -

    wit h a pum p A vacuum tube which was fused on to the U tub e


    . -

    showed no traces of helium after removal of the liqui d air The .

    s pectrum app eared to be that of an unknown element p resumably


    emanation After the app aratus stood four days the helium
    .

    s p ectrum a pp eared This phenomenon ex plains the mysterious


    .

    p ersistent o ccurrence of helium in radium bearing minerals -

    The law governing the rise and decay of radio active sub -

    stances is the same as that for a unimolecular reaction A s we .

    h ave seen in 5 0 the velocity S of such a reactio n can be r e pr e


    ,

    sented by the equation :

    if we let C stand for the concentration and K for a c onstant .

    With the aid of higher mathematics this equation c an be trans


    formed into
    Kt
    C 00 8
    -
    R A DI O A C TI VE E L E M E N TS .
    4 03

    where C 0 is the initial concentration and e the base of natural


    logarithms The lo garithmic form of the equation is :
    .

    This same equatio n holds as above stated fo r the velo city of


    , ,

    de com position of a radio active substance ; in th at case however


    -

    , ,

    we understand by C the intensity of radiation This magnitude .

    can be determined electro metrically .

    If a radio active substance changed into only one new sub


    -

    stance the phenomenon would be very easy to re present graph


    ,

    ic all y ; for u p on plotting the time on the abscissa axis and the
    lo garithm of the activity on the ordinate axis the phenomenon
    would be re presented by a straight line B u t when the subst anc e .

    A is converted in t o an o t h e r active substance B and this again


    '

    into a new active subst ance and so on the situation becomes ,

    much more com plicated A gra phic re presentation with the


    .

    same c O ordinates as before would no longer yield a straight


    line but a rather com plic ated curve N evertheless it has been
    ,
    .
    ,

    found p ossible t o resolve these exp erimental curves and t o


    c alculate with certainty the number O f active substances which
    p artici p ate in the transformations as well as their const
    ,
    ant K .

    This is not the only method O f asce rt aining the number and kind
    of the intermediate p ro ducts We can often distinguish the
    .

    individual subst an ces involved by a study of the kind of radiation


    ,

    given o ff certain of the substances emitting only a rays others


    ,
    -

    o nly rays and still others a mixture of all three rays ;


    -

    indeed there are some of the substances which emit no rays


    at all .

    I n some instances these active substances have been actually


    se p arated by physic al or chemical means C ertain of the sub .

    stances are found to be gaseous ; others form a de p osit on


    solid bodies The gaseous substances c an be condensed by
    .

    co oling .

    The best way to characterize the various radio active sub -

    st ances is by the ex p onent K of the above equation ; this constant


    is to a large degree inde pendent of tem perature and pressure ;
    which is not true of ordinary reactions Frequently however .
    , ,
    IN O R G A N I C C HE M I S TR Y .

    use is made of another magnitude related to K viz , ,


    .
    , the peri o d
    of half decay If in the equation
    .

    we take

    we have the case where the intensity of the r adiation has decrease d
    to j ust half Solving for t we have
    .
    ,


    K K

    as the length of time necessary to reduce the intensity to half .

    I t is this magnitude t that often serves as a characteri z ing constant


    instead of K .

    A s a result of such observations and determinations a series


    of transformations O f radium has been worked out as given in ,

    the table on page 405 .

    Polonium as we see is brought into relationshi p with ra d ium


    , ,
    .

    The transformation of polonium into lead however is far fro m , ,

    being established .

    I n the other (parental ) direction ra d ium is relate d t o uran ium .

    Since the half decay period of radium is about 1 7 6 0 years and


    -

    the age of the solid earth crust is counted in millions of years


    ,
    -

    the radium in the earth would long since have disa ppeared if ,

    it had not steadily been r e formed It is now denitely estab -


    .

    l ish e d that uranium a substance much slower in its transforma


    ,

    tions is the p arent substance of radium O n e of the most sign i


    ,
    .

    c ant evidences oi this is that in the various uraniferous and


    radium bearing ores the ratio of uranium to radium is very
    -

    nearly the same I n order to prove this B O L T W O O D and ST RU T T


    .
    ,

    determined the uranium content of the ores by ordinary an alytical


    methods and the radium content by collecting the emanation
    evolved on dissolving the ores and me asuring its activity with
    an electrometer Since the decom position of uranium p ro ceeds
    .

    much more slowly than that of radium the constant relationshi p ,

    shows that the radium is formed from the uranium Indee d .


    ,
    4 06 I N O R GA N I C C HE M I S TR Y .

    p ower their
    ,
    effective limit in the air being less than 3 cm The .

    p ercentage relationshi p between ionium and radium in the


    di fferent ores is practically constant The most inte resting .

    ro
    p p erty of ionium is that it can p roduce radium .

    A s for radium and uranium so for thorium and actinium seri e s


    , ,

    of successive decom p osition products have been w orked out .

    V arious chemical
    C hem ical Ej ects of R a di oacti ve S u bs tan ces
    '

    reactions are brought about by the inuence of radio active


    substances A mo ng the many which have been observed we
    .

    m ay mention the conversion of oxygen into o zone and of yellow


    phos phorus into red phos phorus the decom p osition of iodic acid,

    an d the disso ciation of water into its elements A n aqueous .

    solution of a radium salt is constantly giving o ff slight amounts



    of detonating gas amounting to c mm d ay pe r gram of
    , p er . .

    radium .

    Furthermore these r ays have the pro perty of develo ping a


    ,

    strong color in different substances such as glass p orcelain , , ,

    and the alkali salts ; the same color can be p roduced by c athode
    r ays The skin is also attacked by these rays
    . .

    O ccu rr e R i S b
    n ce of a d oac ti ve u s t a n ces This is by no means .

    limited to thorium and uranium bearing minerals Indeed it -

    .
    ,

    has been shown that small quantities of radio active substances


    o ccur very extensively in n ature A charged electrosco pe .

    gradually loses its electrication in the air a phenomenon


    ,

    which is traceable chi e y to the ions in the air Se a w ater also .


    -

    contains slight traces of radio active substances ; so does th e


    ea rth pro per M any s prings that come from considerable de pths
    .

    are r ich in radium emanation in this r e s pc ct t he waters of


    ,

    G astein (A ustria ) and Y ellowstone Park are pa i t ic u l a i l y noted .

    R adioac ti vity of O ther E l em en ts The radioactive d ec ay of .

    actinium e m anation pro ceeds times faster than that of


    uraniu m The question at once arises whether there may not
    .

    be other substances with a rate of decay very much Slower than


    that of uranium We could then conclude that there is after
    .

    all no essential di fference between the radioactive and the othe r


    ,

    elements but that all of them suffer decay even though in most
    , ,

    cases the decay is so slow as to escap e observation To be sure .


    ,

    this is by no means proven but there are two reasons for such
    ,
    Z IN C . 4 07

    a hyp othesis I n the rst place it would ex plain why so many


    .
    ,

    p airs and grou p s of elements are found o ccurring togeth er in


    n ature : niobium and t antalum for instance ; selenium and ,

    tellurium the platinum metals ; the rare earths The two last
    , .

    mentioned are grou ps of elements whose pro perties are quite as


    closely allied as those of the decom p osition products of radio
    active elements Secondly a slight radioactivity has been detected
    .
    ,

    in potassium and rubidium .

    SO far as we know the radio active transformations are irre


    ,

    v e rs ib l e We can o n l y st an d by and look on ; we can neither


    '

    p roduce nor sto p them I f these changes should


    .
    p rove to be
    a general p ro perty of matter it would mean that all matter ,

    is engaged in slow dec ay I nasmuch as the transformation can


    .

    not be made to go backwards the inference could be drawn that ,

    the universe was constructed out of a primordial substance by


    some sort of a creative act .

    Z IN C .

    2 68 The mo st imp ort ant z inc mi nerals are cal a m in e


    .

    ( H 2 Zn 2 SiO 5 ) s m i th s
    ,
    o n i t e o r bl en de ( Zn S) and ,

    various o xides The p rinci p al lo c alities are Silesia E ngland


    .
    , ,

    B elgium Poland and more recently certain districts in the Unit ed


    , , ,

    St ates no tably so uthwestern M issouri


    ,
    To obtain the metal th e .

    o r e s are roaste d the gas (S0 2 ) from the sul phide o res is co n

    verte d into sul phu ric aci d yiel ding z inc o xide I n th e ol der .

    p rocesses this is mixe d with co al an d h eated forming carb o n ,

    monoxide and zinc The latter distils over and c ollects in


    .

    the receiver t ogether with a ne gray p owder zin c du s t This



    dust is a mixture of zinc oxide and zinc p owder and is
    , .

    frequently used in t h e lab oratory as a vigorous reducing


    agent .

    Th e m e t a l is bluish white and has a Specic gravi t y of


    -

    At ordinary tem eratures it is bri t tle b u t a t 1 00 1 5 0



    p ,

    it bec omes softer ; it can then be beaten in t o plates A t t h e same .

    t ime the s pecic gravity rises to 7 2 and the metal becomes rmer . .

    A t 2 00 it again bec omes brittle and can be easily pulverize d


    0
    It .

    melts at 4 1 8 and b oils at


    The m e t allic vap or has a Specic
    gravity of hence its molecular weight is

    Since the atomic weight as deduced from DUL O N G an d PE T IT S
    ,
    C HE M I S TR Y 268
    408 I N O R GA N I C

    law is,
    the molecule in the vaporous state can c ontain only
    an d
    0 n e atom The same is true of the related metals cadmium
    .

    mercury Zinc is permanent in the air since it becomes rmly


    .
    ,

    coated with a protective layer of oxide Zinc dust dec om p oses .

    '

    water When heated to boiling in the air the metal burns t e zino
    .

    xide roducing an intensely bright light It is dissolved very


    p
    .

    o ,

    asily by hydrochloric or sul huric acid wi t h the evolu t ion of


    e p
    hy d rogen ; it is an interesting fact however that when a piece O f
    , ,

    absolutel y pure zinc is placed in either of these acids no hydrogen


    is generated I f this piece of zinc is brought in c ontac t with a
    .

    latinum wir e effervesce nce begi ns at once not from the surfac e ,
    p ,

    FI G 6 5. . FI G 6 6 .

    of the z in c however but f rom that of the wire and zinc goes into
    , , ,

    solution Written in ions the process is


    .

    Zn + 2 H
    "
    Zn + 2 H

    formation of a lead tree


    an d its explanation is j ust the same as that given in 2 03 for t h e

    I n this case also the zinc drives
    .
    ,

    cations into the solu t ion with great force itse l f thus assuming a ,

    n egative charge with which hydrogen ions c an be discharged


    ,
    .

    The only difference seems to b e t ha t these hydrogen I ons discharge ,

    themselves at the platinum instead of at the zinc However this .


    ,

    difference is not real Since in the case of the lead tree the fresh
    ,

    p ortions of lead are de p o s i t ed on the outermost p arts of it T b e .

    p erfect analogy is made s t ill clearer by a somewha t modied form


    of the experimen t
    When on the one hand a plate of amalgamated zinc an d one
    , ,

    of platinum are connected by a metallic wire and dipped in dilute


    sul phuric acid (Fig 6 5) h y drogen is evolved fro m the platinum
    .

    p late and when on the other


    , hand a plate of amalgamated
    ,
    zinc
    and one of lead are similarly connected and di pped in a dilute sol n e

    tion of lead nitrate ( Fig 66) lead crystals are de posi t ed n o t on the
    .
    41 0 I N O R G A N I C C HEM I S TR Y . 27 0

    C ADM IUM .

    2 70 . C a dmium
    is very frequently found in zinc ores Being .

    m ore volatile than zinc it distils over rs t in the extraction of ,

    such ores I t is obtained pure by re peated distillation or by c on


    .

    v ersion into the sul phide which is insoluble in dilute acids an d ,

    can therefore be easily separated from zinc sul phide .

    C admium is a white rather soft metal ; Sp g ,


    m pt . .
    , .
    -
    .
    ,

    b pt . I t is u n affected by the air but burns on heat


    -
    .
    ,

    ing forming a brown cloud of oxide I t is difc u l t ly soluble in


    ,
    .

    dilute hydrochloric and sul phuric acids but readily soluble in ,

    dil ute nitric acid The cadmium molec u le in the gaseous stat e
    .

    c ontains only O n e atom .

    C adim u m oxi de GdO is obtaine d as state d above and also b y


    , ,

    heating the carbonate or hydroxide I t is an amorphous brown .

    p owder C adm iu m h ydr oxi de


    . C d ( O H) 2 is insoluble in c austic , ,

    p otash o r caustic soda b ut soluble in ammonia on acc ount of t he ,

    formation of a comp lex ion C admi u m c h l o r i de C dC l g crystallizes .


    , ,

    with two m olecules of water and unlike zinc chloride c an b e d rie d , ,

    without decomp osition C adm i um su l phi de C dS is characterize d .


    , ,

    by a b right yellow c olor ( it is used as a pigment) It is in s olub le .

    in aci d s The su lph at e , C dSO 4 usuall y crystallizes ou t o f its


    .
    ,

    aqueous solution as 3 C dSO 4 8H2 0 There is also a salt -


    .

    C dSO 4 7 HzO which is analogous in c omposition t o t h e s ul ha t es


    -
    ,
    p
    o f magnesium zinc iron etc , , , .

    MER C UR Y ( Q ui ck s il v e r) .

    2 71 . Mercury is the only metal that is liqui d


    n d er or d inary u

    c onditions I t occurs in nature in C in nabar Hg S and also na tiv e


    .
    , , .

    The chief localities are A l maden I n Spain I dria l n I llyria M exic o , , ,


    Peru C alifornia C hina and Ja pan
    , To obtain mercu ry fro m
    , .

    C innabar the latter is w ast e d in furnaces sul phur dioxide and ,

    mercury being formed The mercury va p o r i s c ondensed either .

    in large chambers or in p eculiarly sha ped earthen retorts o r ,

    p i p es
    , called a l u del s I t I S b r ought on t he market In 7 5 l b iro n
    .
    -
    .

    asks .
    M E R C UR Y . 41 1

    Th e c o mm er cial produ c t i s not pure contain ing more or l ess of other


    ,

    m etal s in so lut i on l ead copper Such im pur i t i es c an b e read il y


    , ,

    dete c ted by the fact that they m a k e t h e m erc ury adh ere to a gl ass v essel .

    A s u i tab l e process of puric at i on c ons i sts i n l ett i ng i t fall in ne dro p s


    through a l ong c o lum n of n i tric a ci d (sp g as in Fig 6 7 The. .
    , . .

    forei gn m etals are th us c o m pl etely di sso lv ed whi l e alm ost no m ercury is ,

    FI G . 67 PUR IFIC AT I O N
    '

    OF M E R C UR Y .

    lost by so l ut i on be c ause these fore i gn metal s prec i pi tate m erc u ry from


    ,

    i ts sal t solut i ons A fter bei n g washed wi th water t h e m etal is dried an d


    .
    ,

    i f absolute p uri ty i s des i red i t i s then d ist ill ed in vacuo Bu t a v ac uum


    , .

    d i stillati on of i tsel f i s insufci ent for so m e l ead goes o v er wi th i t


    , .

    Physica l Pr op er ties .
    -
    M ercury solidies at
    and boils
    at E ven at ordin ary tem p eratures it is somewhat volatile ,

    es pecially under redu ced pressure ; when gold l eaf is sus pended in
    a bottle over mercury for instance it eventually becomes white
    , , .
    4 12 I N O R GA N I C C H E M IS TR Y 27 1
    3

    The metal has a s pecic gravity of at The v ap or density


    is for H 1 ; hence the molecule weighs This number
    also re presents the atomic weight as has been found from molecula r ,

    weight determinations of many volatile mercury c om p ounds .

    A ma lgam s M any metals have the property of dissolving in


    .

    mercur y or forming c om p ounds with it These metal solutions


    or c om p ounds are cal led amalgams Besides by the direct .

    c ontact of the two metal s they can sometimes also be obtained

    b y allowing mercury to act on the solutions of metal salts e g


    '

    , .
    .

    s ilver amalgam can thus be pre p ared Some metals such as tin .
    , ,

    dissolve in mercury with he at absorption ; others like p otassium


    and sodium with great heat evolution and vigorous action I f a .

    great excess of mercury is used the amalgams are liquid other , ,

    wise solid Sodium amalgam is exceedingly rm when it c onta ins


    .

    more than three pe r cent of sodium . .

    O p in i o n s h ave b ee n d ivi de d as t o w h e t h er amalg am s an d m et allic allo ys ,

    in g e n e r al a re mixtur e s o r c o mp o u n ds
    , I n o r de r t o s o lve t h e q ue s t i o n a .

    s tudy h as b e e n m ade o f t h e fr e e zi n g
    p o i n t cur ve s ( of 2 3 7 ) o f d i ffere n t p a irs
    -
    .


    FI G . 68 T .
    YP IC A L FREE Z I N G P I NT
    O C UR VE S OF PA I R S or M E T A LS .

    of mt l e a s .
    l i f m ti n ft
    A dd fit i d ci iv
    on a tu e h b e e n
    n or a o , o en o a e s e na r ,
    as
    a ff d d b y t h
    or e e mic
    c p ic l xami ati n f t h e u f c f t h all y ft r
    ro s o a e n o o s r a e o e o a e
    h vi g b e e n t c h d w ith d ilut
    a n eci d d p li h d t h i divi dual c y t ls
    e e a an o s e e n r s a
    ,

    b e i g ge n
    n
    ll y di ti gui h ble i th i w y A a e ult f th e i v t ig
    era ,
    s n s a n s a . s r s o es n es a

    t io n i t h as b e n f un d th at t h e f e zi g po i t curve fo pairs f m t l
    s e o r e n -
    n s r o e a s

    ( b in ary al l oy ) m y b f t h e e di ffe e t t ype (Fig


    s a e o
    I me c a e t h r e
    r r n s .
    n so s s e
    1s no a ci ti
    ss o f th m t l
    a d t h cu v ( I ) t k
    on o
    the m f m
    e a s an t he e r e a es e sa e or as
    fre e z in g po i n t cu v
    -
    f lt lut i h vi r e o
    t ti a sa
    i t T thsos on . a ng a eu ec c n o n n o e r 9 .
    414 IN O R G A N I C C HE M I S TR Y . 27 2

    b uttur ns d ark in t h e t
    light on accoun of the se paration of metal

    lic mercur y A mmonia blackens it by forming a mixt u re o f


    .

    mercuric a mm oni um chloride N HzHgC l and nely d ivide d m er


    , ,

    2 Hg C l + 2 N H3 HZN Hg C l Hg + N H 4 C I .

    C alomel is frequently us ed as a medicament .

    The vapor dens i ty of c al om e l has been fo und to be


    whi c h c orres ponds to t h e m o le cul ar formul a Hg C l When cal o m el .

    e v aporates however a di sso ci at i on i nto HgCl2 and Hg oc curs ; these


    , ,

    p rod uc ts u n i te a ga i n on c oo li n g b u t they c an be
    , pre v io u s l y se parate d
    by di ffus i on I t i s for t h e abov e reason that the v apor dens i ty was fo und
    .

    to be half the am o unt c alculated for HgZClz ; hen c e the correct form ul a
    of c alo m el is n Clz .

    Here al so B A K ER n oted t h e inu en c e of tra c es of water ( cf pp 3 3 3 . .


    ,

    A cc ord ing to h i s i n vest i gat i ons thoro u gh ly dri ed m er c uro us


    chl or ide does not d i sso ci a t e on v ol at ilizing and gives a vapor dens i ty
    which c orresponds to t h e f ormul a n C l z.

    M e rc u r o u s b r o m i de and io di de are even less soluble than t h e


    chloride The solubility decreases as in the case of silve r with
    .
    , ,

    an increase in the atomic weight of the halogen .

    M e rc u r o u s n it rate , HgN 0 3 is formed when cold dilute nitri c


    ,

    acid acts on an excess of mercury It is hydrolyzed b y wate r .


    ,

    a yell ow basic sal t Hg 2 <


    gg 3
    being deposited . It ther efore
    dissolves without decom position only in dilute nitric acid Th e .

    mercurous ion is evidently only very feebly basic A solution .

    of mercurous nitrate is slowly oxidized by the oxygen of the air t o


    the mercuric salt b u t the addition of a little me r cury r econvert s
    ,

    it into the lower form .

    Me r cu ri c C o mpo un ds .

    2 73 . M e r cu r i c
    i de ,
    E g O is red and c rystallize d when pre
    ox ,

    pared by heating mercury or mercur y nitrate but yellow an d ,

    a mor phous when preci pitated from solutions by a hydroxide of

    potassium or sodium The difference between these f orms seems


    .

    to be due o nl y to a di fference in the coarseness of their grains .

    Mercuric oxide turns black on heating and red on cooling .

    M er c u ri c c h lori de Hg C l z corr os ive s u bl im at e is manufactur e d


    , , ,

    o n a large scale by heating a mixture of common salt and mercuri c


    M ER C UR I C C O M PO UN DS .
    4 15

    s ul phate ; it sublimes over whence its name A t room tempera , .

    ture 1 pa rt HgO l z dissolves in 1 5 parts Hg O It is more soluble .

    in alcohol The acid reaction of its aqueous solution indicates


    .

    hydrolytic dissociation ; if sodium chloride or potassium chloride


    is added to the liquid the reaction becomes neutral because of the
    ,

    formation of a d ouble sal t HgC l z KC l HzO This is more soluble - -


    .

    in water than sublimate itself .

    M e r c u ri c io di de , E g I g is yellow when it is rs t preci itated


    , p
    from the solution of a mercuric sal t by potassium iodide but it ,

    soon becomes red I f this modication is heated it passes ove r


    .
    ,

    into a yellow form at the o riginal red color returning on


    c oo l ing howeve r
    , There is evidently a transition p oint here
    .
    .

    A similar c hange of c o l or (red to brown) i s observed i n t h e doubl e


    sal t C u 1 2 Hg1 e ven at a rather l ow te m perat u re O n c oo lin g the
    , 2 2
    0

    2, .
    ,

    r e d c o l or pro m p t l y rea Th i s i s an e xc ellent e x ampl e of a sub


    ppears .

    stan c e whose m od ic at i ons i nter c hange quickly on passing the tran


    s it io n po i nt Us u ally t h e trans i t i on o ccu rs s l owly


    . .

    M ercur ic iodi d e d issolves readily in


    iodide solution potassiu m .

    N E s s L E R s s o l u t i o n a very valuable reagent in testing fo r


    ammonia is made by mi xing the above mercuric iodide solution
    ,

    with caustic p otash I t should be noted however that many .


    , ,

    organic nitrogen com pounds give much the same coloration as


    ammonia with N E s s L E R s solution .

    M e rc u ri c c yan i de , Hg ( C N ) 2 is obtained by boiling Prussian ,

    blue with mercuric oxide It crystallizes in n e large colorless


    .
    '

    crystals .

    2 74 The m ercuric halides in c ontrast to the other salts of the m er


    .
    ,

    c u ric i on are on l y s lig ht l y i oniz ed i n a qu eo u s so lu t i on


    ,
    For th i s reason .

    they e xh ib i t so m e peculi ar rea c tions O n mixing a m er curic so luti on .

    wi th o ne of a c hl ori de for i nstanc e c ons i derab le heat i s given o ff be c aus e


    , ,
    .

    undi sso ci ated Hg Cl2 m o le cules are formed while the mixt ure of so lu ,

    t i ons ordi narily obeys the l aw of ther m oneutrali ty 23 8 2 ) A ga i n , ,

    i f m er curic o xi de i s shaken wi th a sol ut i on of c hl ori de bromide or , ,

    iodi de of potass ium the liqui d be c o m es strongl y alkali ne be c ause of


    ,

    t h e li berat i on of potass ium hydroxi de Thi s i s due partly to the s li ght .

    i oniz at i on of the m er cury hali des and part ly to the c ombinat i on of


    the l atter with the ex cess of alkali ha li de to form very stable 3 1 k a l i .
    16 INO R GA NIC C HE M I S TR Y . 27 4

    me r c u r i c h a 1i d e s The stabi lity of these co m plex co m pounds



    in creases with ris i ng ato mic we i ght of the halogen The same c ause .

    e xplai ns the reverse fact viz that the hal ogen c o m po unds of m er cury
    , .
    ,

    are only wi th d i fculty de c o m posed by alkalies In order to pre cipi .

    tate all the m er cury fro m m er curic chloride a l arge e xcess of potass ium
    hydro xi de must b e e m pl oyed ; m er curi c iodi de an d m er cur i c c yani de
    cannot be de c o m posed by potass ium hydro xi de al one Mer curic cyani de .

    is so li ttle i oniz ed that i ts c onduc t ivi ty can hardly be m eas ured ; henc e .

    it does not give any of t h e ordinary mer cury rea c t i ons e xc ept the forma ,

    ti on of t h e s ulph i de (s in c e the latter i s so very i nso luble ) Thi s cyani de .

    c an be re garded as a type of c o m po u nds rendered inact i ve be c a use of

    non i oniz at i on
    -
    .

    Thi s l o w ioniz at i on also e xpla ins the form ation of m erc uri c c yani de
    a cc ording to the method m ent i oned above Wh en m er c uric ions and .

    cyanide i ons are bro u ght to gether even i n e xtremely dilu te so luti on
    , ,

    they must uni te to for m Hg (C N ) 2 m o le cules The uni on of these i ons .

    ne c ess i tates t h e sendi ng of m ore of the m i nto so lu t i on by the m er curi c


    o xi de an d Pruss i an b lue an d so t h e pro c ess goes on unt il the form at i on
    ,

    of m er cur ic c yani de an d ferric o xi de Fe20 3 i s c o m plete , ,


    .

    The m ercur i c hali des (espe c ially corros iv e subli m ate) are very strong
    anti se pt ics I t i s an i nterest ing fa c t that in thi s respect also they
    .
    ,

    be c o m e m ore e ffe c t ive as the i r i oniz ati on i ncreases The chl ori de i s a .

    m ore powerful antise pt ic than the cyanide The addi ti on of metal .

    chl ori des dimi ni shes t h e ioniz atio n of s ublimate and at the same t im e
    reduces i ts dis i nfe c t ing ability .

    The reason why t h e mer curic chlori de for u se in s ub lim ate tablets is
    ne verthe less mixed wi th a n e xc ess of c o mmon sa lt i s part ly that the s ub
    limate i s thus disso lved m ore rapi dly and also be c a use s uc h so lut i ons
    keep l onger than those of the pure s ublimate es pe ci ally when prepared ,

    w i th we ll water
    -
    .

    M e rcu ri c itr ate , Hg ( N 0 3 ) 2 forms basic salts ve ry r eadily ; on


    n
    ,

    diluting its solution in nitric acid with water there is de posited a


    com pound Hg ( N 0 3 ) 2 2 Hg O H2 0 which is converted into pur e
    - -

    mercuric oxide by boiling with water This shows that the bivalent .

    mercuric ion also is very feebly basic


    , .

    M e r c u ri c s u lph at e is n o t soluble l n water but 1 s converted by


    the latter into a basic salt I n the presence of much water the
    .

    yellow com po und HgSO 4 2 HgO is formed With the sul phates of
    , , .

    the alkalies it forms double salts e g HgSO 4 K2 S0 4 GHzO which ,


    . .
    ~
    ,
    41 8 IN O R G A N I C C HEM I S TR Y . 27 6

    E L EC T R O C H E MI ST R Y .

    2 76 As
    early as the beginning of the nineteenth century when
    .
    ,

    DA VY isola t ed the alkali me t als by means of the electr i c current


    2 2 3 and there was known to be an intimate relat i on
    b etween electrica l and chemical phenomena B ER ZE LI US even .

    went so far as to suppose that afnity co uld be perfectly explai ned


    by assuming tha t the atoms are e l ectrically charged and tha t these
    charges are the a t tractive or re pellent forces The galvanic elemen t
    .

    has been for a long time a familiar means of c onverting chemical


    energy into electrical energy However it was not until 1 889 tha t
    .
    ,

    a theoretical explanation of the connection between chemical and


    electrical phenomena was offered ; this explanation by N ERNST is
    not only a very satisfactory one but it also affords an insight into
    ,


    numerous chemical phenomena The key to the explanation is
    .


    the conce pt of electrolytic solution ten sion which has already ,

    been referred to in a few instances 203 and


    When a metal comes in c ontact with t h e aqueous solution of
    one of its salts a dif eren c e in po ten tial develops between the two .

    This phenomenon is explained by N ERN ST as follows : Jus t as


    a liquid continues to evaporate at its surface unt il t h e pressure of
    the vapor becomes equal to the vap or tension of the liquid so a ,

    sal t must c ontinue to dissolve in water (evaporation and solution


    being an alogous processes ) until the osmotic pressure of its solu
    tion balances the solution tension of the salt N ow acc ording to .
    ,

    N ERN ST every metal also has a certain tendency de pendent only


    , ,

    on its chemical nature to force its atoms into solution as ions


    , .

    This force c alled the e l ec trolyti c s ol u tio n t en sio n , c omes into action
    ,

    when the metal is immersed in an electrolyte and its strength is the


    less the more cations of the metal are already in the solution The
    , .

    amount of cations sent into the solution is very small as e x peri ,


    so
    ment shows much so that it cannot be determined by the
    ,

    u sual chemical means The cause of this is not tha t the solution
    .


    tension is low o n t h e c o n t r ary the latter is often very large
    , ,

    b u t that an equi l ibrium is very soon reached because n o t w it h


    , ,

    standi n g the low concentration of the ions they carry a very ,

    high electrical charge and the n egatively charged metal soon


    attracts its p ositiv e ions in the solution with such force that just
    as many ions are preci p itated on the metal as are sent out into the
    solution If P re presents the solution tension of a metal and p
    .
    E L E C TR O C HE M I S T R Y . 41 9

    th e osmotic pressure of the cations in the solution there are three ,

    p ossibilities to b e d istinguished :
    ( 1 ) P > p The metal then behaves like a sal t in c ontact
    .

    with its own unsaturated solution I t forces cations into the solu .

    tion of the electrolyte so that the solution bec omes p ositively


    ,

    charged and the metal has to t ake on a negative charge An .

    equilibrium is soon established However if the free p osi t ive and .


    ,

    negative electrici t ies acq u ired by the el ectrolyte and the metal are
    c onducted a w ay by a c onnecting wire the metal will again send
    cations into the solution and this action will c on t inue t ill p reaches
    ,

    the value of P .

    P == There can be no p otential diff erence


    ( )
    2 p . .

    ( )
    3 P < p In
    . this case the metal c orres p onds to a sal t intro
    du ce d into its supersaturated solution C ations are n o w de p osited .

    on the metal and charge it posi t ively the el e c t r ol y t e b e c om in g ,


    negative Here also a state of equilibrium must soon arise since


    .

    the negatively charged electrolyte tends in turn to draw the posi


    tive metal io ns b ack into solution

    The relation be t ween the p otential d ifference E an d the mag


    n it u des P an d p is ex presse d by N ERN ST with t he equation
    , _

    P

    ( 1)
    5
    :
    n

    in which R is the gas c onstant T the ab solu te t em pera t ur e n the , ,

    valence of the metal ions and log the natur al logarithm , .

    I f for R in this equatio n the v alue is substituted which was


    calcul ate d in 3 4 E is not obtained in volts since electrical magni
    , ,

    tudes are meas ured in other un its than those there em ployed In .

    this case we mus t introduce for R the value If



    BR I G G s logarithms are to be used the modulus mus t also ,

    be included The value of E in vol t s then bec omes :


    .

    0 86 0 X 1 0
    .
    4
    X 2 3 02 5T
    . log 5
    P
    n

    1 log 5
    1
    2
    E = 10 4

    -
    .
    .

    n I7
    F rom this equati on it is seen that E increases arithmeti cally when
    p decreases ge omet rically For exam p le if the i oni
    . c c oncentration ,

    is reduced t o one tenth -

    , E only increases by zx
    g
    volt . It is
    n
    420 I N O R GA N I C C HE M I S TR Y

    changes in the c oncentration of the electrolyte even though they ,

    be quite large .

    O n bringing together two differen t metals an d their sal t solu


    tions an elemen t or cell of t h e DANI E LL t ype is obtained ( c o pper
    , ,

    in C o pper sul phate and zinc in zinc sul phate the two p airs sep arate d ,

    by a p orous p ar t ition) The electromo t ive force of such a cell is


    .

    found from the difference of the two values of E i e ,


    . .

    P1
    17
    21

    when both metals have the val ence n .

    suc h a c e ll wi th closed cir cui t there are di fference s of potential not


    In
    only between meta l and so luti on bu t a lso between the two liquids a nd
    between t h e two m eta ls Ex per ien c e has sho wn howe ver that both
    .
    , ,

    of the latter are v ery s m all i n c o m pari so n to the form er so that they ,

    m ay be d is regarde d .

    L eaving t h e s ol u t io n t e nsion s P1
    of c onsideration an d P2 ou t ,

    E therefore de pends on the values of the osmotic pressure p l an d


    p2 of the metal ions I f p g can-
    be made extremely
    . small so that ,

    P3
    l oge < log E becomes n e g at 1 v e , 1 e the current m us t alte r
    F
    e , . .

    1 9
    22
    it s direction This can be demonstrated as follows
    .

    In a DAN I E LL cell in which the osmotic pressure of the zinc


    ,

    ions (pl ) is seldom very di fferent from that of the c o pper ions
    ( pg) the curren t goes from the c opper through the c onnecting
    ,

    wire to the zinc for the solution tension (P1 ) of the zinc is much
    ,

    larger than tha t ( P2 ) of the co pper (see below) ; N o w the c on


    centra t ion of the c o pper ions can be made several p owers cf ten
    smaller by adding p otass ium cyanide to the c o pper sulphate solu
    tion for by this means the very slightly ionized c omplex (C U2 0Y4 )
    ,

    is formed This addition actually reverses the dire cti on of


    the current N either the pre ci pitati on of the co pper b y pot assium
    .

    hydroxide nor the preci pitation by ammonium sul phide reduces the
    concent ratio n o f the co pper ions enough to produce this e ffect .

    Since equation ( 2) can al so b e written

    and when 192 p l the last ex pression bec omes zero it is a arent
    , ,
    pp ,

    that the elect romotive force of a DAN I E LL cell is mainly determined


    42 2 I N O R GA N I C C HE M I S TR Y . l 27 6

    with lead peroxide ( positive) and lead sul ph ate ( ne gat ive ) .

    The positive plates are al l c onne cted with each other as are ,

    also the negative ones (From a large num b er o f such cell s


    .

    a battery is c onstructed by c onnecting the positi v e p ole o f


    each cell with the ne gati v e p ole of the adj oining one ) If .

    a current is p assed through the system so that it enters at t h e


    lead peroxide plate and goes through the sulphuric acid to t h e
    other plate lead peroxide c ollects on the p ositive pla t e whil e on
    ,
    ,

    the other the cathode plate the lead sulphate is c onverted int o
    , ,

    s pongy lead By th is process the accumula t or is charged There


    .
    .

    u p on if the p oles are c onnec t ed (by a wire) the O pp osi t e process


    , ,

    goes on ; the lead peroxide is reduced at the one plate and t h e


    s pongy lead is c onverted into lead sul phate at the other During .

    the discharge the p eroxide plate is again p ositive the lead plat e ,

    negative The chemic al process in the accumulator cell is ther e


    .

    fore expressed by
    Ph O z Pb 2H280 414 > 2 Pb 80 4 2 H2 0 .

    The generation of the current has been explaine d in variou s


    ways O n e is as follows : The lead peroxide on the anode plate has

    a certain solution tension and hence goes into solution as nega


    ,


    t iv e l y charged Pb O z ions Thereby it of c ourse imp arts to the
    .

    late i t l f a numerically equivalent ositive charge These


    p p
    "
    s e _ .


    bivalent Pb O z ions encounter positively charged Pb ions at t h e
    cathode plate which are being sent by it into the solution ; the
    ,

    cathode plate charges itself negatively at the same time The t w o .

    sorts of ions now c ombine to form electrically neutral Pb O mole


    ,

    Ph O z "
    cules which yield lead sulphate with t h e s ul phuric aci d presen t :
    Pb 2 Pb O ; 2 Pb O 2H2 SO 4 2 Ph SO 4 + 2H20 .

    A mong r e v e r s i b l e cells are t h e B UN S EN an d


    the n o n -

    the L E C L A N C HF} A reverse current does not restor e these t o


    . .

    their original condition and their electromotive forces E c annot b e


    calculated by the above formula ; nevertheless t h e general prin
    c ipl es of the p ressure theory can be a lied to ex lain t h e r d uc
    pp p p o

    tion of the galvanic current in these cells .

    The arrangement of the B UN S EN cell an amalgamate d zinc


    plate di pp ed in sul phuric acid and a carbon cylinder in nitric o r

    chr omic acid is well known From an electrochemical stan d .
    E L E C TR O C HE M I S TR Y . 4 23

    p oin t t h e genera t ion o f hy d rogen from z in c an d sul hur ic aci d


    p
    amounts to a transfer of the charges of the hyd r ogen ions of t h e
    dilute acid to the zinc atoms and an escape of hydrogen in t h e
    form of d ischarged molecules I n the B UN S EN ce l l however
    .
    , ,

    mos t of the hydrogen ions nd an O pp ortunity to give u p thei r


    p ositiv e charges to the carbon cyl in der and exerc ise a reducing

    action on the nitric or chromic aci d O n the other hand the zinc
    .

    p late sends p ositively charged z inc ions into the solution to the
    same exten t as hydrogen ions d isappear the zinc plate itself ,

    a cquirin g a negative charge .

    The L E C LA N C HE cell c onsists of a zinc b ar in concentrate d


    ammonium chl oride solution an d a porou s earthenware cylinder
    immersed in the same solution and containing some manganese
    p eroxide an d a stick of carbon for c onducting off the curren t .

    Here again the z inc goes into solution


    ZII 2 N H4 C l ZIl C l z 2 N H3 H2 .

    The hy d rogen ions discharge themselves at the carbon an d reduce


    t h e p eroxide . I n this c ase also the carb on is t h e positive the zinc ,

    the negative p ole


    ,
    .

    277. Just as in galvanic cells chemical energy is transforme d


    into electric al energy so reactions between ions in general c an
    ,

    p roduce an electric curren t if the c ondition s are suitable A .

    few exam ples of this may b e


    ci t e d .

    For these experiments a cell


    d evise d b y LiiPK E is very s at isfac
    t ory (Fig . I t c onsists of
    t w o glass vessels Z1 an d Z2 to the ,

    b ottoms of which the platinum


    electro d es k l an d k g are attache d .

    The vessels are connected by


    means of the wi d e siphon H .

    The wires A an d K lea d to a gal


    v an os c O pe .T o show tha t elec
    t r ic al energy can be obtaine d by
    t he oxidation of the stannous to
    FI G 7 0 L t rPx E C E LL
    . . .

    t he stannic ch l o n de an ac idu
    lated sta nnous chloride solution : 1 00) is introduced into Zl

    4 I N O R G A N IC C HE M I S TR Y cr7u .

    an d an ci d ul at e d n ormal s od ium chlori d e s olu tion in t o Zz ; t h e


    a

    si phon also is lled with the la t ter solution A s soon as a few d r o ps


    .
    ,

    of chlor in e water or a solution of auric or mercuric chloride ar e


    -

    allowed t o fall from a pip e t te u pon the electrode (k g ) in the sal t

    solution the galvanosco p e indicates a curren t in the wire circui t


    from K to A
    ,
    "
    N ow in order t ha t the bi v alen t ion Sn may bec om e
    .
    ,

    quadrivalen t it mus t acquire t w o more p ositive charges an d


    this requir es t h e addition of two chlorine ions These are at onc e .

    su pplied by the mercuric or auric chloride The metal li c ions .

    H
    ( g or

    are d e p osited on k g and im p art to the latter a p osi


    tive charge which if conducted by means of the wire circuit
    , ,

    K is at the dis posal of the Sn ions I f free chlorine is added it


    .
    , ,

    Splits u p into ions as a resul t of which p osi t ive electricity is im parted


    ,

    to k g and this flows through t h e wire c ircui t back to k l and raises


    the p otential of the Sn ions .

    The fac t that electrical energy can be obtained b y the neutra l


    izat io n of sul phuric acid is ca p able of demonstration w i t h the
    same a pparatus To this end a normal sulphuric acid is intro
    .
    -

    du c e d into Z2 and a normal p otassium sul phate solution into Z1


    and the si phon I f a large piece of pa l ladium foil ( about 4 sq cm )
    . . .

    that has been saturated electro lytically with hydrogen is placed


    on the platinum disk of the electrode k l and touched for a few
    moments with a stick of caustic potash bubbles of hydrogen ,

    will rise from the platinum plate of the other electrode kg and
    the needle of the galvanosco pe will indicate the passage o f a power
    ful current outward from kg The hydrogen of the palladium .

    foil sends positive ions into the solution which however forth , , ,

    with unite with the O H ions of the potassium hydroxide to form


    -

    neutral water By the emission of these positive ions k l acquires


    .

    a negative potential which flows o u t through the external circui t


    ,

    to kg The hydrogen ions of the sul phuric acid surrounding this


    .

    electrode are thus a fforded an o pportunity of discharging them


    selves against this negative charge so that hydrogen is given o ff in
    the free state .

    I n the combination of chlorine


    ( or oxygen ) and hydrogen
    chemical energy can also be transformed into electricity To .

    accom plish this two tubes sealed at the t o p and tted there with
    ,

    platinum electrodes reaching almost to the o pen end of the tubes


    ,
    ,

    are lled one with hydrogen and the other with chlorine (oxygen)
    ,
    6 IN O R G A N I C C HE M I S TR Y . 27 7

    can b e d one as follows : In the b ottom of each of the cylind e rs


    A and B ( Fig 7 1)
    .
    there is a little mercury A p latinum wire is .

    fused into each cylinder and the two are c onnected by means of a
    metallic wire O n t op of the mercury is some insoluble mercurous
    .

    sul phate ; ab ove this in A is a p aste of N azSO 4 1 0HzO and water , o

    in B 1s a snn il ar mixture of water and N azSO 4 B elow the transi .

    tion p oint the solution in B is


    in the un stable condition an d
    more concentrated than that
    in A which is stable The ,
    .

    result is that sodium ions dif


    fuse through the si phon from
    the c oncent rate d t o the dilute
    solution w hile at the same ,

    t ime an equivalent am ount of


    SO 4 ions in B c ombines with
    -

    part of the mer c u ry to form


    mercurous sul phate the nega ,

    tive charge of the sul phate


    ions b eing t ransferre d to the
    FI G 7 1 . .
    remainin g mercury Thus an .

    electric current is produce d


    which passes through the wire circuit from the d ilute to the c on
    c e n t rat e d solution I t s direction and intensity can be d etermin ed
    .

    by inserting a galvano meter in the c ircuit .

    N ow supp ose tha t the whole apparatus is gra d ually warme d ;


    ,

    the c oncentrations in A and B will approach each other as t h e


    temperature nears the transition p oint and at this p oint they will
    become equal The intensity of the current will therefore decrease
    .

    steadily till the transition p oint is reached when it is zero I f , .

    the tem perature is raised still higher the solution in A will become ,

    u nstable and more concentrated than that in B which latter will ,

    t hen be the stab le solution ; as a result the dir e c t iox o f t h e cu rr ent .

    will be reversed I n this way it is po ssible t o de t e rmine t h e


    .

    transition p oint very accurately .

    2 7 8 A s was remarked in
    . 2 7 6 the electromotive fo c e which
    ,
    r

    can be obtained from chemical reactions depends in large m asure e

    o n the solution tensions of the metals A knowledge of the latter


    .
    EL E C TR O C HE M I S TR Y . 427

    is therefore of very gr eat imp ortance I t b e acquired with


    '

    . c an

    the aid of the equation previously given


    P
    n p
    E, the difference of potential between a metal an d the aqueous
    solution of one of its salts can be measured Al l the other quan
    '
    .

    tities of this equation are known with the exce ption of P which ,

    can therefore be calculated as is illustrated in t h e fo l l o w ing ex


    ,

    ample :
    The potential difference between magnesi um and the no rmal
    solution mole pe r liter ) of its sul phate was determined to b e
    volts The equatio n thus becomes
    .

    P
    1 22 = 1 0 4
    T log

    P
    since fo r magnesium n = 2 p is the osmotic pressure of the Mg
    .

    ions O n the assum ption that the sal t is entirely Split u p into ions
    .
    ,

    p is A t m for
    . osmotic p
    ,
    ressure being equal to gas p ressure 1 ,

    mole gas at 0 and 7 60 mm o ccupies a volume of . liters 3 4 )


    h ence if the volume is a lit er t h e pressure becomes At m

    .
    , ,

    Therefore at 0 we have
    ,

    X 2 7 3 (l o g P log 22
    or log P whence we have a pproximately , ,

    P 10
    = 43
    .

    The following brief table indicates some of the results fo r d iffer en t


    m e tals :

    M e t al .

    N ick e l
    Hydro g en .

    C o ppe r
    M
    di ffers in differen t substances For magnesium and zinc it is
    .

    many millions of atmos pheres for co pper mercury ( ous ) and , ,

    s ilver extremely small fractions of an atmos phere D es pite the .

    com paratively large errors in the above data due to the difficulty ,

    of deter mining the potential difference between the metal and its
    s al t solution the o r d e r of the decimal ex p ressing the value of P
    ,

    can be acce pted as reliable in each instance .

    i l b m t l s a n d th eir
    S om e of th e s e d iffe r e n ce s of p o te n t a e t w ee n e a

    no r m a l s a l t s ol u t io n s are as follows :

    M e t al .

    The algebraic sign of these di fferences of potential can b e


    directly determined from the solution tensions The electrolyte .

    in which zinc is i m mersed mus t assume a positive po tenti al and


    the metal itself a negative potential because no zinc solution can ,

    be concentrated enough to hinde r the emission of ( positive ) zinc


    ions by the metal O n the other hand co pper must become posi
    .
    ,

    tive in res pect to a co pper solution for even in the mos t dilute ,

    s olutions the osmotic pressure o f the co pper ions is greater than

    t h e solution tension of the metal .

    2 79 A knowledge of the electrochemical series of the metals


    .

    in electrolytes is of great practical value Wherever combinations .

    o f various metals alloys metallic crustations etc are ex posed to


    , , ,
    .
    ,

    a tmos pheric action there is an o pportunity to form cells of short

    circuit I n general the m etal with the greatest solution tension


    .
    ,

    goes into solution and the other remains intact A piece of gal .

    v an iz e d ( zinc plat ed ) iron wire does not r u s t


    '

    e v e n in those places
    -

    where the plate has been worn o ff as much as if it were n o t zinc ,


    43 0 IN O R G A N I C C HE M IS TR Y .
    M 2 80

    when E h as b ecom e l arge enough t o separa te ou t o n e of t h e va ri e


    t ies of cations and one of the varieties o f anions present .

    This is the basis of a method of utilizing various elect romotive


    forces to effect an e le c trolyti c s epa r atio n of m etal s I t is not t h e
    .

    current strength which is of primary im portance to the electrolytic


    p rocess ( as was formerly su pp osed ) but
    ,
    the di ff erence of p otential
    between the electrodes A very successful exam ple of this method
    .

    is the se paration of co pper from zinc With a current of low


    .

    voltage it is possible to preci pitate onl y the co pper from a solution


    containing i o ns of both metals ; if the electromotive forc e is in
    creased zinc also is se parated
    ,
    .

    In many cases the ions of the wate r are mo re easily se parat ed


    o u t than those of the dissolved electrolyte In the electrolysis of
    .

    p otassium hydroxide ,
    for exam ple O,
    H ions-
    are liberated a t t h e

    anode ( they are at once decom posed however into water and
    , ,

    o xygen ) ; at the cathode it is not potassium ions but hydrogen


    ions ( in s pite of their extremely small concentration ) whi ch are
    d ischarged since the solution tension of hydrogen is much l es s
    ,

    than that of potassium .

    2 81 Th e d isso ciation tensio ns E for various ions are give n


    .

    b elow The gures are based on equivalent normal solutions


    . .

    The disso ciation tension of hydrogen is xed at ze ro i n t h e


    table I nasmuch as there is always an anode and a cathode
    . .

    it is possible to subtract from all the values of E1 an arbitrary b u t


    constant amount and add it to the values of E 2 without affecting ,


    Th e symbol O represents a secondary ionizatio n
    p roduct of the hydroxyl ion

    th eexistence of which according to N ERNST we are o bl iged


    , , to
    assume al t hough o nl y to an extremely small degre e
    , .

    D I S S O CI A T I O N T EN S I O N S
    .
    E LE C TR O C HE M I S TR Y . 43 1

    These gures lea d us t o im p o rt ant res ul ts In the rst plac e .

    they enable us to know at once the disso ciation te ns ion of any


    combination of ions Zinc bromide for instance wil l require
    .
    , ,

    volts for its electrolysis ; when the coneen


    t rat io n of th e ions is normal th e electrolysis of hydro chloric acid
    ,

    will require volts and so on I t is also obvious


    , .

    that it must be easy to se parat e silve r from co pper electrolytically ,

    since the di fference of th eir disso ciation tensio ns is almost volt .

    It also a ppears theo retically possible to se parate electrolytical ly


    iodine from bromine and bromine from chlorine .

    The o rde r of th e metals in the above electro chemical seri es is


    t he same as that in whi ch one metal is preci pitated from its solu
    tion by the succeeding o nes A s soon as a trace of the dissolved
    .

    metal is deposited o n the other one the two metals form with t h e ,

    liquid an element which electrolyzes the surrounding solution


    , .

    Th e fo rmula
    7 P
    1
    g
    = 4
    E 10 T
    ' '

    -
    '

    log
    n P

    t ells us ,howeve r that the values of E d epen d not only on the


    ,

    s olution tensio n but also on the osmotic pressure of the cations .

    Very decided changes in the concentration of the salt solution


    would make the order of the metals a different one For i ns tance .
    ,

    it woul d be possible to conceive a case in whi ch lead would not b e


    p reci p itated by cadmi u m .

    Th e electrochemical series of the anions also b rings out im


    p o rtant relations
    . B romine mus t quickly liberate iodine from
    io dide solutio ns and chlorine quickly liberate b romine from bromide
    solutions because of the marked di fference in their disso ciatio n
    tensions We see further that chlorine must be able to generate
    .
    , ,

    oxygen in acid solutions but n o t so with bromine or iodine It is


    , .

    also known however that the generation of oxygen by chlo rine


    , ,

    p ro ceeds with extreme slowness in shar p contrast to


    ,
    the r a p idity
    with whi ch chlo rine deprives b romine of it s negat ive charge

    012 ZBI Bl g
    ' ,

    This is not su rprising in the light of the above consid e ratio ns for ,

    the chlorine in order to enter the ionic condition mus t m ake use
    , ,

    Of the ion O of which there is only an extremely small amount
    2 IN O R G A N I C C HE M I S TR Y . 281 g

    present The hydroxyl


    . ion O H which is presen t in r elatively
    ,

    much larger amount and whi ch after the loss of its negative
    charge would also yield a quantity of oxygen equal to that of the
    chlorine holds its charge more than
    ,
    volt rmer than the
    chlorine ion in acid solution .

    The a pplication of electrolysis to commercial pro cesses is


    referred to in connection with the substances concerned (cf .

    2 2 3 226 242
    ,
    2 4 8 and elsewhere )
    , , ,
    .

    BO R O N .

    2 82 . This element o ccurs in nature as sass olite, H3 BO 3 bor acite,


    ,

    Mg7 C l zB l O 3 0 c ol em a n it e, 0&2 B6 0 1 1 5H2 0 , and borax , N a g B4 O 7


    ,

    l OHz O . I t can be obtained in the elemental state by the re


    duction of boric anhydride B2 0 3 or borax by means of magne , ,

    sium p owder I t is pre pared pure by subj ecting a mixtu re o f


    .

    boron chloride and hydrogen to an arc discharge between two


    boron or watercooled co pper electrodes or b ri n gm g the mixture ,

    in contact with an electrically heated graphite tube The .

    element melts between 2 000 and but has such a high vapor

    tensio n that it sublimes rather easily as low as Its


    hardness (exceeded only by diamond ) combined with its amor ,

    p hons structure constitutes a valuable


    ,
    mechanical characteristic .

    The electrical resistance decreases with rising tem perature at


    remarkable rapidity .

    I t dissolves in molten aluminium and on cooling the melt the , ,

    comp ound A1B 1 2 crystalli z es out B oron takes re in fl uorine and .

    chlorine uniting with them directly When ignited in the air


    , .

    it burns to the oxide B 2 0 3 A t a very high tem perature it com


    .

    bines with nitrogen to form boron n itride B N I t reduces many , .

    com pounds such as C u O and Pb O and decom poses water at


    , ,


    r e d heat Heating with nitric and sul phuric acid converts it
    .

    into boric acid I t is also attacke d by boiling caustic alkalies


    .

    (like aluminium

    2B 2 KO H 2 H2 0 2 KB O z 3 H2 .

    B oro n h ydri de When


    boric anhydride is reduced with an
    .

    excess of magnesium powder magn esiu m boride Mg3 B 2 is forme d , , , .


    34 IN O R GA N I C C HE M I S TR Y .

    long a t lead en pan which is warme d b y o ther


    to ab o ut 50 60
    , ,

    soion i A t this temp erature t h e bori c acid v olatilizes but very


    .

    little with steam and when the c oncentration has bec ome grea t
    enough it crys t allizes out I t is p uried by c onver t ing it int o .

    borax which is recrystallized and then dec omp osed by hydrochloric


    ,

    acid se t ting free boric acid


    ,
    .

    C onsiderable b oric acid is also made by de c o mposing n ativ e


    b orates wit h a str ong mineral acid .

    The vo lat ility of bori c a c id with steam has for a long t im e been
    re garded as an es pec i a ll y i nterest i ng pheno m enon be c a u se the an h y ,

    dride EZO 3 i nto whic h i t i s readily c onv erted at an e l e v ated te m pera


    ,

    t ure i s only vo lat iliz ed wi th e xtrem e di fcul ty The quest i on there


    ,
    .

    fore ar i ses as to the part icular c o m po und i n which boric a ci d exists


    in so lut i on a nd the o ne in which i t escapes fro m so lu tion .

    The r st po i nt c an be settled by a determi nat i on of the boil ing


    p o i nt e l e v at i on or va por tens i on l ower i ng of bor ic
    -
    a ci d so lu t i ons M eas .

    u rem e n t s of th i s sort hav e shown that H3 BO 3 m o l e cul es e xi st in d ilu te

    so lut i on As the so lut i on be c o mes m ore c on centrated the vapor tens i on


    .
    -

    lower i ng no longer c orresponds to thi s formula ; the decrease in the


    l oweri ng i ndic ates that the number of m o le cules of disso lved s ubstan c e
    has grown less i e so me s uc h change as 4 H3 BO 3 = H2B40 7 + 5H20 h as
    , . .

    o c curred ;
    If H3 BO 3 m olec ul es vo l at il i z e wi th the water the con c entrations of ,

    bori c a ci d in the so lu t i on an d i n the vapor mu st a cc ording to HE NRY s


    ,

    l aw m aintain a constant rat i o independent of the am o unt of bori c


    , ,

    a ci d present This was fo und to be tru e for d ilu te so lu ti o ns but not


    .

    for c on c entrated ones whic h is in agreem ent wi th the e x perim ents on


    ,

    v a por tens i on l ower i ng be c a u se there a l so the c on c entrat i on of the acid


    -

    in the vapor r r 0 po r t io n al to its con c entration in the so l ution


    '

    I t i s t h e r e fo rated that the co m pound whi ch es c apes with


    the steam is H3 BO 3 .

    Boric ac id crystallizes in lustrous laminae which feel gr easy an d ,

    are difficultly soluble in c old water ( ab out 3 % at o rdinary tem


    t r e s) This solution acts as a weak a tise tic f which
    p e r a u n
    '

    .
    p or ,

    ur
    p p ose it is frequently used A t 1 00 b oric acid loses 1 molecule .

    Hg O p assing over into m e t ab o r i c ac i d, HBO z A t 1 4 0 tet rab o ric


    , .

    ac i d, 11 2 3 4 0 7 is forme d the s od ium s al t of ,

    which is b orax .

    N o salts of t he normal b oric aci d B (O H) 3 are k n own, but , ,


    BO R O N . 43 5

    meta bo ric aci d forms several They are un s t a b le and are c onve rt ed
    .

    b y c arb on d i oxide in t o salts of te t raboric acid :


    4 N aB0 2
    l 00 2
    '
    N 3 2 B 4 O 7 + N ac 3 .

    Th e b es t known sal t
    -
    b oric acid is b o rax , N agB4 O 7 1 2 HQ O
    of -
    ,

    o ften called t in k a l A t presen t mos t of the b orax on the marke t


    .

    is made by b oiling col eman ite C a2 B6 0 1 1 5H2 0 found in C alifornia


    ,
    '

    , ,

    or a similar b orate occur rin g in C hile with soda Borax swells


    , , .

    greatly on heatin g ; this is due to the escape of water of cryst alliz a


    tion from the semi molten salt O n c ont inue d heating it forms a
    -
    .

    vitreous mass This glass has the pro perty o f dissolvin g met allic
    .

    o xi d es some o f which give double borates of a characteristic c olor ;


    ,

    hence its use in qualitative analysis The same property makes .

    it valuable in s o l d e r i n g sold e r adheres o nl y to the untar


    n ish e d metal so a little borax is p lace d on the surface of the m etal
    ,

    an d heated with the soldering iron in or d er to remove the r us t -


    .

    Th e d issolvin g of metallic oxides is easil y u nderstood when we ,

    wr it e N agB 4 O 7 as 2 N aBO z + BzO 3 ; it is the boric oxide 13 2 0 3 , ,

    which c an be regar d e d as combining with the metal l ic oxi d es t o


    form sal t s .

    Boric aci d is a weak acid ; its salts ar e therefore hy d rolyze d



    quite p ercep tibly more so of c ourse as the dilution increases
    , , .

    This can b e illustrated by a s im ple exp erime n t devised m any years


    ago by R O S E T o a c oncentrated solution of b orax some litmus
    .

    is a d de d an d then acetic acid u nt il th e li t m u s is j u s t red ; if the


    l iquid is then diluted it turns blue because the alkali is set free
    ,

    and b oric aci d has scarcely an y e ffect on litmus .

    R ather interes ting also is the behavior of silver b orate which


    , , ,

    is d e posite d as a white salt on mixi n g concentrated solutio ns of


    b orax and silve r n itrate When dilute solutions are mixe d how
    .
    ,

    e ver
    ,
    a p reci pitate of g r ayish brown silver o xide is forme
    -
    d t h e ,

    s ilver borate b eing almost com p letely hy dr olyz e d in the dilut e

    s olutio n .

    O n treati n g a mixture of b ori c acid and so dium peroxi de


    with water a per b orat e is forme d and cryst als of the c om p osi ~

    t io n N aB 0 3 4 H2 0 se p arat e out They are stable when solid


    "
    '
    .

    b ut liberate oxygen fro m a warm solution The solutio n c on .

    t ains hy drogen peroxide also .


    43 6 I N O R G A N I C C HE M I S TR Y . 2 84

    AL UM IN I UM .

    2 84 This metal do es not o ccur native but in c omb inatio n it


    .
    ,

    is found in large quantities an d very widely di ffused C oru n du m .


    ,

    including the precious stones sapph ir e and orien ta l r u by and t h e


    n atural abrasive em ery ( all noted for their hardness ) consists of ,

    alumina A l g colored by traces of other oxides Bau xite is a


    ,
    . .

    hydrate of aluminium and iron C lay and ka olin ( C hina clay ) are .

    p rinci p ally aluminium silicate M any other minerals such


    . as ,

    f p
    elds a r m i
    ,
    ca etc contain it,
    as a base
    .
    ,
    A peculiar aluminiu m .

    mineral cryol ite or ice s ton e 3 N aF A 1F3 is found in G reenland


    , ,
    -

    ,
    .

    The m e t a l can be obtained from the chloride by reduction


    with sodium but at present it is produced exclusively by de co m

    p osing aluminiu m oxide with the electric current .

    The most im portant commercial process is that of H A LL


    ( invented inde pendently in Euro pe by H ER O U LT) A lumina is .

    d issolved in a fused bath consisting of cryolite or an equivalent


    mixture The process is carried out in a large carbon lined po t
    .
    -

    the inner surface of which constitutes the cathode C arbon rods .

    immersed in the bath serve as anodes Fresh alumina is added .

    from time to time an d the metal is drawn 0 3 at the botto m


    periodically The tem perature is a little above the melting point
    . -

    of cryolite A current of several thousand am peres and less than


    .

    8 volts maintains the liquidity of the bath as well as e ffects the


    electrolysis .

    The increase d out put due to im prove d methods has brought


    the price of the metal down from over $90 per pound m 1 856 t o
    about $0 20 at the present time and the production 1s steadily
    .
    ,

    increasing 000 lbs in .

    A luminium is a sil v e ry white metal of low s ecific gravity


    p
    -

    I t is rigid but very ductile and malleable I t softens .

    at about melts at and boils at about


    I t is permanent in the air since it soon becomes co ated w ith a
    ,

    rm thin layer of oxide Small fragments burn with a bright .

    light when heated in an oxygen atmos phere I t is not attacked .

    by dilute nitric acid at ordinary tem p eratures and only slightly so


    by dilute sul phuric acid Hydrochloric acid dissolves it readily
    .
    ,
    43 8 IN O R GA N I C C HEM I STR Y . 285
    .

    t hen be d isintegrated by fusion with p ot assium hy dr oxi d e or


    ac id p otassium s ul phate I t is f oun d c rystal lize d in nature
    .

    Th e art ici al m anufa c t ure of rub ies and sapphires i s acco mpli shed
    by fu s i g a m orpho u s l
    n A w i
    3
    th l ead ox i de at br i ght red heat in a
    H ess i an c ru ci b l e
    . L ead a l um inate i s rst for m e d whereu p on the s
    , ilica
    of t h e c rucib l e causes t h e alumina to separate o ut in beau t iful c rystals ,

    e xa c t ly like t h e nat u ral gem s By add ing a li ttl e potass i um dichro


    .

    m ate w e ge t c rystals having t h e c ol or of the natural rub i es ; s imil arly ,

    t h e add i t i on of c oba l t o xi de giv es sa h i


    pp res .

    Al um in i um h ydr o xi de , A l 3 n HzO is de posited as a h y


    -
    ,

    dro gel 1 9 5) wh en a solution of an aluminium salt is treated


    with ammonia I n the decom position of the aluminates it is
    .

    o btained as a whit e powder A hydrate with a low p ercentage of


    .

    water A l 3 2H2 0 bau xite o ccurs in France and di fferent parts


    ,

    , ,

    of the United States in large de posits A lum i ni um hydroxide is .

    b oth weakly acidic and weakly basic in characte r I t s salts with .

    acids suffer partial hydrolys i s in aqueous solution and hence reac t


    -

    acid I t dissolves in alkalies to fo rm a l u m ina tes such as ,

    Al O zK A l O zN a and A l O g N ag which are de posited in the amo r


    , , ,

    p h ou s state when alcohol is added to their aqueous solutio ns .

    They are decom posed by atmos pheric carbonic acid


    Al uminium hydroxide is insoluble in water but dissolves in
    a solution of aluminium chloride By subj ecting this solution .

    to dialysis it is possibl e to get rid of the hydro chloric acid


    ,

    (which is present because of hydrolytic disso ciation ) entirely


    and thus obtain a colloidal solution of the hydroxide Al umin .

    ium hydroxide does not form salts with weak acids .

    A l u m i n i u m c h lo ri de A l C 13 is most conveniently pre pared by


    , ,

    passing dry hydrochloric acid gas over aluminium lings in a tube


    of porcelain o r glass an d collecting t h e sublime d pro d uc t in a
    wide mouthed bottle (see Fig
    -
    Afte r the tube has been heate d
    .

    to a sufciently high tem perature to start the reaction no furthe r ,

    heating is required ; however it is more practicable to continue ,

    heating in order to collec t the chloride in the receiver .

    A lum inium chloride is very hygrosco pic The aqueous solu .

    tion hydrolyzes so readily de positing alumina that it can only b e


    , ,

    preserve d by the addition of an excess of hydr o chloric acid Such .


    C O M PO UN D S O F A L UM I N I UM . 43 9

    a solution does not yield aluminium chlo ride on evaporation sinc e ,

    it decom poses com pletely into the hydroxide and hydrochlori c


    acid o n account of the continued removal of the latte r dissociation
    product The va por density of the chloride u p to 4 00 corre
    .

    s po n ds to the formula Al zC l e a b ove 7 60 to A l Clg With the ,



    .

    chlorides of potassium and sodium alum inium chlo ride forms ,

    com pounds such as A l C lg KC l whose solutions can be eva p

    orate d withou t decom p ositio n C om pounds such as Al Clg PC lg .


    o

    FI G 7 2 PR E PARAT I O N
    . . or AL U M I N I U M C H L O R I DE .

    iC l3 PO C lg ,

    etc have also been pre pared In organic chemist ry
    .
    , .

    anhydrous aluminium chloride is of great value in synthetical work .

    A l u m i n i u m su lph ate , A 12 ( SO 4 ) 3 I GH2 0 is obtained by treating o

    clay with concentrated sul phuric acid ; the product is dissolved in


    water and allowed to c rystallize A luminium sul phate unites with .

    the alkali salts to form double salts of the general type :

    fi g so4 R 2 ( SO 4 ) 3 2 4H2 0 ,
    .

    which known as al u m s R may b e eithe r K N a N H4 C s


    are .
    , , , ,

    R b TI or an organic base ; R may be Fe (ic ) or C r instead of A l
    , , , .

    The alums all cry stallize in octahedrons and cubes which oft e n ,

    gr ow to la r ge d imensio ns ; they fo rm mixe d c rystals r eadily .

    O rdinary alum ( potassium alum ) is used as a mordant in dyeing


    O R G C HEM
    . . but it is being gradually su perseded as such
    ,

    by aluminium sul phate and sodium aluminate In the vicinity of .

    R ome the mineral a lu n it e or a l u m s ton e is found whose com


    , , ,

    p osition is fr om it a much sought variety of


    alum is made A lum is also made from cryolite etc
    .
    ,
    .

    When two salts c omb ine we may have one of two results
    either the new salt which is formed gives ions in dilute aqueous
    O IN O R G A N I C C HE M I S TR Y . 2 85

    solution that d i ffer from those of the two salts or it gives the same ,

    ions A good example o f the former case is yellow prussiate of


    .

    p otash ; it gives neither ferrous ions nor cyanide ions so that i t ,

    must be regar ded as Such salts are terme d c o In


    p l e x The sec ond case is illustrated by the alums A dilut e .

    alum solution exhibits all the reactions which characterize its c om


    o n e n t s and its c onductivity is the m ean of the two se parate salts fo r
    p
    the same c oncentration When the union is of this sort we hav e
    .

    what is called a d o u b l e salt Between the two k inds there are


    .

    salts of an intermediate nature which form not o n ly c om plex ions


    but also the original ions to a greater or less extent The c o ppe r .

    ammonia com p ounds 24 4 ) behave in this way .

    2 86 . A l u m i n i u m si l i c at e , k a olin is formed in n ature b y t he


    ,

    weathering of the n umerous alkali alumina double s ilicates the -

    alkali sil icate being dissolved out leaving the ins oluble aluminium
    ,

    silicate C l ay is aluminium sil icate ; it is usually c olored brown


    .

    by iron oxide It is t h e essential raw material of the ceramic


    .

    industries be ing used b oth for rough bricks an d the nes t china
    ,

    ware ; of course the better grades requir e better sorts of clay Bricks .

    ,

    are molded out of ferruginous and calcareous clays (loam ) an d then
    baked ( burned or r e d ) till they bec ome rm Un d er the .

    head of ear then ware or porous ware (fa ience maj olica etc an d
    , , , .
    ,

    c ommon crockery) we include all articles which c onsist of burne d


    clay ( frequently mixe d with quartz ) are porous an d d is play ,

    an earthy fracture and which are c ove r e d with a glaz e of easily

    fusible s ilicates The glaze is produce d by intro d ucing salt int o


    .

    the kil n The h ot steam causes the formation of hy d r o chloric aci d


    .

    and s o i 1 un i hydroxide which unite with the clay to form so d ium


    v
    '

    aluminium silicate In por celain the p ores of the earthen mass


    .

    ar e com p letely lled with fused sil icate as a result of the addition ,

    o f fel d spar an d quartz before the b urning The le s s of such admix .

    tures is present the more dii cu l t the porcelain is t o b urn an d the


    less sensitive it is to changes of temperature .

    C lay is the mos t wi d ely diffused r e f r a c t o r y material ; it


    r esists not o nl y high temperatures an d su d den changes of tem ,

    r at u r e b u t chemical action as well


    p e , .

    Ul tram arin e is a very beaut i ful blue pigm ent which is prepared arti ,

    ciall y by heat i ng a m ixture of cl ay soda su l phur and wood char c oal


    , ,

    in t he absence of ai r It occurs in nature as l ap is l azu li I t is usually


    . .
    .
    442 I N O R G AN I C C HE M I S TR Y . 2 88

    dilu te s ul phuric a c id and pre ci pitating with hydro c hloric (or better hydri
    odic) a ci d where u pon the s par ingly solubl e chl ori de ( or iod i de) is
    ,

    de pos i ted Thi s e le ment was a lso di s c o vered wi th the spe c tros c o pe
    .

    (C R o o x E s ); i ts s p e c tr um i s a br i ght g reen li ne .

    Thallium is a soft m etal abou t lik e sod ium an d h as a b lui sh c o l or lik e


    , ,

    lead Sp g
    . .
    m pt
    .
    ,
    .
    I n m o i st a i r i t o xi d iz es v ery rapi dly
    -
    .
    ,

    at the surfa c e ; b u t i t does not de c om pose water at ordinary te m pera


    tures When heated it b urns wi th a beau ti ful green am e Sul phur i c
    .
    .

    a d
    n n i tr i c a ci ds d i sso lv e it read il y b u t hydro c h l or ic a ci,d a c ts very s l ow l y
    be c au se of the s li g ht so lub ili ty of the c hl or i de .

    There are two sets of c o m po unds : the thall ou s c o m poun ds derived ,

    fro m t h e o xi de l O a n d the t h a
    ,
    ll i c c o m p o u nds fro m the o xi de T 12 0 3 ,
    .

    The form er resem ble those of t he a lka lies an d s ilver very muc h Thi s :

    simil ari ty shows i tse lf for i nstan c e in the so lub ili ty of t h e hydro xi de
    , ,

    an d t he c arbonate whose so lu t i ons rea c t a lk a li ne M oreover m any .


    ,
    ,

    thallium sal ts are i so m or pho u s wi th potassium sal ts an d lik e the l atter , ,

    g iv e do u b l e sa l ts w i th p l at i n um c h l or i de e g l P t C l F u rther
    ,
    . . .

    there is an alum n SO 4 A 12 ( SO 4) 3 24 HZO as we ll as other do ub le s ul


    - -
    ,

    p h a t e s ,
    e g l .S O 4 . M g S O 4 6 H ZO~
    wh ic h are -
    ana l ogo,
    u s to the c orre

    s po n din g potass ium do ub l e sal ts O n the other hand thallium rese mb les
    .

    silver an d lead i n the sm all so lubili ty of its hali des (the iodi de i s t h e
    least an d the chl ori de t h e m ost so lubl e) and al so in res pe c t to the
    '

    , ,

    order of solub ili ty of these c o m pounds .

    I n the thallic c o m po u nds the e le m ent is triv al ent lik e the other ,

    e l e m ents of the gro u p ; f u rtherm ore lik e t h e c o m po u nds of the l atter , ,

    t h e th allic c o m po u nds read ily for m c o m pl ex sa l ts and undergo con ,


    ~

    s ide rab l e hydro lys i s when d i sso lved in water .

    SUMMA R Y O F THE G R O UP .

    The ve elements last considered B Al G a In Tl form


    2 89 .
    , , , , , ,

    a natural grou p in which the las t three dis play p articular similarity
    ,

    to each other in their physical pro perties Something analogous .

    was observed with c o pper Silver and gold in the rst grou p and ,

    with zinc cadmium and mercury in the sec ond group The fol
    , .

    lowing table a ff ords a brief c o m parison of

    A to micw e ht ig
    g vi
    S e c ic ra ty .

    e l ti n g p o i n t
    -
    THE R A R E E A R THS .
    4 43

    In
    the spectra of G a I n and TI it is again noticeable that the
    ,

    lines move towards the red end as the atomic weight increases

    As
    to their chemical nature it may be remarked that all the
    elements of this group are trivalent and that the basicity of the ir
    o xides increases with rising atomic weight ; boron hydroxide boric
    (
    acid ) has exclusively acid pro per t ies b u t the hydroxides of the ,

    o ther elements even are also soluble in alk alies As


    , .

    most of the lower oxides of the metals are more strongly basic than
    the higher oxides it is not strang e that thallous hydroxide is a strong
    ,

    b ase .

    THE R A R E EAR THS .

    2 90 . the m iddle o f the peri od ic tabl e ( p 3 01 ) are l ocated a n u m ber


    In
    of el em ents wh ich are cl assed under the term rare earths
    ,

    There i s
    .

    still much u n certa inty i n reg ard to som e of them part icul ar l y as to .

    the i r el e mental nat ure Th i s i s du e in l arg e m easure to t h e great s imi


    .

    l ar it y b etween t h e e le ments an d the c onse qu ent d if cul ty i n se parat i n g


    the m They m ay be arrang ed in two g ro u ps : t h e c erium g ro u p con
    .

    ta i ni ng t h e ele me nts l anthanum c er ium praseodymium neodymium , , ,

    a n d sam ar ium ; a n d t h e yttr ium g ro u p c onta in in g e uro ium terb i u m


    p , ,

    dyspros ium ho lmium yttrium g adolin iu m erbium thulium ytter


    , , , , , ,

    b ium s c and ium and lute cium


    , , .

    These e le m ents o ccur in vari o u s rare minera ls whic h have been fo und
    princi pal ly in Sweden and G reenland viz cer ite gadolinite euxen ite , .
    , , , ,

    or thite , e t c .

    Si n c e the use of the o xi des of c erium a n d thorium in the in c andes c ent


    gas lig ht of A UE R V O N WEL S B A C H has created a dem and for them m i nera ls
    -

    i n whic h t he rare earths o ccur are be ing ardently so ught Th e interesti ng .

    fa c t has de ve l o ped that they are b y n o m eans so rare as was su pposed .

    A n es pe ci ally r ic h so u r c e of these earths has been fo u nd in m on az ite s an d ,

    wh ic h o ccurs in rather large quant i ti es i n t h e Uni ted States (produc ti on


    lbs annu a lly) Canada an d Bra zil I t c onsists chi ey of a phos
    .
    , .

    hate of C L D i Y and E r wi th varying am o u nts of thor ium s i l ic ate


    p a a , , , ,

    an d thor ium phos phate .

    I n order to i s o l ate t h e rare earths fro m the se mi neral s the l atter are
    p owdered v ery ne l y a n d heated to fa i nt re d heat w i th c o n c entrated s ul
    -

    p h u r ic a ci d .Th u s t h e rare earths are c han g ed i nto s ul phates a n d the

    s ilici c a ci d i s c onverted i nto t h e i nso lubl e c ondi ti on Th e Sul phates are .

    then tak en u p in ice water in w hic h they di sso lv e much m ore readily
    -

    than in warm water (s i n c e a dif c u l t ly so lubl e hydrate is fo rm ed at a


    44 4 I N O R GA N I C C H E M I S TR Y . 2 90 .

    higher tem perat ure) Fro m this co l d so lu tion they c an be pre c ipi tat e d
    .

    wi th o xa lic a ci d thei r o xal ates be i ng alm ost i ns o lubl e e v en i n dilu te


    ,

    a ci ds Thu s they are freed fro m C a Fe et c The o xalates are then


    .
    , ,
    .

    c onv erted into o xi des by heat i ng .

    Th e s e p a r a t i o n of these o xi des is a m ore difc ul t task Vario u s .

    methods are in u se by w h ich t h e separat i on of t he ceric earths i s


    ,

    fa i rl y we ll a cc om plished ; b u t for t h e num ero u s y t t er ic earths no suc


    c e s sfu l m ethod has ye t been de vi sed So m e of the m ethods e m pl oyed
    .

    are as fo ll ows : Th e i nsol ub ili ty of the s ulphates of c erium l anthanum


    a n d d i dymium in a sat u rated sod i u m s ul phate so lu t i on (by reason of

    t h e form at i on of do ub l e sa l ts ) i s m ade u s e of to separate the m fro m .

    erb ium ytterb ium and yttrium Th e n i trates of t h e vari o us m eta ls of


    ,
    .

    this gro up d i ffer m arkedly in the i r stab ili ty 0 11 heat ing ; hen c e another
    m ethod of separat i on h as been devi sed by whic h t h e n i trates are de c om ,

    p osed o n e after another by heat i ng and those that re m a i n u n de co m


    p osed after ea c h s ucc ess iv e heat i ng a re e x tra c ted w i th water A th i rd .

    m ethod i s t h e fra c ti onal pre cipi tati on of the so lut i ons wi th a m m on i a .

    Fu rther by fra c t i o n a l pre ci pi tat i on wi th p ot ass ium c hro m ate (the


    ,

    i nso lub l e ne u tral c hro mates be ing depos i ted ) separat i ons c an b e ac c om ,

    p l is h e d wh ic h a r e otherw i se v ery d i fcul t .

    Th e y t t e ric earths are s e parated after UR B A I N by mi xing t h e


    a queo u s so lut i on of the i r n i trates wi th b i s muth n i tra t e whic h i s iso ,

    m orpho u s wi th them Fro m thi s so lut i on they separate o u t as mixed


    .

    c rystal s wi th t h e bis muth n itrate t h e d i fferent kinds of m ix ed c rystals


    ,

    havi ng different solub ili t ies I f a fra c t i onal c rystalliz ati on i s c on


    .

    duc ted certa in of t h e rare earths a ccumulate in t h e fi rst c rys t all iz a


    ,

    t i ons others i n t h e l a st crystalliz at i ons the mi ddle ones cons i st i ng


    , ,

    alm ost who lly of b i smu th ni trate .

    M ost of t h e rare earth m etal s for m onl y one o xi de havi ng the ,

    formul a M O ; c er ium praseodymi um and neodymiu m ha ve hig her


    2 3 ,

    o xi des as well of these 0 6 0 i s able to form sal t s 2 .

    T h e best m ethod of dete c t i n g these m etal s i s by s e c tros c o y


    p p .

    T h e s pe c tra of t h e c er ic m eta l s are sat i sfa c tor il y k nown ; those of t h


    e

    y t t er ic m eta l s a r e n o t so we ll k no w n M any of the l atter are chara c te riz ed


    .

    by abs orpti on bands thu s dys pros ium holmium and th uli um O thers
    , , .
    ,

    like yttr ium gado linium and ytterb ium whose o xi des a n d sal ts are ,

    c o l orl ess do not give an absorpti on s pe c tr um bu t the ir spar k s pe c trum


    ,
    ,

    i s chara c teri st ic Th e spectra of t h e yt t eric earths d i spl ay a great


    .

    m any lines Furtherm ore in vest i gat i ons of t h e ul tra v i ol et spe c tra
    .
    ,

    (photo g raph ic ) ha ve fu rn i shed im portant inform at i on .


    44 6 I N O R GA N I C C HEM I S TR Y . 29 0

    yttrium erb ium e t c Y tterb i a (o xide) i s obtai ned by fra c ti onal heati ng
    , ,
    .

    of t h e n i trate mix t u re (see abo ve ) Th e sal ts of ytterb ium are c ol orl ess
    .

    and give n o absorpt i on spe c trum A U E R V O N WEL S B A C H re c ently s uc .

    c ee de d i n reso lvi ng ytterb ium i nto two el e m ents wh ic h h e c a ll ed a l de ,

    baran iu m (A d) an d cass iop eiu m ( O p) He fo und thei r ato mic wei ghts .

    to be A d = 1 7 2 9 0 and C p = 1 7 4 2 3
    . . .

    Th e sal ts of sam ari u m are ye ll ow an d hav e a c hara c terist i c ab so rp


    ti on spe c trum .

    TI TAN IUM , Z I R C O N IUM ,


    AN D THO R IUM .

    291 .These u n c o mm on el e m ent s ar e re l ated to c arbon an d s ilic on i n t h e


    sa m e way as K R b an d C s a re to Li an d N a an d as C a Sr and Ba
    , , , , ,

    are to Be and M g Ti tanium an d zi r c onium st ill giv e a ci d formi ng


    .
    -

    o xi des whil e thorium form s only basic o xides


    ,
    .

    Ti t a n i u m d i sp l ays v ery cl ose ana l ogy to s ilic on ; i t fre qu ent l y o c curs


    wi th t h e l atter b u t always in a s mall a m o unt I t is best prepared pu re
    ,
    .

    by red ucing TiC l wi th sod ium in a s teel bo mb at l ow re d heat Sp g


    4 . . .

    m . Th e m eta l is hard and to u gh i n the co l d ,

    b u t c an b e work ed on heat i ng ; i t is a good e le c tric al c ond uc tor When .

    heated in a current of n i trogen i t b u rns quant i tat ive ly to the n i tride TiN .

    Titaniu m di o xi de T iO ,
    o ccu rs as mineral in three m odic at i ons : r u til e
    z, ,

    an a ta se and br ook ite Ti t a n i u m c h l or i de TiC l


    . i s prepared by passi ng , ,,

    c hl ori ne o v er t h e c arbide wh ic h is prepared i n the el e c tri c f urna c e TiC l is


    '

    , .
    4

    liquid an d f umes in t h e ai r be c a u se of de c o mpos i t i on by at m ospheri c


    water i nto HC l an d Tita n i c a c i d Ti ( O H) separates out as , 4,

    a wh i te a m orpho u s p owder when t h e hydro c hl oric a ci d so luti on of a


    t i tanate i s treated wi th amm on i a Thi s a c ti on i s du e to t h e weak .

    basic c hara c ter of amm on i a an d t h e wea k a ci d nat ure of t i tan ic a ci d ;


    as a res ul t t h e a mm onium ti tanate i s c o m pl ete ly hydroly z ed
    Lik e s ilicic an d stann ic a ci ds t i tan ic a ci d read ily form s p o ly a ci ds
    ,
    -

    I t d i sso lves in alk ali e s to form t i tanates wh ic h are a l s o ,

    obta ined by fusing TiO wi th alkali es O n t h e other hand ti tani c


    2 .

    ac i d d isso lv es in c oncentrated s ulph uric a ci d ; i t then rem ains i n so lu t i on


    even when p9 ured i nto water be c a use t h e e xc ess of s ulph u ric aci d
    ,

    h inders hydro lytic di sso ci ati on Hi gher as well as l ower o xides of


    .

    t i tan ium are known Th e l em on yell ow o xi de T10 i s form ed on treat


    .
    -

    i ng t h e s ul phuric a ci d solut i on of Ti( O H) wi th hydrogen pero xi de 4

    Zir c o n i u m o ccurs in natu re c hie y as zir con ZrSiO It i s not , ,.

    reduc ed fro m t h e o xi de by aluminium It i s prepared pu re by heat ing .

    K ZrF w it h m e t alli o sod ium


    z 6 Sp . Sma ll p i e c es b u rn bril
    .

    l ian t l y when heated i n t h e a i r M O I S S AN obta i ned zi rc oni um c arb i de


    .

    C Zr fro m zi rc on d i re c t ly by heat ing i t wi th s u gar c harc oal i n an


    ,
    TI TA N I UM , Z IR C O N I UM ,
    A N D THO R I UM .
    44 7
    e l ectric furn a c e ( 1 000 am p and 4 0 vol ts) for t e n m inutes The s il ic on
    .
    .

    for the m ost part v ol at iliz es If the c arbide i s treated wi th c hl orine


    .

    at d ull red heat i t i s c onverted i nto the c hl ori de Zi c o n i u m chl ori de


    -

    , . r

    behav es w i th water i n the sa m e way as TiC l a n d Sn C l Th e h ydroxi de 4 ,. ,

    is pre cip i tated by amm on i a fro m a cid so lu ti ons as a v o lu


    mi no u s m ass I t i s inso lub l e in a lka li es b u t on be ing fused wi th
    .
    ,

    the l atter i t form s sal ts s uc h as N a Zr O an d N a Zr O whic h are de c om z 3 , ,,

    posab l e by water The basic c hara c ter of t h e hydroxide i s apparent


    .

    fro m the fa c t that i t gives a s ul phate w i th s ul ph u ric a ci d


    , ,

    whi ch c an be re c rystalliz ed o u t of water Zir con ia ZrO e mi ts a very .


    , z,

    bri ght li ght when heated strongly .

    Th or i u m i s at present obta i ned m a i n l y fro m m ona zi te sand i t i s


    ;
    also found i n the thor ite of A rendal I t c an be prepared by e l e c tro lys i s .

    of a so lut i on of Th C l i n m o l ten alk ali c hl ori de I t m e l ts abo v e


    4 .

    The hydroxide Th (O H) i s inso lub l e i n alkali es The su lphate c rystal


    , .

    l izes w i th 9 H O Z .

    Thor i a and cer i a are the essent i al c onst i t u ents of the in candes cen t
    g as-
    ligh t of A V O N W EL S.B A C H A nel y wo ven c otton m ant le i s
    .

    sat urated w i th a so lu t i on of the ni trates of thorium a n d c erium i n ,

    whi ch the two are conta i ned i n s uc h a pro port i on that after i gni t i on
    the ash c ontai ns 9 8 99 % thori a and 2 1 % c er i a t e n th i s ashe n

    .

    m ant l e i s heated to i n c andes c en c e by a B u nsen b urner i t giv es o u t an


    intense li ght Thi s i s apparent ly du e to the fa c t that s uc h an ash
    .
    ,

    m ant l e e mi ts onl y a s m a ll pro port i on of red rays and rays of st ill greater
    wave length b u t m a i nly g ives Ou t rays of shorter wav e length ; hen c e
    -

    ,
    -

    very li ttl e i f any energy i s l ost by the e mi ss i on of feeb ly lumi no us rays


    , , .

    Howev er i t i s fo u nd that a m ant l e c ons i st i ng of thor i a or c er i a a l one


    ,

    or of the two o xi des i n a pro port i on di fferent fro m the abo v e produc es
    Very l itt le li ght So far as the c eri a i s con c erned thi s i s d u e to i ts be i ng
    .

    p resent i n s uc h an e xc ess that i t c annot a ll be ra i sed by the a m e to


    full i ncandes c ence A n anal ogo u s pheno m enon i s seen i n an ordi nary
    .

    am e whi ch when sm o ki ng ( i e when too muc h c arbon i s present )


    ,
    . .

    gives l ess light than when not s m o ki ng That i t is not the thori a whic h .

    emi ts the li ght i s pro v ed by the fa c t that a m antl e c ons i st i ng c hi e y


    of c eri a and conta i ni ng only 1 2 % of thor i a produc es very litt l e light
    .

    We must therefore suppose that in t h e m ant l e mi n u te part icles of c eri a


    are spread o u t u pon the v ery poor heat c ond uc tor thori a ; thus s in c e -

    , ,

    the ir m ass i s s m all they are ab l e to rea c h t h e h i gh tem perat ure at whic h
    ,

    they e mi t the des i red b rig ht li ght ; for t h e bri ghtness of a a m e in c reases
    wi th abo u t t h e fth power of t h e te m perat u re .

    Thorium bel ongs to t h e rad i o a c t ive el e m ents When thorium -


    .

    hydroxi de is d i sso lved in an a ci d an d r e p r e c ipit at e d w i th a mm on i a the ,


    4 48 IN O R GA N I C C HE M I S TR Y .
    u 29 1

    intens i ty of radi at i on i s only abo u t 45 % of the ori ginal intens i ty If .

    t h e so lut i on i s e vaporated and the amm on ium sa l ts driv en o ff by i gn i t i on ,

    a res i d u e re m ains too s m all to we i gh ; i t i s thori um X and possesses


    ,

    the rem a inder of the a c t ivity of thoriu m The a c t i vity of thori um .

    in c reases aga in s l owl y ; that of thorium X decreases and n all y d is


    appears The ha lf de c ay peri od of t h e l atter i s
    .
    -
    days The a c tive .

    thorium also gives o ff an e m anat i on ; b u t if i n a thorium sal t so lu ti on ,

    the thori um i s separated fro m the thorium X (by repeated pre cipi tat i on
    wi th a mm on i a) t h e tho ri um is fo u nd to have ent i rely l ost i ts e m anat ing
    ,

    p ower The
    . thor ium X however h as strong e m anat in g p ower ; so we
    , ,

    con cl ude that the e m anat i on i s a transform at i on produc t of thori um X .

    Between thori u m X and thorium c o m e m esothorium and rad i o


    thorium as i nterm ed i ate produc ts a cc ording to t h e form of t h e de c ay ,

    cu rve ; o n t h e other hand t h e emanat i on gives rise s ucc ess ivel y to thori um
    ,

    A B and C
    , , .

    VAN ADI UM , NI O BIUM ( C ol um b iu m ) , TAN TALUM .

    2 These rare e le m ents are alli ed to n i trog en and phosphorus in


    92 .
    the i r propert i es and t h e formul ae of the i r c o m po u nds A s in all the other .

    g ro u p s the m eta llic c hara c ter be c o mes m ore p ro mi nent as the ato mi c

    we ig ht i n crea ses A l l three are p re pared by pass i ng an e le c tric c urrent


    .

    thro ug h rods o f t h e oxi des i n a vacuum


    '

    Van adiu m i s characteri z ed by an abundance of co m pound types -


    .

    There are for exam p l e four chl orides : V0 1 V0 1 VO L and VC l A n


    , , 2, 3, , s.

    oxychl ori de VO C I al so is kno wn whi ch i s deco m p osed by wat er like


    , 3, ,

    PO C l aThe highest oxi de V 0 a bro wn substance i s the start i n g po i nt


    .
    , 2 5, ,
    -

    for m ost vanadium preparations I t i s an ac i d anhydr i de formi n g sal ts .

    which m ay be derived fro m the aci ds H VO (ortho ac i d ) and HVO 3 4


    -
    a,

    m etavanadic acid and is thus anal o gous to P 0 , 2 5.

    Vanadiu m occurs extensi ve ly though in s m all q uantities I n the ,


    .

    Peruvian A ndes is a l ar ge bed of patronite a sul ph i de conta i ni ng 1 9 p er , ,

    cent of vanadium The ore is roasted and fused wi th caust ic soda and
    .

    sal tpetre produ c i n g sodium vanadate whic h i s extracted wi th water


    , ,
    .

    O n saturat i n g thi s solu t i on with a mm oni u m c hl ori de am m on iu m me ta ,

    vanadate N H VO ,
    separates out after a whil e as a sandy powder Heat
    r s, .

    in g converts i t into V 0 Thi s al so serves as the characterist i c test for


    2 3 .

    vanadic a ci d .

    Vanadi um m el ts at about l 6 8o I t is very act i ve che m icall y p re c ip



    .
    ,

    it at in g m any m etal s fro m the i r sa l t so l ut i ons I t i s ndi n g vari ous uses .


    ,

    both as the brown o xi de and i n bron z es and vanadium stee l s I t i s


    '

    fo und i n m eteor i tes .


    4 50 I N O R G A N I C C HE M I S TR Y M

    C HR O M O US C O M PO UN D S .

    Thes e c om pound s have a very strong tendency t o absorb oxygen


    an d go over into chromic c om p ounds ; hence they can o nl y be pr e

    served away from the air A solution of the c h r o m o u s c h l o ri de ,


    .

    C rC l z is obtained by reducing chromic chl oride C I 2 C 16 w ith z inc


    , ,
    '

    and sul phuric acid I t has a beautiful blue c ol or which soon


    .
    ,

    turn s to green because of oxidation I f the solution of chromous .

    chloride is p oured int o a saturated solution of sodium acetate ,

    c h r o m o u s ac e t at e is preci pitated as a red crystalline p owder which ,

    is much more p ermanent in the air than the other chromium salts
    and can therefore be used for their prep aration The h y droxi de

    C r (O H) 2 is yellow .

    C HR O MI C C O M PO UN DS .

    2 94 . C h r o m ic i de , C rz O g is forme d by heating chr omic


    ox ,

    anhydri d e C I O g or ammonium chromate It can be


    , ,

    o btained crystallized by passing chromy l chloride C r O g C l z through , ,

    a red hot tube The amorphous com pound is green ; the crystals
    -
    .

    are black After ignition it is ins oluble in acids When fused


    . .

    with silicates it colors th e latter green whence its us e as a pigment ,

    for coloring glass and ch in aware ( chrom e gr een ) .

    G UI G N E T S gr een a beautiful pigment is pre pare d by fusing



    , ,

    otas sium dichromate ( 1 part ) with boric acid ( p


    3 arts ) The
    p .

    p otassium borate is dissolved out with water leaving the coloring ,

    substance C r 2 0 3 2 HzO
    ,
    -
    .

    The hydrogel of chrom ic oxide C I 2 0 3 71 H2 0 is preci pitate d


    ,
    '
    '

    when a chromium salt is treated with ammonia I t is light blue .

    b ut dissolves in caustic potash or soda to a green solution O n .

    boiling this solution a lower hydrate of another color is de posited .

    The cause of this preci pitation is read ily understood if it is assume d ,

    that the saturated solution of the lower hydrate contains less


    chromium ions than that of the higher hydrate The alkaline .

    solution is thus su persaturated in res pect to the lowe r hydrate and


    the latte r must be de posited The solubility of chromic hydroxide
    .

    ln alkalies shows it s slightly acidic character ;3 it can also form salts


    with other m etals most of which salts are d erived from C r O O H
    ,
    '
    .

    A n exam ple of this ty pe is the mineral ch r o m it e .

    C hromium hydroxide is only a weak base ; it d oes not fo rm


    C HR O M I C C O M PO UN DS . 45 1

    salts with weak acids such as c arbonic acid sul phurous aci d et c , ,
    .

    ( f
    o .

    C h ro m i u m c h lo r i de , C rC l g is pre pared by heating a mixture


    ,

    o f chromic oxide and carbon in a current of chlorine ; it then


    sublimes in brilliant violet crystal lamin ae C hromi c chloride thus -
    .

    obtained dissolves in cold water very slowly but if traces of ,

    chromous chloride are present it dissolves readily A ccording to .

    O ST WA L D this is to be regarded as a catalytic acceleration of t h e


    ,

    Velocity of solution The resulting solution is green ; on eva pora


    .

    tion green deliquescent crystals of the com position cr2 016 1 2 H2 0 '

    se parate out These crystals are also obtained from the solution
    .

    A 1 3 00 the va po r

    of the hydrogel in hydro chloric acid t 1 2 00 .

    density corres ponds to the formula C I C l g


    .

    C h r o m i c su lph at e , C r2 ( SO 4 ) 3 like other chromium salts ,

    ( nitrate chrome
    ,
    alum has the p,
    eculiar ro
    p p erty of disso l v

    ing in coid water to a Violet solution which turns green on warm ,

    ing O n cooling this green color changes back to violet ( rathe r


    .
    ,

    slowly with the sul phate solution but ra pidly with other salts ) .

    O n slowly eva p orati n g the V io l e t s o l u t io n at room tem perature the


    salt crystallizes out the sul pha te for instance w ith fteen molecules
    , , ,

    o f water ; the green solution however yields only an amorphous


    , ,

    viscid mass .

    I n investigating these phenomena the sul phate solution h as


    b een usually em ployed sinc e its green modication can be ke pt
    ,

    the longest Experiments have sh own that the process depends


    .

    o n a s plitting o ff of sul phuric acid ( 1 mol

    sul phate ) and that green chrom sul phuri c acids are formed
    H2 SO 4 from 2 mols
    -
    . .

    i e substances with a com plex chro msul phuric acid ion sinc e
    ,

    -
    . .
    ,

    they do not give tests for either chromium or sul phuric aci d .

    Thus only one third of the sul phuric acid can be preci pitate d from
    -

    a green solution of the sul phate directly with barium chloride o r ,

    in other words onl y a third of the SO 4 ions of the original Viole t


    ,
    -

    solution are still present The transition from the Violet soluti on
    .

    to the g reen can therefore be formulated in this way

    2 C r2 ( SO 4 ) 3 + H2 0 H2 SO 4
    v io l e t com pl ex io n
    g re e n

    O nly t h ose SO 4 gr ou ps in italics are


    -

    p reci pitated .
    4 52 I N O R G A N I C C HE M I S TR Y .

    In a modera t e state of dilution these chrom sulphuric aci d s are -

    as strongly ionized as sul phuric acid itself .

    A n analogous behavior is shown by chromic c hl oride C r C l 3 , .

    A violet solution of i t can be obtained by treati n g the Violet solu


    tion of the sul phate with the theoretical amount of barium chloride .

    The chlori ne can then be com pletely preci pitated with silve r
    nitrate at ordinary tem peratures I f the solution is boil ed fo r .

    a time however and then cooled silver nitrate will pr eci pitate
    , , ,

    only two of the three chlorine atoms directly under the same con
    dit io n s ; the third must have gone with chromium to form a com
    p lex ion .

    C h ro m e al um , K Q SO 4 C r 2 ( SO 4 ) 3 2 4 H2 0 is best pre p are d b y


    - -

    passing sul phur dioxide into a solution of potassium d ichromat e


    c ontaining free sul phuric acid

    K2 C r2 0 7 H2 S0 4 3 80 2 K Q SO 4 C I 2 ( SO 4 ) 3 + H2 0

    .

    It can be obtained in nely develo p ed o ctahedrons with ed ge s


    several centimeters in length I t is use d in dyeing an d t an m ng
    . .

    C HR O MA TE S .

    2 95 There ar e numerous sal t s of the formula Mz C rO 4 which


    .

    are derive d from the oxide C r O g chromic anhydride as i n the , ,

    similar case of sul phuric anhydride SO 3 ; b ut while in the latte r ,

    case the sul phuric acid itself H2 SO 4 is also a stable com pound
    , , ,

    chromic acid HzC rO 4 has not as ye t b een isolated Wh en an


    , , .

    acid is added to a chromate only t h e anhyd ri de is obtained ; t h e


    acid Hz C rO 4 breaks u p forthwith into wate r and anhydride Th e .

    salts of chromic acid are isomorphous with t h e co rr es ponding


    sul phates .

    C h r o m ic an h ydri de is o b tained o n adding sul phuric acid to a


    concentrated solution of potassium dichromate ; it se parates ou t
    in the fo rm o f long r ed rhombic needles which when freed from
    '

    , ,

    all sul phuric acid do not deli q uesce in the air They are re adily
    , .

    soluble in water Heating to 2 50 breaks them u p into ch ro m i c


    .

    oxide and oxygen

    Q C TO 3 C r2 0 3 30 .

    C hromium
    trioxide is a very powerful oxidizing agent ; its solu -

    t ion cannot be ltered through pa per because it destroys the pa pe r


    4 54 I N O R GA N I C C HE M I S TR Y . 29 5

    The resulting s odium chromate is lixiviated and sul phur ic aci d


    is added to its solution ; o n evaporatio n s o di u m di c h rom ate , '

    N az C rz O 7 crystallizes out and this can be converted into pot a ssi um


    , ,

    di ch r o m ate , a well known salt by double decom p osition with


    -

    p otassium chloride .

    The fusio n is much more readily accom plished when caustic


    p otash ( K O H) is used instead of soda ( N aQ C O g ) probably becaus e ,

    fused potassium hydroxide absorbs oxygen from the air and forms
    the peroxide thus becoming a much more active oxygen carr ie r
    ,
    -

    than soda Under these circumstances the oxidation pro ceeds


    .

    ra pidly and com pletely as low as


    Potassiu m dichromate nds frequent use as an oxidizing agen t -

    in sul phuric acid solution being itself reduced to chromic sul phate ;
    ,

    c rz o ] '
    4 HQ SO 4 K2 8 0 4 i O rg (SO 4 ) 3 4 H2 0 30 .

    An im portant c omm er cial task i s the regenerat i on of the chrom ic acid


    fro m s uch a c hro mium s ul phate so lu t i on The m ethod fo ll owed i n the .

    fa c tori es at HOch s t G erm an y i s an e le c tric al one Th e so lu t i on i s e lec


    , ,
    .

    t ro l yz e d between l ead e le c trodes i n a vesse l c onta i ni ng a d i aphragm


    (p oro u s part i t i on) B y the
    . a c t i on of t h e current chro mi c a ci d is form ed
    at t h e anode while at the c athode hydrogen i s e v o lved Bes i des thi s a
    ,
    .
    ,

    change o ccurs i n the c on centrat i on of the s ul phuric a ci d on both s i des of


    t he d i a phrag m ; i t be c o m es h i gher i n the anode port i on and l ower i n ,

    the c athode porti on The liqui d o xi diz ed at the anode c an be u sed for
    .

    o xi dizi ng purposes witho u t any further pre parat i on The chro mi c a ci d .

    is agai n reduc ed to c hro mic o xi de Cr Og and the reduc ed liqui d i s then


    a
    , z ,

    introduced i nto the c athode port i on while the liqui d whic h previ o u sly ,

    o cc upi ed that s pa c e i s bro ught o ver to the anode s i de of the d i aphragm


    , .

    When the current i s aga i n t urned on the liqui d at the c athode whic h , ,

    at the begi nni ng of thi s se c ond o perat i on i s ric her i n s ul ph uric a ci d than
    the liqui d a t t h e an ode yi e l ds i ts s urplus to the c athode liqui d I n thi s
    , .

    way an a ccumul at i on of s ul phur i c a ci d i s avo i ded and the sam e l i quid ,

    can really be used c ont i nu o us ly as an o xi dizi ng agent -


    .

    Th e chromates are yellow ( exce pt silver chromate which is re d) ,

    and the dichromates are red L e ad c h r o m ate , Pb C rO 4 , is insolubl e


    .

    in water and is used as a pigment ( om e


    chr
    yel l ow ) .

    On heating potassium d i chro m ate wi th potass ium chl ori de and sul
    h r ic a ci d a dar k r e d liqui d d i st il s over wh ic h has the c om pos i ti on
    p u -

    Cr O zC l2 and the bo ili ng po i nt 1 1 7 and mu st be cons i dered as the chl ori de


    -

    M O L YB DE N UM . 4 55

    of c hro m ic a c id ; it is called c hr om yl l
    c h oride , or chrom ium oxychl oride
    KzC rzO 7 4KC I 3 H2SO 4 = 2 C r O zC l2 3 KZSO 4 3 HzO .

    Water break s i t up i nto CrO 3 and HC l .

    Cl
    The se mi c hl or i de of c hro mi c a c i d
    -
    Cr O z < is known onl y in the
    OH
    ,

    form of sa lts The potass ium sal t for e xam pl e is obtai ned by heat i ng
    .
    , ,

    potass ium d ic hro m ate wi th con c entrated hydro c hl ori c a ci d :

    Cl
    KZC I 20 7
    2 HC l 2 0r 0 2
    OK
    It crystalliz es in red pri s m s .

    O n treat i ng a c h ro mi c a ci d so lut i on wi th hydrogen perox i de in excess


    a bea u t i ful blue c o l orat i on a ppears whic h i s absorbed by ether on sha k
    ,

    ing It i s du e to a p c h om i c acid whose amm oni um sa lt N H C r O H O 2


    . er r , 4 s Z

    c an be i so l ated as a v i o l et bla ck powder s imilar to powdered potass ium


    -

    p er m anganate I n concentrated
    . a qu eo u s so lu t i on de c o m pos i t i on s oon
    occ urs the dichro m ate be i ng form ed and o xygen g iven o ff
    , .

    M olyb den um .

    9 6 This c om paratively rare element is


    2 . foun d in n ature in
    m olybden it e , M oSz , and w u lfen it e , Pb M o O 4 The former alone is .

    u sed in pre p aring molybdenum and its c om p ounds I t is roasted .

    and so c onverted into the trioxide M O O 3 ,


    .

    The e l e m e n t itself is obta ined from its oxides or chlorid es


    by heat ing them red hot in a c urrent of hydrogen The product
    -
    .

    is a steel gray p owder which fuses with great di fculty to a s ilvery


    -

    metallic mass Sp .Heating in the air c onverts it in to


    .

    the trioxide I t is n o t attacked by hydrochloric or dilute sul


    .

    h u ric acid but is r eadily dissolved by n itric an d c oncentrate d


    p ,

    sul phuric acid M olybdenum a ls o has recently found a m et all u r


    .

    g ic al use in varying the p ro p erties of steel .

    This element is n oted fo r the great variety of its c omp oun d s ;


    some of the more im p ortant ones may be mentioned here .

    I n addition to the oxides M 0 2 0 3 ( weakly basic ) an d M O O 2 (in


    di fferent ) there is m olyb de n u m t rio x i de , M O O 3 which lik e C I 0 3 , ,

    is an ac id anh ydride I t is a white p owder which turns yellow on


    .

    heating It is very s paringly soluble in water With alkalies it


    .
    .

    forms m olybdates I t has a tendency t o form p o l y m olybdates


    .
    -

    e v en stronger than the s imilar tendency of chromic anhydri d e ;


    4 56 IN O R GA N I C C HE M I S TR Y .
    m 29 6 1

    ammonium h ept am ol yb dat e ( N H4 ) 6 M 0 7 O z4 4 H2 0 ( derivable fro m



    - r
    ,

    the ac id 7 H2 M o O 4 4 H2 0 ) commonly known as ammonium



    ,

    molybdate is a typ ical exam ple The addition of a s t r on g ac id


    ,
    .

    t o a molybdate solution precipitates white glistenin g c rys t al fl am ,

    in ae of m olyb di c a c i d, H2 M o O 4 which dissolve in an excess of acid , .

    A solution thus prep ared from ammonium molybdate and an exces s


    o f nitric acid serves as a test reagent for phos phoric acid with

    which it forms a yellow precip itate of ab out the c om p osition


    ( N H 4) 3 PO 4 1 4 M 0 0-
    3 + 4 H 2 0 on warmi n g ( f
    o 1 4 6 and .

    O f t he chlorides the c om p ounds M 0 013 M 0 014 and M o C l 5 are , ,

    known I n the ox ych l or ide s M o O C l 4 an d M oO zC l z m olybdenum


    .

    can be regarded as sexivalent .

    The c hl or i de Mo Cl z does not exist accordi ng to M UTHM A N N (neither


    does M O O ) b u t a c hl ori de M o3 016 i s k no wn
    ,
    .

    A very charact eristic t est for m olybdic a cid ( the most c ommon
    molybdenum c om p ound ) is the followin g : the substance is m ixed
    with zinc and sul phuric acid ; at rst a blue c oloration ( a m olybdate
    o f molybdic oxide ) a pp ears but it soon turns green and then brown .

    Th is brown c oloration is due to a salt of the oxide M 0 2 0 3 .

    TUN G STEN .

    297 . The wh ic h thi s el em ent c hie y o ccu rs are scheelite


    m in e r a l s m ,

    GaW O ,, wolfram ite or wolfram ( Fe M n ) WO


    ,
    and hu bnerite M n W O
    , , ,, , ,.

    Th e m eta l i s obtained pure by the m ethod of G O L D S C H M I D T ie . .


    ,

    by the redu c t i on of pu re tungst i c a ci d with aluminium lings The .

    m eta l so obta i ned i s v ery p u re ; s p g m e l t i ng


    p o i nt so
    . m ewhat
    .
    ,

    abo v e It i s m alleab l e and s c rat c hes gl ass I n c o mb i nat i on wi th .

    carbon i t i s very m u c h harder It i s very perm anent in the a i r Su l


    . .

    h u ric a ci d hydro c h l or ic a ci d a qu a regi a an d hydro u or ic a ci d atta ck


    p , , ,

    i t very sl owly b u t i t rapi dly disso lves in a mix t ure of hydro u oric and
    ,

    n i tric a ci ds Fu sed c au st ic potash d i sso lves i t sl owly wi th the e v o lu ti on


    .

    of hydrogen T ungsten is emp l oyed in t h e i ron ind u stry s inc e a sm all


    .
    ,

    p er c entage of tun g sten i n c re ases t h e hardness of stee l in a m ar k ed degree

    ( tu n gs ten or w o lfram s teel )


    ,
    E x tre m e l y n e wi res of the m etal are
    ,
    .

    m ade u se of in so m e of t h e newer i n c andes c ent e l e c tric l i ghts .

    T ungsten like c hro mium an d m o lybden um i s al so c hara c teriz ed by


    , ,

    an ab undan c e of co m po undtypes Th e c hl ori des WC l WC l WCl .


    z, ,, s,

    a n d WCl are k nown to e xi st


    6 Th e l ower ones a re prep ared fro m t h e
    .
    58 I N O R GA N I C C HE M I S TR Y . 29 8;

    ( K2U20 7 and N a2U20 7) are pre c ipitated whi c h are solubl e in a c ids ,
    .

    Uran in i te c an be regarded as the u ranate of urano u s o xi de , U3 0 8


    2 U0 3 U0 2 -
    B oth o xi des are c onv erted i nto th i s U3 O 8 o xi de by heat
    .

    ing i n the ai r Uran ium sal ts are used to im par t to g lass a beauti ful
    .

    g reen i sh ye ll-
    ow u ores c en c e .

    The detection of u r an yl s a l ts i s a cc o m pli shed wi th the a i d of the pre


    c ipit at e so l ub l e in e x cess wh ic h they g iv e wi th amm on ium c ar b ona te
    , ,

    and by t h e redd i sh brown p re cipi tate w 1 t h potass ium ferro c yan ide For
    -
    .

    the radi o a c t ive propert i es of uran ium see 2 6 7 .

    SUMM AR Y O F THE G R O UP .

    99 The elements chr om iu m , m ol ybden u m , tu ngsten , an d u ra


    2 .

    m u m , in c onnection with sul phur , c ons t itute a n atural group in the


    p eriodic system Partic u larly in the
    . higher oxides there is c on
    s ide r ab l e analogy with the behavior of this metalloid Their acids .
    ,

    for exam ple all have the formula H2R 0 4 M oreover sul phur also
    ,
    .

    has the ability to form pol y ac ids (pyrosul phuric acid ) although it
    is n o t so prominent as in the rs t named four elements Several -
    .

    o f their salts are isomor phous The strength of the acids d ecreases .
    ,

    as in other groups with rising atomic weight A nother character


    ,
    .

    is t ic of all the elements of this grou p is the gr eat abundance of


    formula types ; it is also very noticeable in the case of sul phur ,

    whose acids are remarkably numerous The physical pro perties of .

    these elements have not yet been fully determined b u t a fe w of ,

    them ar e given in the following table

    0 0 0 0 0 0 0 0 0 0

    M AN G AN ESE .

    3 This element
    00 . is widely diffused in nature . Its most im

    p ortant minerals are p yr o l u s it e , M 11 0 2 , hau sm a n n ite, Mn 3 O 4 , and


    rh odochr o s ite , Mn C O g .

    The m e t a l is of minor im p ortance It is best prepared .

    b y the G O L D S C H M I D T method i e by reducing pyrolusite with , . .

    aluminium p owder when it is obtained as a regulus of brilliant


    ,
    3 003 M A N GA N E SE . 4 59

    lustre Sp g = 7 2
    . . . m . b . It under .

    goes surface oxidatio n readily in moist air which gives the ,

    regulus an iridescence and whe n nely divided decom poses


    ,

    b oiling water It dissolves in acids to form manganous salts


    .
    .

    M anganese forms several series of c om p ounds : the m angan ou s


    c om pounds of the ty pe M a ; the m angan ic com pounds Mn X3 ; ,

    m a n ga n ic acid H2 M n 0 4 which can be derived from an anhydr i de


    , ,

    MII O 3 ; perm an gan ic acid HM n O 4 derivable from the oxide Mn 2 0 7


    , .

    M ost of the familiar salts of this element are derived from m an


    g a n o u s o x i de M n O ,
    This oxide which
    . is re
    p p ared by heating the,

    carb onate in the absence of air is an amorphous green p owder tha t , ,

    oxidi z es readily in the air to the higher oxide M n 3 0 4 M an gan o u s .

    h ydr o xi de , Mn (O H) 2 is white when freshly preci pitated from solu


    ,

    tions by an alkali but soon turns brown in the air because of t he


    formation of manganic hydroxide Mn 2 (O H) 6 ,
    .

    The solutions of m an gan o u s salts are pink ( c ol or of the Mn


    ion) The c hl o ri de , M n C l z crystallizes with four molecules o f
    .
    ,

    water . It c an b e ob taine d anhy d rous by heating the double sal t


    s
    Mn C l z 2 N H4 C l l H2 0 since the hydrochloric acid set free hinders

    ,

    the hydrolytic d issociation of the chloride The s u l ph ate , Mu SO 4 .


    ,

    crystallizes below 6 wi t h 7 11 2 0 ab ove this temperatur e with



    ,

    z SO 4 M SO 4 l 6H2 0
    5H2 0 I t forms double salts such as K n s imi - -
    .
    , ,

    lar to ; those of m agnesium and iron ; they are more ove r is om or


    h i h the latter
    '

    p o u s w t .

    M an gan o u s s u lph i de , Mn S has a pink ish whi t e c olor , which


    ,
    -

    distinguishes it from all other sul phides .

    If ammonium chloride is added to the s olution of a manganes e


    salt no hydroxide is precipitate d by ammonia ; t his is analogous
    ,

    t o what is observed with magnesium The solution is ,

    however r eadily oxidized by the oxygen o f t he a1r an d brown


    ,

    manganic hydroxide is de p osited



    .

    The m an gan i c io n Mn is o nly weakly b as ic Its s alts are .

    almos t com pletely hydrolyzed in aqueous solution The sulphate .

    gives alums wi t h c aesium and r ubidium sulphates which are als o ,

    very unstable .

    M an gan i c o x i de , a O g is obtaine d from any of t he o the r


    ,

    o xides by heating in an oxygen curren t Since dilut e sul phuri c .

    acid reacts with it giving manganous sul ph ate and manganes e


    ,

    d i ox ide , the oxide M n2 0 3 is oft en considered as M n O M n 0 2 Th e


    '

    ~
    .
    4 60 IN O R G A N I C C H E M I S TR Y . 3 00

    co rres pon d ing h ydroxide is soluble in cold hydro chloric acid to a


    dark brown solutio n I t is n o t cer t ain whether this solution con
    -
    .

    tains M n2 016 o r M n012 and M n C l4 ; o n being warmed it gives o ff


    chlorine and is then known to co ntain the manganous chloride .

    M an gan o m an gan i c oxi de , M n 3 O 4 or M n O a O g is obtained


    - -
    ,

    o n strongly igni t ing the other oxides in the air I t is a brownish .

    re d powder When heated with hydro chloric acid it yields chlorine


    . .

    M an gan e se di ( or pe r o xi de , Mn 0 2 the b est known man ,


    -

    ganese mineral ( p yr ol u site) is c ommercially of great im portance


    ,

    in the pro duction of chlorine I n the cold it dissolves in hydro.

    chloric acid to a very dark liquid probably c ontaining the tetra ,

    chloride and gives o ff no chlorine ; when warmed it decom p oses


    ,
    ~

    into chlorine and manganous chloride


    Since pyrolusite is c om p aratively ex pensive ; various methods
    h ave been devised for reconverting the manganous chloride into
    the p eroxide O n e which is of p ractical im p ortance is the W E L D O N
    .

    p ro cess A n.excess of milk of lime is added to the chloride solutio n ,

    whe reupo n air is fo r ced thr ough the warme d l iquid The manganous
    '

    hydroxid e which is preci pitated undergoes oxidatio n and is con


    verted into calcium manganite O aMn 0 3 ( = C aO Mn O z) whi ch ,
    -
    ,

    s ettles down as a black slimy mass :

    Mn 012 2C aO O C aM n O 3 C aC lz .

    The calcium chloride solutio n is run o ff and the mangani t e is use d


    for generating chlorine since it acts towards hydro chloric acid lik e
    ,

    a mixtur e of lime and manganese dioxide .

    The value of the peroxide de pends o n the amount of chlorine


    i t can produce with hydrochloric acid I n orde r to determine this .
    ,

    the mineral nely pulverized is warmed with hydro chloric acid


    , ,

    and the evolved chlorine passed into potassium iodide solutio n ,

    where upon an equivalent amount of iodine is libe rated This .

    iodine can b e titrated with thiosulphate

    M an ganic ac id an d Pe rm an gan ic acid.

    3 When
    01 manganese
    . c om p ounds are fused with p otassium
    hydroxide in the air or better in the presence of an oxidiz ing age nt
    , ,
    -

    (p otassium nitrate or chlorate ) a gree n mass results which is dis ,

    solved by cold water forming a dark green solution O n e v ap o r at


    ,
    -
    .

    in g this solution in a vacuum dark green rho mbic prisms of po t as -


    4 62 IN O R GAN I C C H E M IS TR Y . 3 01

    d issolve rea d ily water forming a d eep vi ole t liqui d


    in ,
    This sal t -
    .

    is isom or phous with p otassium p e r chl ora t e Al l solutions of per .

    manganates display the sam e abso rp tion s pectrum viz ve dark ,


    .
    ,

    b ands in the yellow and green no matter what the base is It is


    , .

    t hus evident that the ion Mn O 4 is really the coloring agent



    '

    The solution of p otassium perman ganate acts as a p owerful


    o xidizing agent ; in acid solutions two KMn O 4 m olecules yiel d
    f i v e oxygen atoms

    2 K MII O 4 + 3 11 2 8 0 4 K Q SO 4 2M n SO 4 H "
    3 2 0 i 50

    Th e process may be regarded as a transformation of the anhydri d e


    o f p erma n ganic =
    acid M n 2 0 7 ( 2 HM n O 4 HQ O ) into two m ole
    , ,

    cules of basic oxide Mn O an d ve atoms o f oxygen ; thus :


    , ,

    Mn 2 0 7 ZMII O l"50

    .

    In neutral o r alkaline soluti ons however t w o KMn O 4 molec ules , ,

    y iel d only t h r e e atoms of oxygen manganese p eroxi d e being ,

    de p osite d at t h e s ame time ( transformation o f a O 7 into


    2 Mn 0 2 + 3 0 ) 2
    K
    2 Mn O 4 l Hg O 2 Mn O z 2 KO H 30 .

    Since in oxidation s with p otassium permanganate in aci d s olu


    t ion the dee p c olor of the permanganate is re placed by the very
    faint c olor of manganous sul phate many substances can be ti t rated ,

    with p otassium p ermanganate in acid solutio n withou t an indi


    cator Ferrous sul phate is oxidized to fe rric sulphate ; oxalic
    .

    acid goes over into carbon dioxide an d water ; ni t rous acid in very
    d ilute solutions is converted into nitric aci d from hydrogen
    p eroxide water an d oxygen gas are forme d Al l these reactions .

    p rocee d quickly and quantitatively a t ordinary tem p eratures so


    that they are suitable for titration .

    Per m an gan ic is k nown only in a queo u s so lu tion ; however its


    acid ,

    anh y dride M nZO 7 c an be obta i ned


    , , I t i s pre pared by carefully treat
    .

    ing dry perm anganate wi th c onc entrated s ulphuric a ci d It i s a vo l a .

    tile bro wnish green o ily liqui d whose vapor e x pl odes easily yi elding
    ,
    -

    , , ,

    oxygen and m anganese d i o xi de .

    M anganese occu pies an isolated p osition in the perio d ic system .

    No elements are known which are related t o it as the elements


    Mo W and U are to chromium
    , M o reover only in its highest .
    ,

    stage of oxidation permanganic acid does it disp lay analogy with


    , ,
    IR O N .
    4 63

    ch l orine c om p ound HCIO 4 Th e salts of b o t h


    t h e c orres p onding , .

    acids are is omorphous and b oth are p owerful ox idiz ing agents -

    IR O N .

    3 62 Iro n is t h e mos t useful metal an d is therefor e pre p are d


    .
    ,

    commer ci ally o n an enormous s cal e (a ppro ximately


    metri c tons a y e ar) It o c curs o nl y rarely n a tiv e e g in meteori c
    .
    ,
    . .

    r oc ks I n the for m of oxi d es sulphides and silicates it is widely


    .
    ,

    di ffused in nature and is found in very large quantities The .

    mo s im p ortant iro n industry


    F e ; 4 hem a tite
    , ,
    an d The p yrite s
    etc ) are w orked u p into iron after they have b ee n roaste d i n the
    .

    sul phuri c acid fa ct ories .

    The m etall u r gy of ir o n is theoretically very simple ; it is base d


    on the ability of carb on to re du ce th e o xides of iro n t o the metal
    at an elevate d tem peratur e This p ro cess ( s m e l t i n g ) is car
    .

    rie d o u t in bl as t fu r n aces .

    Th e ir on o re is rs t roaste d ( c a l c i n e d ) t o r emove volatile


    s ubstances ( H2 0 0 0 2 S A s etc ) and loosen u p the mineral
    , , , ,
    . .

    Then it is c r u s h e d and mixed with a slag forming substance -

    ( u x see
    ,
    according t o the grade of the ore I f the gangue .
    ,

    o r earthy matrix c ontains much silica or alumina limestone or


    , ,

    dolomite is em ployed as the uxing agent but ores rich in lim e


    '

    or magnesia are mixed wit h quartz or aluminous ore to e ffect the


    necessary fusion and formation of slag (silicates of A l Mg and C a) , .

    The blast furnace previously warmed to the pro per tem pera
    ,

    ture or already in O peration is charged from ab ove with alternat e


    ,


    layers of c oke an d the mixture of ore and u x b o t h being intro

    ,

    du c e d in rounds / or charges 7
    of denite weigh t ( Sometim e s
    , .

    charco al o r a n t h rac it e is use d as fuel ) Th e mo dern furnac es ( Fig . .

    7 3 ) are b uilt of re brick encase d in iron and are o f much li gh ter


    -

    co nst ructi on than t hose formerly used They vary greatly i n size .

    but co nsist mainly of a long sh aft ta pering towards b oth ends .


    I n order to u tiliz e th e esca ping h o t gases (C O etc ) an a pparatus

    ( c u p and cone ) is tte d o n the t o p to co ndu ct them o ff and
    ,
    .

    als o allo w th e intro duc tion o f the ch arge The air necessary for .

    the p r oc ess is fo rced in h ot throu gh pi p es ( twyers) at the botto m


    , ,
    '

    4 64 IN O R G A N I C C HE M I S T R Y 3 02

    fu r nac e The b urning c o ke pro duc es carb o n m on oxid e


    of t h e .
    ,

    which is t h e princi pal facto r in the redu ctio n o f t h e ore

    F8 2 0 3 3 00 2Fe 3 00 2 .

    The red uced iro n sinks downward and c om e s in c on t a c t wi t h


    c ar b on at a high t e m p era t ur e ; as a r esul t s om e o f t h e c a rb o n is

    FIG . 73.
    B LAS T FURNA C E .

    d issol v e d b y i t an d its melting p oint c onside ra b ly d epr es s ed


    -
    .

    Wh en a denit e st age is reache d the fus ed iro n is d rawn o ff b el ow .

    I t is p rotec t e d fr o m atmos p heric o xidation by t h e slag o ating


    o n it .
    4 66 IN O R G AN I C C H EM I S TR Y . 3 0 4;

    3 04 . The pro perties of iron are in uence d in great m eas ur e


    b y the slight admixtures which it c on t ains p articularly by t h e ,

    carb on The p ercentage of carb on forms the ordinary ba sis of


    .

    classication of the d ifferent grades of iron under the hea ds pig ,

    iron an d malleable iron ; however in the ind u strial world this ,

    classic ation is n o t always adhered to .

    Pig i r o n , or c ast iro n , c ontains carb on It fuses very .

    eas ily but there is no previous softening ; hence it is not malleable .

    It is brittle Pig iron is the direct produc t of the blast furnaces


    .

    an d the iron is therefore mixed with small amounts of silic on phos ,

    p h o r u s sul hur etc


    , p ,
    The p resence
    . of manganese makes it c oar s ely
    crystalline and it is then known as p g eis en Th is is utilize ds ie e l .

    mainly for steel .

    R e n e d ir o n containing less than


    , carb on is harder t o ,

    fuse but is extensible and malleable and the more s o the less t h e
    , ,

    im purities I f the carbon amounts to


    . the iron can b e
    hardened ; in this manner ste el is obtained If there is less tha n .

    carbon it c an no l onger be hardened ; this is wrou ght iron


    , .

    It is obvious that between these main varieties there are numero us


    intermediate sorts which are pre pared in such a way as to suit t h e
    ,

    purp ose for which they are intended .

    Th e imm e n s e c o mmer ci al import an c e o f t h e iron c arb on syste m h a s l e d -

    to e xte n s ive inve st ig at io n s reg ardi n g i t n otw ith stan di n g that s uc h i n ve s tig a
    ,

    t io n s ar e atte n de d b y g re at e xpe rime n tal di fculti e s , p art ly b e c au s e o f t h e


    ve ry h igh t e mperature s in volve d B e c au se o f th e se di fcult i es it is n ot yet
    .

    p o s s i b l e to giv e an e n t i re ly s at i s fa c to r y re pre s e n t at i o n o f t h e e qu ili b r ium

    c on diti ons c on c e r ned BA K H U I S R O O ZE B O O M C HA R PY R O B ER T A U ST EN an d


    .
    , ,
    -

    othe rs h ave succ ee de d in w orkin g o u t t h e acc om pan yi n g graphic represen ta


    ti on w h ich i n dic ate s t h e b e h avi o r o f t h e system in t h e m a i n at l e ast T o .

    ap p re ci ate thi s d i a gram i t is n e c e ssary in t h e rst p l a c e t o kn ow a fe w g e ne ral

    fac t s r e gardi n g t h e c om p on e n t s that a r e n ow r e garde d a s e xi sti n g in t h e


    i ro n c arb on system D i stin cti on is m ade b e twe e n : 1 ferrite o r c h em
    -
    . .
    ,

    ic all y pu r e i r on ( pu r e w rough t i ron ) ; 2 m a rt en s it e ( s te e l ) a s olid s olut ion


    .
    ,

    o f c a rb o n in i ro n I t i s s o re g arde d b e c au s e m ic ro s 0 0 p ic s tu di es h av e sh own
    .

    th at m a rt e n s i t e is alw ays h om o gen e ou s in sp ite o f it s c h an gin g c arb on


    c on ten t w hich m ay b e as h igh as
    ,
    3 c em en tite (t h e c omm e rci al w h i te
    .

    c ast i ron ) an iron c arb on c ompoun d o f t h e form ul a Fe 0 ; an d 4 p erl ite


    ,
    -

    3
    . ,

    c arb on i fe ro u s iron th at is s e en un de r a h igh pow e r mic ros c ope to b e -

    h e te ro ge n e o us an d is re garde d as a e ute c t ic mixtu re o f fe rri te an d


    c e m e n t ite .

    Th e s o li dic at i on c urve o f a b i n ary syst e m 2 3 7 ) d oe s n o t t ak e a n o r


    m al c o urs e in t h e iron c arb on syste m -
    Th re e ci rcum stan c e s c om plic ate t h e
    .
    IR O N . 467

    s ituation Th e rst is th at pure iron does n ot separate ou t of t h e m olte n


    .

    mass b u t th at w ob t in t h s lid s lut i n m arte n ite Th e se c o d is t h at


    ,
    e a e o o o s . n

    c h n ge c o tin u e t o occur in t h e c ooli g m as s aft r c ompl et s olidic ati on ;


    a s n n e e

    t h e th i rd t h at oth er s u b st an c e s s p arat e o u t with v ery sl ow c oolin g th ane

    w i th quick c oo lin g .

    W e m ay c on i de r rs t t h e c as e o f sl ow c oolin g w h e re t h e e quili bria th at


    s ,

    e sta b li sh the m s lv s b e tw e e n s o li d an d liqui d ph as e


    e e r p e s um ab l y s tab le s a e r

    L t u s a s sum e th at w e h ave l iqui d i ron w ith a c arb on c on t n t b l ow


    e e e

    O n c oolin g t h e liqui d t h e i ron b e gi n s t o s li di fy at a de nit t m pe rature (t h e o e e

    p in t
    o in Fig
    01 h ow eve r i t is n o t pure i ron b u t a s o li d s olut i on o f
    .
    , ,

    92
    FI G . 7 4 I R 0 N 0 AR
    .
    -
    B O N SYS TE M .

    ca rb on in i ron th at r t ; it s c om p o s i t i on is sh ow n in t h e d i a gram
    sepa a e s o u t

    b y t h e p oin t d I f t h e c arb on c on te n t o f t h e fu s e d i ron is a di ffe re n t o n e


    l .
    ,

    w e h av e s e p arati n g o u t at c , fo r e x am p l e t h e s o li d s u b st anc e w h o s e c om
    , , ,

    p o s i t i on is a g a i n giv e n b y t h e p o i nt d Thu s fo r e ve ry s o li dic at i on p o i n t


    z
    .

    o f t h e cu rve A C w e c an n d a p o i n t d d e t c t h at give s t h e c om p os it i o n
    l, 2,
    .
    ,

    o f t h e s oli d s u b st an c e w h ic h b e gi n s t o s e parat e o u t Th e cu rve A D is .

    t h e g e om e tric a l l o cu s o f th e se po in t s I f t h e r e fore a h oriz onta l l in e is


    .
    , ,

    d raw n through t h e tri an gl e A D C t h e po in t 0 give s t h e c om p os it i on o f t h e


    ,

    liquid s o lut i on w hich s o lidie s at t h e c orre sp o n din g de n ite t emp erature


    ( i n dic at e d b y t h e ord i n at e ) a n d t h e poin t d t h e c om pos it i on o f t h e s o li d
    s o lut i on w h ic h b e gin s t o s e p arat e o u t a t t h at t em p e rat u re A t C t h e e ut e c tic .

    p o i n t is r e ac h e d A l o n g C B grap h i t e s e p a rat e s o u t ;
    . a t C i t s e l f a mixtu r e

    o f gr aphit e a n d m a r t e n s i te t h e c om p o s it i o n b e i n g give n b y D
    ,
    Th e p o i n t .

    C is at 1 1 3 0 an d o f c a rb o n Th e m a rt e n t it e form e d at th i s t e m

    .

    p e r a t u r e c o n t a i n s 2 % o f c arb on .
    68 IN O R G A N I C C H E M I S TR Y .

    Be l ow D C oli d ; b u t as w e h ave already e xpl ain e d c h an ges c on


    all is s , , ,

    tin ne to o ccur in t h e s oli d m a ss Fo r e xam ple if m art e n s ite is h eated i t


    .
    , ,

    b reak s u p w i th t h e form at i on o f gra ph i te Th e cu rve D E re pr e se n t s t h e


    .

    c h an ge o f c om positi on o f t h e s olid s o luti on w ith fallin g te m pe rature o r in ,

    oth e r w ords it re pre se n ts t h e e quili b rium b e tw e e n graph ite an d t h e mixe d


    ,

    c rystals (s oli d s olut ion ) at di ffe re n t te m pe rature s A roun d E w h e re t h e .


    ,

    tem pe rature h as re ac h e d ab out t h e m art e n s ite c on t a i n s on l y ab o u t


    c arb on A t t h e poin t E t h e for m ati on o f fe rri te b e gin s
    . .

    Fin ally t h e cu rve E G in dic a te s t h e c om pos i t i on o f t h e so lid s olut i on s


    ,

    from w h ic h fe rri te s e parate s out He n c e if t h e m art e n s i te c on ta in s le ss


    .
    ,

    th an o f c arb on fe rri te is de pos ite d al on g E G e x act ly a s ic e se parate s


    , ,

    out o f a dilute salt s olut i on w ith fa llin g te m pe rature .

    If t h e c oolin g is s u dde n oth e r ph ase s a re form e d t h e lim it s o f w h ic h


    , ,

    are re pre s e n t e d in t h e gure b y lin e s w h ich are re adily un de r ,

    s to od .In st ead o f t h e e ut e c t ic p oin t C at w h ic h grap h it e an d m ar ten s it e


    ,

    s e p arat e out w e h av e a e ut e c t ic p o in t a t C
    ,
    ve ry clos e t o C w h ere c e m en t ite
    1, , ,

    Fe 0 s e p arate s o u t w i th t h e m art e n s i te
    3 , Fu rth er t h e lin e C E r e p re s e n ts
    .
    , , 1

    t h e e quil ib rium b e tw e e n c e m e n t it e an d t h e mix ed c ry st al s ( m art e n si t e ) .

    A t E fe rrite is form e d to ge t h e r w i th c e m e n t i te
    1
    M arte n s i te c h an ges o ve r.

    a t t h i s t e m pe rat u re i n to a e u te c t ic m ixt u re o f t h e s e l a s t t w o s u b s tan c e s w h ic h ,

    h as t h e n e c on gl om e rat e s truc ture s o c hara c te ri st ic o f e ute ct ic s a n d is kn own


    as
    pe rlite A lt h ough th is w h ol e syste m s h ow n b y
    .

    lin e s is m eta
    st ab l e i t c an e xi s t fo r a n in d e n i te p e ri o d at o rdin a ry t e m p e rat u re s b e c au s e
    , ,

    o f t h e re d uc t i on o f t h e v e l o ci t i e s o f rea c t i on s w h ic h migh t res t ore t h e s tab l e

    form s .

    I t is e vi de n t from t h e a b ove th at w i th s l ow c oolin g m art en s it e e n t i re ly


    di sapp e ars I f t he c ooli n g is rap i d h o w eve r as in t h e h ar de n in g o f s te e l
    .
    , , ,

    m arten s ite c an b e b rought to exist at o rdin ary temperature s e ven th ough :

    it is in a me tastab le c on dit ion ; it s tran s fo rmati on ve locity is th e n e xtrem el y


    sm all .If t h e harde n e d s te e l is re h e ate d i t c h an ge s ov e r p ar t ia lly in to t h e
    ,

    s o ft c o n gl o m e rate o f fe rri t e a n d c e m e nt ite ;

    tem pe rin g o f st e e l
    .
    th i s is w h at take s plac e in t h e

    Small admixtures of other elements have an e ffect on the


    ro
    p p erties of iron equally as great as that o f carbon The p resence .

    of s il icon has ab out the same e ffec t as tha t of carb on but it is ,

    less intense Su lphu r even in a small amoun t re n ders the iron


    .

    bri t tle when h o t and therefore useless for forging O n this , ,


    .

    acc ount sul phurous ores as such are unsuitable for the manu

    fac t ure of i r on Phosphoru s makes the iron bri t tle at ordinary


    .

    tem peratures I t should also be m entioned that as a ge n eral rule


    .

    the effec t of these admixtures is strongly m odied by the pres


    e nce of others .

    3 5
    0 From the
    . crude i
    pg iron the direct p roduc t of the blas t ,

    furnace the other varieties of iron are pre pared For this purpose
    ,
    .
    470 I N O R GA N I C C H E M I S TR Y .
    3 05 ,

    so as t o pro d uc e a very go o d steel A basic lining can a l s o b e


    .

    use d with this p rocess .

    The increased demand for s pecial steels where physical and ,

    c hemical conditions have t o be regulated c arefully h as given ,

    greater si gnicance to the old cr u cibl e proces s the steel being ,

    m ade in graphite cru cibles in a laboratory m anner but o n about


    ten times the laboratory scale R ecently el ectric fu r n aces of the
    .

    arc and inductio n ty p e have been found very successful in pr o


    du c in g c rucible steel and with much less labor than t h e

    FI G 7 6 . .
    HER O U LT FURNA C E .

    c rucible process requi res The cradle sha ped H ER O U LT furn ace
    .
    -

    is shown in the accom panying c o mbined end view and vertical -

    section ( Fig . M is the molten metal S the slag and E , ,

    one of the carbon electro des ; B is brick lining and L a layer


    of m agnesium silicate . A s the resistance of the metal 1 s small
    c om p ared with that of the slag and the air most of the heat
    '

    is generated at the surface where the chemical action goes on


    ,

    between the slag and the metal The furnace is eventuall y


    .

    em ptied by rocking forward .

    Steel however made is a very com plex alloy containing


    , , ,
    IR O N .
    47 1

    carbon and manganese silicon sul phur


    ,

    and p hos phorus and p ossibly co pper arsenic alu , ,

    m inium oxygen nitro gen and cyanides and is c a p able as has


    , , , , ,

    been explained of containing the iron and carbon in various


    ,



    c ombinations Steel of the above description is
    . ordinary
    steel R ecently a large market has develo ped for
    . s pecial
    steels having new qualities es p ecially with res pect to hardnes s
    , ,

    and brittleness and serving new purp oses notably in tools


    , , ,

    military materials and materials of construction They may be .

    roduced by changing the hysico chemical character with


    p ( 1 ) p
    '

    res p ect to the iron carbon system (2) removing harmful o ccluded
    -

    gases (3 ) combining other elements chemic ally with iron or carbon


    ,

    or both and (4 ) adding other elements to form isomorphous


    ,

    solutions with iron Steel beco mes very hard and brittle for .
    ,

    instance when it is suddenly cooled from a high tem perature


    ,
    .

    If however it is then heated for a denite p eriod and allowed


    , ,

    t o cool slowly it becomes more or less te m p er ed according to the


    ,

    tem perature it can be made to have any desired hardness


    ,

    and elasticity (within certain limits) .

    O f the s p ecia l a ll oy s t eel s the nickel steels chrome nickel ,


    -

    steels and chrome vanadium steels seem to be most im port ant -

    The maximum hardness of steel is r e a c h e d when it contains


    1 2 % carbon ; if however some manganese (u p t o

    ,
    or c h ro ,

    mium (u p t o is added a much harder modication of steel ,

    is p roduced The addition of nickel gives a tougher steel which


    .
    ,

    is es pecially valuable for armor plate Tungsten (cf 2 9 7 ) and . .

    molybdenum are also added for di fferent purp oses I n any .

    c ase however a careful heat treatment is essential to develo p


    , ,

    the desired pro perties .

    Th e p rod uc t i on of wro u ghti ron fro m pig i ron i s us u ally a cc o mplished


    by t h e p uddl in g pr oc ess Pig i ron i s m elted i n a re verberatory furnac e
    .

    lined wi th i ron o re (o xide ) ; t h e c arb on and also t h e s ilic on are o xid ized
    ( an d so re m o ved ) part l y by t h e a c t i on of t h e a i r b u t m a inl y by that ,

    d u e to es c ap i ng c arbon m ono xi de g ives t h e pro c ess t h e na m e of



    of t h e o re wh ic h i s st i rred in with t h e m eta l Th e vi o l ent rea c t i on
    ,

    i
    p g
    .

    bo iling T h e i ron i s then a ll owed to be c o m e pasty when i t i s


    .

    ,

    worked u p i nto large m asses (bloom s ) wh ic h are rem o ved an d ha m ,

    mered an d ro lled Th e cinder i s thus s quee z ed out and t h e i ron i s


    .

    formed i nto bars .


    47 2 IN O R GA N I C C H E M I S TR Y .

    is obtained electrolytically an d by re du c
    C hemical l y p u r e ir on
    ing the oxide or chloride in a current of hydrogen I f the r e du c .

    tion takes place at a low temp erature the resulting iron p owder is ,

    p yro p horic It is a silvery white lustrous metal with a -

    s p ecic gravity of and a melting p oint as high as It -

    boils at 2 4 50 I t is the most magnetic of the metals ; p ure ir on


    0
    .

    and wrought iron can be magnetized only tem p orarily ; steel ,

    however permanently I ron is permanent in dry air or in water


    , .

    free from air (0 O 2 ) I n moist air it rusts ra pidly


    . fo rming
    ferric hydroxide ; as the rust does not form a co m p act lm it ,

    kee ps on forming .

    The rust ing of iron is greatly retarded by c ontac t with water c onta i n
    ing a litt l e a lkal i or sal ts of alkal ine reaction I n a soda so l ut i on for .
    ,

    instance iron re m a ins bright The rusting of iron in conta c t with


    , .

    water can be e x pla ined by assum ing that the oxygen dissolved in water
    endeavors to for m hydroxyl i ons with the hydrogen ions I n order to .

    c om pensate the ir negat ive potential the iron sends its positive i ons i nto
    the so lu t i on ; i n a short ti m e the so l ubil ity product of ferri c hydro xi de
    is rea c hed and the l atter is de posited ; in other words the iron rusts ,
    .

    N o w if hydro xyl ions are previo us l y introduced into the l i qu i d"


    ,
    by
    the addition of a base or a sal t of alkali ne reaction the ioni z ation of the ,

    water i s dim inished so m uch that the oxygen can nd a lm ost no hydro
    ge n i ons with whic h to for m hydro xyl ions ; therefore the iron does not
    send any m ore ions 2 7 6 and 2 7 7 ) into the solution and rus ting i s
    greatl y retarded .

    diss olves readily in hydrochloric an d sulphur ic acids with


    I ron
    the evolution of hydrogen A t red hea t it decomp oses water but
    .
    -

    the oxide 1s als o reduced by hydrogen s o that an equil ib r ium ,

    results
    3 Fe 4 H2 0 z Fe 3 O 4 4 11 2 .

    In nitric acid (no t too c oncentrated ) iron dissolves rea d ily with
    the evolution of nitric oxi d e N O but if the iron is rs t dippe d
    , ,

    in concentrate d nitric aci d an d then rins ed 0 0 it b ecomes in dif a

    fe r en t to the action of nitric acid This so called p a s s i v i t y


    .
    -

    of iron is p robably caused by a very thin co ating of oxide .

    I ron forms two sets of salts the ferr ou s and the ferric
    ,
    .
    I N O R G A N I C C H E M I S TR Y .

    Ferric C o m po u n ds .

    3 07 . The fe rric ion has only very slightly b asic pr operties .

    Fe rric sal t s of weak aci d s such as carb onic acid d o n o t e xist


    ,
    In ,
    .

    aque ous s olu t i o n most of the ferric salts even thos e o f strong ,

    a ci ds are p artially hydrolyze d


    ,
    F or tha t r eason they are b rown i
    .
    -

    ish re d since th is is the c olor of ferric hy d roxide in c olloi d al s bl u


    -

    tion O n the a d dition of an excess of sul phuric or nitric acid this


    .

    color disappears b ecause there is no longer any hy d rolysis From


    ,
    .

    this it app ears tha t the ferric io n itself in aqueous solution is o nly
    slightly c olored The ferric salts are readily c onverted in t o ferr o us
    .

    salts by reducing agents -


    .

    Fe rr i c oxi de , Fe 2 0 3 ir on sesquio xi d e is forme d o n heatin g


    , ,

    v arious iron com p ounds in the air and is manufac t ured by igni t ing

    green vitriol I t is a dark red p owder and nds use as a -

    p igmen t ( c o l c oth a r ) and in p ol ish ing glass etc ,


    .

    Fe rri c h y droxi de sep arates o u t as a reddish brown hydrogel -

    Fe 2 0 3 + n H2 0 w hen a ferric sal t solu t ion is t reated with an


    ,

    alkal i . The freshly pre cipitated hydrogel dissolves in a s olution


    o f ferric chl oride or ace t ate I f this solution is dialyzed a p ure
    .
    ,

    c o lloidal solution o f the hydroxide is nally o btained ; from th is ,

    the hydrogel is repr e cipit at e d b y a small amoun t of alkali o r


    acid .

    Fe rr o u s f e rri c o xi de , Fe g O 4 also c al l ed ferro so ferric oxide or


    ,
    -

    magnetic iron oxide occurs in nat u re as m agn etite I t is produce d


    ,
    .
    ~

    b y heat ing iron in steam


    Fe rr i c c h lori de is obtained b y passing chlorine into a solu
    t ion of ferrous chloride I t crystallizes at differen t tem peratures
    .

    wit h differen t amoun t s of water being an exam ple of t h e case ,

    d escribed on p 3 4 1 O n hea t ing the sal t hydrochlori c acid escapes


    . .

    with the water of crystallization A nhydrous ferric chloride can .

    b e pr epared by heating iron in a current of dry chlorine .

    B etween 3 2 0 and 4 4 0 the va p or density is approximately tha t


    calculated for Fe 2016 ; between 7 50 and 1 050 it falls to ha l f


    ,

    indicati n g a S p litt i n g o ff of chlorine or a disso ciation into 2 Fe 0 13 .

    The re d dish brown colo r of the aqueous solution of ferric chl oride
    -

    m ust be asc ribed chiey to u n ionized Fe 013 m olecules for the sal t

    ,

    has this sam e colo r when dissolved in ether in which n o ioniza ,

    tion o ccu rs In p a rt also this color c ome s from ferric hydroxide


    .
    , ,
    .
    FER R I C C O M PO UN DS . 475

    which is forme d b y hy dr olytic dissociation This d isso ciation .

    inc r eases on warming the dilute aqueous solution for a very dilute , ,

    almos t colorless solution of ferric chloride turns reddish brown o n -

    b oilin g When c o oled the liqui d gradually r es umes its original


    .

    c olor .

    Fe rr i c su l ph at e , obtain ed by dissolving ferric oxi d e in sulphuri c


    acid fo rms alums e g po tassium iron alum K zSO 4
    , ,
    . .
    ,

    2 4 H2 0 .

    When a fe rr ous sal t is conve rte d into a fe rr ic salt in aqueous


    s olution the bivalent fe rr ous ion is transfo rme d into a trivalent

    ferri c ion The oxygen r equire d for the conversion serves t o


    .

    o xi d ize the hydrogen ions of the aci d (which mus t b e ad d ed ) t o

    w at e r whe r eu pon t hes e hydr ogen io ns sur ren d e r their charge t o


    ,

    the ir on ions :
    2 ( Fe
    '
    2 (H

    el f
    ) o 2 (Fe
    ' " Hg O
    de Hy d d F de
    .

    Fe r r o u s c h l o ri r oc h l o ric ac i e rr ic c hl o ri

    Inversely the re d uction of ferric salts t o ferrous salts can b e


    ,

    e x pla ined by su ppo sing tha t every ferr ic ion gives u p a third of its

    charge to another atom and thus makes the latter an ion or n eu


    t raliz e s its charge .

    Sal ts f i ron ao r e a l s o k nown whi c h are deriv ed fro m the hyp othet ic a l

    o xi de Fe O They are obta i ned by heat i ng i ron lings wi th sa l t petre or


    a
    .

    p ass i ng c h l or i ne i nto an a lk a line sus pens i on of the ferri c o xi de hydrogel .

    Fro m s uc h so lut i ons po t as sium ferrat e KzFe O A crysta lliz es o u t i n dark , ,

    r e d pr i s m s i so m or pho u s wi th the c hro m ate and s ul phate of potass ium


    ,
    .

    These c rystals ar e readily so lub le in water b ut the i r dark re d so lu t i on ,


    -

    soon de c o m poses wi th the se parati on of ferr i c hydroxi de and o xygen


    as T h e free ferr ic a ci d i s u n k nown
    g
    .
    .

    08 unites I ron
    with c y a n o g e n t o fo rm com p lex an d
    3 .

    u nusually stable ani ons v iz the ferrocyan ic ion ,


    . and
    ion F 0 N ) 6] Their best known salts are t
    t h e ferr icya n ic [ (e p o as -

    s ium ferro cyanide K 4 Fe ( 0 N ) 6 3 H2 0 and potassium ferricyanide -


    .
    , ,

    K3 Fe ( 0 N ) 6 the y e l l o w and r e d p r u s s i a t e s of p otash


    ,
    ,

    r esp ectively The ionization of the com plex ions themselves is s o


    .

    s ligh t that they give none of the ordina ry reactions for ir on


    .

    For the commercial m a n f


    u a c tu r e ofy el l ow p ru s s ia te ofp o ta s h

    tw o p rocesses are used : I n the rst animal ref u se ( e g. blood ) ,


    . . .

    is charred yielding a black highly nitrogenous m ass This is


    , ,
    .
    47 6 IN O R G A N I C C H E M I S TR Y .
    3 08

    ign ite d wi t h potash an d ir on lings cooling h ot wate r is


    . A fter ,

    ad d e d an d t h e m ixture ltered ; fr om this ltrate the yello w


    p russiate c rystallizes o u t on standing This salt is.not forme d
    until the ignite d mass is treated with water fo r yell ow prussiate is
    ,

    decom p ose d by heat and cannot therefore be pr esent in the ignited


    mass The latter p robably c ontains p otassium cyanide iron and

    .
    ,

    iron sul phide ( animal refuse always contains sul phur c om poun ds) .

    Thes e s ubst ances can interact according to the equa t i ons :

    6 KO N Fe S K 4 Fe (C N ) 6 K 2 S;
    2KC N + Fe Hz o Fe (O N ) 2 2KO H H2 ;
    Fe (O N ) 2 4 KO N K 4 Fe ( C N ) R .

    The second process is em ployed in illuminating gas factories -

    for the u n pu rie d gas contains a little cyanogen and prussic acid .

    A fter being freed from tar and ammonia it is passed through a


    washer (scrubber) containing a solution of p otash in which ferrous
    carbonate ( ferrous s u l ph at e + po t ass iu m carbonate ) is sus pended .

    The foll o w m g reactions among others are known to go on her e


    , ,

    FGC O 3 2 HO N Fe (C N ) 2 Hg O 00 2 ;
    K200 3 2 HC N 2 KC N Hg O 00 2 .

    N otwithstanding that these reactions are reversible the hydr o ,

    cyanic acid can be quantitatively xed in this way because the ,

    ferrous cyanide and p otassium cyanide i n teract to form p otassium


    ferrocyanide which is b u t very slightly a e c t e d by carb on dioxide
    , .

    Potas s i u m f e r r o cy an i de , K 4 Fe (C N ) 6 3 H2 0 forms large sul phur


    ,

    c olored crystals I t s three m olecules of water can be expelled by


    .

    gently warming whereu p on the salt is left as a white p owder I t


    , .

    is not p ois onous Wi t h dilute sul phuric acid it produces prussic


    .

    acid on warming ; w ith concentrated sulphuric acid it yields


    carb on monoxide .

    The free fe r ro c yan i c a c i d, H4 Fe (0 N ) 6 se parates out as a white


    ,

    crystalline preci pitate when concentrated hydrochloric acid is


    added to a s t rong solution of p otassium ferrocyanide The pre .

    c ipit a t e soon turns blue in the air on acc oun t of the formation of

    Prussian blue ( and partial dec om p osition as well ) Various salts .

    of this acid have characteristic colors and are ins oluble ; hence
    p otassium ferrocyanide nds use in analysis I t is an interesting
    .
    47 8 ,
    I N O R GA N I C C HE M I S TR Y .

    Besi d es the oxide 0 0 3 0 4 j ust r eferre d to there are two o thers


    , , ,

    c o b alto u s oxi de 00 0 an d c o b altic oxi de 0 0 2 0 3 The salts are all


    ,
    " ,
    .
    ,

    cobaltous corres ponding to the bivalent ion 00


    ,

    C O BAL TO US C O M P UN DS O .

    The solutions of t h e salts are red ; h e n ce this is the color of


    the cobal t ion The non ioni z ed cobalt salts are blue e g the
    .
    -

    ,
    . .,

    anhydrous 00 012 the silica t e etc This di ff erence in color enables


    , ,
    .

    us to tell read ily whether a cobalt sal t in solution is ionized o r


    no t. Thus in concentrated solutions for instance all those cir , ,

    c u m s t an c es which reduce the ioni z ation cause a change of colo r

    from red to blue e g when a co n centra t ed cobal t chloride solu


    ,
    . .

    tion is warmed o r treated with hydrochloric acid That the ioni .

    zat io n is diminished by warming was mentioned in connection wi t h

    c u pric chloride

    C o b altous c h l oride , C O C 12 6 HQ O forms red mono clinic crys

    tals which turn blue on heati n g because of dehydration C o b alt


    ,
    .

    s ul phate , C O SO 4 7 HQ O is obtained in dark red monocli n ic prism s


    an d is isomor phous with Fe SO 4 7 H2 O I t forms double sal t s -


    .

    with alkal i sul phates e g K 2 S0 4 00 SO 4 + 6 H2 0 C o b al t n itr ate ,


    ,
    . .
    ~
    .

    a ppears in red hygrosco pic prisms C o b alt sili .

    c ate is very dee p blue ; hence its use for colori n g glass Pulverized .

    cobal t silicate serves as a pigment ( s m a l l ) in painting etc TH E ,


    .

    NARD S bl u e is a pigment obtaine d by igniting cobal t salts with



    ,

    alumina .

    C O BAL TI C C O M PO UN D S .

    3 10 oxi de , 00 2 0 3 is obtained by igniti n g cobal t


    . C o b alti c ,

    nitrate I t is a black powder which passes over into cobalto


    .
    ,

    cobaltic oxide 00 3 0 4 at red heat and at white h eat yields cobaltous


    , ,

    oxide I t has the character of a peroxide ; for by the a ddition of


    .

    sul phuric acid it is converted into a cobaltous s alt with the e vo l u


    tion of oxygen and it yields chlorine with hydro chlori c acid How .

    eve r in cold dilute hydro chloric acid it dissolves without g e n erat


    ,

    I ng scarcely any chlorine .

    L ike iron cobalt also forms com plex ions of which those with
    , ,

    cyanogen are very stable There are cobalt salts corres ponding in .

    com position to the yellow and the red prussiates of potash ; the
    sal t K3 00 ( 0 N ) 6 potassi u m c o b al t ic yan ide crystallizes in colorless
    , ,
    rh ombic prisms A pe c uliar com plex ion o c curs in the potassiu m
    .
    C O BA L T A N ) " N IC K E L . 47 9

    c o b alti c nitrite , 6 KN O z or
    n HzO It is form ed on t rea t i n g a solu tion of a c obalt sal t wi t h
    .

    p otassium nitrite and ace t i c acid I t is a yello w crysta l line pre .

    c ipit a te which is ve ry slightly solu ble when po t assiu m ions are


    ,

    p rese n t in excess in t h e li q ui d .

    C obal t also fo rms n umerous com plex io n s with am m onia

    N i ckel .


    3 1 1 o.c curs N ickel
    in n ic c ol il c N iAs an d n ickel g l an ce o r , , ,

    gcr s d oril e N iA s S E s pecially


    ,
    im po r.tan t is the n ic k e l sili c ate ,

    gar n ier ite ,


    which was d is c ove red by AR
    N I E R in N e w C aledonia where it oc c u rs in enormous q ua n t ities
    , .

    C anada to o has so m e rich n ickel ( l e p0s it s


    , ,
    From this o re t he .

    n ickel is o b tained by a blas t fu rn iw e pro c e ss simila r to tha t fo r -

    iron Th e discovery of ga rn ierite marke d t he beginning of a


    .

    n e w era in the nickel in dust ry Much nickel is re line d c le c t ro .

    lytically .

    N ickel is almost as whi t e as silver is v e ry to u gh a n d h as a ,

    high metal l ic l ustre Sp g 8 8 9 l ; rn = . . I t is


    . . . .

    feebly m agnetic l t dissolves s pa ringly in hy dro c h loric an d


    .

    su lphuric aci d s but freely in n itric aci d I t is pe rm a nen t in t he .

    air .

    It is em ploye d in n ickel pla tin g metallic obj ects an d as a con -

    s t it u e n t of several a l l o y /s G e r m a n s i l v e r contains about


    .

    50% C o pper 2 5 96 n ickel and 2 5 % zin c ,


    Th e n ickel coi ns of
    ,
    .

    G e rmany and t h e Uni t ed Stat es consist of 7 5 % co pper an d 2 5 %


    nickel The u s e of nickel to va ry t h e pro perties of iron has alrea dy
    .

    b een men t ioned


    The oxid es o f n ickel N iO an d N l2 0 3 are very simi l ar to th ose
    , ,

    of cobalt The nick elou s o xi de , N iO is t h e only one which fo rms


    '

    .
    ,

    sal t s .

    N ickel chlori de N iC l g GHQ O yie l ds green m onoclinic pris m s


    ,
    -

    ,
    .

    When heated it tu rns yellow on a c coun t of l oss of w ater .

    N ic k el s u l ph ate , N iSO 4 7 HzO crystalli z ing in g reen r h ombic '

    isms is isomo rph ous with the corres pon di n g ferro u s a n d o t he r


    p r ,

    salts and also fo rms anal ogous doub l e salts .

    N i c k eli c o xi de , N i2 0 3 als o behav es as a peroxi de ; w h en warmed


    ,

    with hydroc h loric acid it yields chlorine gas and ni ckel c hloride .
    4 80 IN O R G A N I C C HE M I S TR Y . 3 11

    N i ck e l ,
    ca rb o n yl
    is formedN i( C O ) 4 ,
    when carbon monoxide is
    led over nely di v ided nickel at ordinary tem peratures A state .

    o f equilibrium results here v1z ,

    Ni -
    N i( 0 0 ) 4 ,

    which is dis placed to the left with rising tem perature since t h e ,

    decom position of nickel carbonyl takes place with a considerabl e


    absorption of heat Even as low as 6 0 the decom po sition

    is of an ex plosive nature It follows from the above equation that


    .

    an increase of pressure 1 22 ) must greatly increase the pro por


    tion of nickel carbonyl formed Ex p eriments conrming thi s
    .

    S howed at the same time that both the formation and the de c o m

    p osition of this com p ound are very sensitive to traces of foreig n

    substances .

    N ickel carbonyl is a colorless highly r efractive liquid which , ,

    b oils at 4 3 an d congeals ( crystalline ) at



    When heat ed in
    the air it burns with a very sooty ame This c ompound is of .

    i
    a d in extracting nickel fro m low grade ores .

    N ickel also forms a com plex ion wit h cyanogen O n dissolving .

    n ickel cyanide in an excess of potassium cyanide the com p ound

    KzN i(C N ) 4 is produced ; it is however unstable being decom posed


    , , ,

    b y hydrochl oric acid with the de position of nickel cyanide N i(C N ) 2 ,


    .

    3 1 2 A.
    p e culiar ro
    p p erty is exh ibited y t h e s u l ph i de s o f c o b al t
    and nickel 0 0 S and N iS Hydrogen sul phide does not pr eci pitate
    ,
    .

    these sul p hides from acid solutions b ut o nce preci pitate d ( by , ,

    ammo n ium sul phide ) they are a pparently not redissolved by dilute
    ,

    aci ds This is c o ntrary t o the general rule of 1 4 6 ( see also 7


    .

    for th e sul phi de sh ould either be prec ipitate d by h ydrogen sul phid e
    fro m a feebly acid solutio n (e g C u S) which is the case whe n t h e
    . .
    ,

    solubility p ro duct is very small o r else wh en the solubility pro duc t


    , ,

    is larger it sh oul d diss olve in d ilute acids as is th e case with ferrous


    , ,

    sul phid e As a matter of fact h owever no real ano maly exi sts
    .
    , ,

    h ere for the rate of solub ility of th ese sul phi des is only very slow
    ,

    u nder the usual conditions of th e re action viz dilute aci d an d ,


    .
    ,

    r o om tem perature I t increases with th e conc entratio n of the acid


    .
    ,

    tem p erature of reac ti on an d neness o f grai n o f t h e preci pitate .

    N i ckel sul phide is soluble in al kali sul phides immedia tely u po n i ts


    form ation b ut wh en onc e dep osite d in the s olid state i t is insol
    ,

    uble or nearly so This is s een when a nickel s olutio n is treat e d


    '
    .
    ,
    4 82 IN O RG A N I C C HE M I S TR Y . l 3 13

    tion Further the presence of iron ( which o ccurs in all platinum


    .
    ,

    o res ) is often very disturbing ; for exam ple pure platinum solu ,

    tions are not precipitated by soda or barium carb onate but if iron ,

    is present more or less platinum comes down with the hydroxide of


    ir on I n Spi t e of these difculties platinum p alladium rhodium
    .
    , ,

    an d iridium can now be p urch a sed in a remarkably p ure state .

    For m an ufac t u re of pl at inum an d the other m etals of the gro up


    t he
    in t h e p u re state the vari o u s fa c tori es e m pl oy the i r own se c ret m ethods .

    I n genera l t h e p ro c ed u re i s abo u t as fo ll ows : Th e o re i s rst treated


    w i th a qu a regi a to di s so lve o u t t h e m a j or part of t h e nob l e m eta l s
    ,

    l eaving in t h e res i du e t h e all oy i ri dos mine bes ides m ore or l es s sand , .

    The o re thu s c ons i sts n o t of on e all oy b u t of two : t h e c ru de pl at i nu m ,

    and t h e i ri dosmine Both c ontain all s ix plat in um m etals al tho u gh in


    .
    ,

    d i fferent rel at ive a m o unts The c ru de p l at in um c ontai ns besi de s


    .
    ,

    p l at i n um p r i
    ,
    n ci p a ll y p a ll ad ium rhod ium and
    ,
    i r i d ium wh il e,
    the i r i dos ,

    mine as i ts nam e indic ates c ons i sts m ai nly of i ri d ium and os mium
    , , .

    I t i s c o m parat ive l y easy to s eparate o u t the os m ium an d r u then ium


    they form v o l at il e o x ygen c o m po unds and c an therefore b e re m o ved
    by d i st ill at i on Pl atin um and i ri dium give dif c u l t l y so lub l e c o m
    .

    p ounds w i th a mm on ium c h l or i de wh ic h i n t u rn
    ,
    are red uc ed to the
    m eta l for m by i gn i t i on Howe ver i f the so lu t i on of the c ru de pl at in um
    .
    ,

    i s pre ci pi tated wi th a mm on ium c hl ori de t h e res ul ting pre cipi tate i s ,

    fo und to c onta i n c ons i derabl e a m ounts of rhod ium an d pa ll ad i um and ,

    an e xtended pro c ed ure i s ne c essary for t h e i so l at i on of the p ure m etals .

    O n t h e other hand i t i s not p oss ib l e to pre ci p i tate t h e pl at i n um and


    ,

    i ri dium c o mpl etely i n thi s way ; t h e l trate fro m t h e a mm on ium c hl ori de


    c ontains pall ad ium an d rhodium wi th s mall er a m o unts of i rid ium and ,

    p l at i n um and ,
    i n order
    ,
    to wor k i t u p a fu r t h e r c o m pl icat e d p rocedure
    , .

    i s ne c essary .

    R u t h en i u m .

    3 4 1 Th i.s stee l gray m eta l o-


    ccu rs on l y i n v ery s m a ll qu ant i t i es ; i t
    i s hard very brittl e and very d i fcul t to f use a temperat ure of at l east
    , , ,

    1 800 be i ng ne c essary E v en when ne l y d ivi ded i t i s b u t v ery s pari ngly



    .

    so lub l e in a qu a regi a forming R u C l b u t when all oyed wi th pl ati num


    , z s, ,

    i t d issolves read il y Th e c o m po und R u C l i s known onl y in do ub le salts


    . 4 .

    A s a p owder t h e m eta l o xi d iz es i n t h e a i r to R u O and R u O R u the z s .

    n ium also form s c hara c teri st ic sal ts i n whic h i t p l ays t h e part of an ,

    a ci d.

    Po t ass i um ru t h e n a t e K R uO res ults fro m fu s i n g ru thenium wi th


    , z ,,

    c au st ic p ot ash an d sal tpetre I t c rystalliz es wi th 1 H 0 i n b l a ck pri s ms of


    . 2
    PL A TI N UM M E TA L S . 4 83

    a greenish lu stre Wi th water it form s a dar k orange c ol ored so l ut i on


    .
    -
    .

    I t s c ond uc t re mi nds one of potass ium m anganate for u nder the i nu en c e ,

    of d ilu te a ci ds i t i s c onv erted i nto p t a iu m p rrut h n at e K R u O wi th


    o ss e e , 4,

    the s imul taneo u s pre ci pi tat i on of a b la ck o xi de h O 5 (or It ,

    c rysta lliz es in b l a ck o c tahedrons of m eta llic lu stre whic h d i sso lv e in ,

    water to a dar k green so lu t i on


    -
    A pe culi ar c o m po u nd i s the t e t o i de
    . r x ,

    R uO 4,
    wh ic h v o l at iliz es when c hl or i ne i s passed i nto the c on c entrated
    s o lu t i on of potass ium r u thenate I t ca n b e so li d i ed by c oo li ng when
    .
    ,

    i t form s a go l de n crysta lline m ass f us ibl e at , There i s n o a ci d


    c orres pond i ng to thi s o xi de R u O 4 i s u sed for the preparat i on of pure
    .

    rutheni um .

    Th is m etal is very ana l ogous to ru theni um ; it m elts as hi gh as


    The chl or i des O s C l2 an d O s C l 4 a n d the o xi des O s O O s2 O 3 and O SO 2 are ,

    known The great s imil ar i ty to ru thenium i s es pe ci ally not iceab le i n


    .

    t h e h i ghes t o xi des Thu s fus i on wi th c a ust ic potash and salt petre pro
    .

    d uc es potassium o s m i at e KzO s O 4 whic h c rysta lliz es fro m a queo us so l u


    , ,

    t i on i n dark vi o le t o c tahedrons c onta i ni ng t w o m o le cules of water


    -
    .

    The c hara c teri st ic os mi um c o m pou nd i s the t etr o xide O s O , formed , ,

    by i gni ti ng ne ly powdered osmium in the ai r or by the a c ti on of chl o


    r i ne on the m etal i n the presen c e of water Th e a queo us so lution of
    .
    .

    O s O 4 rea c ts ne u tral b u t i s often (wrongly) ca ll ed o smi c a c id


    ,
    I t is .

    e m pl oyed I n m 1 cr o s co py s i n c e organic s ubstanc es (i e reduci ng agents) . .


    -

    reduc e i t to bl a ck os mium N o sa lts der i ved fro m O SO 4 are kno wn


    . .

    Thi s c o m po u nd i s u sed i n pre par i ng pu re os m iu m .

    R h o diu m .

    The m etal i n the fu sed state has the a ppearan c e of al um inium and
    is j u st as e x tens i b l e ( m a ll eab l e and d uc t il e ) as s ilver I t i s pre pared .

    p ure i n the arts by way of the c h l oro p u r p u reo rhod ium -


    c h l or i de ,

    R h ( N H3 ) 5 C l 3 ( cf
    . N e i ther ac i ds nor a qu a regi a affe c t i t When .

    heated in t h e a i r i t i s o xi d iz ed to the rh o dio u s o xi de R h O I t i s abl e to ,


    .

    absorb a c ons i derable a m o unt of hydrogen Th e rhodic oxi de h O 3 .


    , ,

    yi e l ds sa lts wi th a ci ds O f the chl or i des only h C l6 i s k no w n ; thi s i s


    .

    obta i ned by d ire c t synthes i s as a reddi sh brown s ubstan c e ; it form s s ol


    -

    u b l e doub l e sal ts w i th the a lk a li c h l ori des T h e m ost sat i sfactory .

    therm o c o upl e for m eas u ring h igh te mperat ures is m ade of pure plat inum
    a n d an a ll oy of pl at i num a n d rho dium .
    4 84 I N O R G A N I C C H E M I S TR Y .
    l 3 14

    This very refractory m eta l i s obta ine d fro m iridosmine by heat ing i n a

    c urrent of o xygen when the os mium v o lat iliz es as tetroxi de I n the form
    ,

    of a pl at inum all oy i t is e m pl oyed in the m anufa c t u re of platinu m


    .


    c ru cibl es d i shes di st illing vesse ls for the c oncentrat i on of s ul phu ri c a ci d
    , ,

    et c The prototype of the m eter at Pari s i s m ade of an all oy


    .

    of 9 0% p lat inum and 1 0 % i ri d ium The ad mix ture of i ri d ium m a kes t h e .

    p l at i n um m ore i nd i fferent to c he mic a l agents a l tho u gh at h i gh te m ,

    e r at u res t h e v o l at ili ty of t h e i r i d ium i s often tro u b l eso m e When p ure


    p .
    ,

    i rid ium i s n o t attacked by a qu a regi a .

    I r i di um form s two chl or i des I rzC l 0 and I r 0l 4 Both of the m giv e


    , .

    do ub le sa l ts w i th the alkali chl ori des ; e g I r2 016 6 l ( 01 + 6 H2O a n d . .


    -

    Ir C l4 2K C l
    ~
    Th e for m er d i sso lves in water readil y the l atter wi th
    .
    ,

    d ifcul ty The tetra chl or i de appears as a bl a ck s ubstan c e formi ng


    .

    wi th water an i ntense ly re d so lu t i on For thi s reason a pl at i num c hl o .


    e

    ri de so lu tion whi ch c onta ins ir i dium has a much deeper c o l or than a


    p ure so l ut i on .

    Pall adi u m .

    3 5 The si l very wh ite m e t a l f u ses at


    1 i e m ore easi l y than
    -
    . . .

    p lat i n um W hen . ne l y div i ded it d i sso lves i n bo ili ng c on c entrated


    hydro chl or ic s ul phur ic an d n i tr ic a ci ds
    , O n i gni t i on i n t h e a i r i t i s .

    at rst oxi d iz ed thu s l os i ng i ts lustre b u t at a hi gher tem perat ure the


    , ,

    m etalli c lustre reappears The m ost pec uliar chara c ter isti c of the
    .

    m etal i s i ts ab ili ty to abs orb hydr ogen in l arge qu ant it ies (occlu sion )
    . .

    Freshl y igni ted pa ll adium fo il absorbs 3 7 0 t im es its o w n vo l u m e of


    hydrogen at roo m te m perat u re By m aki ng pall adium fo il the cathode .

    i n a water ele c trol ys i s apparatus the m etal c an be m ade to tak e u p


    e ven 960 t im es i ts own vo lum e This absorption does not al ter i ts .

    m etallic appearan ce The absorbed hydrogen can all be e x pe ll ed by


    .

    heat i ng in a va c uum .

    Pa ll ad i um c harged w i th hydrogen i s a strong redu cing agent ; chl o -

    ri ne an d i od i ne are reduc ed by i t (se e 2 00) to hydrogen c hl ori de and


    hydrogen i od i de respe c t ivel y and ferric sal ts are redu c ed to ferrous sa lts
    , , .

    Pall ad ium form s two ser i es of c o m po unds the O u s PdX and the ,
    -
    z,

    -
    ic PdX
    ,
    A c haracter i st ic c o mp o und of the rst seri es is p a ll ad i o u s
    4.

    i odi de Pdl wh ic h i s pre cipitated by p otass ium i od i de fro m so lut i ons of


    , z,

    - o u s sa lts as a b l a ck inso lub l e s ubstan c e Th i s rea c t i on i s o cc asi onally .

    u sed to separate i od ine fro m t h e other hal ogens s in c e thei r pall ad ium ,

    c o mpo unds are read ily so lub l e Pal l a di c ch l or i de Pd01 i s produc ed


    .
    , 4,

    by d i sso lving the m etal i n a qu a regi a Wi th K C l or N H 01 i t form s .


    4

    a d i fficul tly so lub le do ub le c hl or i de K d C l e or (N H ) PdC l O n the, , 2 e.

    e vaporat i on of i ts solu t i on PdC l d i sso ci ates in to PdC l and 012 4 z. .


    4 80 IN O R G A N I C C H E M I S TR Y .
    3 16

    t he sal t remains in t h e form of small b u t well formed o cta ,


    -

    h e dro n s of a golden hue The potassium salt is often made .

    us e of in determining p otassium when s odium is also present ,

    the s odium platinic chl oride being very soluble even in alcohol , .

    O f the remaining platinum comp ounds a fe w may be referred


    t o I f a s olution of the ab ove acid Ht C IG is treated with
    .
    , ,

    sodium hydroxide and then with acetic acid pl ati n u m h ydr oxi de , ,

    Pt ( O H) 4 is precip itated ,
    I t is soluble in strong acids and also in .

    alkalies so that basic as well as acidic pro perties must be ascribe d


    ,

    t o it (pla tin ic a cid) Salts of this acid are m oreover formed when
    .

    latinum is fused with alkalies P l ati n o u s c h l o ri de , Pt 0 12 is


    p .
    ,

    roduced by heating c h l o r l at in ic acid to 2 00 and in small amount



    p p ,

    also when the s olution of this aci d is strongly c oncentrate d I t is


    , .

    a green p owder insoluble in water With the alkali chlorides i t


    ,
    .

    gives soluble double salts such as Pt 012 2 N a01 D o u b l e c yan i de s ,


    o
    .

    of platinum with many metals are also known e g K 2 Pt (C N ) 4 ,


    . .

    3 H2 O Ba Pt (C N ) 4 4 H2 O etc
    ,
    The latter has come int o prominence
    -

    ,
    .

    because of its abil ity to make R entgen rays visible A l l these .

    d ouble salts are noted for their beautiful col ors and strong dichroism .

    METAL AMMO N IA -
    C O M PO UN DS S EXTEN SI O N S . WER N ER
    OF
    THE N O TI O N O F VA L EN C E .

    3 7 1 . Se ve ral
    m e t al n o t a b l y t h o e o f t h
    s, e e igh th g ro u p o f t h e pe ri o di c s

    s y t e m a e c ap b l e
    s ,
    r f f rm in g c mpl e x c o mpound w i th ammon i a an d a ci d
    a o o o s

    r dic l s Such c mpou d h ve l g b e en kn w s me h vin g be e n pre


    a a . o n s a on o n, o a

    p a re d b y t h e l d m a t e r oB ER ZE LI U Ss Th e t u dy o f t h e se
    , u b t c e o ccu i
    p ed . s s s an s

    v ari u s i ve t ig at rs f t h e n i t e th c e n tury e pe ci lly JOR G E N S N


    o n s o o ne e n , s a E .

    I n re c e nt y e ars h ow e ve r t h i e l d h as b e n e xpl o e d
    , , d g e atly e xte de d
    s e r an r n

    b y t h e i ve t ig t ions f W ERNER a d h i p u p il
    n s a o o th t a t t h e p r e t t ime n s s, s a es n

    o ve r 1 7 00 c o m po un ds f t h e g en r l t ype M Xp ( A m ) q a e al e dy k n ow n
    o e a , r r a ,

    M b e in g a met al at o m X an ci d radic al a d A m ammo i a or an org ani c


    ,
    a n n

    ba e (s e v e n w t r)
    or C h i f c re di t is al o d e WERNER f r h avi g t ake n u p
    a e . e s u o n

    t h e th e r t ic l tu dy o f t h e re l t i o n h ip b e t w ee n t h e e c omp ou ds a d as
    o e a s a s s s n n ,

    a re sult g e r liz t ions o f c o i de r b le import anc e fo r t h e structure of


    ,
    en a a ns a

    i rg ic c omp o u d
    no an e p ci lly t h e m pl x l t h ave be en e st ab lish e d
    n s, s e a co e sa s, .

    Th e w h l e s u b j e c t de e rve a li ttle atte nt i n at t h i po int


    o s s o s .

    C o n c e rn in g t h e m e th o d o f prep r in g the e m et l ammon i a c ompo u nds


    s a s a -

    v e ry li tt l e f a g e e ral n t ure c n ye t b e s t te d
    o n It is re ad ily ap pre ci ated
    a a a .

    th t t h e prepa t io n f s uch a l rge number of c ompl e x c ompo un ds c alls for


    a ra o a

    t h e mo t d ive r ie d s yn th e t ic al me tho ds
    s s .
    M E TA L A M M O N I A C O M PO UN DS -

    . 4 87

    In order to acquir e in igh t i to t h e n at ure o f t h e c o mpounds c on ce rned


    an s n

    w e m ay r s t e x ami n e t h e t in it it o t iam m in e c b al t r r r o ,

    wh ic h c an b e o b t ain d b y mixi g c o l d o lut i ons o f c o b alt c h l or i de ammo


    e n s
    ,

    n ium c hl or i de an d so d ium n itr i te a d tre at in g t h e mixt ur e w i th a curr e n t of n

    a ir . Th e c omp o un d th en se parate s o ut as a dif c u l t l y s olu b l e c y t allin e r s

    w d r I t c an b e re cry t lliz e d fro m h o t w at e r c o n t a in in g a li tt l e a ce t ic


    s a
    p o e .

    a ci d w i th o u t li b e rat in g n itro u s a ci d an d is n o t att a ck e d b y dilut e min e ral


    , ,

    a ci ds in t h e c o l d Th e e le ctric al c onduct n c e o f it s a qu e o u s o lu t ion is


    . a s

    appro xim at e l y z ero E vi de ntly th ere fore t h e u b st n c e l a cks t h e ordi n ary


    .
    , ,
    s a

    p pro e r t i e s o f a n i tr i te ; t h e N O g ro u p s mu st b e j o in e d to t h e m o l e cul e d i ffe r


    z
    -

    e nt l y th an in t h e n itr it e Th e ammon i a t o o is oth erw i e c om b i n e d th an


    s .
    , , s

    in t h e a mmon ium alt s Thi follow s at onc e fro m t h e fa ct th at t h e c o m


    s . s

    p o u n d i a no
    s e l e ctro lyt e :
    n -
    fu rthermore fro m t h e fa c t th at t h e a c t i o n o f ,

    e v en c onc e trat e d a ci d i i su fci ent to p li t o ff amm o n i a


    n s s The N H g oup s
    n s .
    -
    r
    s

    a e n t h e l d b y t h e a ci d rad ic l
    r o prese nt in t h e m o l e cul e fo b y ene rg et i c a s , r

    r e a c t i o s i t is po
    n ib le to s ub t itute oth er a ci d radic al for th ese w ith out
    ss s s

    li b erat in g t h e ammoni a mole cule s Th e s uppo it ion o f an act ive part icipa . s

    t i on o f t h e a ci d r adic l s in t h e link ag e of t h e N H mol e cul e s is th u s e xcl u de d


    a s
    -

    I n d e ci di g h o w t h e amm o i s a e c o n n e ct e d to t h e m o l e cul e i t is ign ic an t


    n n a r s

    t h at t h e amm n i a m o l e cul e c an b e re pl ac e d s ucc e s ive ly b y oth e r mol e cul


    o s s es .

    Th i sh ow s th at e ach ammo i a mo l e cul e mu st be linke d in de p e de n tl y o f


    s n n

    t h e oth e r in t h e c o mp le x mol e cul e


    s A b ou t t h e o n ly s at i sfa ctory e xp l an a .

    t ion is th at t h e N H mol e c u le a att c h e d d i e c tly t o t h e m et al at o m


    -

    s
    s re a r .

    WE RNER h ow e ver m ake s t h e am a umpt ion fo r t h e aci d radic al s in order


    , ,
    s e ss

    t o e xp l ain th e ir ab norm al be h avior Th i s th eory wh ereby t h e spe ci al .


    ,

    p pro e r t ie s o f t h e g ro u p s in c o mpo un ds o f t h e typ e M X ( N H )


    p q
    are e xpl ained 3

    o n t h e as umpt i on that the se gro up s a e in d ir c t c o m b in at i o n w i th t h e


    s r e

    met al h as prove d to be o f gre at import n c e for t h e cl a ic at i n o f th e e


    ,
    a ss o s

    c o mpo und Th e s . cce pt ance f thi prin ciple h ow e v r n e ce s itate s an


    a o s , e ,
    s

    exten si n o f t h e
    o p en t n t i n f v
    r es l en c C o b alt fo e x mple is at mo st
    o o o a e .
    ,
    r a ,

    trival e nt in it lt a d oxide ; b t if w e a ume dire ct lin k ge t o t h e


    s sa s n s u , ss a a

    met al o f t h e thre e N H d t h e th e e N O gro u p t h e c o b alt mu t h ve a


    3 an r z
    -
    s, s a

    valenc e o f ix Th e e n e w app i g af it i e s f t h e metal ato m c a t


    s . s e ar n n o nno

    o ffh an d b e cl a e d w ith sst h e ordi a y v l e n c e b nd Fo r th i re a o n it n r a o s . s s

    s ee m appro pr i at e to a ig n a Spe ci l name to th e m I n order to di t in gui h


    s ss
    a . s s


    th em from t h e ordin ry v l enc e s w h ich a e te rme d princip al or prim ary


    a a , r

    valences they a e c alle d ubordinate or s e co n d ry val e c e s


    ,
    r

    s ,
    a ,
    n .

    C o mpo un d o f t h e typ e o f t h e t in it it o t i m m in e c o b alt th at is o f


    s r r r a , ,

    t h e g eneral formul a M X ( N H ) h ave t h e pro pe rty o f c om b i i g w ith more 3 3 3


    n n

    ammo n i a mo l e cul e t ill Th u s th ere a e c o mpounds o f t h e type M X


    s s . r s 3

    MX (N H )3 3a d M X (N H )
    5, n Th e add it ion o f a mmo ni a give s r i e t o a
    3 3 3 . s

    pe culi ar chang e in t h e fu n c t ion f t h e a ci d r dic al s b e c au se f r e very addi o a ,


    o

    t io n al N H m l e cul t h t is t k n o n o n e o f t h e a cid r d ic al s ent e rs t h e


    3
    -
    o e a a e ,
    a

    ioniz le co it i n e c o mp are t h e mo l e cul ar c onduc t ivi t i e


    a b d o n I f w . s in
    F i
    n orm al s o lut i o n at to w i t
    or
    3 0 0 :
    4 88 I N O R GA N I C C H EM I S TR Y .
    M 3 17 ,

    GO ( N H3 ) X
    5 3
    0 (N H 94X3
    24 5 1 17 7

    With t hose of t he l ts
    sa

    we n d th at t h e rst of t h e ab o ve co mpl ex s alts mu st be a qu aternary , t he


    seco nd a te rn ary , t h e th ir d a b inary , e l e c tro lyte , an d t h e fo urth a n on e l ec
    -

    t ro l yt e .

    Th e ch emic al propert i e s of th e se c o mpoun ds a cc ord perfe c tly w i th th is


    th eo ry . I n t h e c o mpound, 0 0 ( N H3 ) 40 13 , formerly c all e d pr ase o c o b al t
    -

    ch l or i de , onl y o n e ch lor in e c an b e dir e ctly pre ci pitate d b y s ilve r nitrate ;


    in C o ( N H3 ) 50 13 t w o c an b e s o pre cip itate d, w h ile in C o (N H3 ) 6013 , h ex ammi n e


    c o b al t ic c h lo r i de , all th re e c h l or in e ato m s appe ar t o be i on iz e d in aqu e o us

    so lut io ince al l th re e re act at once w ith a s il e r lt lution Th i is


    n, s v sa so . s

    e x pl in e d o n t h e a
    a umpt ion that t h e adde d ammoni a mole cul e di pl ce
    ss s s a

    t h e aci d r d i c l s fro m th e ir imme di at e c o n n e c t ion w ith t h e me t al ato m an d


    a a

    th e m elve s e ter i nto th i s dire c t u n ion w ith t h e metal I n order to di stin


    s n .

    gui h t h e ammoni a mo l e cule w h ich a e linke d u p in th is w ay WERNE R


    s s r

    appli e s t o th e m t h e t e rm a m m in a n d de vi e t h e fo ll o w in g formul ae an d n ames


    e s s

    t o e xpress t h e c o ns t i tut ion o f t h e ab o ve


    named c ompo un ds :

    M ( N H3 ) 3 X3 Tr i aci do t riam m in e c o mpo u n ds


    -

    M ( N H3 ) ,X3 Di a ci do te trammine s alts


    -

    M ( N H3 ) ,X3 A ci do pe n t am m in e s al t t [M (N H3 ) 5X] X2 ,

    M ( N H3 ) ,X3 He xammine s alts

    the atoms or groups w ith in brackets b e ing re garde d as m d i r e c t u n i 0 n


    w ith t h e m e t al ato m Th e i o n iz ab l e gr ou ps X ou t s i de o f t h e brack e ts ar e
    .

    in i n d 1 r e c t u n i o n w ith t h e c o mpl e x a n d a cc ord in g to W ERNER , ,

    ar e n o t j o i n e d t o a de n ite e l e m e n t al ato m .

    I f w e c ompare t h e c ompo s it ion o f t h e var iou s me t al ammon i as w e n d -

    that t h e formation o f c ompl exe s is n o t w itho ut it s limitat ion s b u t th at after ,

    t h e addit ion o f a de n ite n umb e r o f N H mo l e cul e s it c o me s t o an e n d


    3
    -

    Part icul arly sh arp is t h e limi t in re s pe c t t o t h e n umb er o f gro up s w h ich c an


    un ite dire ctly w ith an atom s erving as t h e c ente r o f a comp le x radic al I t .

    is a s trik in g fac t th at th i s limit is t h e s ame fo r a goo d m an y e l e ments an d


    is c o mmo n l y s ix I t s ee ms mo s t like ly th at th i s limiti n g n umbe r is
    ch aracterist ic o f t h e e le mental ato m an d o f con s i derab le importanc e W E R .

    NER c alls it t h e co ordi n at i on n umb er an d de ne s i t as t h e m aximum n umb e r


    o f i n d ivi du al gro u p s th at c an b e d ire c t l y u n i te d t o an e l e m e n t al ato m As .

    alre ady s t ate d t h e c o o rdin at i on n um b e r fo r mo st e l e ments is 6 ; for a fe w


    ,

    e l e ment s b o ro n c ar bo n
    , ,
    an d n itro g e n, it is 4 , .
    4 90 I N O R GA N I C C HE M I S TR Y .
    3 18 .

    t h ree in N o 1 it h as b e c om e z ero in N o 4 i e t h e mo le cule h as b e c ome a


    .
    , .
    ,
    . .
    ,

    n o n c on duc tor
    -
    If t h e s u b st i t u ti on is c arri e d furt he r as in N o s 5 6 an d 7
    . .
    , , , ,

    t h e c ompl ex in b rack e ts assume s t h e ani on role an d it s n e gat ive c h ar ge

    FI G 7 7 . .

    incre as es fro m o n e to th ree If t h e mo l e cul ar c onduc t ivi ty fo r a .

    c onc entrat i on is p l otte d o n t h e ord inat e a xis in a d i agram , w e o b ta in fo r

    t h e s e r i e s o f c o mpo unds a cur ve , as is sh o w n in Fig 7 7 N umerou s an al o . .

    gou s trans it ions of metal ammonia compounds to comple x -


    sa lt s ha ve been
    dis c o vere d e g , .

    ti [Pt C l ]K2 ; 1< )


    [Pt C l JKz z e t c .

    Furt h e rmo re , re l at io n sh ips


    ve b e f u d t o e xi t b e tw ee n me tal ha en o n s

    amm o n i d h yd t
    as anI t i a ig ic t fac t th at f
    r a es . l g e n umbe r
    s s n an or a ar

    o f a lts f me t l w h ic h give h e x mm in e
    s o a s lt w ith mm i a h ydrate w ith a sa s a on ,
    s

    s ix m o l cul e s e f w at p r e d mi t e
    o T h i i t h e c
    er e w i th t h e
    o al t of
    na . s s as s s

    c b lt ch omium icke l t c M eover Jo G N S N o b erve d th at c o m


    o a ,
    r ,
    n ,
    e . or ,
    R E E s

    p o u n d es d e r
    ariv d f m t h e h e x mmi e
    e l ts b yrot h e xc h g e f n or a n sa e an o o e

    tw oN H mol e cul e f
    3
    -
    w te w h ich c omp u n d
    s orcor po d in b h vi or
    a r, o s re s n e a

    t o t h e h e x ammin e lts Th i s fo ll o w s fro m t h e f ct t h at t h m l e cul ar


    sa . a e o

    c o n duc t ivi ty in a qu e o u s s lut i on is b t li ttl e a ffe c t e d b y t h i s e xc h n g e e g


    o u a ,
    .

    It is l o c on me d by t h e f ct th at w ith t h e remo val o f e ch w at er m o l e


    a s r a a ~

    cule an cid dic al l a it i o n izi g pro p e rty ju t


    ra w t h e c a e fo t h e
    oses s - n , s as as s r n
    i

    re m v l f ch mmo i mo l cule f o m t h e h e xammi e s lt :


    o a o ea a n a e r n a s
    3 18 g M E TA L A M M O N I A C O M PO UN DS
    -
    . 491

    HgO .

    Aq uo p e n t am m in e
    c h ro m ic c h l o ri de

    Th e a dd it i o f
    onter h as t h e o ppo s ite e ffe ct Th e trich l oro t r iam m in e
    wa .

    c ob alt for ,
    e x amp l e
    is kn ow n t o form h yd at e s w ith 1 2 an d 3 mo l s w ate r
    ,
    r , , . .

    Si n c e all o f t h e th re e chlori n e ato m s in t h e tr ih ydrate h ave an i o n iz in g c h ara c


    t e r w h il e in t h e diyh dr at e o n ly t w o h ave th i s propert y in t h e mo n o h y dr at e
    , ,

    o n e an d in t h e an h ydrou s c o m p o u n d n o n e w e ar e ju st ie d in as cr i b in g t o
    ,

    th em in t h e fo llow in g co n st ituti on

    C o ( H2 0 ) 012, an d Co
    ( N H3 ) 3 ( N H3 ) 3

    A n e arl y c om pl ete tran s it i o n s eri e s fro m a m etal amm oni a to -


    a h ydr ate
    h
    ( y dro u s s al t ) is to b e fo u n d in t h e c a s e o f c h r o mium

    013 ,

    Bl ue h e xahy d r at e

    Al l th e s e c o mpo un ds c on t ain t h re e c h lorin e ato ms in i on iz able l in kage ;


    a cc o r d i n gl y s ilve r n i tr at e at on c e pre cip itate s a ll t h e ch l o r ine as s ilver
    c h loride e ve n fro m fre sh ly pre pare d s o lutio n s o f t h e s alts Th e fun ction o f
    ,
    .

    w at e r in th e s e c o mpo u n ds c o rre s po n ds p e r fe c tl y t o th at o f t h e w at e r in t h e
    a qu o s alt s o f t h e c o b al t ammo n i as i e
    -
    w i th t h e re l e as e o f e ac h w at er mol e
    ,
    . .
    ,
    ~

    cule a ch lori n e ato m s acr ice s it s ion izin g ab ility .

    Tw o h e x ah ydrate s o f c h romic c h l o ri de GrC l 6 H 0 ar e kn ow n o n e b lu e , 3


    -
    2 , ,

    an d t h e oth e r gr ee n Th e b lu e o n e c o n t ai n s th ree io n iz ab le C l atoms an d


    .
    -

    a cc ordin g t o it s g e n e ral b e h avi or s h o ul d b e r e g ar de d a s h e x aq u o


    c h romic ch loride Upo n t h e l o ss o f t w o w ate r mo le cul e s it go e s ove r i nto
    .

    dic h l o r o t e t r aq u o c h ro mic c h l ori de w h ich c ont ain s b u t o n e


    ion iz ab l e C l atom -
    .

    If th is dic h l o ro t e t r aq u o ch l o ri de is c ry st alliz e d o u t o f w ate r i t a dds ,

    o n t w o m o l e cul e s o f t h e w at e r a n d g o e s o ve r i n to t h e gr ee n h y drate ,

    w h ic h is th u s i s o me r ic w i th t h e b lu e h ydrate Th e .

    g r ee ri h y d r at e m o re,
    o ve r c o n t ai n s o n l,y o n e c h l or i n e a t o m t h at c a n b e p re

    c ipit at e d d i r e c t ly w ith s ilve r n i trate I t s h o ul d al s o b e me n t i o n e d th at


    .

    t h e gr e e n h ydr at e c an b e t ra n s fo rme d i n t o t h e b lu e o n e an d t h e w ate r mo le


    cule s t h at c o n dition t h e i so me r ism sh ifte d Sin c e t h e i so meris m must
    , , .
    4 92 I N O R G A NI C C H E M I S TR Y . 3 18 ,

    de p e n d on t he di ffere n c e in t h e man n er of att ach ment of t h e w ater WE R N E R ,

    h as c ll e d it h ydrat e
    a is o m erism .

    V i u c
    ar o a es s f i ms e r i om t h t
    so a m e ts w i th in t
    a h e mre t l mm o a e a -
    a ni

    co m p
    u do n b e
    s t x
    e p
    ar e l a i sd c a e o f s
    net er e o is
    aso m e iss m s N e e s r . o s ri

    of c m po
    o u n d a k n o w
    s n f
    re t h e g e e l f mul
    o n ra t h e y a
    ore c a
    a,ll ed r
    4

    p
    l at in d i amm ine c o m p o u n d s a n d h a v e b e e n k n o w n s in c e 1 87 0 L ate r in .

    I
    I
    f
    I
    I

    FI G 7 8 . . FI G 7 9 . .

    v e st igat io n s ha ve sh o w n th at th i s kina
    isomeri m o ccurs o ly w ith c o m of s n

    u e type M
    g um t i t r or m t at t h e
    z
    p o n ds f t h o T h e a p o n c an h.e e f e b e a de ssh
    4

    s ix g o u ps a e arr an g e d at t h e ap e xe o f an o c t ah e dro n a o u n d t h e c e n tral


    r r s r

    ato m O nly w ith t h e type abo ve de scri b e d a e t w o i omers po ss i bl e as


    . r s ,

    t h e acc o mp an y i g gure s ( Fig C o mp o unds o f t h e M


    ?

    7 8 an d 7 9 ) sh ow
    n s . .

    type c annot th ere fore h ave i mers an d as a matter o f f c t n o o n e h as yet


    , ,
    so , a ,

    b ee n ab le t pre p ar s uc h i me r
    o e so s .

    WE R N E R h l o di covere d met l ammon ias of more th an o n e n ucl e us


    as a s s a -

    i e w h e re t h e m l cul e c o n tai n e ve ral me t al ato m s j o ine d to o n e an o th e r


    . .
    , o e s s

    in s uch a w ay as t o u n de go n o se parat ion e ith e b y i oniz t i on or b y spon


    r r a

    t an e ous h ydro lys i s ; b u t we c annot dwe ll longer upon t h e s u b j e c t h ere .


    94 I N DEX .

    Antim ony, p entoxi de, 23 6 Bar mp ero de , 53 , 3 8 7


    iu xi
    tetroxi de 2 3 6 ,
    Baryta w ater , 3 87
    -

    tric h lori de 23 3 , B as e s, 3 9 , 1 02
    tri oxi de 23 4 ,
    BA S ILI
    US VA ENT NU S, 23 1 L I
    tri sulp hi de 23 6 ,
    B AU M E de rees , 1 42 g
    An tim on y l 2 3 5 ,
    Ba uxi
    te, 43 6 , 43 8
    A nti se p tic 4 1 6 ,
    BE CK
    ER, 1 2 9
    An gle s i te 286 ,
    C
    B E Q UERE , 3 9 7 L
    A n g strom 3 9 2
    Be ll m
    e ta , 2 7 6 l
    B ER M ANN , 9 9
    G
    ,

    A p atite 1 99 3 7 6
    , ,
    B E R NT H SE N , 1 3 3
    A qu a re gi a 1 98 ,

    Ar agon i te 3 7 6 3 82
    Ar genti te 3 59
    , ,
    L
    B ERT H E O T s pr n p e , 1 57

    i ci l
    B ER T H E O T L
    M A H ER a or etrL c l im ic
    ,

    Argon 1 7 0 3 00 3 09
    ,

    Ar gyr odi te 2 86
    , ,
    m
    b o b , 1 53
    A R I STO T L E 3 7 1
    ,
    l
    Bery , 3 7 2
    A RR HEN I U S 95 1 01
    ,
    B ery i ll um
    ,
    3 03 , 3 7 2
    Ars en ic 22 1 ,
    , ,
    LI
    B ER ZE U S , 2 3 , 2 9 , 3 0, 1 4 8, 280, 2 9 3 ,
    ac d,i 22 9
    BE SS E M ER pro e ss , 4 6 9 c
    m l e a , 22 6
    B im l cul
    o e ar rea t on s , ci
    2 06 , 2 55
    oxi de , 228
    s ulphi des 2 2 9 2 68
    I K L
    B R E AND , 1 9 1
    s ulp h o alts 2 3 0 s
    , ,
    B s i muth , 2 3 6
    c l i
    -

    h or de , 2 3 7
    ,

    trich loride 226


    w h i te 224 2 2 6
    ,
    gl c
    an e , 2 3 7

    Arse n i
    ,

    tun gstat s 4 57
    ,

    e
    xi
    h y dr o des , 23 8
    Ar se n i u s a ci d 22 8
    o
    ,
    xi
    o des , 23 8
    oxi d 226 e,
    ,
    x c l i
    o y h or de , 2 3 7
    Ar seno li te 221
    u i
    s b n tr ate , 2 3 9

    A rsen op yri te 2 2 1
    ,
    s ul
    ph ate , 2 3 9
    Ars ine 22 3
    ,
    s ul i
    ph de s , 2 3 9
    ,

    A sb e sto s , 3 7 4
    B a l ck as h , 3 1 9

    ci i
    A sso at on, 82 , 1 85
    l c
    B an xe , 3 88
    m
    A t o sp h ere , 1 65
    "
    ,
    l c
    B ast furna e , 4 6 3
    eac h in g , 3 6 , 6 1 2 6
    A tomic h eat, 2 89
    theory, 27 gl e ac h in g p o w e r , 85 3 8Q/
    -
    3
    v lum
    o e , 29 7
    l
    B ende, 407 z /

    ig
    w e h ts, 2 9
    l m
    B oo s , 4 7 1
    D etermin at i on of 44 , 4 7 , 4 9 , 2 88, B O DEN ST E N , 1 5 I
    3 05 il g i
    B o in p o nt , e e at on o f, 6 1 , 2 7 2
    -
    lv i
    B O L TW O O D , 404
    l
    T ab e , o f, I n s ide back cover
    B O NE , 2 49
    m
    A to s , 28 , 4 9
    l ck
    B oneb a , 2 44
    A ugi te, 3 7 4
    ci
    Bora te , 4 3 2
    u ic c m u
    A r o po nds, 3 7 0
    x
    Bora , 4 3 2 , 43 5
    u u c m
    A ro s o pou n ds , 3 6 9
    ic ci
    Bor a d, 4 3 3
    u um
    A r m u siv u m , 2 8 1
    Boron, 4 3 2
    A v o G A D R o s hyp oth e s s, 44, 60, 2 9 3

    i I G L
    B O U SS N AU T , 1 6 6
    zi
    A des , 1 7 9
    BO EYL
    zu i
    A r te, 3 53
    BO YL
    E S l aw , 4 7 , 58, 1 60, 2 95
    B RAND , 1 9 9
    c
    Ba ter a, 1 9 4i Brass , 3 5 5
    Y
    BAE ER , 1 44 Br ick
    s , 440
    K
    BA ER , 1 85, 3 3 3 , 4 1 4 Br im
    sto n e , 1 03
    BA L A R D , 6 5 , 84 Bro ne, 6 5mi
    B A M ER , 3 9 2 , 3 93
    L x g
    o y en o po n ds of, 9 0 c m u
    i
    B ar te , 3 87 z
    Br on e , p h osp h or,
    Bar ium , 3 87 s ilic
    on, 2 7 6
    IN D E X .

    Bron es , 2 7 6z C ations , 96
    Brook t e , 44 6 i C at s e y e , 4 55
    -

    Brownian o e ent , 49 m vm C aus tic potash , 3 23


    BR Q W N I N G , J s pe tros o pe , 3 89 c c soda, 3 1 3
    B RU H , 55 L A V E N D I SH ,
    B UN S EN , 3 2 9 , 3 89 , 3 9 1 , 3 98 l i
    C e es t t e, 3 86
    u
    b rner , 2 58 LI
    C E S U S, 2 0
    c e ll 422 ,
    m
    C e ent, 3 7 8
    Burette 1 47 ,
    m i
    C e ent te, 466
    C er a mic
    s , 440
    C ad mium ,
    410 C er argyn t e , 3 59
    '

    C ae s ium , 3
    29 i
    C er te, 44 3
    I
    C A N , 24 9 iu
    C er m , 44 5
    l mi
    C a a ne , 407 u i
    C er ss te, 2 8 1
    lci i g
    C a n n , 3 53 , 46 3 lc ci
    C h a o te, 3 53
    lci
    C a te, 3 7 6 , 3 82 C h a op yrite,
    lc
    Ca lcium , 3 7
    6 C ha , 3 7 6 lk
    c i
    ar b de , 1 7 1 , 2 4 9 C h a ae eon m l mi nera e , 46 1 l
    c ar b onate , 3 82 m
    C h a b er a d, ci 3 19
    c l i
    h or de , 3 2 1 , 3 4 0, 3 79 c l
    rysta s , 1 9 5
    c imi
    yan de, 1 7 5 c l
    C har o a , 24 5
    u i or de , 3 80 C H A R PY , 4 66
    xi
    hydro de, 3 7 8 mc l
    C h e i a af nity,
    c l i
    h yp o h or te , 3 80 operations 5 ,

    m g i
    an an te , 4 60 C hem i stry eld o f 3 , ,

    i
    n trate, 3 82 C h ili saltpetre 6 9 1 89 ,

    C hinese w hite 409


    , ,

    xi
    o de, 3 7 7 ,

    i
    p erox de, 3 7 9 C hl oramine 1 7 7 ,

    p hosp h ate s , 3 82 C hlor aur ic aci d 3 7 0


    -

    p lum b ate , 2 85 C hlorazide 1 7 9 ,

    il c
    s i ate, 3 84 C hl oric acid 88 ,

    sul ph ate , 3 3 8, 3 8 1 C hl oride o f lime 3 80


    ,

    sul i p h de , 2 9 1 , 3 1 9 , 3 80 C hl orination pro c ess (gold) ,


    3 68
    l ml
    C a o e , 413 C hl orin e 3 3 ,

    l ic c
    C a or e ffe t , 1 52 , 3 3 6 , 3 57 , 43 7 hydrate 3 7 ,

    l im
    C a or et er, 1 53 oxygen comp oun ds of 83 ,

    lx
    C a , 1 65 C h lorous aci d 88 ,

    l
    C ana r ays , 4 00 C h lorosulphon ic a cid 1 42 ,

    C ar at , 3 68 C h l orpl at in ic a d, 4 85 ci
    i
    C arb des , 24 7 , 24 9 , 4 57 m
    C hr o ates , 4 52
    C arb on, 2 4 1 m
    C hr o e a m , 4 52 lu
    m u
    a orph o s , 2 44 g
    reen, 4 50
    i xi
    d o de , 2 52 llow 454
    ye ,

    m xiono de , 2 49 C hr om sul ph uric acids 4 5 1


    -

    x ul i
    o ys ph de , 2 5 1 C h om ic anh ydri de 4 52
    r ,

    t e t r a u o r id e , 24 7 chl oride 4 5 1 ,

    C arb on ado , 2 4 1 oxide 4 50 ,

    C arb on a d, 2 53 ic ci s ulph ate 4 5 1 ,

    C arb or nd u , 24 7 u m C hr om ite 44 9 4 50 , ,

    arb ur e t t in g , 2 50 C h romium 449 ,

    ll
    C arna ite , 3 2 2 , 3 2 9 , 3 7 4 , 4 4 1

    in stee l 4 7 1 ,

    C A R o s a d, 1 44 ci oxy chl o i de 455 r ,

    i
    C ass ope m , 446 iu C hromous c omp oun ds 450 ,

    i
    C ass terite, 2 7 4 C h romyl ch lori de 4 55 ,

    i
    C as t ron, 4 66 C h y sob ery l 3 7 2
    r .

    C A s rN E R , pro ess , 3 1 4
    '
    c C i n b ar 1 03 4 1 0
    na , ,

    l i
    C ata ys s , 3 4, 55, 7 3 , 1 29 , 1 3 4 , 1 3 7 , C L AR K E 3 8 6 ,

    C l ay 4 3 6 440
    , ,
    4 96 I N DE X .

    C l e e1 t e , 1 7 2 C u pric sul ph ate, 3 58


    C o a , 24 5 sul p h i de , 3 5 9
    C o arse m e tal , 3 54 C u pr i t e , 3 5 3
    C ob alt , 4 7 7 C u prou s c h lori de , 3 56
    comp oun ds (ammon i a) , 487 cy anide 3 57
    C ob altite , 22 1 , 4 7 7 iodi de , 3 56
    G O E HN, 1 29 oxi de , 3 55
    C O H EN , 4 2 5 s ul ph at e , 3 5 7
    C ok e , 2 4 5 C UR I E , 3 9 7 , 3 9 8
    '

    C o lc oth ar , 4 7 4 C URT I U S , 1 7 8
    C o ld h o t tub e o f D E VILL E , 1 2 8
    -
    C y an i de pro c e ss , 3 60,
    C o le m ani te 4 3 2 , 43 5 ,
    C y a n ogen, 2 55
    C o ll argo l , 2 69
    o ll o ids , 2 6 6 , 268 , 3 6 5 , 4 3 8, 4 7 4 AL TO N27 , 43 , 293 , 3 97
    ,

    C olumb ium , 44 9 A N IE LL e , 42 0 c ll
    C omb u sti on, 1 1 , 1 6 5 VY
    D A , 2 4 1 , 2 58, 3 1 1 , 3 22 , 4 1 8
    C omp o n ents , 1 1 0 C
    D EA O N pro e s s ( h or ne ) , 3 4 c c l i
    C o mp o u n d , 2 5 D E B I E R N E , 3 98
    C o n denser , 6 c
    D e a n t at o n , 5 i
    C onduc t ivity, mol e cul ar, 9 7 c
    D e ay o f e e ent s , 4 02 , 4 04 lm
    C onservati o n o f m atter, 1 6 e n it e p ro p ort ons , l aw o f, 2 7 i
    en e rgy 1 5 3 ,
    e gr e e o f fre e do ,
    111 m
    C on s tancy o f n atur al p h e n om ena ,
    e liq u e s c e n c e , 3 1 8
    C on t ac t a c t i o n Se e C atalysi s
    . . DE M O C R I T E s , 2 8
    p ro c e ss ( s ul p hur ic a ci d ) 1 37 ,
    l gi ic
    D e p h o s t ate d air, 1 6 6
    C onv erter 4 6 9 ,
    De s icc
    ators , 1 42
    C oord inati on numb er 488 , e t o n at in g g as , 1 5 , 22 -

    C o p p e r 3 53
    ,
    E VILL
    E , STE C A RE , 7 3 , 1 27 . L I
    ammon i a c o mp ounds 3 5 9 D E WAR , 1 4 , 1 7 2

    ,

    c om p o u n ds 3 5 5 ,
    i l i
    D a ys s , 2 66 , 2 6 9
    (Se e C upric an d C uprous . i mi
    D a de , 1 7 7
    C opp eras 47 3 ,
    i m
    D a on d, 24 1
    C orros ive s ub lim ate 41 4 4 1 5 , ,
    D dy i mium ,
    445
    C orundum 4 3 6 , il m
    D ato e ter, 1 08
    C oun ter current pri ncip le 1 9
    -

    , ii ci
    D s nfe t on, 3 6 ,
    C O URT O I S 6 9 ,
    isp e r s e , p h ase , e t c , 2 7 2 .

    C ov e r i n g p o w e r 2 8 7 , 121,
    C R E D N E R , 1 68
    c i
    C ro o te , 2 8 1 , 449 2 59 , 2 7 7 , 2 86 1 3 3 3 , 3 55, 3 7 0, 3 83 ,
    C R O O K E s , 44 2
    Cr uci l c
    b e p r o ess ( stee ) , 4 7 0 l e lectrolytic ,
    9 4, 1 3 1 ,
    ic
    C ryohydr p o nt , 3 3 9 , 3 41 , 3 7 9 i 2 68,
    C ryohydrate, 3 3 9 , 3 43 4 09 , 4 1 5, 4 1 7 , 4 7 2 , 4 7 5, 4 7 8,
    l
    C ryo ite, 3 1 1 , 4 3 6 4 89 .

    C ry os o p c ic m e th o d, 6 5 h d y ro lytic,
    1 00 , 207 , 2 6 9 , 2 7 7 , 2 7 9
    r y s t al liz at io n , 6
    l i
    C rystal o ds , 2 68 4 42 , 4 4 7 , 4 7 4
    mix
    r y s t al s , ed , 468 i
    tens on, 4 3 0
    u p an d c one ap parat s , 4 63 u is t ill at io n , 6 , 1 9
    u ll i
    C pe at on , 3 6 0, 3 6 8, 3 69 ci l
    fra t on a , 6
    u ic
    C pr arsenite, 3 59 i i ui
    D str b t on l aw o f BER TH E LO T , 3 25,
    b ro mi de, 3 58
    carb onate , 3 59 it hio n ic 1 45 a cid ,

    c l i
    h or de , 3 58 iv i
    D ar ant syste , 1 1 4 m
    xi
    h ydro de , 3 58 I
    D X O N , 2 55
    i i
    od de , 3 58 DO E B E R E I N E R , 2 1 2
    i
    n trate , 3 59 l mi
    D o o te , 3 7 4
    o xi de , 3 58 D oub l e de c omp os i ti on ,
    41
    4 98 IN DE X .

    G old compounds See Aurous c o m . Hydri odic aci d, 7 1


    p ou n ds an d A u ric c omp ounds . Hydr ob romic a ci d 6 7 ,

    G o ld p lating 3 68
    -

    ,
    Hydr o c arb ons, 2 4 8
    G O L D S C HM I D T reducti on m eth o d 4 3 7 , ,
    Hydro ch loric a ci d, 3 7
    compos ition o f
    41 ,

    L
    G O D STE N , 4 00 I Hy dro u ob o ric a d, 4 3 3 ci
    u i
    G rad at on s a t pro es s, 3 1 5 l c Hy dro u o ric a d, 8 1 ci
    G RA HAM , 2 6 6 , 2 68 Hy dr o u osil ic ic a d, 2 64 ci
    G ra m quiv l
    e a ent, 1 4 6 gl
    Hydro e , 9 7 0, 3 58, 43 8, 4 50, 4 7 4
    mole cule 3 2 ,
    Hydro en, 1 3 g
    G r p h ite 2 44
    a ,
    i
    ant m on ide , 2 3 2
    G raph itic a ci d 244 ,
    i
    arsen de , 22 3
    G R I E SH E I M pro c e s 3 1 3 3 2 5 s , ,
    mi
    b ro de, 67
    G RO VE s g b ttery 4 2 5

    as a ,
    c l i
    h or de , 3 7
    G U I G N E T S gr n 4 50

    ee ,
    . c i
    yan de, 256
    G u n m etal 2 7 6
    -

    ,
    i ul i
    d s p h de , 1 2 0
    G u n p ow d e r 2 6 3 2 7 , ,
    lu i
    f or de , 8 1
    G U T E I T S t es t ( ar e ni c ) 222 i i
    od de, 7 1

    Z s , ,
    2 24
    G U YE 29 4 ,
    xi
    p ero de , 5 3 , 64 , 3 67 , 4 55
    G Y P SUM 1 03 3 7 6 3 81, , ,
    ul
    p ers p hide , 1 2 0
    i
    p h o sph de , 2 04
    Hali te, 3 1 1 l i
    se en de , 1 4 9
    HALL pro c e s s ( aluminium ) , 43 6 s ilicide , 2 62
    H amm er s c al e 1 2 ,
    s ul i
    ph de, 1 1 5
    HA M P S O N , 1 0, 1 7 0 llu i
    te r de, 1 50
    Har dn ess o f w ater, 3 83 i ul i
    tr s p h de , 1 2
    HAR G REAVE S m eth o d, 3 1 7

    Hydro lys i s Se e D i sso ci ati on hydro
    .
    ,
    Hartsh orn, salt o f, 3 3 4 lyti c ;
    Hausm anni te , 4 58 Hydroso l 2 7 0 ,

    He at ato mic , 29 0
    ,
    Hyd oxy l 1 4 3
    r ,

    mole cul ar 1 7 3 2 91 , ,
    Hydroxyl mi n e 1 80 a ,

    o f d iluti on 1 53 ,
    di sulp h onic a ci d 1 98
    -

    formati on 1 52 1 55 , ,
    Hypo , 1 3 2 , 3 1 7
    n eutraliz at i on 1 5 3 3 50 , ,
    Hyp o c h loro us a ci d, 84
    s o lu ti on 1 53 1 61 3 3 6 , , ,
    oxi de 84 ,

    Sp e cic 2 90 ,
    Hypon itrou s a ci d 1 87 ,

    He vy sp
    a 3 87 ar , Hypoph os p h oric a ci d 2 1 8 ,

    He lium 1 7 9 3 00 3 9 4 4 00 4 02
    , , , , ,
    Hypop h osphorou s a ci d 220 ,

    HE LM H O LT Z 1 58 ,
    Hypo sulp h ur o us aci d 1 3 3 ,
    Hem t ite 4 63
    a ,
    Hyp oth es i s 2 ,

    HENR Y S l aw 1 1 3 9 9 5 1 3 3 3 3 2

    , , , , , ,
    43 4
    Hep ar su lp h ur is , 3 2 8 I ce m c
    a hine , 1 7 5
    -

    HER O U LT , 4 3 6 I c e ston e , 3 1 1 , 4 3 6
    furn ace 470 ,
    Il lumi i g
    nat n g as , 4 7 6
    HE SS ,
    l aw o f, 1 53 c
    I n andes ent e e tr c l c ic lig
    h t , 4 56
    Hexammine c ob alt s alts, 489 ig LB C
    g as l h t ( W E S A H ) , 44 3
    Hi ttorf 202 ,
    i l
    Inde l b e in k , 3 6 6
    HO FM ANN , 2 4 ic
    Ind ators , 3 50, 3 5 9
    Holmium , 44 3 Ind ium , 3 05 ,
    44 1
    Hop p er c r y stal of s al t 3 1 7 ,
    uc c ivi
    I nd e d r adi o a t t y , 4 01
    -

    Hor n b l ende 3 7 4 ,
    v i i
    I n ers on , p o nt , o f, 1 06
    Horn Silv er 3 59 3 6 3 , ,
    i
    I o d ne, 6 9
    H ub n erite 4 56 ,
    c l i
    h or des , 83
    Hydra te i so meri sm , 19 2 x g c m u
    o y en o p o n ds o f, 9 1
    Hydrate s 4 90 ,
    m
    I o do e try, 226 , 2 28
    Hydraulic mi n ing , 3 68 I on ic quili ium
    e br , 98

    Hydrazin e 1 7 7 ,
    qu i
    e at on , 1 1 8 , 1 3 2 , 2 7 7 , 282 ,
    Hy draz oic aci d, 1 7 8
    I N D EX
    i

    c equil ib rium t h eory of 9 4 1 1 8


    /
    I oni , , , Lead, 28 1
    I on ium 4 05 , c arb onate 2 86 ,

    I on iz ation See Disso ciation elec.


    , ch amb er crystal s 1 95 ,
    t ro l y tic . ch amb ers 1 3 5 ,

    3 56 , ch lori de 285
    1
    ,

    4 5 1 453 , 4 5 9 , chromat e 4 54 ,

    v l c
    a en e o f, 1 2 3 glas 3 84 s,

    i ium
    Ir d ,
    4 84 ni trate 2 86 ,

    i i
    Ir do s m n e, 4 82 , 484 oxi de s 2 83 ,

    Ir on, 4 6 3 p eroxi de 9 9 4 4 22 , ,

    an d carb on m xide
    ono ,
    47 7 p ersul p h at e 2 86 ,

    I someri sm " s ul phate 2 86 ,


    _m
    1 861 m h is 92 ,
    s ul phi de 2 87 ,

    sot e m c so lu ti ons 6 2 tree 2 82


    ,

    w h ite 2 86
    ,

    L E B L AN C s oda pro cess 1 4 2 3 1 9 3 27


    Jas per, 2 6 5 , , ,
    L E C H A TE L I E R S rule 1 6 0 1 86
    250,
    JOR G E N SE N , 4 86 , 4 90 , , ,
    338

    Kain i te 3 22 3 7 4 L E C L A N C H E e l , 4 23 cl
    , ,
    L E C O Q DE B O I SB A U D R A N , 44 1
    Kaolin 4 3 6 440, ,
    i l
    L ep do ite , 3 1 0, 3 2 9
    KA SS NER pro cess 285 , ,
    L EU PPU S , 2 8 CI
    KA Y SER 3 92 3 9 3 , ,
    L E Y D E N FR O ST , pheno en on, 1 7 0 m
    K e lp 6 9
    ,
    im
    L e, 3 7 7
    Ki e serite 3 7 4 ul u lu i
    ph r s o t on , 3 8 1
    ,

    Kinetic th e ory 47 249 s -

    KI PP generator 1 1 5
    ,
    im
    L e stone , 24 1 , 3 7 6
    K I R CH O FF 3 2 9 3 89 3 9 1
    ,

    3 98
    I
    L ND E, 1 0, 1 7 0
    K N I ET S C H , 1 3 7
    , , , ,
    L iqu i
    at on , 2 7 4

    K O HL RAU S C H 19
    L iqu c i x g
    efa t on of o y en, 1 0
    KO PP 2 9 1
    ,
    i g
    L thar e , 2 83
    K RY PT O N
    ,
    L th a i i mic a , 3 1 0, 3 2 9

    K DH N E method
    ,

    26 1
    L thi i um ,
    3 10
    ,
    Y Y
    L O R R DE B RU N , 1 7 8, 2 7 2
    LO CKY
    ER , 1 7 2
    L ab il e, 1 08 u c u ic
    L nar a st , 3 66
    B G
    L AD EN UR , 5 3 ~
    L 11 p c ll
    e , 42 3

    m l ck
    L a pb a , 2 4 5 L te u cium ,
    4 43
    L anthan um ,
    44 5
    i l zuli
    L ap s a ,
    4 40
    V II
    L A O S ER , 1 0, 1 3 , 1 8, 1 6 5, 2 4 1 M agn alium , 4 3 7
    V G
    L aw o f A O ADR O , 44, 4 7 , 60, 2 93 M agnesi a , 3 7 4
    BO YL E See BO E S l aw
    . YL . lb 3 7 6
    a a,

    t he c onstan y of nat ra ph e c u l mixture 229 ,

    n o m en a , 3 u sta 3 7 4 ,

    o n s t an t o pos t on (de n te c m ii i M agnes ite 3 7 4 ,

    prop ort ons ) , 2 7 i M agnesium 3 7 4 ,

    i i ui
    d str b t on ( B ER T H E O T ) , 3 25 L mmonium ph osphate
    a , 3 76
    339 b ori de 43 2 ,

    L G
    D U O N an d PE T T , 2 90, 4 07 I c rb on ate 3 7 6
    a ,

    G A Y L U SSA , 4 3 , 4 7 58
    -
    C chloride 3 7 5 ,

    HENR Y
    Se e H ENR S l aw

    . Y . hydroxi de 3 7 4 ,

    HE S S , 1 53 ni tri de 1 7 4 3 7 4 , ,

    M IT SC H E R L I C H , 2 9 2 oxi de 3 7 4 ,

    mul i l
    t p e proport ons , 2 9 i sulph ate 3 7 6 ,

    c mic l m
    he a as s a t on , 7 5 ci M agn etite 4 6 3 4 7 4 , ,

    N EU M ANN , 2 9 1 M l c h i te 3 5 3
    a a ,

    c v
    o ta e s , 2 9 6 M ll ab le iron 4 66
    a e ,

    m
    t her one tra ity, 3 50, 4 1 5 u l M AN C HO T 55 ,
    00 I N D EX .

    M ang an ese , 4 58 M i spickel , 22 1


    di oxide , 3 3 , 460

    l aw , 292
    '

    I TS C H E R L I C H s

    in t l 47 1 s ee ,
    te st 203 ,

    M an g anic c ompoun ds ,
    4 59 M i xtur e 1 69 ,

    cid 46 0
    a ,
    M ob ile equilib rium V A N ,

    T HO FF
    S
    M ang nou c omp ounds
    a s ,
    4 59 pr inci p le o f 1 6 0 3 3 6 , ,

    M arb l e 3 7 6 O H R s s a lt 4 7 3

    , ,

    M A R C K W A L D , 3 99 M O I SSAN 1 6 3 8 6 7
    2
    , , , ,

    M ar l , 3 7 6 24 4 , 2 4 7 , 4 4 6 44 9
    M arsh g as , 2 4 8 ol e, 3 2

    M AR S H te s t, 9 9 5 , 2 3 3 M ole c u l ar de press i on, 6 5


    M artensi te , 4 6 6 e levati on ,
    65
    M ass a ction l aw , 7 5 . See also E qui h eat , 1 7 3 , 99 1
    l bri ium . w e h t, 4 5 ig
    M as s ,
    icot 2 83 deter nat on o f, 4 7 mi i
    M A SS O N , 2 99 b y b o n p o nt ili g -
    i met h od ,
    61 ,
    M at ch es 2 03 ,
    22 7
    M atte, 3 54 b y free n p o nt zi g -
    i method , 6 5,
    M atter, 3 9 8, 3 12
    un ity o f 3 08 3 95 , ,
    Mo e l cul
    e, 9 8 , 44 , 4 9
    M e rs ch aum 3 7 4
    e ,
    l i
    M o yb de n te , 4 55
    M e lli tic ci d 24 6 a ,
    o l yb d e n u m , 4 55
    M e lting po in t curve-

    ,
    1 22 , 3 42 , 4 1 2 , i xi
    tr o de, 455
    4 67 o l y bdic a d , 4 56 ci
    M E N D E L i E FF, 2 96 , 2 9 9 , 3 03 , 3 07 , 4 4 1 , o n a z it e sand, 4 4 3
    44 5 M o n ob a s a d , 8 3 ic ci
    M E N D E L EE FF S
    tab le (peri odic sy s L Y
    M O R E , 2 9 , 2 1 2 , 294
    t e m ) , 3 01 M ortar , 3 7 8
    M E N S C H I N G , 23 2 M os a ic g l
    o d, 2 8 1
    M ercur ic ammon ium chlori de ,
    414 u i ic ci
    M r at a d, 3 8
    c h loride 4 1 4 ,
    M UT HM A N N , 4 56
    cy i de 2 6 8 4 1 4
    an , ,

    h ali de lk ali 4 1 5
    s, a ,
    c
    N as en t state, 3 7 , 5 4
    iodide 4 1 5 ,
    u l
    N at r a g as , 24 8
    n i tr t e 4 1 6
    a , g iv
    N e at e ( photo raphy) , 3 65 g
    oxid 9 408 e, ,
    N eody mium ,
    44 5
    sul ph te 4 1 6 a ,
    N eon
    s ulp h i de 4 1 7 ,
    N ERN S T , 1 04 , 1 84 ,
    M rcurou s c omp ounds 4 1 3
    e ,
    gl ow er, 5 1 , 54
    M rcur y 4 1 0
    e , L
    N E S S ER S s o t on, 4 1 5 lu i
    M e oth orium 44 8
    s ,

    N E UM A N N S l aw , 2 9 1
    M etal ammoni a c omp ounds
    -

    ,
    4 86 N E W AND S , 2 9 6
    L
    M e t l lo i ds 8
    a ,
    N E W TO N S

    m
    eta , 23 7 l
    M e t llur gy o f iron 4 63
    a ,
    N ic c o lit e , 4 7 9
    M t p h o sp h oric aci d 2 1 7
    e a , N ick l e , 47 9
    M tap h o p h orous aci d 2 1 9
    e s , l
    s te e , 4 7 1
    M e tastab le ystem 1 08 3 4 6 s , , i ium
    N ob ,
    4 49
    M e tastannic aci d 2 80 ,
    i
    N ton , 4 02
    M eth ane, 24 8 N it r am ide , 1 99
    M ethyl orange, 3 53 it ric a d , 1 89 ci
    M E Y ER , L O T H AR , 4 1 , 2 96 , 3 00, 3 08 xi
    o de , 1 83
    M E Y ER , VIC T O R , 2 3 2 it r ides , 1 6 4
    M ic a, 4 3 6 it r il o su l p h o n a t es, 1 9 8
    M IC H E L SO N , 3 9 2 i t ro g e n , 1 6 2 1 7 0
    ,
    M icro c o smi c s alt , 3 3 4 a d derci iv iv
    at es of, 1 9 5
    M i n er aliz ati on of org anic matter , 1 6 8 i xi
    d o de , 1 85
    M i n er s s afety l amp , 2 58

    l g c m u
    h a o en o po nds of, 1 7 9
    M i n ium, 2 84 g m u
    1: y o ro en c o p o nds o f, 1 7 4

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