Академический Документы
Профессиональный Документы
Культура Документы
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
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 .
notably those on the sulp hur oxides and acids rare gases nitroge n , ,
,
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) -
13 .
Hydr ogen ( I L 1 3 ) -
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 .
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 ,
-
O zo ne ( 3 6 , 3 7 )
Formul a O f, 52 ; All otrop i sm , 5 3 .
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
- -
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 , , ,
re c t io n s 7 6
a ,
.
Fl uorin e ( 52, 5 3 )
Hy dro en g uoride 8 1 ,
.
oxygen 83 ,
.
N OM EN C L A TURE 92 .
E L E C TR O L Y TI C D I SSOC IAT I O N ( 65 66 ) ,
1 01 .
S u l p hu r ( 67 9 3 ) -
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 , , ,
l ium 1 4 8 ; T el lurium 1 50
Se en , , .
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 ,
Phos phorus ( 1 3 1
0
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 .
m ry O f t h e c rb on group
a 2 87
a .
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 ,
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 )
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 .
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, .
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 ,
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 .
Summ ry o f t h g up
a e ro 44 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 , .
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 .
which deal with the things o n t h e ea rth and in the outside unive rse .
but sim ply the im pressions which they make upo n our sense orga n s -
.
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
.
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
.
the study O f the sens atio ns that we receive The se ns atio ns tak e
.
to divide the natural sciences into Zool ogy B otan y M in era l ogy , ,
and A str on om y .
Sion int o Phys ics C hem is try and B iol ogy the latte r b eing t h e s tudy
, ,
eu t ics
p .
p henomeno n When co
.
pp er is heate d in the ai r it tu r ns into a ,
"
when the phenomenon was better unde rstood b y assuming that ,
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
int o the r eal essenc e O f things and the investigato r Very soo 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
.
, ,
p lanets for
,
exam p le still takes place in t h e,
s ame manne r as in t h e
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
.
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
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 .
ame it burns with the emission of a brilliant light and turns into
,
begins to boil then distils over and condenses in the receiver The
, .
rst but soon the sugar tur n s darker ; a brownish liquid distils
,
the latter ceases the wire returns to its original condition This
, .
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 .
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
,
all pro po rtions t o im p ercep tible solubility Thus cane sugar is dis .
-
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 .
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
l
is then allowed to cool the dissolved substance frequently se parates
,
FI G 1 D I S TI L L AT I O N
. , .
former distil over and the latter remain in the distilling ask -
t his manner . Take for exam ple a mixture O f alcohol and water
, , .
The more volatile constituent alcohol passes over for the most , ,
Su bl im atio n C ertain
solids e g cam phor when heated ( at
. .
,
.
,
THE EL E MEN TS .
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
-
,
The undissolved part is dried and then shaken with another sol
.
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
.
,
remains which gives O ff red fumes on treatment with sul phuric acid ,
something that salt petre does not do Salt petre can evidently .
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 .
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
,
.
,
p osed .
cause on the one hand not all the substances that possibly exist
, ,
A s may be seen fro m this list the m etal s are incl uded in the ,
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 .
,
combines with al most all others caus ing what is called combustion ,
.
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 .
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
.
,
-
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 ,
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
.
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
.
at mm pressure Its co l or is . .
The latter is a vessel enclosed in nan air tight j acket the s pace b e -
,
~
1 oxygen
. The gas is also somewhat soluble in alcohol
.
F IG 4
. . VA C UU M Thus when the pressure becomes a fold the solu
-
,
-
' -
.
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
, ,
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 .
ul
S p hur which burns
,
in air with o nly a small ame burns in ,
with a blind ing white light steel wat ch Sp ring that has been . A -
these and analogous cases the oxygen as well as the burning mate ,
c oo ling the s c ale pan atta c hed to the m agnet Si nks I n a Similar way one
,
-
.
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
, ,
the burning of zinc ,for exam ple may be proved by heating the ,
as o x i datio n .
c ombines with them N eve rtheless the nitrogen O f the air is heated
.
,
H Y DR O GEN .
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
.
HYDR O G EN .
found on the earth in the free state The gases O f some volcanoes
.
2
( ) T he acti on of zinc on dilute sul phuric acid This
is the c omm onest method .
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
(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 ,
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
.
ro
p p ert y serves for the identication of hydrogen gas
.
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 .
, ,
heard in this case because the steam at the moment of its form a
,
509 for 50 minutes of the whole is changed to water N O W
, .
take 1 00 minutes till the p art of the gas had formed water .
cal reactio ns When we see that wood sul phur etc burn quickly
.
, ,
.
,
has the power to withdraw oxygen from many of its comp ounds .
will usually unite with the hydrogen to form water C o pper oxide .
a pplied ; one soo n sees the black oxide change to red co pper and ,
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 , ,
. .
C o pper p owder for exam ple may be placed in a tube and the
, ,
led over the co pper at a high tem perature The a pparatus should .
tube with the co pper oxide and heat a pplied Here also arrange .
co pper oxide is trans formed back to co pper When the tube and .
d o to day -
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 .
pumic e s to ne so aked in sul p huric acid The dry gas is ignited and
.
,
heated .
burning of alcohol .
pound with o ne of oxygen This is the case when ammo nia gas
.
Water is placed
in the ret ort A ,
e d The dissolved
.
which is c o oled by
water in the vessel
D . The c ondensed
water no w p ure
, ,
wate r ows out nea r the t o p The steam thus meets with cooling
.
way very com pletely condensed (princi ple of the counter current ) -
.
c o lle cted .
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
water has at 0 the sam e res i stanc e as a c o pper w ire of the sam e c ross
e qu ator one tho u sand t im es The sli ghtest tra ces of sal ts or even c on .
1 6 . Wate r at
rdinary tem peratures is an o do rless tasteles s
o ,
co nstants of water its freezing point being called 0 and its boiling
,
-
5 pe r atmos phere ) This is the reaso n why ice melts unde r
.
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 .
There are many liquid substances that mix with water in all pro
portions and many also which do not
, ( Se
, e , .
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
, ,
.
in the country ) and gas es from the air as well as traces of amm o ,
nium salts .
some carbo nic acid and air i n solution both of which give i t it s ,
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
,
the no zzl e .
w ork s on balneology .
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
-
ri vers l akes and seas vari es howev er thro u gh m any nu an c es fro m pure
, , ,
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 .
strong e le c tri c current is then sent thro ugh the wi re a c b so that the ne ,
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 ,
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
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 ,
is shown in Fig 1 1 . .
O F W AT E R
o xygen
.
a .
wash b o t tle B t o free it from imp urities and also through the U
-
FI G . 1 2 SYN
. TH E S I S OF W A T ER A FT ER D U M A S
,
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 f c ourse unlimited
,
They are distinguished from com pounds by
.
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
.
, ,
magnetic and insoluble in carbon disul phide and under the micro
s co p e only a homogeneous scoriaceous mass is seen The constituents .
washing etc
,
.
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
, , ,
o f ben z ene and tur p entine however rises gradually as the more
, ,
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 .
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 .
f th e r ea cting s u bs tan c es .
elements unite to form a certain com pound are always the same .
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 .
,
.
of the E l eatics (so ca lled fro m the ci ty of E L EA) whose m ost pro mi nent ,
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
,
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
.
, ,
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
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 ,
L aw of M u lti pl e Pr o po rt io n s .
of oxygen has a hist ori c reason For a l ong time hydr ogen was .
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;
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
.
such as N = 1 4 Br = 80 et c , ,
.
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
, , , ,
rr u m and A g from a rg en tu m
f e ,
.
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
, , ,
r
p p o e r gure to the right of an d b elow the Symbol Sul p huric .
formul a is therefore H 2 S O 4
, , .
o xy gen an d m ercu ry by
Hg O Hg 0;
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.
Zn + H2 80 4 2H 2 11 8 0 4 .
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 ,
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
.
su l phu r ic a cid?
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
therefore required
g potassium chlorate
.
. Hence
.
500 g c o pp er require
.
W :
2 HC 1 + O E 2 0 + C 12 .
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 .
for exam ple the m et al uni t es w ith the oxygen whereu p on the
, ,
catalyzer .
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 -
g at 0 and 76 0 mm
ressure At 3 4 it becomes liqui d
.
p . .
yellow C hlorine gas dissolves in about o ne half its volume of
.
-
water ; The aqueous solutio n bears the name chlorine water
-
.
gas being conducted to the bottom where it remains and drives out ,
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 .
, ,
m olten sodium etc The pre cio us met als are in general quite
,
.
c hlori d e .
36 IN O R GA N I C C H E M I S TR Y .
l 27
p h o r u,
s which burns in it with a p ale ame to phos p ho ru s
chloride .
chem ica l
or t y for the latter is so strong that
f
a ttr a cti no
,
a n it ,
If sul phur etted hydrogen gas HzS is p assed into chlorine wate r
, ,
-
2H2 0 2C 12 = 4 HC l 02 .
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
, .
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
tion O rdi nary at m ospheric o xygen does not produc e these e ffects Lit
. .
chlo r ic aci d
A gC l + H = A g + HCL
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 .
2 N aC l + m o, = N a2s o, 2 HC 1 .
weighs gr .
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 .
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 ,
s olution of the gas is called hy dro chlori c acid also m u r ia tic ,
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
p ressure causes only a small increase in the solub ility Such con .
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
'
,
. .
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
. .
, ,
ro
p p erties as those that are described here for hydrochloric acid .
, ,
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
.
,
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
~
Na H2 O = N aO H H .
N aO H HC l N aC l Hg O .
MO H + HA = MA + H2 0 .
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 .
A gN 0 3 HC 1 HN O 3 A gC l .
c h l o ri e .
nitric acid from its salt I t is also p ossible to liberate a base fro m
.
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 .
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 .
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
.
2 vols Hg O
. .
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
,
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 .
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
. .
A V O G ADR O
further supposes tha t the molecules of oxygen h y ,
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.
2H2 02 2 H2 0 .
2 v ols . 1 v ol . 2 v o ls .
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
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
,
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 ,
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
p ounds as,
com p ared with that of hydrogen are then de t ermined , ,
S b stanu ce . Sp G
. .
Q u ant ity of H .
Hydrogen chloride 0 5 .
Hy drogen bromide 0 5 .
Since ,
therefore no com p ound contains less th an h alf a
,
, , , ,
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
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 .
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 .
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
.
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
,
.
P V = R T, or R,
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 .
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
, , ,
32
1
. 223 9 3
of g pe r sq cm i e P = 1 0 1 3 2 5 A t 0 the absolute
. . .
,
. . . .
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 .
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 ,
O ZO N E .
and the exit tube e are sunk in a vessel of sul phuric acid int o
-
, ,
tem perature ) i t i s part i ally c onver t ed i nto o z one and the m ore so the ,
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
, ,
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
.
are oxi d ized to phos phoric acid sul phuric acid and arsenic acid , , ,
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 ,
st uff sol utions like indigo and lit mus are d e c ol ori zed (b y oxida
, ,
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
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
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 .
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 .
. .
, .
mg .
,
mg being the we ight o f 1 c c o xygen at normal pressur e
. . .
v X 1 43 + a .
1 2 times as much
1 The molecule of oxygen being O z that of
.
,
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
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.
N3 0
"H
02 i 280 4
= N 3 9 80 4 + H20 2 .
free its atoms have not yet united to form molec ul es so that t he
, ,
give hy drogen peroxide since the zinc and the water generate a
.
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 ,
with air an d dilute sul phuric acid for the same reason as in t h e ,
and air A fter a time the water in the bulb gave th e tests fo r
.
r at u r e and melts at
2
p e
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
, .
c ause an ex losion
p .
l Pb SO 4 ; s ul phuretted hydrogen H2 S
'
d elicate test for hydrogen per oxide O ther tests are fo un d in the .
The ferrous s ul phate c arries the active oxyg en of the hydrogen per
'
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
o cc urs water and metallic silver bein g forme d at the same time
, .
lead oxi d e Pb O ,
.
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 .
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 .
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 .
-
. .
58 IN O R GA N I C C HEM I S TR Y . 40
thr ough however for if the c u p be closed with a perforated sto pper
, ,
seen to rise slowly in the tube till it reaches a deni te height above
t he level outside .
ins erted in the c u p the force which one would have to exert on it
,
tube till the pressur e of the column prevents the entrance of any
more .
p the
, p ressure which n a kg of the gas at the same tem p erature
.
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
.
PV = R T, .
C ons t .
really the case in PFE PFE R s m eas ure ments of a queous s ugar so lutions
C onst .
60 I N O R G A N I C C HEM I S TR Y .
I 41
g .
51 0 2 87 1 5 1 78
544 3 05 1 78
567 3 09 1 83
o ccu pies a given volume the gas pressure which it exerts is j ust as
,
atm osphere If there is really e quali ty bet w een os m ot ic press ure and gas
.
was fo u nd to be e of an at m osphere or g A 1% , .
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
.
.
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 .
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
molecular weights .
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 ,
magnitudes which are pro portio nal to the osmotic pressure and ,
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 , ,
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 .
for instance t h e vapor tension of the solid were greater than that
,
given off fro m the solid co nde ns ing to a liquid and the former grad
FI G . 18 . FI G . 19 .
solid were less than that of the liquid the entire li q uid would , ,
the va por pressure cu rves a b and be of the solid and the liquid r e
,
va por pressure is lower than that of the pure solvent so its inter ,
The c onne c tion between these m agnit u des and the os m otic
43 .
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
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 .
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
-
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 .
are c onne c ted with ea c h other As s umi ng that the vapor tens i on of A
.
they hav e the sam e vapor tens i on B will therefore have t h e sam e .
, ,
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 .
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 -
d e pression A we have , ,
AM C onstant .
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
,
,
liquor still contains the most soluble salts among which is mag ,
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 ) .
through a tower lled with round stones so that the expos ed sur ,
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
.
drie d b y shaking it with concentrated sul phuric acid and then dis
t ill ing again .
Sp g at
. 1 00 parts of water
.
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
.
r eacts vigorously with bromine while the latter does not react with
,
2 atoms .
manufacturing it .
hydr ogen com pou nds For this purpose numerous organic com
.
-o
pounds can be used For exam ple bromine reacts with n aph
.
,
s BI 2 '
S ZHBr .
P h o s p h o ric
aci d .
A s ph O Sph O I l C
'
The most of its salts are soluble in water ; silver bromide however , ,
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 .
I O DIN E .
p h ur ic acid .
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
,
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
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
, ,
.
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
, ,
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
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
,
is also used for the laboratory pre paration of the gas but the ,
PI 5 by water
, As was ex pl ain ed in 4 5 it is possible to use
.
,
a cid .
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 ,
0 and 4 atmos pheres pressure it condenses to a colorless liquid ,
liberation of iodine .
C h ica l
e m Pr op r ti
e e s Hydrogen iodide has all the charac
.
being given o ff These are ahn os t all soluble with the exceptio n
.
,
hyd riodic acid possesses another pro p erty which is not found in ,
into hydrogen and iodine it can act as a strong reduc ing agent
,
-
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
.
DI SSO C I AT I O N .
same stages are passed thr ough in in verse order so that the degre e ,
c oll isions with each other The atoms of a molecule mus t also b e
.
above c ertain limits ; henc e we see a reaso n for par tia l decom msi
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
, ,
.
.
,
, , ,
A =R +a
in which A B and C re present single molecules O f the su b
,
.
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 .
,
d im inishing as ,
it
does in real ity However we can a pproach .
,
Ax
small becomes the exac t expression o f the velocity It is
22
.
dl
7
A +B= C m
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
.
Si
g; K '
<
a x > b x
( >.
'
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
.
x of these are decom posed after a give n period the reactio n velocity ,
de n t l y bimolecular ) is
S C (a x) 2
,
C being a co nstant .
g gr am m ol e
-
in which C
is a co ns tant . A ccordingly equilibrium will e xis t
when
C (a
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 ,
ff
lp
k
2
x .
,
. .
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
,
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 ) .
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 .
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
.
The o pen ends of the U t ube are cl osed w i th sto ppers FF m ade of
-
The c yli ndric al e lectrodes ti of plati num i ri dium pass th rough the -
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 ,
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 )
.
C hem ica P p ti s
l r o er e Of
all the elements now known uorine
p
'
p ounds ,
such as hydrogen p otassium uoride K F H F which . ,
-
,
at Sp g ( H = 1 ) . at . I t has an extremely
soluble in water .
C hem ica l Proper ties The aqueous solution of hydrogen
.
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 .
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 ;
.
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 .
so that when the l atter i s s ubse qu ent ly d isso lved o ff (by t ur pentine or
,
mined in exactly the same way as was done for the analogous
chlorine and bromine com pounds .
,
. .
, ,
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
, .
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 .
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 .
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 .
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
'
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
p e r a t u r e s I t can
. be condensed by strong cooling to a dark brown -
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 .
HY PO C IILO R O US A C I D , E C l O
-
C 12 0 HgO 2 HC l O .
H Y PO C HL O R O US A C I D .
85
Hg o + 2 01 2 + H 20 = Hg01 , + 2 010 H .
So l u l eb .
hy
( p och l orite ) is formed :
2 K O H + C 12 KC l + KC l O + 1 1 2 0 .
2C l O H 2 HC l + 0 2 .
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
,
. .
,
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 .
,
'
other hand when sha ken wi th m er cury gives white m er curi c c hl ori de
, , ,
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 .
57 This gas
. is formed when p otassium chlorat e KC l O 3 is , ,
C h l o ric P e r c h l o ric
aci d . ac i d .
burned sugar .
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
.
. .
,
crystalli z ing dish is the n covered with a glass plate The chlorine
.
Po t . c h l o r it e . Po t . c h l o rat e .
of the bulbs he decom posed the gas the actio n being non ex pl o ,
-
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
-
.
,
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 ,
C HLO R O US A C I D, E GIO
2 010 , N ap , zN aCio, o, .
C HL O R I C A CI D, HC 10 3 .
however on the addition of a little sul phurous acid the color dis
,
The com position of chl oric acid was ascertained by STA S from
an analysis of silver chlorate A n accurately weighed amount of
.
drive off all the oxygen The loss in weight indicates the amount.
HC l O 4 .
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 ,
In s o l .
O XYG EN C O M PO UN D S O F IO DINE .
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
.
.
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
-
2 HI 0 3 HzO I zO 5 ,
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 .
ful oxidizing agent setting free chlorine from hydrochl oric acid
-
, ,
2 HI O g 1 0HC l 12 5C 12 6 HzO .
r ather easily .
l emon yell ow c rysta lline powder that brea k s u p into i ts el e ments above
-
on p erchloric acid :
HC l O 4 I 2 H2 0 HI O 4 Q HZO 01 .
N O M E N C L ATUR E .
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
- -
,
. .
_ ,
,
. .
, ,
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 .
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) .
-
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
-
.
-
, ,
-
,
-
,
-
.
, .
there are two oxides the name of the one with the more oxygen ,
,
-
,
. .
,
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 -
and those s ubse qu ent ly di s c o vered were nam ed a cc ordi ngly a s i n the ,
E LE C T R O LY TI C DI SSO C I A TI O N .
sio n a nd the boiling p oint elevatio n are both greater than they
-
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
,
. .
,
the osmotic pressure i s pro portio nal to the freezing p oint de pre s -
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
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 .
, .
,
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
.
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
.
a bcd ,
Fig 23 is nearly lled with d ilute sul phuric acid
.
, Th e .
FI G . 23 .
ZIl H2 SO 4 ZUSO 4 H2 .
by the two m ethods The values o pposi te ro were calc ul ated fro m the
.
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 .
H the hy d rogen ion
divide d into two ions each then the equil ibrium is r epresente d b y ,
a x =K
I t also follows that the degr ee of diss ocia tion depen ds on the con 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 .
is also formed The acid or base that can ex pel another from its
.
chl oric acid is for exam ple stronger than hydrouoric acid At
, , .
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 , ,
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 .
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 .
, ,
H2 O H OH
,
el e c tro c he mi stry The res ul ts of the d i fferent m ethods agree well and
.
. .
,
.
-
.
freely side by side ; but not so with H O H for these must unite
'
tion of the salt we therefore have only the H and O H ions unitin g
'
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
'
, ,
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
.
d eed seem to be com plete ; we shall examine the cas e more tho r
o ughly in 73 .
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 ,
this is apparently much different wi th the ions than with the atoms ,
SUL PH UR .
in the United States but large quantities are also found in other
,
FI G . 24 D
. I ST ILL AT I O N OF SU L PH UR .
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
, , ,
The crude sul ph ur th u s obta i ned i s st ill im pure It i s re ned ( Fig 24)
. .
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
-
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 .
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 .
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 ) , ,
p h id es ) and ch a l co py ri t e co
( pp er p yrites C o pper and iron sul ,
ll
'
,
A little ab ove its melting p oint -
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 .
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
Sz molecules .
atoms ; at 2 000 and atmos phere pressure the disso ciation has
known while in the liquid state there are two more The solid
,
.
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
.
,
directly Powdered Iro n and sul phur when mixed and heated
.
, ,
p h i d e s .
THE TR A N SI TI O N PO I N T .
n ary tem p eratu res sul phur is rhombic and rema ins so till the
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 , ,
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
, ,
the other .
spo n din g to different tem peratures The result is the line marke d .
,
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
.
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
.
d isappe ar .
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
-
rhombic sul phur for exam ple has been placed in the dilato meter
, ,
STAB LE,
M ETA STA B LE ,
AND
LA BI L E .
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 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
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 .
as one of the c om p onents ; but then in case the solid phase was ,
inde pendently in any phase neither are they found in any other ,
s olutions ) .
orate ; since the solut ion was saturated the result will be that a ,
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 .
,
b eing left .
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 .
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 .
Sol id L iq u id R h om b ic
G a s e ou s
FI G . 27 FI G . 28 .
p p ;
o n e degree of freedom or as we say it is u n iv ar i an t To every
, , , .
the rhombic phase passes into the monocli nic phase The or di .
mon to both crystall ized phases and the gaseous phase A t B the .
,
, ,
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
,
-
p ressure The
. lines O C and B C are not p arallel but intersect ,
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 ,
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 .
only one phase I n the suc ceeding cha pters we shall have
.
72 .This gas occurs in nature chiey in volcanic regions C er .
bodies .
at high tem peratures illustrates the former case while the boiling ,
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
.
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
, .
gu re (s ee nex t page) .
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
,
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 ,
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
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
, .
7 60 mm pressure
.
water dissolving
The gas is rather soluble in water 1 vol
.
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
,
lled entirely and closed air tight The latter condition is best
-
.
C dS, the brown stannous sul phide SnS the yellow stanni c sulphide
, , ,
r est of the sul phi des named are black O ther metals such as .
,
are p reci pitated by amm onium sul phide Still other metals such .
,
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 ,
Cu S0 4 + 2 OH +
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
-
, ,
0 11 80 4 s Cu S 11 2 8 0 4 ,
In so l .
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
actio n law to the case is very sim ple C o pper sul phide when in .
,
ab= k -
c,
be preci pitated .
of the sul phide will dissolve ; to be sure the H ions of the strong
-
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 -
Fe SO 4 will cause no preci pitate of iron sul phide and iron sul phide
, ,
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
,
-
when dilute hydrochloric acid is added to iron sul phide the H ions ,
-
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
.
,
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 ,
alk ali es i t de c o mposes v i ol ently Under ordinary pres sure the liq ui d
.
inc o mbustible A t
. 5 5 it solidies with t h e fo r m at ion of crystals
.
'
VA L EN C E .
o n the one hand and hydrogen on the o ther are able to form only
p les : H g S Hg O ) These
,
are therefore
. called b i v al e n t .
\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
.
, ,
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 .
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 .
vale nces are of the same sort ; the halogens and sulphur illustrate
this However these are exce ptions t o this rule
.
,
.
O
xivalent tow ards oxygen at l o w e r tempe ratu / it on ly qu adri
se re s 2 0
is
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 .
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
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
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
, .
,
studied .
l
Su ph ur Se s q ui oxi de ,
820 3 .
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 .
when sul phur burns in the air or in oxygen ; the well known odo r -
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
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
and iodine :
Pb O z S0 2 Pb SO 4 .
.
,
for exam ple loses color in it The gas probably reacts with
,
.
80 2 2 H2 0 11 2 80 4 H2 .
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 ,
reactions co m e into pl ay
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 .
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
.
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
,
-
barium c hl or i de) .
tain two atoms of oxygen The s pecic gravity of the gas has
.
79 This
. c om p ound is found in a small amount in th e fume s
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
,
2 80 2
02 3 280 3 .
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
.
s ubl ime on heat ing This modication is the stable one for the
.
,
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 .
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
-
, .
p roducts S 0 2 ,
and 0 2 are formed in the
,
volume ratio 2 : 1 N o w .
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 .
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 .
9 . Pentath i oni c a ci d Hs O B .
sul phu r i c aci d has really been isolated ; all the others are kn own
gen atoms which each o f these acids possesses are both replaceable
by metals ; they are therefore diba sic acids With such acids it .
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
.
o f t h e same concentration .
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
SO 3 S S2 0 3
2 08 82 3 02 2 03 82 0 3 .
C al c iu m di
su l p hi d e .
ph ide
4 N ag S 68 0 2 4N a2 S2 0 3 S2 .
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
,
, .
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 .
A n io n o f s u l hur
o u s ac 1
supposed that the thi os ul phu ric a ci d re m a i ned ent ire ly unc hanged u nt il
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 ,
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
.
,
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 be formed directly from sul phur and oxygen and this yields ,
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) .
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 ,
and these are no lo nger able under the conditio ns of the indus
,
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 -
.
,
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
.
,
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
.
( )
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 , ,
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
.
,
lea d c hambers are c onnected with each other with the G love r ,
in the lead chambers the residual gas p rincip ally nitrogen p asse s
, , ,
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
,
reduc ed .
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 ,
fro m the G ay L ussac tower dilute d with the acid ( cha m ber a cid)
-
9 6 9 8% H2 SO 4
It is prepared from the chamber acid by ev dp
.
a platinum vessel .
13 8 IN O R G A N I C C H E M I S TR Y .
86
2 80 2
2
29 1 19 2 K P3 2
~
or 2
p1 p = K 2
2 p3 ,
C al ,
S ULPH UR I C A C ID . 13 9
the aid of a fresh p ortion of the gas mixture as the next p aragraph ,
sets forth .
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
,
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
.
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 .
which is only slowly absorbed by sul p huric acid ; sec ond that at ,
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
.
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
.
,
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 ,
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
,
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 .
all other mineral aci d s from thei r salts In the manufacture of soda
.
The determ ina tion of the con cen tra tion of su l ph u ric acid is an .
areometer T here are tables so pre pared that the pro p ortion of
.
C HL O R I DES O F SULPHUR I C AC I D .
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
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
Pe r su l ph u r ic A c id, m , os .
. .
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
into H 0 an d 0
2 Suc h a h i gh c oncentrat i on at the anode i s reached
.
very hi gh there .
2 K 2S20 8 2 K28 20 7 02 .
K -
py r os u l ph at e .
8 0 3 + H20 2 HzSO s,
2 2 + HC I .
\ C l + H20 2 \ O OH '
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
form i ng persul phuri c a cid wh i ch can be obta ined in th is way pure and
,
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
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 .
93 . On
adding sodium thiosul phate to an iodine solution t h e ,
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 .
for deter m ining the amount of free iodine in a solution This is done .
iodine molecules have now enti rely disa ppeared Since according .
1 27 i e a certain amount bleaches exactly this much iodin e
N o rm al sol u ti on
. .
of analytical chemistry .
( 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
-
FI G . 32 PI PE T TE
. . FI G 3 3 B URE T T E S
. . AND SUPP O R T .
necessary before the color com pletely disa ppeared R equired the .
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 . .
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 ,
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 ,
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
,
.
selenium fusing at 1 7 0
,
The n there is a metallic form fusing
ph u r ic acid The barium. sal t of the acid like that of sul p huric ,
T e ll u riu m .
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
.
white of a m etalli c l ustre and a c ond uc tor of heat and electricity The
, .
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
, ,
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 .
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 ,
.
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 ,
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
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 ,
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 .
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 .
,
2H O Hg O C al .
far as this is not self evident because the latent heat of fusio n
-
amoun t ,
2H O H2 0 1iq uid C a1 .
,
1 54 IN O R G A N I C C HE M I S T R Y .
( )
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 .
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 .
below .
, , , ,
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 ,
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)
2 (2 H
s H2 S) + 3 (2 o oz ) 2 soz + 2 n zo C l
p a .
2 (2 H H2 ) ( 0
2 0 2) 2 H2 0 q C al.
;
(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 .
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 .
( were in
o n e another which were in a certain agreement with each other
for exam ple dened it as the force which holds the p a rts of a
,
amount of work will be the greater the greater the counter force ,
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 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 .
i nto work but only seem s to in c rease the m o l e cular m o vem ents of the
,
thermi c .
TH E R M O C HE M I S TR Y . 1 59
t h e reaction in question .
al e n t amount of each com p o und requires according to FA R A DA Y s
,
force must be pro p ortional to the afn ity ; in other wo rds that ,
THE DI S P L A C EMEN T OF EQ U I L I B R I UM .
( 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 .
the rul e .
p ressure exerted on it .
(2) M onoclinic sul phur when com pressed near the transition ,
over into rhomb ic sul phur since this pro cess involves a lessening ,
p revious case .
( )
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,
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
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
.
,
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 ,
N I TR O G E N .
when burned in the air absorbs the oxygen to form phos phorus ,
N I TR O G E N . 1 63
n itrogen lef t .
the ai r i s rst passed thr o ugh amm oni a water t h e pro cess can be c arri ed ,
m o niu m carbo nate M ois t phos phorus combines with oxygen even
.
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 .
N H4 N 0 2 N2 2 H2 0 .
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
, ,
.
K2 0T20 7 2N H4 Cl N2 l C I '
20 3 2 KC l 4H2 0 .
At 2 1 4 it becomes solid
I t is o nly slightly soluble in wate r ,
.
e leme nts combine directly with nitroge n at red heat form ing ,
bath prevents the decomp osition of the nitri d es forme d in the arc .
the fact that nitrogen is not able to su pport comb ustion serve fo r
the identication of nitrogen gas .
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
.
1 08 . C on s titu en ts
f th e B esides oxygen an d
o A t m os pher e
etc .
with th e globe V all air having b een removed from both The en d
, , .
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
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
A NA LYS IS AIR .
with 1 vol oxygen one third of the volume tha t disa ppeared must
.
,
-
the c om pos ition of the a ir is n ear l y con sta n t I n all parts of the .
reached it consists of
,
M oreover the com po sition does not a ppear to change with time ;
,
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 ,
; 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
, , ,
.
res piration of animals and plants and the burning of fuels carb o n ,
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,
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.
nitrogen from the air directly There are also bacteria which.
,
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
,
.
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
-
.
M g + C aO = M g O + C a,
When cal cium carb ide (better mixed with 1 0% calcium chl oride )
,
2 GaC 2 02 2 C a0 4 0 ; C aC 2 N2 C aC N2 C .
ing that no one has yet succeeded in p re p aring a com p ound of argon .
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
howe ver in obta in ing i t in s m all a m ounts on heat ing the rare mi neral
,
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
, .
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 .
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
,
C om po u n ds of N it r o gen an d Hy dr o gen .
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
~
.
,
AM M O N I A .
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
. .
2N O 5H2 2 N H3 2H2 0 .
M g3 N 2 3 H2 0 2 N H3 3 M g0 .
A M M O N IA .
1 75
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 .
C hem ical Proper ties The characteristic pro perty of this com
.
-
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 .
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
2 N H4 2 N H3 H2 .
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
,
. .
,
.
,
known fact that ammo nia can be entirely ex pelled fro m its
a queous solutio n b y b oiling .
oxygen conveyed by soil bacte ria may also cause the oxidation of .
n it ri de Mg gN z
,
When ammo nia is conducted over hot potassium
.
being doubled :
2 N H3 N2 3 11 2 .
2 v ol s . 1 v ol . 3 v ols.
N HZ C I
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 ,
:
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
,
zine i s strongly bas ic I t s sal ts are eas ily so lubl e in wat er e xc ept ing
.
,
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
, ,
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 ,
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 .
un der the mouth of the ask These dro ps contain some hydrogen
.
N C 13 4 N H3 3 N H4 C 1 + N 2 .
N 3 Cl N C 13 C al .
N C l + 2 N aO H
. N aN 3 + N a O C l + HzO .
I o di I
N itrogen i de
a solution of iodine in p otassium
71 1 .
ex plosive .
.
,
solutio n it is stable .
N HzI HC l N H3 1 01.
Hydr o xyl am i n e , N H2 O H .
Th e free hydro xyl amine i s best prepared by heat ing the phosphate .
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
N 2 O at 0 and 7 60 mm p ressure weighs . g It is rathe r .
s oluble .
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 .
mercury It is easy to ex plain B E R T H E L o r s observation When
.
'
.
evolving still more heat and so o n The wh ole mass will thus
,
.
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 ,
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 ,
w as foun d to be
NI TR I C O XI DE, N O .
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
3 Cu 8HN0 3 3 C u (N 0 3 ) 2 4 H2 0 2N o .
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
.
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
,
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 .
latter takes u p exactly half the volume of the ori ginal gas The .
N 2 0 4 Tf 2 N 0 2 ,
1 v ol . 2 v ols .
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 ,
=
P x hx2
,
with alkalies nitrous and nitric acids are formed ; we may therefore
,
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 .
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
.
, ,
O xy g en Ac i ds of N itr o gen .
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
.
3 HN O 2 = HN 0 3 + 2 N O + H2 O .
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 .
Hypo n i tr o u s A c i d, H2N202 .
m ethyl alc oho lic solu t i on of hydroxyl amine Th e free a ci d does not
-
.
ac i d i s form ed .
are k nown .
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
.
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 , .
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
because this makes the residue easier to remove from the reto rt .
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 .
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 .
time as follows :
2HN 0 3 2N O 2 H2 O O
r eaches a diamete r o f 2 m in .
I nstead of b roa d ening out the electric arc t o a sun sha ped dis c -
turne d on the arc forms at the rst instant in the l ower par t
,
into the pipe so that the arc comes to o c cup y the p ortion of
,
p roduct ,
for it diss o ciates at ab out 6 00 into N O an d 0 2 With
.
N2O 4 H2 O HN 0 3 HN O 2 .
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
.
, ,
dissolve with the evolution of nitric oxide This and the other .
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 ,
iron lings and dilute sul phuric acid the reduction of nitric aci d
to ammonia in d ilute solution is quantitative There are also .
the sul phur is conv erted to sul phuric acid similarly phos phorus to ,
The com pos ition of nitric acid can be deduced from that of its
anhydride A weighed amount of the latter is introduced into
.
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
i i c Ac i d HN O
Pe rn t r , ,.
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
,
2 80 2 N 20 4 + O Hg O Q SO 5 N H .
S0 2 HN 0 3 SO 5 N H .
SO 5 N H H2 O H2 SO 4 HN O 2 .
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 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 , ,
O N S0 ,H HN O , ON /
\ So, H
but the nitrosi sul phonic aci d likewise very unstable so on s plits
-
, ,
ON
< s o, H
acid :
2N O O H,O 2 HN O , .
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 .
851 8g
0
2 s0 2 2R 20 80 2 3 s0 2 + 2N o
O THER N I TR O G EN C O M PO UN D S .
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 .
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 .
,
-
+ 2 H,
0 = HO N H,
2 s o,K H .
PHO S PHO R US .
1 99
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 .
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
.
PHO SPHO R US .
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 ,
p hos p hate .
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 '
d istils over :
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
.
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 .
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
.
Sul phuri c acid when warmed with it is reduced t o sul phur dioxid e ;
, ,
nitrate for instance gives silver and silve r phos phide A g3 P with
, , , ,
are very mysteri ous The o xi dat i on and hen c e the l uminosity is
.
, ,
666 m m fo r .
,
and at 7 60 mm for The o xi dat i on i s there
.
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 . .
water in a distilling ask connected with a condenser by a tub e ,
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
-
,
-
substi t u tes The red phosphorus and phosphoru s ses qui s ulphi de
.
-
C o m p o u n ds of Ph o s ph or u s an d Hy dro gen .
( ) q
2 l i u id hydrogen p hos p hide P2 H4 ; and ( 3 ) s o lid hydrogen ,
b ringing phos phorus together wit h z inc and dilute sul phuric a cid ,
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 .
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
was describe d in 2 9 .
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
,
.
g at O an d 7 6 0 mm p ressure
.
0
. .
2 PH3 40 2 P2 0 5 3 H2 O .
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 .
reaction is decidedly sim ple and that chemical processes are almos t
always mono or bimolecular A ccordin gly when the quantita .
,
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 .
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
. .
general behavio r of the latter thus shows that it is very much less
basic than a mmonia .
p h o r u s trichloride .
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 .
2 PH3 3 H2 2P .
2 v ol s .
3 v ol s . s o l id.
,
.
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
,
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
.
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
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 ,
mois t air being imme d i ately decomposed by water with the forma
,
almos t colorless takes on the yellow color of chlorine for the ab ove
,
PCl 5 H2 O PO C l 3 2 HC l .
With more wate r pho sphoric and hydro chloric acids are produced .
1 0 013 4
3 -
11 01 .
1 43 These are very anal ogo u s to the chl orine derivatives They are
. .
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
.
q uite sl owly .
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
.
importance .
to the pentoxide .
i
Ph os ph oru s Tetr o x de , P20 4 ,
co l orl ess gli stening crystal s that break u p i n water into phosphorous
,
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
-
line subliming at
,
the other amor phous and not volatile
below red heat ; the va p or condenses crystalline When heated .
A c i ds of Ph o sph o ru s .
1 . O nly
two of the above described oxides of phos phorus
45 ,
we have :
21 4 I N O R GA N I C C HE M I S TR Y . 1 45
,
. .
, ,
M51 0 6 et c
,
These c an be derived fro m a h yp et ical a ci d I ( O H) 7
.
fro m I (O ) 7
H 2 H, O ; and M I O 4 fro m I ( O H) 7
3 H, O .
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 .
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
. .
. I t generates .
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 ,
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
'
, ,
the more the association since the hydrochloric acid reduces the ,
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
, ,
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
.
-
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 .
"
t at io n is practically com plete .
acetic acid is only very slightly ionized and its ionization is more ,
.
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
.
fully explained .
is ca pable of s plitting u p into the ions H and HPO 4 the former '
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 ,
.
,
reaction .
for phos phoric acid is that in nitric acid solution a nely crystal
line yellow preci pitate is produced by ammonium m olybdate
,
,
b o iled in aqueous solution it goes over into ortho phos phoric acid .
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 .
, .
of t h e a ci ds H4P40 1 2 and ,
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
M e t a ph o s ph o r o u s A c i d, HPO z .
PH3 02 = H2 + HP0 2 .
vapor .
PHO SPHO R O US A C I D , H3 PO 3 .
P013 3 H 2 0 = H3 P0 3 3 HC l .
m i xed .
p olybasic acids sometimes a ffects only one If ion at rst the othe r s ,
it may be supp osed that ionization beyond 2 11 and HPO 3 is in
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 .
into hydrogen pyro phos ph ates and phos phide The double , .
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 .
Th e e qu at i on are : s
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 .
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
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
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
A rseno pyrite yields arse n ic on mere heating the latter sublim ing , .
2A 8 2 0 3 60 AS 6 00 .
Va p or D en s ity .
The lemon yellow v a por of arsenic has a
-
A s ga 3 H2 80 4 = 2ASH3 3 ZII SO 4 .
disagreeable odor .
It is an endothermic compound ,
As + 3H As H3 C al ,
A s H3 6 Ag N O 3 A s A g3 3 A g N O g .
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 -
A r in e If
f
C om pos ition arsine is passed over hot co pper
o s .
, .
De t e c t ion of A rsen ic .
are st ill u sed tho ug h muc h less than form erly i n dye ing tapestr i es
, , ,
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
, .
chl or i ne has been e xpelled by warming and the liqui d has been ltered ,
the liq ui d to be tested for arseni c The least tra c e of the latter reveals .
arsenica l gases .
, ,
having a s pecic gravity of )
( dZ I t freezes at 1 8 and
.
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 .
brick walled chambers where it collects as a white powder
-
Phy ical
s P r op er ti e s A rsenious oxide is an odorless solid tha t ,
A bove this tem perature dissociation begins and at 1 800 the va por
'
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 .
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
.
grad u ally warm ed we have rst a transform at i on i nto m ono clinic and
,
, ,
2 H3 As O 4 3 Hg O As zO 5 .
O xy ac i ds of A r sen i c .
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
. .
and not the acid se parates out This acid forms three classes of
.
,
.
The salts of the alkalies are soluble in water ; those of the other
metals are not but dissolve easily in acids however A neutral
, ,
.
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 ,
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
.
acids .
1 64
The trisul phide and the p entasul phide of arsenic dissolv e
.
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 .
dride , e .
g
BaO + SO g = Ba SO 4 .
A N TI M O N Y . 23 1
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 .
,
-
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 , ,
1 .
11 . 2s o 3 + 3 c = 4 Sb + 3 C O z .
The crud e antimony thus obtained usually still con t ains arsenic ,
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 -
'
-
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 .
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 ,
-
s e .
.
irn por t an t of these is typ e metal from which printer s ty pe is -
1 66 Stibine
is formed when nascen t hydrogen acts o n a solu
.
but contains 1 0 1 4 % Sb H3
I f this gas mixture is p assed through
.
denses to a White solid mass that soon melts after the tube is ,
to be de posited .
, ,
-
The pr e .
SbC l 5 4 HzO
o
Hot water decom poses it into h ydgpc h l o r ic an d
.
p yroantimonic acids .
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 .
to the tetroxide .
and passes over into the hydroxide Sb O O H m eta a n tim on iou s a cid ,
-
.
2 Sb C l 3 3 N a 2 00 3 HgO 2 Sb O O H GN a C I 3 00 2 .
, .
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
-
.
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 ,
.
ta rtrate,
A N TI M O NY PEN TO XI DE A N D A N TIM O N I C A C I D
'
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, ,
case of antim ony as in that of phos phorus we meet with three kinds
, ,
heating but resumes its original c olo r on cooling This tet ro xide .
Su l ph u r C o m po u n ds of An ti m o n y .
o range red p owde r which Splits u p in t o sul phur and the trisul phide
-
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
.
,
p entasul p hide ; even carbonic acid causes this hence the crystals ,
is not known .
BI SM UTH .
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
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
,
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 .
, .
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 .
,
over into the com pound BiO O H with the loss of a molecule of -
BiO O H basic
-
.
addition of much water converts it into the basic n itra tes several ,
+ 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 .
Su l ph u r C o m po u n ds .
in alkalies and their sul phides hence forms no sul pho salts Whe n ,
-
.
S UM M A R Y O F T HE N I T R O G E N G R O UP .
relation shows itself even in the formula types of their com pounds .
ro
p p erties This is shown by. the following small table :
A to mic w igh t e . 31 0 .
( 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 , ,
that the metallo id character g ives w ay to the metallic c haracter
contrary dis plays a very feebly basic charac ter in arsenious oxide ;
,
since this oxide forms the trichloride with hydrochloric acid 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
,
excess of water .
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
. ,
and Bis black The rst three are sul pho anhydrides of sul pho
.
-
FI G . 39.
A RT IFICIA L D I A M O ND S ( M A G N IFI ED ) .
at once covering the cavi t y with an iron sto pper When the Iron
,
.
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 ,
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
,
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 .
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 ) .
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
, .
'
Sp g = 2 09
. . . A s was stated above gra phite can be pre ,
addi t ion to carbon and called gra phitic a cid This subs t ance is
,
.
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
.
remove the mineral m atter and nally heated re d hot in a curr ent -
tion of coal They conduct heat and electricity Wood char coa l
. .
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 .
,
. .
salts from liquids The charcoal obtained from the dry distilla
,
.
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 .
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 , .
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 .
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 .
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
,
m ar sh ga s -
H
C 4 is p assed through a red ho t tube ethyl en e O 2 H 4
, , , , ,
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
.
to glow ; when uorine was present in excess car bon tetrau oride ,
C F4 was formed
,
.
, , ,
.
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
C o m po u n ds with Hy dr o gen .
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
.
l 1 82
C + CO z = 2 C C .
C + CO z 2 2C O .
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 ,
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
.
,
This resul t is sur prising because the same chan ge should also
,
I I
. CO + O = CO z I f we assume that the second stage has an
.
unimolecular reaction .
C aC 0 3 Zn C aO Zn O CO .
2 1 4 and
O n accoun t of its tendency to combine with oxygen it displays ,
metals when hot Some com po unds are reduced by carbon mon
.
, ,
which can be isolated in the crystalline state but decomp oses again
very readily .
'
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
.
extremely small cavities partly lled with liquid carbon dio xide
,
.
an d magnesia
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 .
they are heated together with co pper oxide and the c arbon dioxide
formed is absorbed i n a weighed amount of caustic potash .
Sp g =
. 1 52 9 . I t is thus ab out half again as heavy as
.
,
at 0 u n der 3 5 atm os pheres press u re I t s critical tem perat u re is .
tween carbonic acid and its ions The result of this is that other .
. .
In the solid state also the acid carbonates give o ff carbonic aci d
gas very readily on warming .
1 v ol . l v ol .
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
.
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
, ,
C yanogen
has a penetrating o do r Wh en liqueed it boils at .
e quatio n
C2N 2 20 2 2C 0 2 J
r N2 .
C zN z l O z 2C O + N 2
'
r:
.
ie
. . a bimolecular p ro cess .
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
, ,
Hy dr o gen
y an i de , HC N (pru s sic a cid) is im po rt ant in inor
c ,
s oluble .
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
Thi s can be eas il y obtained with the aid of the apparatus of Fig 4 3 . .
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 ,
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 ,
. .
,
-
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
Fm 4 7 .
.Ma m a s cools o fresh portions of the gases unite
,
Their .
SA F E TY L A M P
FI G . 48 .
Z O NE S L U M I N O U S FL A M E .
48 .
The narro w tube conducts o ff the inammable gases and they
can be lit at the outer end .
across a ame ; the wire only g l ows a t the edges of the ame .
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 .
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
gen and some metals ; these s il icides have been pre pared main ly
by M O I SSAN in his electric furnace .
pe r a t u r e forming
,
sil icon tetrachloride an d silico chloroform I t -
.
Si 2 KO H H2 0 K2Sl O 3 2 H2 .
Hy dr o g e n Sil i c i de , SiH4 .
b ecomes liquid at 1 u n der a pressure of 1 00 atmos pheres I t has
.
esca pes from the ge n erat or forms a cloudy ring of hydrated silica .
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 , ,
hydrated silica .
Sl ii -
t h e a i r bo il s at
, and i s deco m posed by water .
, z e, .
2 03 F2 J
r 810 2 i H2 80 4 2
Sl F4 2 03 80 4 2 H2 0 .
action .
t iall y eva porated the residual liquid is able to dissolve silica becaus e
,
which silicic acid is dep osited because the excess of silicon tetra
,
FI G . 49 .
PREPARA T I O N OF HY DR O FL U O S ILICIC A CI D .
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
.
into col d wate r at once without cracking They are atta cked only .
Sili c i c A c i ds .
through the parchment b u t that the silicic acid does not T his
,
.
many of thei r salts and doub le salts are known which occur as -
minerals in na t ure .
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
.
g o u nd water
r This pheno m enon is sai d to be caused by the a bsorptive
.
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
.
,
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 .
s ide r able number of such sub stanc es is now known and the ,
of small diff usibility G radually the vie w develo ped that the
.
, ,
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 ,
r etained in c ollo idal solution ; yet the usual p recip itate can b e
,
a ci d
.
270 I N O R GA N I C C HE M I S TR Y .
1 96 .
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
.
, ,
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
'
does not p enetrate at all into the agar agar a s ab ove The ,
.
p h id e s hydrated
,
oxides etc M ost of them are mobile
,
liquids
.
,
71 mill e quivalents of N a Cl
-
p e r liter ,
of M gC l z and
Of Al C l g .
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 .
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
,
tion exists in this case between the colloid and the solvent .
so soon as dust pa rticles enter the air the path of the beam can ,
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
i u
s na ffe c te d b y h e t 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
Fo g erm an ium cf al o
r 218 . s .
TIN .
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
,
any sul phur or arsenic it may contain and then reduce d with car ,
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 .
ally pure .
like etch g u res are p roduced on the surface ( tin moir e ) When t in
- -
.
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 .
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 .
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 .
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
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
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
it an b e e a ily p l veriz e d
c s u .
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 .
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 .
and is then known as tin pl ate or sheet tin This is done by simply ,
-
.
Many all oys of tin are in use Solder consists of tin and lea d
.
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
) .
C o m po u n ds of Tin .
STA NN O US C O M PO UN D S .
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 ,
( f
c .
Mn 0 2 4H 4 Cl M IT 2 C l l 2 H2 O
O lg ;
' ,
, , '
the manganese and the rest serving to discharge two chlorine ions ,
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
n ate e g
,
K zSn O g formed
. . The h ydroxide is also soluble in
,
.
They
_
.
ar e termed am ph o t e ri c c o m p o u n ds .
, ,
.
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 .
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 .
, ,
Sn C l 4 3 HQ O the s o called
-
,
t in bu tter A fresh solution of stannic
-
wate r has thus s pli t u p the stannic chloride into a basic hyd r oxide
an d an acid .
Su C l 4 PO C 13 Sn C l 4 SC l 4 e t c
-
I t combines with hydrochloric acid
-
,
.
,
,
-
,
KZSnFG which corres ponds to potass ium uo s ilic ate ; the sa lts of hydro
,
-
di ffer from each other b oth chemically and physically ; they are
c alled stannic and metastannic acids .
sium stannate solution This preci p itate reacts acid when moist
.
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
-
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 .
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
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
.
, ,
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 .
ie .
zinc is changed into the ionic condition and the lead ions are
.
,
discharged How it comes about that one metal thus assumes the
.
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
-
.
Distilled water from which the air has been entirely removed
,
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
-
, ,
m ost likely to d isso lve l ead The l ead eave tro ughs e t c wh ich were .
-
,
.
,
wi th an i nso lubl e l ayer of l ead s ul phate and bas ic carbonate (as well
.
absorbed by t h e water .
O xi de s of L e ad .
Pb 2 0 3 , Pb 3 0 4 , Pb O z .
cooling .
2 84 IN O RG AN I C C H E M I S TR Y .
a1 r .
lead nitrate and lead peroxide are formed henc e minium may b e ,
r egar ded as 2 Pb O Pb O z -
.
2 Pb C 12 C a(O Cl) 2 2 H2 O 2 Pb O z C aC l z 4 HC 1 .
O n warming it with sul p huric acid lead sul phate and oxygen are
-
,
p i n k sa l t
-
O th er L ead Sal ts .
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
,
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 .
turns black if any hydrogen sul phide ( from drainage p i pes etc )
, ,
.
gets into the lungs Wh ite lead is particularly valuable for its .
and barite which are frequently substituted for white lead becaus e
,
s ix wee ks the pl ates are alm ost ent i re ly changed to whi te l ead Th i s .
L e ad
l ph i de , Pb S is black and comes down amorphous when
su ,
SUM M A R Y O F THE CA R BO N G R O UP .
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 -
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
.
,
following facts :
1 O nly carb on and Silicon are known to form hydrogen com
.
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 ,
~
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 .
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
.
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 .
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
,
. .
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
,
ac c ord i ng to R EG NAU L T .
2 92 I N O R GA N I C C H E M I S TR Y .
209
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
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 ,
2 10 3 Th e l aw of M it sc h erl ic h
. . The crys ta l form of com
.
the case of manganese suppos ing its a t omic weigh t t o be unk n own ;
,
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
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
gr aph s .
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
( 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
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 .
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
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
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 .
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
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
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
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
it .
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
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 .
of method .
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
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
. .
w e ight o f t h e g as b e c o me s
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 .
t he a ir .
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
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
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 ,
The questio n now arises whether all elements can be thus arrange d
into grou p s ; the re ply is a frmative .
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
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 ,
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
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 .
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 .
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
Spo n din g pro p erties we are led to the su pposition that these
,
z
",
,
.
,
K 39 2 . C a 40 1 . Sc 44 1 . Ti 4 8 . 1 V 5I 2. C r 52 1
. Mn 55 0, .
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 , , ,
Cu Zn C a 70 Ge As Se B r 80 0 . .
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
. .
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 .
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 , .
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 :
,
-
,
. .
,
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
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 ,
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
-
,
-
Very well .
G rou p VII I as has b een said owes its origi n to the setting
, ,
p pro erties
1 A l l these elements are of a gray color and dif cu l t l y fusi
.
melting point of iron is higher than that of c obalt and the latte r
-
din ary tem peratures The former pro perty is especially developed
.
c om pound s O SO 4 and R u O 4 for exam ple are known and also those, , ,
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 .
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 .
r eference to the large periods it is apparent that not all the ele ,
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 :
, ,
com poun d s .
p ro m i nent in the o dd ,
rows the acidic ro
p p erties .
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 .
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 .
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
.
,
, ,
Thus beryllium would not t in the sys tem with that atomic weight .
This is indee d its t place i e its properties are those which must
,
. .
beryllium chloride .
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
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 ,
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 .
for this p osition are cadmium and tin The oxides of both are easily .
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
-
Ag > Cd ; Sn < Sb .
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
, , .
s pec ic gravity is
The position of the metal requir es tha t its oxi d e b e feeb ly b asic ,
Since cadmium is at the left and thall ium farther down in the system
as the following sets forth : the oxides of alum inium and tin b e ,
nite com pounds with the latter The oxi d es of cadmium and .
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
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 ) . .
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 .
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
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
2 1 8 In
the grou p of the platinum metals the atomic weight s
.
rs t of the three on account of its analogy with iron and ruthe nium ,
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 .
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
.
,
electro p ositive on the ascending the electro negative elements -
.
, ,
t he u nity o f m a tte r .
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
.
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 , ,
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
.
,
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 .
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 .
to c aust i c soda ; it d isso lves i n water produ cing a strongl y alk aline ,
so lut i on .
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
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 .
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,
,
If .
3 12 IN O R GA N I C C HE M I S TR Y .
j 2 23
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 .
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
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 .
it kee ps its metallic lustre for days Sodium can b e heated in the .
ignites only when heated strongly whereu pon it burns with a very ,
, ,
O XI DE S A N D HYDR O XI DE S O F SO DI UM .
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
.
,
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 .
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
,
is em p loyed .
the two outside ones containing brine and the carbo n anodes ,
mercury c overs the botto m of the whole cell I n the brine com .
com petitive pro cesses the reader must refer to the technical
j ournals or the most recent works on industrial chemistry .
SALTS O F SO DI UM .
,
. .
,
from sea water and the water of salt wells Three metho ds are .
. . .
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 .
and yields pure salt L ater on the other salts s e parate out ;
.
,
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
. .
.
Wh en a crystal of G lauber s salt is ex posed to the air it el oresces ,
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
.
has begun at any p oint it Spreads over the crystal The phase rule .
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 .
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 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 .
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 -
, , ,
This pro cess c onsists of three p arts I n the rst place common .
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
.
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
.
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 .
are wor ked u p N ev erthel ess thi s pro c ess wh ic h for a l ong peri od of
.
, ,
( )
2 The ammonia -
soda p rocess o f S O L V A Y .
p lace :
N aC l ( N H 4 ) H C 0 3 N a HC O g N H 4Cl .
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 ,
,
ways by fusing sand with G lauber s salt and charc oal This
,
.
mable text iles l ike theater dec orations etc ; it is also used for ,
.
lling Soaps .
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 , .
p ensable P otassium
. salts are also found in sea water The -
.
s alts mainly double salts of p otassium and magnesium ,
, ,
- -
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 .
C O IlI PO UN D S O F PO TA SS I UM . 3 23
air ; when heated in the air it burns with an intense violet light .
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 .
which unites with water to form the hydroxide with the evolution
of much heat .
an d free oxygen .
sticks .
etc besides the c arb onate whic h is gradually formed by the action
.
,
the alc oholic solution is evap orated in a silver dish C aus tic soda .
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 ,
white mass of soda For this reason c austic p otash is a much more
.
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 .
re
p p ared by mix ing bromine with a p otassium hydroxide solution ,
of 1 3
'
ions in the latter c ase Th at the io dine has entered i nt o
.
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
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 .
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 .
KC l N aN 0 3 KN 0 3 N aC l .
For this purpose hot saturated solutions of the two salts are brought
-
.
PO TA SSI UM S A L TS . 3 27
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 .
b orh oo d of the melt ing p oint the former is the stable variety
-
tion p oint of the two forms has not yet been determined 1 00 .
o btained solely from wood ashes these being soaked in water and ,
e xtensively from
p otassium chloride after the L E B L AN C p rocess .
t ories that c ontain s the p otassium salts in which the sugar beet is
,
-
rich .
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 .
H2 0 at the solut ion has a strong alkaline reac tion The salt .
Pot ass i um sili c ate , p otassium water glass is formed when san d-
,
.
water glass-
.
It absorb s o xygen from the air going over into the thio ,
2KgS Hg O 20 2 K 2 S2 0 3 l 2 K O H .
KO H H2 S K SH Hg O .
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
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 ,
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 ,
The sal ts of c aesium are v ery Similar to those of r ub id ium ; som e of the m
.
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 .
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 -
the c arb onates and phos phates are soluble in water ( although in ,
d ifferent degrees ) the carb onates with basic reaction The metals
, .
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
, .
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 .
, , , ,
o f its salts The sodium salts are almost all readily soluble in
.
, ,
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 .
with the alkali group a descrip tion of a few amm onium salts may .
nd a place .
c onduct the electric current very well this is not the c ase with an ,
a gas between a liquid and a vacuum while the other law has to ,
water for the quaternary base cannot be thus dec omp osed
,
.
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
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
-
.
ous solution some ammonia esca pes acid sul ph ate being forme d , .
(
A m m o n iu m n itr at e N H4 N 0 3 deliquesces in the air ; when
, ,
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 .
p hos p hate ,
N a P 03 .
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
.
the air (hence the o d or of ammonia) an d goes over into the rst
named salt .
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
,
p art of the hydrogen sul p hide and thus sets free sul p hur which ,
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
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
.
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
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 ,
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
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 .
p ressure I n the great maj ority of cases the solub ility increases
.
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 ,
l
i
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 .
the heat of s o lu tion i e with the caloric e ffec t which acc omp anies
,
. .
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 '
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
,
, ,
p roved to be at 1 4 it is abov e
+ 02 4 .
c omp onents is water than as water in which substances are
,
0
dissolved .
, ,
f
two degrees o f freedom We will supp ose that the s ol u t ibn 1s then
.
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
,
This is none the less true when water is added or the vap or
volume increased so l ong as the three phases remain
, .
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
.
r equired B elow this p oint the s ol u tion can be r egarded as s atu rated
.
in which c ase also the solid phase goes into solution I f the tem .
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 ,
therefore c omplete .
, ,
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
.
N a zSO 4 I n sodium sul phate the Special case a ppears where the sol
.
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
become equal at the transition p oint I ndeed the same gure can .
than that of the salt with m mols no matter what the form of .
,
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 .
.
, ,
o r melt i ng p oint curve is then esp ecially valuable for the d isc ove ry
-
alone sep arates out of the fused mass on free z ing A t E however .
, ,
fused mass .
FI G 55 . .
FI G 5 6
. .
now sep arates out of the fused mass The c ont inued additio n .
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
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 .
out and thereafter the melting p oint again rises along E QB t ill
,
-
dr at es which are indicated by the melting p oint c urve ( Fig
,
.
FI G . 57 .
of the above c omp osition The further addition of sul phur tri
.
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
.
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 .
, ,
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 ,
nature of the solute the temperature of the solution and its con
,
srum sodium and the alkaline earth metals are almost com pletely
,
s alts ; those o f the al k al ies are practically com pletely ioniz ed whil e ,
FI G . 59 .
, ,
~
c onta c t .
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 , ,
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
, ,
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
, ,
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
,
the anion Mn 0 4 in the co pper solutions the cation C u
, which ,
When the so lvent i s one i n whic h i oniz at i on does not occur the ,
so lu t i ons of cu pric chl ori de and nitrate ; t h e form er i s dar k green the ,
,
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
, ,
.
when two dilute salt solutions are mixed there is no caloric e ffect ,
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 .
Slowly added from a burette When the point has been found at .
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 .
a hundred t imes as m u ch or g , .
f .
basis for all of these are crystallized solids and can be easily obtained
,
etc gram equivalent of sodium hydroxide or potassium hydroxide
.
,
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 .
'
less in acid solutions ) m ethyl ora nge ( yellow in alkaline red in acid
, ,
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
241 From the stand point of the ionic theory the following
.
existence the alkali com pound of the latter being strongly diss o
,
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
.
, ,
is com pleted in other words the cha nge of col or bec om es m or e
, ,
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
,
the acid itself and whose alkali salts are sufciently ionized t o
produce a distinct change of color A very suitable one for this
.
reasons set forth above O n the other han d in case a weak bas e
.
, .
54 IN O R G A N I C C HE M I S TR Y . g 242 .
p rocess is re p eated until all the iron is eliminat ed The resul ting .
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 .
ti es re mai n i n so lut i on or are depos ited as powder Fro m thi s powder .
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 .
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
-
, . .
, .
o ther metals .
C O M PO UN DS O F C O PPER .
For b r o n z e s see 1 99 .
p laster cast in c om p act form so that all the detail s of the original
,
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 ,
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
,
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 ,
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 ,
Of the c u pro u s s alts the Sul phate and halides are known .
e rt y in gas analysis .
liberated
2Cu S0 4 + 4 KI = 2 K2 80 4 + C u2 1 2 + 1 2 .
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
, , ,
o rga ni c a nalysis .
~
, ,
formed .
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 ,
2 0 1 00 parts Hg O dissolve
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
.
,
a
p p er etc
,
1 5 7 )
. is being restricted .
hydrogen sulphid e .
SI LVER .
troy ounces kg ) .
by blowing air into the solution and thereby oxidizing the sodium
,
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
,
. .
by the p orous material ( bone ash or clay and limes t one) o f the
-
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 . .
,
metal hard er .
Th e m arket pric e of Silver o n a gol d bas is was alm ost c onstant fro m
, ,
, .
be ing in 1 9 1 1
C o m po u n ds of Sil v e r .
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 .
bon dioxide from the air and the Silver salts react neutral while t h e ,
heati n g to 2 50 Silver oxide 1 s broken u p into its elements It is .
o
,
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 .
c onta ins no other s ilver sa l t nor any other c hl or i de I n View of the very
.
chl ori ne ions are now introdu ced into the liqui d the ioniz at i on of the ,
them .
Silve r chlo rid e dissolves readily in ammo nia potass ium cyani de ,
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
,
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 ,
"
,
- 2 KO N + Ag .
64 I N O R GA N I C C HE M I S TR Y .
M 246
if the ano d e is of platinum cyanogen gas is set free from the anion
,
All the S ilver salts p ar ticularly the chloride bromide and iodide
, , ,
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
.
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.
t here
apparatus which is essentially a cam era O bscu ra and the plate is
,
,
,
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 .
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 ,
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
.
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
.
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 .
water .
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 .
,
.
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 ,
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 .
2A u + 4 K C N 2HzO =
O z 2KA U( C N ) 2 + 2K O H HZO z .
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 .
,
[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
,
. . .
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 .
very soft ( much like lead ) and extremely malleable and ductile
, .
. .
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
-
for industrial p ur p oses For these purposes the pure m etal is too .
.
3 70 IN O R G A N I C C H E M I S TR Y .
M 2 5o
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
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
wh ich can be regarded as chl orau ric acid M any salts of this aci d .
s alts give the ordinary tests for gold hence this acid eithe r fo r ms ,
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 ,
obtained which dis plays acid instead of b asic pro pe rties Salts
, , , .
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 , ,
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 .
fro m the baser m etals I t i s needless t o say that the i r efforts were ne ver
.
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 .
lim ited knowledge that the pro pert i es of the m etal s c oul d vary N one
, .
, .
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
,
Moreov er at the t ime of the a lc he mi sts the present conce pt e lem ent
,
,
.
, ,
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
.
depended on t h e co Ope r
,
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 ,
10 5 19 3 3
8 94
.
.
1 08 3 961 1 06 3
re d wh eit re d
l arit y in the pro per t ies of the higher s t ages of oxi d a ti o n This is .
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 , .
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 .
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
-
, ,
- -
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 .
, , ,
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
.
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
.
, ,
M A G N E SI UM SAL T S .
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 -
chloric acid set free attacks the iron M any double salts of mag .
,
-
red heat .
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 -
, ,
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
,
- -
,
.
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
'
calcium phos phate phosphorite apatite etc part icu l arl v in Spain
, , , .
,
.
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 ,
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
-
.
( forming l im e w a t er ) but
-
more soluble
,
in c old water than in wa rm .
stones A fter some time the m ass bec omes as hard as stone ; this
.
t he older the wall the harder the mortar The formation of cal .
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 .
the R hine region such a mixture occurs as tu ffstone which
, ,
with water sets very rmly in a short time ; this is due in all ,
C al ci u m pe roxi de , C aO z 8HQ O ,
is de p osited when lime water - -
on heating .
SALT S O F C A L C I UM .
u se d t o dr y t h is gas
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
,
.
p rod uc ed .
l ibrium at for the sal t so lu t i on has a free zing po i nt muc h l ower than -
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 ,
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 .
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
.
ble in alcohol and almost all the chlor ine is ex pelled by a current
,
of carbon dioxide .
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 .
as a c atalyz er .
'
tem perat ure Moreo ver t h e greater solub ili ty of the hal f hydrate as
.
-
4
-
,,
the air and dissolves rea dily in alcohol I t is converted into s alt .
ca me ) ,
2H28 0 4 2CaSO 4 .
, ,
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 .
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
.
2 59 . C al c i um ca rb o n ate
is dimorphous o ccurring , C aCO g , ,
,
S A L TS O F C A L C I UM . 3 83
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
,
p osition into lime and carbon dioxide can only occur therefore , ,
GLASS .
and easily fusible The calcium silicates however are ins oluble
.
, , ,
are ve ry many diffe rent so rts in use Some of the mos t im port ant .
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 .
, ,
6 IN O R GAN I C C H E M I S TR Y 26 0
fro m liquids .
gold solidies the com p onents do not se p arate but solid ify
, ,
II . Stront i u m .
to those of c alciu m .
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
.
,
-
II I . B a ri u m .
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 .
, ,
( )
2
wa ter .
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 .
a nhydro u s
.
3 88 I N O R G A N I C C HE M I S TR Y . 262
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 ,
.
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 .
0 0 0 0 0 0 0 0
O O O O O O O O O O O O O O O O
"
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 .
closely related in their pro perties while the two other members of ,
the group are unlike them in many res pects B eryllium displays .
s atisfactory for some ele m ents e g those of the alkali and alkaline
,
. .
latter s pectra are their greater light intensity the greater con ,
be co n tinu ed at length .
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 .
FI G . 63
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
- -
, ,
s pe c t iv el y
,
the s pectrum of barium contains 1 6 3 lines and that .
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 .
'
Thanks to the researches of R O W L AND M I C H E L S O N K A YS ER , ,
m 4
constant ex presses the wave lengths A of the lines
of the s pectrum of the element with very close a pproximation ,
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 .
Sp ectral lines of one and the same substanc e o n the one hand ,
light from the latter is passe d through a p rism line s p ectra are ,
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,
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
, ,
,
t u al l y b een t h e c ase .
is not the e ntire ato m but smaller p a ti cles o f whi ch the atoms r
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
.
tions of radi o active elem e nts C ath ode rays are generated when
-
.
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
the condu ctivity o f a layer of air that was ex p osed t o the rays .
radio active ele ments woul d h ave been imp ossible becaus e they
-
r adium chloride .
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
.
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 ) .
cath ode and obtained a radium amalgam from whic h the mer
, ,
sto p them ; they form only a small p art of the total radiation .
[
ii
-
rays are to be regarded as cathode rays of great velo city .
enormous velo city ex plains the great penetrating p ower of rays .
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
.
the mass of the proj ectiles formed by the rays and the cathode -
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
,
cent .
well known vi z h e li u m
,
. R AM SA Y and SO DD Y have demon
,
. - 4
The law governing the rise and decay of radio active sub -
, ,
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 .
line but a rather com plic ated curve N evertheless it has been
,
.
,
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
.
co oling .
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
being established .
the radium in the earth would long since have disa ppeared if ,
p ower their
,
effective limit in the air being less than 3 cm The .
ro
p p erty of ionium is that it can p roduce radium .
V arious chemical
C hem ical Ej ects of R a di oacti ve S u bs tan ces
'
radium .
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 .
.
,
elements but that all of them suffer decay even though in most
, ,
this is by no means proven but there are two reasons for such
,
Z IN C . 4 07
tellurium the platinum metals ; the rare earths The two last
, .
Z IN C .
( H 2 Zn 2 SiO 5 ) s m i th s
,
o n i t e o r bl en de ( Zn S) and ,
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 .
t ime the s pecic gravity rises to 7 2 and the metal becomes rmer . .
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
.
'
water When heated to boiling in the air the metal burns t e zino
.
o ,
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
, , ,
Zn + 2 H
"
Zn + 2 H
cations into the solu t ion with great force itse l f thus assuming a ,
difference is not real Since in the case of the lead tree the fresh
,
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 .
dil ute nitric acid The cadmium molec u le in the gaseous stat e
.
MER C UR Y ( Q ui ck s il v e 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
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 .
FI G . 67 PUR IFIC AT I O N
'
OF M E R C UR Y .
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
, .
.
s ilver amalgam can thus be pre p ared Some metals such as tin .
, ,
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 uttur ns d ark in t h e t
light on accoun of the se paration of metal
2 Hg C l + 2 N H3 HZN Hg C l Hg + N H 4 C I .
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 .
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 ,
2, .
,
crystals .
undi sso ci ated Hg Cl2 m o le cules are formed while the mixt ure of so lu ,
e xplai ns the reverse fact viz that the hal ogen c o m po unds of m er cury
, .
,
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 ,
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
, ,
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 .
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
-
.
mercuric oxide by boiling with water This shows that the bivalent .
yellow com po und HgSO 4 2 HgO is formed With the sul phates of
, , .
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
.
,
numerous chemical phenomena The key to the explanation is
.
the conce pt of electrolytic solution ten sion which has already ,
This force c alled the e l ec trolyti c s ol u tio n t en sio n , c omes into action
,
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
, ,
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 .
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 .
( )
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 .
P
( 1)
5
:
n
tudes are meas ured in other un its than those there em ployed In .
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 ,
, 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
be quite large .
in C o pper sul phate and zinc in zinc sul phate the two p airs sep arate d ,
P1
17
21
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 ,
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
.
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
,
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 .
and when 192 p l the last ex pression bec omes zero it is a arent
, ,
pp ,
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 ,
the other the cathode plate the lead sulphate is c onverted int o
, ,
the discharge the p eroxide plate is again p ositive the lead plat e ,
fore expressed by
Ph O z Pb 2H280 414 > 2 Pb 80 4 2 H2 0 .
t iv e l y charged Pb O z ions Thereby it of c ourse imp arts to the
.
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
,
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 .
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 ,
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 .
H
( g or
.
, ,
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 , , ,
accom plish this two tubes sealed at the t o p and tted there with
,
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
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
.
the tem perature is raised still higher the solution in A will become ,
2 7 8 A s was remarked in
. 2 7 6 the electromotive fo c e which
,
r
. c an
tities of this equation are known with the exce ption of P which ,
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 ,
.
, ,
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
.
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
.
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
,
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 .
tive in res pect to a co pper solution for even in the mos t dilute ,
goes into solution and the other remains intact A piece of gal .
e v e n in those places
-
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
, ,
Th e symbol O represents a secondary ionizatio n
p roduct of the hydroxyl ion
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
metal is deposited o n the other one the two metals form with t h e ,
Th e fo rmula
7 P
1
g
= 4
E 10 T
' '
-
'
log
n P
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
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 .
2 2 3 226 242
,
2 4 8 and elsewhere )
, , ,
.
BO R O N .
element melts between 2 000 and but has such a high vapor
r e d heat Heating with nitric and sul phuric acid converts it
.
(like aluminium
2B 2 KO H 2 H2 0 2 KB O z 3 H2 .
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 .
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 ,
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 ,
.
p or ,
ur
p p ose it is frequently used A t 1 00 b oric acid loses 1 molecule .
which is b orax .
meta bo ric aci d forms several They are un s t a b le and are c onve rt ed
.
Th e b es t known sal t
-
b oric acid is b o rax , N agB4 O 7 1 2 HQ O
of -
,
, ,
vitreous mass This glass has the pro perty o f dissolvin g met allic
.
e ver
,
a p reci pitate of g r ayish brown silver o xide is forme
-
d t h e ,
s olutio n .
AL UM IN I UM .
hydrate of aluminium and iron C lay and ka olin ( C hina clay ) are .
f p
elds a r m i
,
ca etc contain it,
as a base
.
,
A peculiar aluminiu m .
,
.
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 ,
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
.
, .
fi g so4 R 2 ( SO 4 ) 3 2 4H2 0 ,
.
The alums all cry stallize in octahedrons and cubes which oft e n ,
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 ,
alkali sil icate being dissolved out leaving the ins oluble aluminium
,
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
, , , .
,
ar e com p letely lled with fused sil icate as a result of the addition ,
Ul tram arin e is a very beaut i ful blue pigm ent which is prepared arti ,
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 .
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
-
.
,
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 .
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
, ,
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
,
. . .
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
'
, ,
I n the thallic c o m po u nds the e le m ent is triv al ent lik e the other ,
SUMMA R Y O F THE G R O UP .
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
, .
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 ,
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 .
still much u n certa inty i n reg ard to som e of them part icul ar l y as to .
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 .
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
-
then tak en u p in ice water in w hic h they di sso lv e much m ore readily
-
higher tem perat ure) Fro m this co l d so lu tion they c an be pre c ipi tat e d
.
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 ,
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 ,
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 ,
m any lines Furtherm ore in vest i gat i ons of t h e ul tra v i ol et spe c tra
.
,
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
.
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
. . .
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, ,
, .
4
, . r
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
.
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 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
-
,
-
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
.
gives l ess light than when not s m o ki ng That i t is not the thori a whic h .
, ,
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 .
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
, ,
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
, , .
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
cent of vanadium The ore is roasted and fused wi th caust ic soda and
.
vanadate N H VO ,
separates out after a whil e as a sandy powder Heat
r s, .
vanadic a ci d .
C HR O M O US C O M PO UN D S .
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 .
, ,
a red hot tube The amorphous com pound is green ; the crystals
-
.
substance C r 2 0 3 2 HzO
,
-
.
salts with weak acids such as c arbonic acid sul phurous aci d et c , ,
.
( f
o .
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 .
( nitrate chrome
,
alum has the p,
eculiar ro
p p erty of disso l v
slowly with the sul phate solution but ra pidly with other salts ) .
salt crystallizes out the sul pha te for instance w ith fteen molecules
, , ,
viscid mass .
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
-
solution are still present The transition from the Violet soluti on
.
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
p reci pitated .
4 52 I N O R G A N I C C HE M I S TR Y .
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 .
K2 C r2 0 7 H2 S0 4 3 80 2 K Q SO 4 C I 2 ( SO 4 ) 3 + H2 0
.
C HR O MA TE S .
case the sul phuric acid itself H2 SO 4 is also a stable com pound
, , ,
, ,
all sul phuric acid do not deli q uesce in the air They are re adily
, .
Q C TO 3 C r2 0 3 30 .
C hromium
trioxide is a very powerful oxidizing agent ; its solu -
p otassium chloride .
fused potassium hydroxide absorbs oxygen from the air and forms
the peroxide thus becoming a much more active oxygen carr ie r
,
-
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 .
the c athode porti on The liqui d o xi diz ed at the anode c an be u sed for
.
introduced i nto the c athode port i on while the liqui d whic h previ o u sly ,
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
, .
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 -
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 .
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
.
, ,
Cl
KZC I 20 7
2 HC l 2 0r 0 2
OK
It crystalliz es in red pri s m s .
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 .
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 .
TUN G STEN .
i t very sl owly b u t i t rapi dly disso lves in a mix t ure of hydro u oric and
,
( K2U20 7 and N a2U20 7) are pre c ipitated whi c h are solubl e in a c ids ,
.
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 .
and by t h e redd i sh brown p re cipi tate w 1 t h potass ium ferro c yan ide For
-
.
SUMM AR Y O F THE G R O UP .
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 .
,
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
lustre Sp g = 7 2
. . . m . b . It under .
z SO 4 M SO 4 l 6H2 0
5H2 0 I t forms double salts such as K n s imi - -
.
, ,
p o u s w t .
very unstable .
~
.
4 60 IN O R G A N I C C H E M I S TR Y . 3 00
whe reupo n air is fo r ced thr ough the warme d l iquid The manganous
'
Mn 012 2C aO O C aM n O 3 C aC lz .
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
, ,
-
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
Mn 2 0 7 ZMII O l"50
.
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 .
tile bro wnish green o ily liqui d whose vapor e x pl odes easily yi elding
,
-
, , ,
acids are is omorphous and b oth are p owerful ox idiz ing agents -
IR O N .
rie d o u t in bl as t fu r n aces .
( u x see
,
according t o the grade of the ore I f the gangue .
,
The blast furnace previously warmed to the pro per tem pera
,
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
, .
co nst ructi on than t hose formerly used They vary greatly i n size .
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 .
4 64 IN O R G A N I C C HE M I S T R Y 3 02
F8 2 0 3 3 00 2Fe 3 00 2 .
FIG . 73.
B LAS T FURNA C E .
fuse but is extensible and malleable and the more s o the less t h e
, ,
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
,
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
.
3
. ,
w i th quick c oo lin g .
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
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
, , ,
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,
.
,
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 .
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
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.
form s .
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
acc ount sul phurous ores as such are unsuitable for the manu
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 ,
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
.
-
res p ect to the iron carbon system (2) removing harmful o ccluded
-
solutions with iron Steel beco mes very hard and brittle for .
,
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 ,
i
p g
.
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 ,
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 .
,
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 ,
.
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 .
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
, ,
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 .
aque ous s olu t i o n most of the ferric salts even thos e o f strong ,
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
.
v arious iron com p ounds in the air and is manufac t ured by igni t ing
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
,
inc r eases on warming the dilute aqueous solution for a very dilute , ,
c olor .
2 4 H2 0 .
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
e x pla ined by su ppo sing tha t every ferr ic ion gives u p a third of its
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
08 unites I ron
with c y a n o g e n t o fo rm com p lex an d
3 .
.
,
iron sul phide ( animal refuse always contains sul phur c om poun ds) .
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 .
for the u n pu rie d gas contains a little cyanogen and prussic acid .
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 .
c ipit a t e soon turns blue in the air on acc oun t of the formation of
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 .
C O BAL TO US C O M P UN DS O .
,
. .,
c u pric chloride
c ate is very dee p blue ; hence its use for colori n g glass Pulverized .
alumina .
C O BAL TI C C O M PO UN D S .
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 rese n t in excess in t h e li q ui d .
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 , , ,
lytically .
air .
.
,
sal t s .
,
.
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 .
Ni -
N i( 0 0 ) 4 ,
which is dis placed to the left with rising tem perature since t h e ,
S howed at the same time that both the formation and the de c o m
substances .
i
a d in extracting nickel fro m low grade ores .
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
,
.
ammo n ium sul phide ) they are a pparently not redissolved by dilute
,
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
. .
,
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
,
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 ,
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
, , .
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
.
,
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 .
a ci d.
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
.
,
rutheni um .
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
.
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 .
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 .
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
,
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
, ,
Ir C l4 2K C l
~
Th e for m er d i sso lves in water readil y the l atter wi th
.
,
Pall adi u m .
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 )
. .
heat i ng in a va c uum .
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.
u sed to separate i od ine fro m t h e other hal ogens s in c e thei r pall ad ium ,
the s odium platinic chl oride being very soluble even in alcohol , .
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 .
t o it (pla tin ic a cid) Salts of this acid are m oreover formed when
.
3 H2 O Ba Pt (C N ) 4 4 H2 O etc
,
The latter has come int o prominence
-
,
.
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
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
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 ,
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 ,
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, .
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 .
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
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 ,
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 ,
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
s
s re a r .
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 ,
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
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
GO ( N H3 ) X
5 3
0 (N H 94X3
24 5 1 17 7
With t hose of t he l ts
sa
t ro l yt e .
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
M ( N H3 ) ,X3 A ci do pe n t am m in e s al t t [M (N H3 ) 5X] X2 ,
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 .
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 .
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
. .
, , , ,
FI G 7 7 . .
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
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
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 , , . .
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
013 ,
Bl ue h e xahy d r at e
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
,
. .
,
~
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
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
b ee n ab le t pre p ar s uc h i me r
o e so s .
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
,
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
-
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 ,
xi
o de, 3 7 7 ,
i
p erox de, 3 7 9 C hl oramine 1 7 7 ,
il c
s i ate, 3 84 C hl oric acid 88 ,
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 ,
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 or nd u , 24 7 u m C hr om ite 44 9 4 50 , ,
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 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 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
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 ,
w h ite 2 86
,
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
,
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,
n o m en a , 3 u sta 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 .
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
,
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