(2099) Lecture Notes P Block 15 16 E.pdf - TMP

Lecture # 1
p- Block Element
Group fifteen elements (Nitrogen family) :
Group 15 includes nitrogen phosphorus, arsenic, antimony and bismuth. As we go down the group, there is
a shift from non-metallic to metallic through metalloidic character. Nitrogen and phosphorus are non-metal,
arsenic and antimony metalloid and bismuth is a typical metal.
Element N P As Sb Bi
Atomic Number 7 15 33 51 83
Atomic Mass 14.01 30.97 74.92 121.76 208.98
2 3 2 3 10 2 3 10 2 3 14 10 2 3
Electronic configuration [He] 2s 2p [Ne] 3s 3p [Ar] 3d 4s 4p [Kr] 4d 5s 5p [Xe] 4f 5d 6s 6p
Covalent Radius / pm 70 110 120 140 150
Ionic Radius / pm a a a b b
3– +3 171 212 222 76 103
a=M ,b=M
 1402 1012 947 834 703
Ionization enthalpy
 2856 1903 1798 1595 1610
/ (kJ mol–1)
 4577 2910 2736 2443 2466
Electronegativity 3.0 2.1 2.0 1.9 1.9
Trends of some of the atomic, physical and chemical properties of the group are discussed below.
Electronic Configuration :
The valence shell electronic configuration of the these element is ns2 np3 the s orbital in these element is
completely filled and p orbital are half- filled, making thier electronic configuration extra stable.
Atomic and Ionic Radii :

Covalent and ionic (in a particular state) radii increase in size down the group. There is a considerable
increase in covalent radius from N to P. However, from As to Bi only a small increase in covalent radius is
observed. This is due to the presence of completely filled d and / or f orbitals in heavier members.
Ionisation Enthalpy:
Ionisation enthalpy decreases down the group due to gradual increase in atomic size. Because of the extra
stable half- filled p-orbital electronic configuration and smaller size, the ionisation enthaply of the group 15
element is much greater than of group 14 elements in the corresponding periods. The order of successive
ionisation enthalpies, as expected is iH1 < iH2 < iH3
Electronegativity :
The electronegativity value, in general, decreases down the group with increasing atomic size. However,
amongst the heavier elements, the difference is not that much pronounced.
Physical Properties:
All the elements of this group are polyatomic. Dinitrogen is a diatomic gas while all others are solids.
Metallic character increases down the group. Nitrogen and phosphours are non – metals , arsenic and
antimony metalloids and bismuth is a metal. This is due to decrease in ionisation enthalpy and increase in
atomic size. The boiling points , in general , increase from top to bottom in the group but the melting point
increases upto arsenic and then decreases upto bismuth. Except nitrogen , all the elements show allotropy.
RESONANCE p-Block Elements (Group 15 & 16) - 1

Chemical Properties :
Oxidation States and trends in a chemical reactivity :
The common oxidation states of these elements are – 3 , + 3 and + 5. The tendency to exhibit – 3 oxidation
state decreases down the group , bismuth hardly forms any compound in –3 oxidation state. The stability of
+ 5 oxidation state decreases down the group. The only well characterised Bi (V) compound is BiF5 .The
stability of + 5 oxidation state decreases and that of +3 state increases (due to inert pair effect) down the
group. Nitrogen exhibits +1 , + 2 , + 4 oxidation states also when it reacts with oxygen. Phosphours also
shows + 1 and + 4 oxidation states in some oxoacids.
In the case of nitrogen , all oxidation states from +1 to +4 tend to disproportionate in acid solution.
For example ,
3 HNO2  HNO3 + H2O + 2 NO

Similarly , in case of phosphorus nearly all intermediate oxidation states disproportionate into +5 and –3
both in alkali and acid. However +3 oxidation state in case of arsenic , antimony and bismuth become
increasingly stable with respect to disproportionation.
Nitrogen is restricted to a maximum covalency of 4 since only four (one s and three p) orbitals are
available for bonding. The heavier elements have vacant d orbitals in the outermost shell which can be used
for bonding (covalency) and hence , expand their covalence as in PF6– .
Anomalous properties of nitrogen :

Nitrogen differs from the rest of the members of this group due to its smaller size , high electronegativity ,
high ionisation enthalpy and non – availability of d orbitals. Nitrogen has unique ability to form p – p
multiple bonds with itself and with other elements having small size and high electronegativity (e.g., C ,O).
Heavier elements of this group do not form p – p bonds as their atomic orbitals are so large and diffuse that
they cannot have effective overlapping. Thus, nitrogen exists as a diatomic molecule with a triple bond (one
s and two p) between the two atoms. Consequently , its bond enthalpy (941.1 kJ mol–1) is very high. On the
contrary , phosphorus , arsenic and antimony form metallic bonds in elemental state. However , the single N
– N bond is weaker than the single P – P bond because of high interelectronic repulsion of the non – bonding
electrons , owing to the small bond length. As a result the catenation tendency is weaker in nitrogen. Another
factor which affects the chemistry of nitrogen is the absence of d orbitals in its valence shell. Besides
restricting its covalency to four , nitrogen cannot form d – p bonds as the heavier elements can e.g.,
R3P = O or R3P = CH2 (R = alkyl group). Phosphours and arsenic can form d – p bond also with transition
metals when their compounds like P(C2H5)3 and As(C6H5)3 act as ligands.
(i) Reactivity towards hydrogen : All the elements of Group 15 form hydrides of the type EH3 where
E = N , P, As, Sb or Bi. Some of the properties of these hydrides are shown in Table. The hydrides show
regular gradation in their properties. The stability of hydrides decreases from NH3 to BiH3 which can be
observed from their bond dissociation enthalpy. Consequently , the reducing character of the hydrides
increases. Ammonia is only a mild reducing agent while BiH3 is the strongest reducing agent amongst all the
hydrides. Basicity also decreases in the order
NH3 > PH3 > AsH3 > SbH3  BiH3 .
Properties of Hydrides of Group 15 Elements
Property NH 3 PH3 AsH3 SbH3 BiH3
Melting point / K 195.2 139.5 156.7 185 –

Boiling point / K 238.5 185.5 210.6 254.6 290
(E – H) Distance / pm 101.7 141.9 151.9 170.7 –
0
HEH angle ( ) 107.8 93.6 91.8 91.3 –
– –1
fH / kJ mol – 46.1 13.4 66.4 145.1 278
– –1
dissH (E – H) / kJ mol 389 322 297 255 –
(ii) Reactivity towards oxygen :

All these elements form two types of oxides : E2O3 and E2O5 . The oxide in the higher oxidation state of the
element is more acidic than that of lower oxidation state. Their acidic character decreases down the group.
The oxides of the type E2O3 of nitrogen and phosphours are purely acidic , that of arsenic and antimony
amphoteric and those of bismuth is predominantly basic.

(iii) Reactivity towards halogens :
These elements react to form two series of halides : EX3 and EX5 . Nitrogen does not form pentahalide due
to non – availability of the d – orbitals in its valence shell. Pentahalides are more covalent than trihalides. All
the trihalides of these elements except those of nitrogen are stable. In case of nitrogen , only NF3 is known
to be stable. Trihalides except BiF3 are predominantly covalent in nature.
(iv) Reactivity towards metals :

These elements react with metals to form their binary compounds exhibiting –3 oxidation state , such as ,
Ca3N2 (calcium nitride) Ca3P2 (calcium phosphide) , Na3As2 (sodium arsenide) , Zn3Sb2 (zinc antimonide) and
Mg3Bi2 (magnesium bismuthide).
Dinitrogen (N2) :
Preparation :
Dinitrogen is produced commercially by the liquefaction and fractional distillation of air. Liquid dinitrogen
(b.p. 77.2 K) distils out first leaving behind liquid oxygen (b.p. 90 K).
Laboratory method of preparation :

In the laboratory , dinitrogen is prepared by treating an aqueous solution of ammonium chloride with sodium
nitrite.
NH4Cl (aq) + NaNO2 (aq)  N2 (g) + 2 H2O (1) + NaCl (aq)
Small amounts of NO and HNO3 are also formed in this reaction ; these impurities can be removed by
passing the gas through aqueous suplhuric acid containing potassium dichromate.
Common methods of preparation :

Heat
(i) (NH4)2 Cr2O7   N2 + 4 H2O + Cr2O3
(ii) Very pure nitrogen can be obtained by the thermal decomposition of sodium or barium azide.
Ba (N3)2  Ba + 3N2
(iii) By heating ammonium dichromate:


(NH4)2Cr2O7  N2  + 4H2O + Cr2O3
(iv) By oxidation of ammonia

(A) At lower temperature
(a) By reaction of ammonia with calcium hypochlorite or Br2.
4NH3 + 3Ca(OCl)2  3CaCl2 + N2 + H2O
(b) By the action of Cl2 gas on liquor ammonia:
8NH3 + 3Cl2  6NH4Cl + N2
If excess of Cl 2 is used in this reaction, nitrogen trichloride is formed as per the following
reaction,
NH3 + 3Cl2  NCl3 + 3HCl
Nitrogen trichloride is an explosive substance.
(B) At higher temperature.
(a) By passing ammonia over heated cupric oxide:

2NH3 + 3CuO  N2 + 3Cu + 3H2O
(b) By heating urea with a nitrite in presence of dilute H2SO4:


NH2CONH2 + 2NaNO2 + H2SO4  Na2SO4 + 2N2 + 3H2O + CO2 
(v) By passing HNO3 vapours on red hot copper:
5Cu + 2HNO3  5CuO + N2 + H2O

Properties :
(i) Physical properties :
Dinitrogen is a colourless, odourless, tasteless and non – toxic gas. It has two stable isotopes:
14
N and 15N. It has a very low solubility in water (23.2 cm3 per litre of water at 273 K and 1 bar pressure) and
low freezing and boiling points.
(ii) Chemical properites :

Dinitrogen is rather inert at room temperature because of the high bond enthalpy of NN bond. Reactivity,
however, increases rapidly with rise in temperature.
(i) At higher temperature it directly combines with some metals to form predominantly ionic nitrides and with
non–metals , covalent nitrides. A few typical reactions are :
Heat
6 Li + N2  2 Li3N
Heat
3 Mg + N2   Mg3N2
(ii) It combines with hydrogen at about 773 K in the presence of a catalyst (Haber’s Process) to form ammonia:
N2 (g) + 3 H2 (g) 2 NH3 (g) ; fH– = – 46.1 kJ mol–1
(iii) Dinitrogen combines with dioxygen only at very high temperature (at about 2000 K) to form nitric oxide , NO.
N2 + O2 (g) 2 NO (g)
(iv) Reaction with CaC2 and BaC2: At 1100oC, these carbides react with N2 forming CaCN2 and Ba(CN)2 respectively.
 
CaC2 + N2 +  CaCN2 + C (nitrolim, a fertilizer) ; BaC2 + N2 +  Ba(CN)2
CaCN2 reacts with H2O in the soil to produce NH3 gas. NH3 gas is converted by the nitrating bacteria present
in soil into nitrates. (The nitrates are readily absorbed by the plants and meet their requirement of the
element nitrogen.)
The main use of dinitrogen is in the manufacture of ammonia and other industrial chemicals containing
nitrogen, (e.g., calcium cyanamide). It also finds use where an inert atmosphere is required (e.g., in iron and
steel industry ,inert diluent for reactive chemicals). Liquid dinitrogen is used as a refrigerant to preserve
biological materials , food items and in cryosurgery.
Lecture # 2
COMPOUNDS OF NITROGEN
(1) Ammonia :
Preparation :
(i) Ammonia is present in small quantities in air and soil where it is formed by the decay of nitrogenous orgainc
matter e.g., urea.
NH2CONH2 + 2 H2O  (NH4)2CO3 2 NH3 + H2O + CO2
(ii) On a small scale ammonia is obtaned from ammonia salts which decompose when treated with caustic
soda or lime.
2 NH4Cl + Ca (OH)2  2 NH3 + 2 H2O + CaCl2
(NH4)2 SO4 + 2 NaOH  2 NH3 + 2 H2O + Na2SO4
(iii) On a large scale , ammonia is manufactured by Haber’s process.

N2 (g) + 3 H2 (g)  2 NH3 (g) ; f H– = – 46.1 kJ mol–1
In accordance with Le Chatelier’s principle , high pressure would favour the formation of ammonia. The
optimum conditions for the production of ammonia are a pressure of 200 × 105 Pa (about 200 atm) , a
temperature of ~ 700 K and the use of a catalyst such as iron oxide with small amounts of K2O and Al2O3 to
increase the rate of attainment of equilibrium.

(iv) By hydrolysis of metal nitrides like AIN or Mg3N2
AIN + NaOH + H2O  NaAIO2 + NH3
For drying, dehydrating agents like H2SO4 , P2O5 or CaCl2 can not be used as these react with NH3.
CaO(quicklime) is used  CaO + H2O  Ca(OH)2
2NH3 + H2SO4  (NH4)2SO4 ; 6NH3 + P2O5 + 3H2O  2(NH4)3PO4
CaCl2 + 8NH3  CaCl2 8NH3 (Adduct)
Properties :
Physical properties :
Ammonia is a colourless gas with a pungent odour. Its freezing and boiling points are 198.4 and 239.7 K
respectively. In the solid and liquid states , it is associated through hydrogen bonds as in the case of water
and that accounts for its higher melting and boiling points than expected on the basis of its molecular mass.
The ammonia molecule is trigonal pyramidal with the nitrogen atom at the apex. It has three bond pairs and
one lone pair of electrons as shown in the structure.
Ammonia gas is highly soluble in water. Its aqueous solution is weakly basic due to the formation of OH–
ions.
NH3 (g) + H2O (1) NH4+ (aq) + OH– (aq)
Chemical properties :
(i) It forms ammonium salts with acids , e.g., NH4Cl , (NH4)2 SO4 , etc. As a weak base , it precipitates the
hydroxides of many metals from their salt solutions. For example ,
2 FeCl3 (aq) + 3 NH4OH (aq)  Fe2O3 . xH2O (s) + 3 NH4Cl (aq)
(brown ppt)
ZnSO4 (aq) + 2 NH4OH (aq)  Zn(OH)2 (s) + (NH4)2 SO4 (aq)
(white ppt)
 NiCl2 (aq.) + 2NH4OH (aq.)  Ni(OH)2(green) + 2NH4Cl

CrCl3 (aq.) + 3NH4OH (aq.)  Cr(OH)3(green) + 3NH4Cl
CoCl2 (aq.) + 2NH4OH (aq.)  Co(OH)2 (pink) + 2NH4Cl
Cr(OH)2 is partially soluble in ammonia (excess) whereas
Ni(OH)2  , Co(OH)2 are soluble in excess of ammonia forming soluble complex.
(ii) The presence of lone pair of electrons on the nitrogen atoms of the ammonia molecule makes it a Lewis
base. It donates the electrons pair and forms linkage with metal ions and the formation of such complex
compounds finds applications in detection of metal ions such as Cu2+ , Ag+ ; Cd2+ :
Cu2+ (aq) + 4 NH3 (aq) [Cu(NH3)4]2+ (aq)

(blue) (deep blue)
Ag+ (aq) + Cl–1 (aq) AgCl (s)

(colourless) (white ppt)
AgCl (s) + 2 NH3 (aq)  [Ag (NH3)2]Cl (aq)

(white ppt) (colourless)
Cd2+ + 4NH3(aq)  [Cd(NH3)4]2+ (aq)

(colourless)
(iii) Na + NH3 

 NaNH2 + 1/2 H2
Amides decompose back with water to form NH3 and NaOH.
(iv) 4NH3 + 5O2   4NO + 6H2O (Ostwald’s process-Mgf. HNO3)
Pt , 550 º C


(v) Cupric oxide and PbO are reduced to metal when NH3 is passed over heated CuO and PbO.
3CuO + 2NH3  3Cu + 3H2O + N2; 3PbO + 2NH3  3Pb + 3H2O + N2
(vi) M(NO3)2 + 2NH4OH  M(OH)2 (white) + 2NH4NO3

MCl2 + 2NH4OH  M(OH)2(white) + 2NH4Cl
(M = Mg, Ca, Sr, Ba, Ra, Sn, Pb)
(vii) Mercuric salts, NH4OH forms a white precipitate

HgCl2 (aq.) + 2NH4OH  HgNH2Cl (white) + NH4Cl + H2O
Tests of ammonia/ammonium salts :

(i) When NH3 gas is passed into the colourless solution of Nessler’s reagent a brown precipitate or coloration is
formed. This is a test for NH3 gas.
2K2HgI4 + 3KOH + NH3  H2N·HgO·HgI (brown) + 7KI + 2H2O
(ii) Ammonium salts gives yellow ppt. with H2PtCl6

2NH4Cl + H2PtCl6  (NH4)2 [Pt Cl6]  + 2HCl.
(iii) Turmeric paper turns brown when exposed to ammonia gas.
Uses :
Ammonia is used to produce various nitrogeneous fertilisers (ammonium nitrate , urea ammonimum phosphate
and ammonium sulphate) and in the manufacture of some inorganic nitrogen compouns , the most important
one being nitric acid Liquid ammonia is also used as a refrigerant.
 Ammonium salts decompose quite readily on heating. If the anion is not particularly oxidising
(e.g. Cl– CO32– or SO42–) then ammonia is evolved.
 
NH4Cl  NH3 + HCl; (NH4)2SO4  2NH3 + H2SO4
If the anion is more oxidising (e.g. NO2–, NO3– , ClO4– , Cr2O72–) then NH4 is oxidised to N2 or N2O.
–III 
NH 4NO 2  N2 + 2H2O
–III 
NH 4NO 3  N2O + 2H2O

(NH4)2Cr2O7  N2 + 4H2O + Cr2O3
 NH3 burns in dioxygen with a pale yellow flame.

4NH3 + 3O2 2N2 + 3H2O
Neutral
 2NH3 + 2KMnO4    2KOH + 2MnO + N + 2H O
2 2 2
medium
 Ammonia is oxidised by sodium hypochlorite in dilute aqueous solution:-
NH3 + NaOCl NH2Cl + NaOH (fast)
2NH3 + NH2Cl NH2NH2 + NH4Cl (slow)
(Rasching process for mfg. of hydrazine)
A small quantity or all the product may be destroyed by the side reaction given below.
2NH2Cl
N2 H4 + N2 + 2NH4Cl
Chloramine
This reaction is catalysed by heavy metal ions present in solution. For this distilled water is used (rather than
tap water) and glue or gelatin is added to mask (i.e. complex with) the remaining metal ions. The use of
excess of ammonia reduces the incidence of chloramine reacting with hydrazine. The use of a dilute solution
of the reactant is neccessary to minimize another side reaction.
3NH2Cl + 2NH3 N2 + 3NH4Cl

When dissolved in water ( in neutral or basic solutions) hydrazine or its salts are powerful reducing agents.
They are used to produce silver and copper mirror and to precipitate the platinum metals. Also reduces I2 and
O2.
N2H4 + 2I2 4HI + N2

N2 H4 + O 2 2H2O2 + N2
N2H4 + CuSO4 Cu + N2 + 2H2SO4
In acidic solutions, it usually acts as mild reducing agent. Strong/powerful reducing agent can reduce N2H4 to
NH3, thus causing N2H4 to be oxidised.
N2H 4 + Zn + 2HCl 2NH3 + ZnCl2
(– II) (– III)
 N2H4.HCl (aq) + HNO2 HN3 + HCl + 2H2O
 NH2OH weaker base than is ammonia and hydrazine salts contain the hydroxylammonium ion [NH3OH]+.
NH2OH + H2SO4 [NH3OH]+ HSO 4–
–1 I – III
It disproportionates slowly in acidic solutions:- 4[NH2 OH.H]  N2 O  2NH 4 + 2H+ + 3H2O
–I O – III
and rapidly in alkaline solutions:- 3NH2OH N2  NH3 + 3H2O
NH2OH and its salts are very poisnous and they are also strong reducing agents.
CH3NO2 + H2SO4 [NH3OH]+ HSO 4– + CO 
|
–– |
C
NH 2 OH Oleum
     
 –– NH
CH2
Caprolactum
  CO – [NH – (CH2 )5 – CO]n – NH  

Nylon  6
 HN3 liquid and the gas both explode on heating or with a violent shock.
2HN3  3N2 + H2
It reacts with electropositive metal forming salts called azides but unlike other acid + metal reactions no
hydorgen is evolved.
6HN3 + 4Li  4 Li N3 + 2NH3 + 2N2
 N2O + 2NaNH2  NaN3 + NH3 + NaOH.
 NaN3 + H2S + H2 O  NH3 + N2 + S + NaOH.
Fertilizers :
o
100  200 C
(i) 2NH3 + CO2 high
    NH CONH  NH2CONH2  H2 O
pressure 2 4
(urea )
In soil, it slowly hydrolyses to ammonium carbonate.
NH2 CO NH2 + 2H2O  (NH4)2 CO3
3 Ca (H2PO 4 ) 2  7 CaSO 4
(ii) [3 (Ca3(PO4)2 CaF2 ] + 7 H2 SO4     + 2HF
Superphosp hate
Phosphate rock (fluoroapatite).

10 Ca (H2PO 4 )2
(iii) [3 Ca3(PO4)2 CaF2 ] + 14 H3PO4   + 2HF
triple sup rphosphate
H3 PO4 is used to avoid the formation of the insoluble CaSO4 (waste product).
(2) Oxides of nitrogen :
Table : Oxides of Nitrogen
Nitrous oxided (N2O) :

2 NO + H2SO3  N2O + H2SO4
Nitric Oxide (NO) :

Pt
4 NH3 + 5 O2 750
 4 NO + 6 H O (on commercial scale)
– 900 2
It is not an acid anhydride.

2HNO2 + 2 I- + 2H+  2NO + I2 + 2H2O
Odd electron molecules are usually highly reactive and tend to dimerize. It is unusually stable for an odd
electron molecules.
2 NO + Cl2  2NOCl.
Sn 2  or Cr 2 
2 NO + 6 H     2 NH4OH.
Nitrogen Sesquioxide (N2O3) :
4NO + O2 (in appropriate amount)   2N2 O3

  20 o C
o
 30 C
N2O3   NO + NO2

Mixture of NO and NO2 can be prepared in the laboratory by the reducion of 50% HNO3 with arsenious oxide
or 5N HNO3 with metallic copper
2 HNO3 + As2O3 + 2 H2O  NO + NO2 + 2 H3AsO4
It is the anhydride of nitrous acid.

N2O3 + NaOH  2NaNO2 + H2O
With the concentrated acids, form nitrosyl salts.
N2O3 + 2HClO4  2NO [ClO4] + H2O
N2 O3 + 2H2SO4  2NO [HSO4] + H2O.
Nitrogen dioxide and dinitrogen tetraoxide (N2O4) :
N2O4 is a mixed anhydride as HNO2 and HNO3 are formed with water.
N2O4 + H2O  HNO3 + HNO2

decompose
2HNO2    NO2 + NO + H2O
NO2 + H2O  HNO3 + HNO2

Moist NO2 or N2O4 gases are strongly acidic.
Liquid N2O4 self ionizes as
N2 O 4 NO+ (acid) + NO3– (base)
N2O4 is used as a solvent for preparing anhydrous metal nitrates and also nitrato complexes.
Ti Br4 + N2 O4  Ti (NO3)4 + 4NO + 2Br2.
NO2 – N2O4 system is strong oxidising agent, oxidises HCl to Cl2 and CO to CO2.
NO2 + CO  CO2 + NO
2NO2 + Cl2  2NO2Cl
 In solid state, the oxide consists only of N2O4 molecules (colourless). At –11.20 C solid melts liquid may be
considered as a dilute solution of NO2 and N2O4. Colour gradually changes from yellow to orange with the rise
in tempt. indicating an increase in the precentage of NO2 . At 220, the liquid boils giving brown vapours.
At 6200 C ,
SO2 + H2O + NO2  H2SO4 + NO

(oxidising agent)
 Dinitrogen pentoxide (N2O5) :

Anhydride of HNO3
N2O5 + Na  NaNO3 + NO2
N2O5 + NaCl  NaNO3 + NO2Cl
decomposit ion
N2O5 (gas)     NO2 + NO + O2
 NO3 may be formed by treating N2O5 with O3
N2 O5 + H2 SO4  H3O+ + 2NO2+ + 3HSO4–
 5 N2O5 + I2  10 NO2 + I2O5
(strong oxidising agent)

Lecture # 3
Nitric Acid :
Nitrogen forms oxoacids such as H2N2O2 (hyponitrous acid) , HNO2 (nitrous acid) and HNO3 (nitric acid).
Amongst them HNO3 is the most imoprtant.
Preparation :
In the laboratory , nitric acid is prepared by heating KNO3 or NaNO3 and concentrated H2SO4 in a glass retort.
NaNO3 + H2SO4  NaHSO4 + HNO3

On a large scale it is prepared mainly by Ostwald’s process.
This method is based upon catalytic oxidation of NH3 by atmoshperic oxygen.
4 NH3 (g) + 5 O2 (g) (from air) 4 NO (g) + 6 H2O (g)
Nitric oxide thus formed combines with oxygen giving NO2.

2 NO (g) + O2 (g) 2 NO2 (g)
Nitrogen dioxide so formed , dissolves in water to give HNO3.
3 NO2 (g) + H2O (1)  2 HNO3 (aq) + NO (g)

NO thus formed is recycled and the aqueous HNO3 can be concentrated by distillation upto ~ 68% by mass.
Further concentration to 98% can be achieved by dehydration with concentrated H2SO4.
Properties :
It is a colourless liquid (f.p. 231.4 K and b.p. 355.6 K). Laboratory grade nitric acid contains ~ 68% of the
HNO3 by mass and has a specific gravity of 1.504.
In the gaseous state , HNO3 exists as a planar molecule with the structure as shown.
In aqueous solution , nitric acid behaves as a strong acid giving hydronium and nitrate ions.
HNO3 (aq) + H2O ()  H3O+ (aq) + NO3– (aq)
(i) Concertrated nitric acid is a strong oxidising agent and attacks most metals except noble metals such as
gold and platinum. The products of oxidation depend upon the concentration of the acid , temperature and
the nature of the material undergoing oxidation.
Some metals (e.g., Cr , Al) do not dissolve in concentrated nitric acid because of the formation of a passive
film of oxide on the surface.

Table : Reactions of Elements (Metals/Metalloids with HNO3)
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Element Nature of HNO3 changes to Reactions
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
(A) Metals placed above H in
electrochemical series (ECS)
1. Mg, Mn dilute (cold & dilute) M(NO3)2 M + 2HNO3  M(NO3)2 + H2
2. Zn, Fe (a) very dilute NH4NO3 4Zn+10HNO3  4Zn(NO3)2 + NH4NO3 + 3H2O
(b) dilute N2O 4Zn + 10HNO3  4Zn(NO3)2 + N2O + 5H2O
(c) conc NO2 Zn + 4HNO3  Zn(NO3)2 + 2NO2 + 2H2O
Fe becomes passive with 80% HNO3
3. Sn (a) dilute NH4NO3 refer 2(a).

(b) conc. NO2 Sn + 4HNO3  H2SnO3 + 4NO2 + H2O
meta stannic acid
4. Pb (a) dilute NO 3Pb + 8HNO3  3Pb(NO3)2 + 2NO + 4H2O

(b) conc. NO2 Refer 2(c).
(B) Metals below H in ECS

5. Cu, Ag (a) dilute NO Refer 4(a). Hg forms Hg2(NO3)2
Hg (b) conc. NO2 Refer 4(b).
(C) Metalloids
Sb, As Conc. NO2 Sb + 5HNO3  H3SbO4 + 5NO2 + H2O
antimonic acid
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
(ii) Concentrated nitric acid also oxidises non – metals and their compounds. Iodine is oxidised to iodic acid ,
carbon to carbon dioxide , sulphur to H2SO4 , and phosphours to phosphoric acid.
I2 + 10 HNO3  2 HIO3 + 10 NO2 + 4 H2O
C + 4 HNO3  CO2 + 2 H2O + 4 NO2
S8 + 48 HNO3 (conc.)  8 H2SO4 + 48 NO2 + 16 H2O
P4 + 20 HNO3 (conc.)  4 H3PO4 + 20 NO2 + 4 H2O
Brown Ring Test :

The familiar brown ring test for nitrates depends on the ability of Fe2+ to reduce nitrates to nitric oxide, which
reacts with Fe2+ to form a brown coloured complex. The test is usually carried out by adding dilute ferrous
sulphate solution to an aqueous solution containing nitrate ion , and then carefully adding concentrated sulphuric
acid along the sides of the test tube. A brown ring at the interface between the solution and sulphuric acid
layers indicate the presence of nitrate ion in solution.
NO3– + 3 Fe2+ + 4H+  NO + 3 Fe3+ + 2 H2O
[Fe (H2O)6]2+ + NO  [Fe (H2O)5 (NO)]2+ + H2O
Uses :
The major use of nitric acid is in the manufacture of ammonium nitrate for fertilisers and other nitrates for use
in explosives and pyrotechnics. It is also used for the perparation of nitroglycerin ,trinitrotoluene and other
organic nitro compounds. Other major uses are in the pickling of stainless steel , etchiing of metals and as an
oxidiser in rocket fuels.

Phosphorus
Phosphorus Allotropic Forms :
Phosphorus is found in many allotropic forms , the important one being white , red and black.
White phosphorus is a translucent white waxy solid. It is poisonous , insoluble in water but soluble in
carbon disulphide. Molecular formula is P4. Ignition temperature is around 30ºC. When exposed to air it
undergoes oxidation which gradually raises it temperature and ultimately catches fire when the temperature
exceeds 30ºC. That is why it is kept in water. It dissolves in boiling NaOH solution in an inert atmosphere
giving PH3.
P4 + 3 NaOH + 3 H2O  PH3 + 3 NaH2PO2
(sodium hypophosphite)
White phosphorus is less stable and therefore , more reactive than the other solid phases under normal
conditions because of angular strain in the P4 molecule where the angles are only 600.
It glows in dark due to slow oxidation. This property is called phosphorescence (chemiluminescence).
P4 + 5O2  P4O10
It consists of discrete tetrahedral P4 molecule as shown in Fig.
P
Å
2.21
0
60
P P
P
Fig White phosphorus
As readily oxidised, acts as a reducing agent

P4 + 20HNO3  4H3PO4 + 20NO2 + 4H2O ; 3CaO + 8P + 9H2O  3Ca(H2PO2)2 + 2PH3
P4 + 5CuSO4 + 6H2O  Cu3P2 + 2H3PO3 + 3H2SO4
Cu3P2 + 5CuSO4 + 8H2O  8Cu + 5H2SO4 + 2H3PO4
Colloidal solution of gold may be prepared by reducing a solution of gold chloride with phosphours dissolved
in ether.
Red phosphorus is obtained by heating white phosphorus at 573 K in an inert atmosphere of CO2 or coal
gas for several days. This red phosphorous may still contain some white phosphorus which is removed by
boiling the mixture with NaOH when white phosphorus is converted in to PH3 gas but red phosphorus remains
inert.
P4 + 3NaOH + 3H2O  PH3(g) + 3NaH2PO2

When red phosphours is heated under high pressure, a series of phase of black phosphorus are formed. Red
phosphorus possesses iron grey lustre. It is odourless , non – poisonous and insouble in water as well as in
carbon disulphide. Chemically, red phosphorus is much less reactive than white phosphorus. It does not
glow in the dark. Ignition temperature is 260ºC.
Red phosphorus
It is polymeric, consisting of chains of P4 tetrahedra linked together in the manner as shown in Fig.

Black phosphorus has two forms  – black phosphorus and  – black phosphorus ,  – Black phosphorus
is formed when red phosphorus is heated in a sealed tube at 803 K. It can be sublimed in air and has opaque
monoclinic or rhombohedral crystral. It does not oxidise in air.  – Black phosphorus is prepared by heating
white phosphorus at 473 K under high pressure. It does not burn in air upto 673 K.
-black phosphorus is a good conductor of electricity whereas -Black phosphorus is non-conductor.
black phosphorus has layered structure like graphite. The distance between the two layers is found to be
3.68 Å.
Density :
WP = 1.83 ; RP = 2.20 ; BP = 2.70 gm/cc ; as polymerisation  compactness   density 
Compounds of phosphorus
(1) Phosphine :
Preparation :
(i) Phosphine is prepared by the reaction of calcium phosphide with water or dilute HCl.
Ca3P2 + 6 H2O  3 Ca(OH)2 + 2 PH3
Ca3P2 + 6 HCl  3 CaCl2 + 2 PH3
(ii) In the laboratory, it is prepared by heating white phosphorus with concentrated NaOH solution in an inert
atmosphere of CO2.
P4 + 3 NaOH + 3 H2O  PH3 + 3 NaH2PO2

(sodium hypophosphite)
When pure, it is non inflammable but becomes inflammable owing to the presence of P2H4 or P4 vapours. To
purify it from the impurities , it is absorbed in HI to form phosphonium iodide (PH4I) which on treating with
KOH gives off phosphine.
PH4I + KOH  KI + H2O + PH3
(iii) 2Na3P + 3H2SO4  3Na2SO4 + 2PH3 
Properties :
It is a colourless gas with rotten fish smell and is highly poisonous. It explodes in contact with traces of
oxidising agents like HNO3 , Cl2 and Br2 vapours.
It is slightly soluble in water. The solution of PH3 in water decomposses in presence of light giving red
phosphorus and H2. When absorbed in copper sulphate or mercuric chloride solution, the corresponding
phosphides are obtained.
3CuSO4 + 2 PH3  Cu3P2  (Black) + 3 H2SO4
3HgCl2 + 2 PH3  Hg3P2  (Brownnish black) + 6 HCl
3AgNO3 + PH3  Ag3P  (yellow) + 3HNO3. It later on decomposes to black Ag
Ag3P + AgNO3 + 3H2O  3Ag  (black) + 3HNO3 + H3PO3
Samples of PH3 can be dried using quicklime or NaOH sticks.
Phosphine on heating at 150ºC burns forming H3PO4
PH3 + 2O2  H3PO4
Phosphine is weakly basic and like ammonia, gives phosphonium compounds with acids e.g.,
PH3 + HBr  PH4Br
Uses :
The spontaneous combustion of phosphine is technically used in Holme’s samples. Containers containing
calcium carbide and calcium phosphide are pierced and thrown in the sea when the gases evolved burn and
serve as a signal. It is also used in smoke screens.

(2) Phosphorus Halides :
Phsophorus forms two types of halides , PX3 [X = F , Cl , Br, I] and PX5 [X = F , Cl , Br,]
(a) Phosphorus Trichloride :
Preparation :
(i) It is obtained by passing dry chlorine over heated white phosphorus.
P4 + 6 Cl2  4 PCl3
(ii) It is also obtained by the action of thionyl chloride with white phosphorus.
P4 + 8 SOCl2  4 PCl3 + 4 SO2 + 2 S2Cl2
Properties :
(i) It is a colourless oily liquid and hydrolyses in the presence of moisture.
PCl3 + 3 H2O  H3PO3 + 3 HCl
(ii) It reacts with organic compounds containing – OH group such as CH3COOH , C2H5OH.
3 CH3COOH + PCl3  3 CH3COCl + H3PO3
3 C2H5OH + PCl3  3 C2H5Cl +H3PO3
Preparation :
Phosphorus pentachloride is prepared by the reaction of white phosphorus with excess of dry chlorine.
P4 + 10 Cl2  4 PCl5

It can also be prepared by the action of SO2Cl2 on phosphorus.
P4 + 10 SO2Cl2  4 PCl5 + 10 SO2

(b) Phosphorus pentachloride :
Properties :
(i) PCl5 is a yellowish white powder and in moist air , it hydrolyses to POCl3 and finally gets converted to
phosphoric acid.
PCl5 + H2O  POCl3 + 2 HCl
POCl3 + 3 H2O  H3PO4 + 3 HCl

(ii) When heated it sublimes but decomposes on stronger heating.
Heat
PCl5   PCl3 + Cl2
(iii) It reacts with organic compounds containing – OH group converting them to chloro derivatives.
C2H5OH + PCl5  C2H5Cl + POCl3 + HCl
CH3COOH + PCl5  CH3COCl + POCl3 + HCl
(iv) Finely divided metals on heating with PCl5 give corresponding chlorides.
2 Ag + PCl5  2 AgCl + PCl3
Sn + 2 PCl5  SnCl4 + 2 PCl3

It is used in the synthesis of some organic compounds , e.g., C2H5Cl , CH3COCl.

Lecture # 4
(3) Oxoacids of Phosphorus :
Phosphorus forms a number of a oxoacids. The important oxoacids of phosphorus with their formulas ,
methods of preparation and the presence of some characteristic bonds in their structures are given in Table.
Oxidation state
Characteristic bonds and
Name Formula of Preparation
their number
phosphorus
One P – OH
Hypophosphorous H3PO2 –+1 Two P – H white P4 + alkali
One P = O
Two P – OH
Orthophosphorous H3PO3 –+3 One P – H P2O3 + H2O
One P = O
Two P – OH
Pyrophosphorous H4P2O5 –+3 Two P – H PCl3 + H3PO3
Two P = O
Four P – OH
Hypophosphoric H4P2O6 –+4 Two P = O red P4 + alkali
One P – P
Three P – OH
Orthophosphoric H3PO4 –+5 One P = O P4O10 + H2O
Four P – OH
Pyrophosphoric H4P2O7 –+5 Two P = O heat phosphoric acid
One P – O – P
Three P – OH phosphorus acid +
Metaphosphoric (HPO3)3 –+5 Three P = O Br2 ,
Three P – O – P heat in sealed tube
The compositions of the oxoacids are interrelated in terms of loss or gain of H2O molecule or O – atom.
In oxoacids phosphorus is tetrahedrally surrounded by other atoms. All these acids contain one P = 0 and at
least one P – OH bond. The oxoacids in which phosphorus has lower oxidation state (less than +5) contain

in addition to P = O and P – OH bonds ,either P – P (e.g., in H4P2O6) or P – H (e.g., in H3PO2) bonds but not
both. These acids in + 3 oxidation state of phosphorus tend to disproportionate to higher and lower oxidation
states. For example , orthophosphorus acid (or phosphorus acid) on heating disproportionates to give
orthophosphoric acid (or phosphoric acid) and phosphine.
4 H3PO3  3 H3PO4 + PH3
The acids which contanin P – H bond have strong reducing properties. Thus , hypophorous acid is a good
reducing agent as it contains two P – H bonds and reduces , for example, AgNO3 to metallic silver.
4 AgNO3 + 2 H2O + H3PO4  4 Ag + 4 HNO3 + H3PO4
These P – H bonds are not ionisable to give H+ and do not play any role in basicity. Only those H atoms
which are attached with oxygen in P – OH form are ionisable and cause the basicity. Thus , H3PO3 and
H3PO4 are dibasic and tribasic , respectively as the structure of H3PO3 has two P – OH bonds and H3PO4
three.
(a) Phosphoric acid (H3PO4) :
Preparation :
(i) PCl5 + 4H2O  H3PO4 + 5HCl.
(ii) Ca3(PO4)2 + 3H2 SO4  2H3PO4 + 3 CaSO4 
(iii) P4 + 5O2  P4O10

P4 O10 + 6H2O  4 H3 PO4 (pure)
This is called furnace process.
Propertics :
(i) H3 PO4 is hydrogen bonded in aqueous solution and because of this the ‘concentrated’ acid is syrupy and
viscous.
gentle  strong 
(ii) H3 PO4   o
 H P O 
4 2 7
o
 (HPO )
3 n
220 C 320 C
(b) Phosphorus acid (H 3 PO 3 )

Preparation:
(i) By dissolving P2O3 in water:
P2O3 + 3H2O  2H3PO3
(ii) By hydrolysis of PCl3 with water:
PCl3 + 3H2O  H3PO3 + 3HCl
The solution containing H3PO3 and HCl is heated to 180oC and HCl gas is driven out. The resulting solution
on crystallization gives white crystals of H3PO3.
(iii) 
3H3PO2 (Concentrated solution) 40  PH + 2H PO
º C or above 3 3 3
Pr oper ties:
(i) It is a white crystalline solid, soluble in water and having melting point of 74oC.
(ii) It is a weak acid and a reducing agent

(iii) When neutralized with bases or alkalies, it forms neutral salts called phosphites which are unstable.
H3PO3 + 3NaOH  Na3PO3 + 3H2O
(iv) 4H3PO3 

 3H3PO4 + PH3 (Disproportionation)
(v) H3PO3 + 3PCl5  PCl3 + 3POCl3 + 3HCl

(vi) It is a strong reducing agent :
2AgNO3 + H3PO3 + H2O  2Ag + 2HNO3 + H3PO4
2HgCl2 + H3PO3 + H2O  Hg2Cl2 + 2HCl + H3PO4

(4) Oxides of Phosphorus :
(a) Phosphorus trioxide (P 2 O 3 ) :
Preparation:
It is prepared by burning phosphorus in a limited supply of oxygen when gaseous P4O10 and P4O6 are formed.
On lowering the temperature using a condenser, P4O6 remains in gaseous form whereas P4O10 condenses as
a solid which is stopped by glasswool. On passing the remaining gaseous mixture through freezing mixture,
it converts into colourless crystals of P4O6.
Pr oper ties:
(i) It is colourless crystalline solid having mp 23.8oC and bp 178oC.
(ii) It dissolves in cold water to form phosphorus acid. It is thus the anhydride of phosphorus acid.
P2O3 + 3H2O  2H3PO3
(iii) It dissolves in hot water liberating PH3
2P2O3 + 6H2O  3H3PO4 + PH3
(iv) It slowly gets oxidized in air to form P2O5
P2O3 + O2  P2O5

(v) It burns in Cl2 gas forming phosphorus oxytrichloride (POCl3) and phosphoryl chloride (PO2Cl)
P2O3 + 2Cl2  POCl3 + PO2Cl
(b) Phosphorus pentoxide (P 2 O 5 ) :
Preparation:
It is obtained by burning phosphorus in air.
P4 + 5O2  P4O10
Pr oper ties:
(i) It is a white powder acidic in nature and is the anhydride of orthophosphoric acid. Its empirical formula is
P2O5 and its molecular formula is P4O10.
(ii) It sublimes on heating at 250oC.
(iii) Action of water:
It dissolves in water with hissing sound forming metaphosphoric acid and finally orthophosphoric acid.
P4O10 + 2H2O  4HPO3 ; HPO3 + H2O  H3PO4
(iv) Dehydrating power:
It dehydrates conc. H2SO4 and conc. HNO3 to SO3 and N2O5 respectively.
distillation
2HNO3 + P2O5  distillation
  2HPO3 + N2O5 ; H2SO4 + P2O5    2HPO3 + SO3
Action of heat :-

 Polyphosphates like calgon (NaPO3)n is widely used for softening water. It sequesters Ca2+ and Mg2+
(present in hard water). Forms soluble complex with Ca2+ and Mg2+ which do not form precipitate with CO32–
and soap.
 Polyphosphates are also used for descaling boilers and pipes.
 Sodium tripolyphosphate as filler and water softner
Important questions :
1. What happens when ?
(A) Copper reacts with nitric acid. (B) Nitrous oxide reacts with sodamide.
(C) Ammonia reacts with more of sodium hypochlorite (D) Nitrous acid reacts with iodide ions.
(E) Nitrosyl chloride reacts with ammonium nitrate.
Cold dilute
Ans. (A) 3Cu + 8HNO3    2NO + Cu(NO3)2 + 4H2O
 1M
Cu + 3HNO3  Stronger acid

  NO2 + H2O + Cu(NO3)2
(B) N2O + 2NaNH2 NaN3 + NH3 + NaOH
(C) 2NH3 + 3NaOCl 3NaCl + 3H2O + N2 (exces of NaOCl must be avoided otherwise explosive
NCl3 may be formed.
(D) 2H+ + 2HNO2 + 2I– 2NO + I2 + H2O
(E) NOCl + NH 4NO 3 NH 4 Cl + N2 O 4

(acid) (base ) salt solvent
2. Give equations for the reactions of the following compounds with water.
(A) P4O6 (B) P4O10 (C) PCl3 (D) PCl5 (E) Na3P
Ans. (A) P4O6 + 6H2O 4H3PO3 (B) P4O10 + 6H2O 4H3PO4
(C) PCl3 + H2O 3HCl + H3PO3 (D) PCl5 + H2O POCl3 + 2HCl ;
PCl5 + H2O (excess) H3PO4 + 5HCl
(E) Na3P + 3H2O PH3 + 3NaOH
3. What product is formed when a mixture of NO and NO2 is passed through Na2CO3 solution ?
Ans. Na2CO3 + NO + NO2  2NaNO2 + CO2
4. Copper reacts with HNO3 to produce NO and NO2 in the ratio 2 : 1. Write chemical reactions involved.
Ans. 7 Cu + 20 HNO3  7 Cu(NO3)2 + 4NO + 2NO2 + 10H2O
5. Write the product formula which are formed when nitrous acid reacts with sulphurous acid.
Ans. HNO2 + 2H2SO3 + H2O  NH2OH + H2SO4.
6. What happens when mixture of (NH4)2 SO4 is heated with mixture of NO2 and NO ?
Ans. (NH4)2SO4 + NO + NO2  2N2 + H2SO4 + 3H2O
7. What happens when mixture of PH3 and N2O is put in electric spark ?
Ans. Mixture explodes forming N2 and H3PO4 .
8. Arrange the following oxy-acids of phosphorous in the order of their strenght of reducing character; H3PO2,
H3PO4, H3PO3.
Ans. H3 PO2 > H3 PO3 > H3PO4 as no. of P-H bonds 

Lecture # 5
Group Sixteen Elements (Oxygen family)
Oxygen, sulphur, selenium, tellurium and polonium constitute group 16 of the periodic table. This is sometimes
known as group of chalcogens. The name is derived from the greek word for brass and points to the association
of sulphur and its congeners with copper. Most copper minerals contain either oxygen or sulphur and frequently
the other members of the group.
Occurrence:
Oxygen is the most abundant of all the element on the earth. Oxygen forms about 46.6% by mass of earth’s
crust . Dry air contains 20.946% oxygen by volume.
However, the abundance of sulphur in the earth’s crust is only 0.03-0.1%. Combined sulphur exists primarily
as sulphates such as gypsum CaSO4.2H2O, epsom salt MgSO4 .7H2O, baryte BaSO4 and sulphides such
as galena PbS, zinc blende ZnS, copper pyrites CuFeS2 . Traces of sulphur occur as hydrogen sulphide in
volcanoes.
Selenium and tellurium are also found as metal selenides and tellurides in sulphide ores. Polonium occurs
in nature as a decay product of thorium and uranium minerals.
The important atomic and physical properties of group 16 along with electronic configuration are given in
table.
Table Some Physical Properties of Group 16 Elements
Element O S Se Te
Atomic Number 8 16 34 52
Atomic Mass 16 32.06 78.96 127.6
2 4 2 4 10 2 4
Electronic configuration [He] 2s 2p [Ne] 3s 3p [Ar] 3d 4s 4p [Kr] 4d105s2 5p4
Covalent Radius / pm 74 103 119 142
–2
Ionic Radius X / pm 140 184 198 221
 1314 133 941 869
Ionization enthalpy / (kJ mol–1)
 3388 2251 2045 1790
Electronegativity 3.5 2.44 2.48 2.01
–3
Density/[g cm (293 K)] 1.32 2.06 4.19 6.25
Melting point / K 54 393 490 725
Boiling point / K 90 718 958 1260
Some of the atomic, physical and chemical properties and their trends are discussed below.
Electronic Configuration :
The elements of group 16 have six electrons in the outermost shell and have ns2 np4 general electronic
configuration.
Atomic and Ionic Radii :

Due to increase in the number of shells , atomic and ionic radii increase from top to bottom in the group. The
size of oxygen atoms is however, exceptionally small .
Ionisation Enthalpy :
Ionisation enthalpy decrease down the group. It is due to increase in size. However, the element of this group
have lower ionisation enthalpy values compared to those of group 15 in the corresponding periods. This is
due to the fact that group 15 element have extra stable half-filled p orbitals electronic configurations.

Electron Gain Enthalpy :
Because of the compact nature of oxygen atom, it has less negative electron gain enthalpy than sulphur.
However from sulphur onwards the value again becomes less negative upto polonium.
Electronegativity :
Next to fluorine, oxygen has the highest electronegativity value amongst the elements. Within the group,
electronegativity decrease with an increase in atomic number. This implies that the metallic character increase
from oxygen to polonium.
Physical Properties :
Oxygen and sulphur are non-metal, selenium and tellurium metalloids, whereas polonium is a metal. Polonium
is radioactive and is short lived (Half-life 13.8 days). All these element exhibit allotropy. The melting and
boiling points increase with an increase in atomic number down the group. The larger difference between the
melting and boiling points of oxygen and sulphur may be explained on the basis of their atomicity; oxygen
exist as diatomic molecules (O2) whereas sulphur exists as polyatomic molecule (S8).
Oxidation states and trends in chemical reactivity :
The elements of group 16 exhibit a number of oxidation states. The stability of -2 oxidation state decreases
down the group. Polonium hardly shows -2 oxidation states. Since electronegativity of oxygen is very high,
it shows only negative oxidation states as -2 except in the case of OF2 where its oxidation states is + 2.
Other elements of the group exhibit + 2 + 4 + 6 oxidation states but + 4 and + 6 are more common. Sulphur,
selenium and tellurium usually show + 4 oxidation in their compounds with oxygen and +6 oxidations state
with fluorine. The stability of +6 oxidation state decreases down the group and stability of + 4 oxidation state
increases (inert pair effect). Bonding in + 4 and + 6 oxidation states are primarily covalent.
Anomalous behaviour of oxygen :

The anomalous behaviour of oxygen, like other member of p-block present in second period is due to its
small size and high electronegativity. One typical example of effects of small size and high electronegativity
is the presence of strong hydrogen bonding in H2O which is not found in H2S.
The absence of d orbitals in oxygen limits its covalency to four and in practice, rarely exceeds two. On the
other hand, in case of other elements of the group, the valence shell can be expanded and covalence
exceeds four.
(i) Reactivity with hydrogen : All the elements of group 16 form hydrides of the type H2E (E = S, Se., Te, Po).
Some properties of hydrides are given in Table. Their acidic character increases from H2O to H2Te. The
increase in acidic character can be explained in terms of decrease in bond (H-E) dissociation enthalpy down
the group. Owing to the decrease in bond (H-E) dissociation enthalpy down the group, the thermal stability
of hydrides also decreases from H2O to H2Po. All the hydrides except water possess reducing property and
this character increases from H2S to H2Te.
Table : Properties of Hydrides of Group 16 Elements
Property H2 O H2 S H2Se H2Te

m.p./K 273 188 208 222
b.p./K 373 213 232 269
H-E distance/pm 96 134 146 169
HEH angle (º) 104 92 91 90
fH/kJ mol-1 -286 -20 73 100
diss H (H-E)/kJ mol-1 463 347 276 238
Dissociation constanta 1.8 × 10-16 1.3 × 10-7 1.3 × 10-4 2.3 × 10-3
a
aqueous solution, 298 K

(ii) Reactivity with oxygen : All these elements form oxides of the EO2 and EO3 types where E = S, Se, Te or
Po. Ozone (O3) and sulphur dioxide (SO2) are gases while selenium dioxide (SeO2) is solid. Reducing
property of dioxide decreases from SO2 to TeO2 ; SO2 is reducing while TeO2 is an oxidising agent. Besides
EO2 type sulphur, selenium and tellurium also form EO3 type oxide (SO3, SeO3, TeO3). Both types of oxides
are acidic in nature.
(iii) Reactivity toward the halogens : Elements of group 16 form a larger number of halides of the type
EX6, EX4 and EX2 where E is an element of the group and X is an halogen. The stabilities of the halides
decrease in the order F > Cl > Br > l. Amongst hexahalides, hexafluorides are the only stable halides. All
hexafluorides are gaseous in nature. They have octahedral structure. Shulphur hexafluoride SF\6 is exceptionally
stable for steric reasons.
Amongst terrafluorides, SF4 is a gas , SeF4 liquid and TeF4 a solid These fluorides have sp3d hybridisation
and thus, have trigonal bipyramidal structure in which one of the equatorial position is occupied by a lone pair
of electrons. This geometry is also regarded as see - saw geometry.
All elements except selenium form dichlorides and dibromides. These dihalides are formed by sp3 hybridisation
and thus have tetrahedral structure. The well known monohalides are dimeric in nature, Examples are
S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These dimeric halides undergo disproportionation as given below :
2Se2Cl2  SeCl4 + 3Se.
Oxygen
(A) Dioxygen (O2) :
Perparation :
Dioxygen can be obtained in the laboratory by the following ways :
(i) By heating oxygen containing salt such as chlorates, nitrates and permanganates.
Heat
2KClO3 MnO
  2KCl + 3O ;
2
NaNO3 
 2NaNO2 + O2
2
(ii) By the thermal decomposition of the oxides of metal low in the electrochemical series and higher oxides of
some metals.
2Ag2O(s)  4Ag(s) + O2(g); 2Pb3O4(s)  6PbO(s) + O2(g)
2HgO(s)  2Hg(l) + O2(g) ; 2PbO2(s)  2PbO(s) + O2(g)
(iii) Hydrogen peroxide is readily decomposed into water and dioxygen by catalysts such as finely divided metal
and manganese dioxide.
2H2O2 (aq)  2H2O(l) + O2(g)
(iv) By the action of conc. H2SO4 on MnO2, KMnO4 and K2Cr2O7.
2MnO2 + 2H2SO4  2MnSO4 + H2O + O2 ; 4KMnO4 + 6H2SO4  2K2SO4 + 4MnSO4 + 6H2O + 5O2.
(v) On larger scale it can be prepared from water or air. Electrolysis of water leads to the release of hydrogen at
the cathode and oxygen at the anode.
Industrially dioxygen is obtained from air by first removing carbon dioxide and water vapour and then the
remaining gases are liquefied and fractionally distilled to give dinitrogen and dioxygen.
(vi) By Brins process (manufacture) ;

500 º C 800 º C
2BaO + O2 (air)    2BaO2 ; 2BaO2   2BaO + O2.
Properties :
Dioxygen is a colourless and odouless gas. Its solubility in water is to the extent of 3.80 cm3 in 100cm3 water
at 293K which is just sufficient for the vital support of marine and aquatic life. It liquefies at 90 K and freezes
at 55 K . It has three stable isotopes: 16O, 17O and 18O. Molecular oxygen ,O2 is unique in being paramagnetic
inspite of having even number of electrons.

Chemical properties :
Dioxygen directly react with nearly all metals and non-metals except some metal (e.g., Au, Pt) and some
noble gases. Its combination with other element is often strongly exothermic which help in sustaining the
reaction . However, to initiate the reaction some external heating is required as bond dissociation enthalpy of
oxygen- oxygen double bond is high (493.4kJ mol–1).
Some of the reaction of dioxygen with metal, non-metal and other compounds are given below :
2 Ca + O2  2 CaO
4 Al + 3O2  2 Al2O3
P4 + 5O2  P4O10
C + O2  CO2
2 Zns + 3O2  2ZnO + 2SO2
CH4 + 2O2  CO2 + 2H2O
Some compounds are catalytically oxidised. For e.g.,

V2 O5
2SO2 + O2   2SO3 (Contact process)
CuCl2
4HCl + O2   2Cl2 + 2H2O (Deacon’s process)
Uses : In addition to its important in normal respiration and combustion processes, oxygen is used in oxyacetylene
welding, in the manuafacture of many metal, particularly steel. Oxygen cylinders are widely used in hospitals
high altitude flying and in mountaineering. The combustion of fules e.g. hydrazines in liquid oxygen, provided
tremendous thrust in rockets.
(B) Types of oxides :
(1) Acidic oxides : They dissolve in water to forms oxy acids, examples : CO2,SO2 ,SO3 , N2 O5, N2O3 , V2O5
P4O6 , P4O10 , Cl2O7, CrO3, (anhydride of H2CrO4 ; chromic acid)), Mn2O7 (anhydride of HMnO4, permanganic
acid))
SO2 + H2O  H2SO3
(2) Basic oxides - They either dissolve in water to form alkalies or combine with acids to form salts & water or
combine with acidic oxides to form salts. In general, metallic oxides are basic.
Examples ; Na2O , CaO, CuO, FeO, BaO.
CuO + H2SO4  CuSO4 + H2O, Na2O + H2O  2NaOH,
BaO + SO3  BaSO4 , BaO + HCl  BaCl2 + H2O
(3) Netural oxides :

They neither combine with acids, nor with the bases to form salts.
Examples ; CO, N2O, NO
(4) Amphoteric oxides :

These can combine with acids as well as bases.
ZnO + 2NaOH  Na2 ZnO2 + H2O
ZnO + 2HCl  ZnCl2 + H2O
Examples : ZnO , Al2O3 , BeO , Sb2O3, Cr2O3, PbO etc.
(5) Mixed oxides :

Mixture of two simple oxides ; one with lower oxidation state and another with higher oxidation state
Pb3O4 (2PbO + PbO2)
Fe3O4 (Fe2O3 + FeO)
Mn3O4 (2MnO + MnO2)
(6) Peroxides :
These compounds react with dil acids & form H2O2 and have O22– ion
Examples ; Na2O2, K2O2 , BaO2, CrO5 etc.

(7) Dioxides :
Contain excess of oxygen but do not forms H2O2 with dilute acids. They evolve Cl2 with conc, HCl and O2 with
conc.H2SO4. They contain O2– ion.
Examples ; PbO2 , MnO2

MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
2MnO2 + 2H2SO4  2MnSO4 + O2 + 2H2O
(8) Superoxides :
They contain O2– ion and reacts with water forming H2O2 and O2 ;
Examples ; KO2, RbO2, CsO2 etc.
 Distinction between simple basic oxide, peroxide and superoxide
Simple basic oxide K2O + H2O  2KOH
Peroxide K2O2 + 2H2O  2KOH + H2O2
Superoxide 2KO2 + 2H2O  2KOH + H2O2 + O2
(9) Suboxides : They Contain less Oxygen than expected from the normal valency of the elements.
Examples ; C3O2, Pb2O, Hg2O
 O=C=C=C=O
Sp Sp Sp
Lecture # 6
(C) Hydorgen peroxide (H2O2) :
Methods of preparation :
(i) Laboratory method
BaO 2  2 HCl  BaCl 2  H2 O 2


not possible to isolate H2O 2 from this solution
Anhydrous BaO2 cannot be used as BaSO4 formed by the reaction with H2SO4, forms a thin protective film
around BaO2 and reaction slowly ceases and finally stops after sometime. So hydrated barium peroxide is
used.
H2O2 + Ba (OH)2 + 6 H2O  BaO2 . 8 H2O
sat.soln.
Acidifying barium peroxide and removing excess of water by evaporation under reduced pressure gives H2O2.
BaSO4 is removed by filteration.
BaO2 . 8 H2O + H2SO4  BaSO4  + H2O2 + 8 H2O
cold ppt.
Since H2SO4 can decompose H2O2 at a higher temperature, therefore, this reaction should be carried out at
low temperature. H3PO4 can be used in place of H2SO4.
3BaO2 + 2H3PO4  Ba3(PO4)2  + H2O2; Ba3(PO4)2 + 3H2SO4  3BaSO4  + 2H3PO4 (can be used
again)
(ii) Industrial Method (Auto oxidation) :

(iii) By electrolysis of conc. H2SO4 (50%) at 00C using inert electrodes :
Cathode : Platinum
Anode : Graphite
H2SO4 H+ + HSO4–
At anode : 2 HSO4–  S2O8–2 + 2 H+ + 2e–

or
(2 HSO4– (aq)  HO3SOOSO3 )
1
Cathode : H+ + e–  H
2 2
0
80–90 C
distillation
BaCl2
BaSO4 + H2O2 (aq)
 K2S2O8 (s) + 2 D2O ()  2 KDSO4 (aq) + D2O2 ()
(iv) Modified method :

Equimolar mixture of sulphuric acid and ammonisum sulphate for electrolysis is used.
(NH4)2 SO4 + H2SO4  2 NH4HSO4 (Ammonium hydrogen sulphate)
NH4HSO4  NH4SO4– + H+
1
At cathode : H+ + e–  H.
2 2
At anode : 2 NH4SO4–  (NH4)2 S2O8 (Ammonium persulphate) + 2e–

distillation
(NH4)2 S2O8 + H2O     2 NH4 HSO4 + H2O2
 In this case 1% H2O2 is formed. It is extracted with water and concentrated to approximately 30% (by mass)
by distillation under reduced pressure. It can be further concentrated by careful distillation under low pressure
to approximately 85%. The remaining water can be frozen out to obtain pure H2O2 .
Properties of H2O2 :
(a) Physical properties :
(1) It is a colourless viscous liquid which appears blue in the large quantity.
(2) It is H–bonded and therefore, miscible with water in all proportions and forms a hydrate H2O2 . H2O (mp
221 K)
(3) Its boiling pt. (1440C) is more than water , freezing point (–40C) is less , density is more and dielectric
constant is also more than water.
Its aqueous solution is more stable than the anhydrous liquid where it decomposes into water and O2, slowly
on exposure to light.
2 H2 O 2 2 H2 O + O 2
 H2O2 is not kept in glass/metal containers because traces of alkali metal ions and metal ions from the glass
and metal surface respectively can catalyse the explosive decomposition of H2O2. Therefore, H2O2 aqueous
solution is stored in the plastic or wax–lined glass containers in dark and some urea, phosphoric acid or
glycerol is added to that solution because these compounds have been found to behave as negative catalyst
for the decomposition of H2O2. It is also kept away from the dust because dust can also induce explosive
decomposition. Commercially it is marketed as 10 V, which means it contains 3% H2O2.

(b) Chemical properties :
(1) Acidic nature :
Aqueous H2O2 behaves as a weak acid according to following equation
H2O2 (aq) H+ + HO2– Ka = 1.5 × 10–12 at 250 C
A 30% soln. of H2O2 has pH = 4
Aqueous H2O2 turns blue litmus red. Which is bleached by oxidising property of H2O2.
Na2CO3 + H2O2  Na2O2 + H2O + CO2 
Ba (OH)2 + H2O2 + 6 H2O  BaO2. 8 H2O
(2) H2O2 as an oxidising agent :
2e– + 2 H+ + H2O2  2 H2O SRP = + 1.77 V (in acidic medium)
2e– + H2O2  2 OH– SRP = + 0.87 V (in basic medium)
On the basis of above potential, we can say that H2O2 is a stronger oxidising agent in acidic medium than in
basic medium but kinetically it is found that reactions are faster in basic medium.
(a) Oxidation by H2O2 in acidic medium :
2 Fe2+ + 2 H+ (aq). + H2O2  2 F3+ (aq) + 2 H2O ()
FeSO4  Fe2 (SO4)3

[Fe(CN)6]4–  [Fe(CN)6]3–
AsO33–  AsO43–
SO32–  SO42–
I– (KI)  I2
H2O2  H2O + [O] × 4

PbS + 4[O]  PbSO4
––––––––––––––––––––––––
PbS + 4H2O2  PbSO4 + 4H2O
This property is utilized in restoring the white colour in old paintings which turns black due to formation of
PbS by the action of atmospheric H2S.
H2O2  H2O + [O]
H2S + [O]  H2O + S
––––––––––––––––––––––
H2O2 + H2S  2 H2O + S
2H2O2 + NH2 .NH2  N2 + 4H2O. (reaction is explosive)

hydrazine
(b) Oxidation by H2O2 in basic medium :

2 Cr(OH)3 + 4 NaOH + 3 H2O2   2 Na2CrO4 + 8 H2O.
or
10 OH– + 3 H2O2 + 2Cr+3  2 CrO4–2 + 8 H2O
Pb+2(aq) + CrO42– (yellow solution)  PbCrO4  (yellow)

2 Fe2+ + H2O2  2 Fe3+ + 2 OH–
Mn+2 + H2O2  Mn+2 + 2 OH–
2 NaBO2 + 2 H2O2 + 6 H2O  Na2 [(OH)2 B2 (O – O)2 (OH)2] . 6 H2O
(Sodium meta borate)
Sodium dihydroxoborate (III) –  – diperoxodihydroxoborate (III)

(3) H2O2 as reducing agent :
H2O2  O2 + 2 H+ + 2e–
2 OH– + H2O2  O2 + 2 H2O + 2e–
In alkaline medium, its reducing character is more than in acidic.
(a) Reducing action in acidic medium :

2 MnO4– + 6 H+ + 5 H2O2  2 Mn2+ + 8 H2O + 5 O2
HOCl + H2O2  H3O+ + Cl– + O2
Ag2O + H2O2  2 Ag + H2O + O2
(b) Reducing action in basic medium :

I2 + H2O2 + 2 OH–  2I– + 2 H2O + O2 .
2 MnO4– + 3 H2O2  2 MnO2 + 3 O2 + 2 H2O
[Fe(CN)6]3–  [Fe(CN)6]4–
Tests for H2O2 :

(1) With K2Cr2O7 :
Cr2O7–2 + 2 H+ + 4 H2O2  2 CrO (O2)2 (bright blue compound soluble in ether) + 5 H2O
4 CrO5 + 6 H2SO4  2 Cr2(SO4)3 (green) + 6 H2O + 7 O2
–
OH
(2) 2 HCHO + H2O2   2 HCOOH + H
Pyrogallol 2
When this reaction is carried out in dark, it is accompanied by emission of light (yellow coloured). It is an
example of chemiluminescence.
(3) An acidified solution of titanium salt gives yellow or orange colour with H2O2.
Ti+4 + H2O2 + 2H2O  H2 TiO4 + 4H+
 When Cl2 is reduced by H2O2 in aqueous medium into Cl– ion liberating O2. It has been proved experimentally
that when H2O2 behaves as a reducing agent the O – O bond in its molecule is not broken down.
O
+ Cl2  HCl + O2
O
H
Mechanism :
18 18
Cl2 + H2O218  H+ + Cl– + H  O O Cl
 H+ + Cl– + O218

Uses :
(i) It is used as a hair bleach and as a mild disinfectant. As an antiseptic it is sold in the market as perhydrol.
(ii) It is used to manufacture chemicals like sodium perborate and per carbonate used in high quality detergents.
(iii) It is used in synthesis of hydroquinone, tartaric acid and certain food products and pharmaceuticals
(cephalosporin) etc.
(iv) It is employed in the industries as a bleaching agent for textiles, paper pulp, leather, oils, fats, etc.
(v) Also used in Environmental (Green) chemistry. e.g., in pollution control treatment of domestic and industrial
effluents, oxidation of cyanides, restoration of aerobic conditions to sewage wastes, etc.?

(D) O3 (Ozone) :
O3 is an allotropic form of oxygen. At a height of about 20 Kms it is formed from atmoshperic oxygen in the
presence of sunlight. This O3 layer protects the earth’s surface from an excessive concentration of ultra violet
radiations.
Preparation :
It is prepared by passing silent electric discharge through a slow stream of pure and dry oxygen to prevent its
decomposition.
energy
O2   O + O
O2 + O  O3
___________________
3 O2 2 O3 HV (298 K) = + 142 kJ mol–1
The product is known as ozonised oxygen. If concentration of O3 greater than 10% are required , a battery of
ozonisers can be used , and pure ozone (bp 385 K) can be condensed in a vessel surrounded by liquid
oxygen.
Properties :
(1) It is a pale blue gas which forms a blue liquid and one solidification forms violet black crystals.
(2) It has a strong fish – like smell
(3) It is slightly soluble in water but more in turpentine oil or glacial acetic acid or CCl4 .
(4) O3 molecule is diamagnetic but O3– ion is paramagnetic (1 unpaired e–)
(5) It is explosive and unstable with respect to O2 as its decomposition into O2 results in the liberation
of heats and an increase in entropy.
(6) It can be used for sterlising water and air and as germicide and disinfectant. Also used for
bleaching oils, ivory, flour, starch, etc.
(1) As Oxidising agent :

In acidic medium :
O3 + 2 H+ + 2e–  O2 + 2 H2O SRP = + 2.07 V.
In alkaline medium :
O3 + H2O + 2e–  O2 + 2 OH– SRP = + 1..24 V
Therefore , Ozone is a stronger oxidising agent in acidic medium.
(a) It oxidises :
I–  I2
O3  O2 + [O]
2 KI + H2O + [O]  2 KOH + I2

––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
2 KI + H2O + O3  2 KOH + O2 + I2
S–2  SO42– (But not H2S)
NO2–  NO3–
SO3–  SO4–
AsO3–3  AsO4–3
Sn+2  Sn+4
PbS  PbSO4

O3  O2 + [O] × 4
PbS + 4 [O]  PbSO4
–––––––––––––––––––––––––––––––––––––––––––––––––
PbS + 4 O3  PbSO4 + 4O2

CuS  CuSO4
ZnS  ZnSO4
CdS  CdSO4
2–
MnO4  MnO4– (basic medium)
O3  O2 + [O]
2 K2MnO4 + [O] + H2O  2 K MnO4 + 2 KOH
––––––––––––––––––––––––––––––––––––––––––––––
2 K2MnO4 + O3 + H2O  2 K MnO4 + 2 KOH + O2
[Fe(CN)6]4–  [Fe(CN)6]3– (basic medium)

O3  O2 + [O]
2 K4 [Fe(CN)6] + H2O + [O]  2 K3 [Fe(CN)6] + 2 KOH
––––––––––––––––––––––––––––––––––––––––––––––––
2 K4 [Fe(CN)6] + H2O + O3  2 K3 [Fe(CN)6] + 2 KOH + O2
(b) It oxidses moist S , P , As into their oxy acids
O3  O2 + [O] × 3
S + 3[O]  SO3
SO3 + H2O  H2SO4
_______________________________
S + H2O + 3O3  H2SO4 + 3O2
P4  H3PO4
As  H3ASO4
(c) It oxidises H2S to sulphur
H2S + O3  H2O + S + O2
(d) 2NO2 + O3  N2O5 + O2
(2) Reaction with dry I2 :

2I2 + 9[O3]  I4O9 (yellow solid) + 9O2
I4O9 solid has the composition I3+ (IO3–)3 ; Iodine triiodate
Formation of this compound is a direct evidence in favour of basic nature of I2 (i.e., its tendency to form
cations).
 Reaction with moist iodine (I2)

O3  O2 + [O] × 5
I2 + 5 [O]  I2O5
I2O5 + H2O  2 HIO3
______________________________
I2 + 5 O3 + H2O  2 HIO3 + 5 O2

(3) Reaction with Ag : Silver articles become black in contact with ozone , due to the formation of Ag2O.
(Silver articles also become black in the atmosphere due to formation of Ag2S)
2 Ag + O3  Ag2O + O2 (Black)
(4) Reaction with H2O2 :
H2O2 + O3  H2O + 2 O2
Que. In the above reaction explain which one is oxidising agent and which one is reducing agent ?
Sol. Ozone is behaving as an oxidising agent and H2O2 is behaving as reducing agent.
2e– + 2 H+ + O3  O2 + 2 H2O
+
H O  O + 2 H + 2e
2 2 2
–
_______________________________________________________________
H2O2 + O3  2 O2 + H2O

The above interpretations is further supported on the following grounds.
SRP of H2O2 is + 1.77 V while SRP of O3 is + 2.07 V. Therefore , O3 is stronger oxidising agent than H2O2 .
(5) Bleaching Action : O3 also bleaches coloured substances through oxidation. Bleaching is permanent.
(6) Ozonolysis :
O
CH2 CH2 
Zn / H2O
CH2 = CH2 + O3   2HCHO
 ZnO
O O
(7) Reaction with KOH :

2KOH + 5 O3  2 K+O3– + 5 O2 + H2O
Pot. Ozonide (orange solid)
Tests for ozone :
(i) A filter paper soaked in alcoholic benzidine becomes brown when
brought in contact with O3 (This test is not shown by H2O2).

(ii) Tailing of Mercury :
Pure mercury is a mobile liquid but when brought in contact with O3 , its mobility decreases and it starts
sticking to glass surface forming a type of tail due to the dissolution of Hg2O (Mercury sub–oxide) in mercury.
2 Hg + O3  Hg2O + O2
Structure :
O – O B.L. = 1.28 Å
O – O distance in case of H2O2 = 1.48 Å

O3 = 1.28 Å , O2F2 = 1.22 Å
O2 = 1.21 Å
O – O bond length decreases in order
H2 O 2 > O 3 > O 2 F 2 > O 2
 Amount of O3 in a gas mixture may be determined by passing the gas into a KI solution buffered with a
borate buffer (pH : 9.2). The iodine that is liberated is titrated with Na2S2O3
O3 + 2 K + 2 I– + H2O  I2 + KOH + O2
Alternatively the gas may be decomposed catalytically and the change in volume is measured.
2 O3 (two volume)  3 O2 (three volume)
G = – 163 kJ mol–1
Uses : It is used as a germicide, disinfectant and for sterilising water. It is also used for bleaching oil, ivory, flour
starch etc. It acts as an oxidising agent in the manufacture of potassium permangante.

Lecture # 7
Sulphur
Sulphur Allotropic Froms :

Sulphur forms numerous allotropes of which the yellow rhombic ( - sulphur) and monoclinic ( - sulphur)
forms are the most important. The stable forms at room temperature is rhombic sulphur, which transfroms to
monoclinic sulphur when heated above 369 K.
Rhombic sulphur (- sulphur) :

This allotrope is yellow in colour , m.p. 385.8 K and specific gravity 2.06. Rhombic sulphur crystals are
formed on evaporating the solution of roll sulphur in CS2. It is insoluble in water but dissolved to some extent
in benzene, alcohol and ether. It is readily soluble in CS2 .
Monoclinic sulphur ( - sulphur) :

Its m.p. is 393 K and specific gravity 1.98. It is soluble in CS2. This form of sulphur is prepared by melting
rhombic sulphur in a dish and cooling till crust is formed. Two holes are made in the crust and the remaining
liquid poured out. On removing the crust, colourless needle shaped crystals of  - sulphur are formed. It is
stable above 369 K and transforms into  - sulphur below it . Conversely, - sulphur is stable below 369 K
and transfroms into  - sulphur above this. At 369 K both the forms are stable. This temperature is called
transition temperature.
Both rhombic and monoclinic sulphur have S8 molecules these S8 molecules are packed to give different
crystal structures. The S8 ring in both the forms is puckered and has a crown shape. The molecular dimensions
are given in figure.
S
20 S 205.7 pm
S
4 pm S S S
107o o
S S 102.2
S
S S
S S (b)
(a)
S
Fig. : The structures of (a) S8 ring in rhombic sulphur and (b) S6 form
Several other modifications of sulphur containing 6-20 sulphur atoms per ring have been synthesised in the
last two decades. In cyclo- S6, the ring adopts the chair form and the moleculatr dimension are as shown in
fig. (b) At elevated temperatures (~ 1000 K ), S2 is the dominant species and is paramagnetic like O2.
Compounds of sulphur :
(A) Sulphur Dioxide:
Perparation :
(i) Sulphur dioxide is formed together with a little (6-8%) sulphur trioxide when sulphur is burnt in air or oxygen:
S(s) + O2(g)  SO2(g)
(ii) In the laboratory it is readily generated by treating a sulphite with dilute sulphuric acid.
SO32 – (aq) + 2H+ (aq)  H2O(l) + SO2(g)
(iii) H2SO4 + S  3SO2 + 2H2O ; 2H2SO4 + C  3SO2 + 2H2O
(iv) Cu (turnings) + H2SO4 (hot and conc.)  CuSO4 + SO2 + 2H2O
(v) 2CaSO4 (gypsum) 

2CaO + 2SO2 + CO2
(vi) Industrially it is produced as a by- product of the roasting of sulphide ores.

4FeS2(s) + 11O2 (g)  2Fe2O3(s) + 8SO2(g)
The gas after drying is liquefied under pressure and stored in steel cylinders.

Properties :
(i) Sulphur dioxide is a colorless gas with pungent smell and is highly soluble in water. It liquefies at room
temperature under a pressure of two atomsphere and boils at 263 K.
(ii) Sulphur dioxide, when passed through water, forms a solution of sulphurous acid.
SO2(g) + H2O(l) H2 SO3 (aq)
(iii) It reacts readily with sodium hydroxide solution, forming sodium sulphite which then reacts with more sulphur
dioxide to form sodium hydrogen sulphite.
2NaOH + SO2  Na2SO3 + H2O
Na2SO3 + H2O + SO2  2NaHSO3
2NaHSO3  
H2SO3 + Na2SO3
When normal salts are heated to fusion they decompose giving sulphides and sulphates. Acid bisulphites on
heating first lose H2SO3 before undergoing disproportionation.
4Na2SO3  Na2S + 3Na2SO4
(iv) In it reaction with water and alkalies, the behaivour of sulphur dioxide is very similar to that of carbon dioxide.
Sulphur dioxide reacts with chlorine in the presence of charcoal (which acts as a catalyst) to give sulphuryl
chloride, SO2Cl2 It is oxidised to sulphur trioxide by oxygen in the presence of vanadium (V) oxide catalyst.
SO2(g) + Cl2(g)  SO2Cl2(l)
Addition reactions
V2 O5
2SO2 (g) + O2 (g)   2SO3(g)
(v) When moist, sulphur dioxide behaves as a reducing agent. For example it converts iron (III) ions to irons (II)
ions and decolourises acidified potasssium permanganate (VII) solution; the latter reaction is a convenient
test for the gas.
2Fe3+ + SO2 + 2H2O  2Fe2+ + SO42– + 4H+
5SO2 + 2MnO4– + 2H2O  5SO42– + 4H+ + 2Mn2+
 Reduces acidified KIO3 to I2 ; K2Cr2O7 to Cr3+ (green coloured solution)
(vi) Bleaching action :
SO2 + 2H2O  H2SO4 + 2H
+
H
coloured matter colourless matter
Air oxidation
 Bleaching is through reduction but it is temporary.

It is a more powerful reducing agent in alkaline medium than in acidic medium.
(vii) It neither burns nor helps in burning but burning Mg and K continue to burn in its atmosphere.
3Mg + SO2  2MgO + MgS ; 4K + 3SO2  K2SO3 + K2S2O3
(viii) Acts as oxidising agent with strong reducing agents.
2SnCl2 + SO2 + 4HCl  2SnCl4 + 2H2O + S
2H2S + SO2  Moisture
 2H2O + 3S
CO to CO2 and Fe to FeO
cold SO2
 SO2 + Na2CO3(aq) NaHSO3 (aq) Na2S2O5
in excess
NaOH
+
Dry
Na2SO3(aq) H SO2
SOCl2 POCl3
Zn + SO2
S2O42–

Uses : Sulphur dioxide is used (i) in refining petroleum and sugar (ii) in bleaching wool and silk and (iii) as an anti-
chlor, disinfecatant and preservation. Sulphuric acid, sodium hydrogen sulphite and calcium hydrogen sulphite
(industrial chemicals) are manufactured from sulphur dioxide. Liquid SO2 is used as a solvent to dissolve a
number of organic and inorganic chemicals.
(B) SULPHUR TRIOXIDE (SO 3 ) :

PREPARATION:
(i) 6H2SO4 + P4O10  6SO3 + 4H3PO4
 P4O10 is dehydrating agent
(ii) Fe2(SO4)3 

 Fe2O3 + 3SO3 ; 2SO2 + O2 2SO3
PROPERTIES:
(i) Acidic Nature :
Dissolves in water forming sulphuric acid
SO3 + H2O  H2SO4
(ii) H2SO4 + SO3  H2S2O7 (oleum)
(iii) SO3 + HCl  SO2(OH) Cl (chlorosulphuric acid)
(iv) Oxidising Nature :
0
(a) 100 C
2SO3 + S   3SO2

(b) 5SO3 + 2P  5SO2 + P2O5
(c) SO3 + PCl5  POCl3 + SO2 + Cl2
(d) SO3 + 2HBr  H2O + Br2 + SO2
 SO3 is a powerful oxidising agent when hot.
 NH2 CO NH2 + SO3 + H2SO4  2NH2SO3H (Sulphamic acid) + CO2.
USES:
(i) Used in manufacture of H2SO4 and oleum.
(ii) Used as a drying agent for gases.
(C) Oxoacids of Sulphur :
Sulphur forms a number of oxoacid such as H2SO3, H2S2O3, H2S2O4, H2S2O5 ,H2SxO6 (x = 2 to 5,) H2SO4
H2S2O7, H2SO5, H2S2O8. Some of these acids are unstable and cannot be isolated. They are known in
aqueous solution or in the forms of their salts. Structures of some important oxoacids are shown in figure.
O
O
O O O
S
S
S S S S O
O O
O O O O HO
HO HO O O
HO
HO HO HO HO
Sulphurous acid Sulphurous acid Peroxodisulphuric acid Pyrosulphuric acid (Oleum)

(H2 SO3) (H2SO4) (H2S2O8) (H2S2O7)
Fig. : Strucutres of some important oxoacids of sulphur

Sulphuric Acid :
Manufacture :
Sulphuric acid is one of the most important industrial chemicals world wide .
(a) Sulphuric acid is manufactured by the contact process which involves three steps:
(i) burning of sulphur or sulphide ores in air to generate SO2

(ii) conversion of SO2 to SO3 by the reaction with oxygen in the presence of a catalyst (V2 O5), and
(iii) absorption of SO2 in H2SO4 to give Oleum (H2S2O7)
The SO2 produced is purifield by removing dust and other impurities such as arsenic compounds.
The key step in the manufacture of H2SO4 is the catalytic oxidation of SO2 with O2 to give SO3 in the
presence of V2O5 (catalyst.)
2SO2(g) + O2 (g)  V2 O5 -1
 2SO3(g)  r H = - 196.6 kJ mol

The reaction is exothermic reversible and the forward reaction leads to a decrease in volume. Therefore, low
temperature and high pressure are the favourable conditions for maximum yield. But the temperature should
not be very low other wise rate of reaction will become slow.
In practice the plant is operated at a pressure of 2 bar and a temperature of 720 K. The SO3 gas from the
catalytic converter is absorbed in concentrated H2SO4 to produce oleum. Dilution of oleum with water gives
H2SO4 of the desired concentration. In the industry two steps are carried out simultaneously to make the
process a continuous one and also to reduce the cost.
SO3 + H2SO4  H2S2O7
(Oleum)
The sulphuric acid obtained by Contact process is 96-98% pure.

(b) Lead chamber process :
2SO2 + O2(air) + 2H2O + [NO] (catalyst)  2H2SO4 + [NO] (catalyst).
Acid obtained is 80% pure and is known as brown oil of vitriol.
Properties :
Sulphuric acid is a colourless, dense, oily liquid with a specific gravity of 1.84 at 298 K. The acid freezes at
283 K and boils at 611 K. It dissolves in water with the evolution of a larger quantity of heat.
The chemical reaction of sulphuric acid are as a result of the following characteristics: (a) low volatility (b)
strong acidic character (c) strong affinity for water and (d) ability to act as an oxidising agent in aqueous
solution,
(i) Sulphuric acid ionises in two steps.
H2SO4(aq) + H2O()  H3O+ (aq) + HSO4– (aq); K a1 = very larger (Ka1 > 10)
HSO4- (aq) + H2O()  H3 O+ (aq) + SO42– (aq); K a2 = 1.2 × 10-2

The larger value of Ka1 (Ka1 > 10) means that H2SO4 is largely dissociated into H+ and HSO4–. Greater the value
of dissociation constant (Ka) the stronger is the acid.
(a) The acid froms two series of salts: normal sulphates (such as sodium sulphate and copper sulphate) and
acid sulphate (e.g.,sodium hydrogen sulphate)
(b) Decomposes carbonates and bicarbonates in to CO2
Na2CO3 + H2SO4  Na2SO4 + H2O + CO2 ; NaHCO3 + H2SO4  NaHSO4 + H2O + CO2
(c) Sulphuric acid, because of its low volatility can be used to manufacture more volatile acid from their
correrponding salts.
2MX + H2SO4  2 HX + M2SO4 (X = F, Cl, NO3) ; NaCl + H2SO4  NaHSO4 + HCl
(M = Metal)
 KNO3 + H2SO4  KHSO4 + HNO3

(ii) Concentated sulphuric acid is a strong deyhydrating agent. Many wet gases can be dried by passing them
through sulphuric acid, provided the gases do not react with the acid. Sulphuric acid removes water from
organic compound; it is evident by its charring action on carborhydrates.
H2SO 4
H2 SO 4
C12 H22O11   12C + 11H2O ; H2C2O4  H O CO + CO2
2
(iii) Hot concentrated sulphuric acid is a moderately strong oxidising agent. In this respect it is intermediate
between phosphoric and nitric acids. Both metal and non- metals are oxidised by concentrated sulphuric
acid, which is reduced to SO2.

Cu + 2 H2SO4 (conc.)  CuSO4 + 2H2O
3S + 2H2SO4 (conc.)  3SO2 + 2H2O
C + 2H2SO4 (conc.)  CO2 + 2SO2 + 2H2O
H2SO4 + KBr  KHSO4 + HBr
2HBr + H2SO4  2H2O + Br2 + SO2
(iv) With PCl5 forms mono and di-acid chlorides

HO – SO2 – OH + PCl5  Cl – SO2 – OH + POCl3 + HCl
HO – SO2 – OH + 2PCl5  Cl – SO2 – Cl + 2POCl3 + 2HCl
(v) K4[Fe(CN)6](s) + 6H2SO4 + 6H2O 

 2K2SO4 + FeSO4 + 3(NH4) SO4 + 6CO
(vi) 3KClO3 + 3H2SO4  2KHSO4 + HClO4 + 2ClO2 + H2O

Uses :
Sulphuric acid is a very improtant industrial chemical . A nation’s industrial strength can be judged by the
quantity of sulphuric acid it produces and consumes it is needed for the manufacture of hundreds of other
compound and also in many industrial processes. the bulk of sulphruic acid produced is used in the
manufacture of fertilisers (e.g., ammonium sulphate, superphosphate). Other uses are in : (a) petroleum
refining (b) manufacture of pigment, paints and dyestuff intermediates (c) detergent industry (d) metallurgical
applications (e.g.,cleansing metal before enameling, electroplating and galvanising) (e) storage batteries (f)
in the manufacture of nitrocellulose products and (g) as a laborattory reagent.
Lecture # 8
(D) HYDROGEN SULPHIDE (H 2 S) :
PREPARATION:
(i) FeS + H2SO4  FeSO4 + H2S
It is prepared in kipp’s apparatus
(ii) Preparation of pure H2S gas
Sb2S3 (pure) + 6 HCl (pure)  2 SbCl3 + 3 H2S
PROPERTIES :
(i) Colourless gas with rotten egg smell
(ii) Moderately soluble in water but solubility decreases with increasing temperature.
(iii) Reducing Agent :
Acts as a strong reducing agent as it decomposes evolving hydrogen.
(a) H2S + X2  2 HX + S;
(b) H2O2 + H2S  H2O + S + O2

(c) 2HNO3  H2O + 2NO2 + [O]
H2S + [O] H2O + S
2HNO3 + H2S 2H2O + NO2 + S
 It also reduces KMnO4  Mn2+, H2SO4  SO2 & K2Cr2O7  Cr3+

(iv) Acidic Nature :
Its aquesous solution acts as a weak dibasic acid according to following reaction
H2 S HS + H+ S2- + 2H+

Therefore, It forms two series of salts as given below
NaOH + H2S  NaHS + H2O ; NaOH + H2S  Na2S + 2H2O
(v) Formation of Polysulphides :
They are obtained by passing H2S gas through metal hydroxides.
Ca(OH)2 + H2S  CaS + 2H2O ; CaS + 4 H2S  CaS5 + 4H2
NH4OH + H2S  (NH4)2S + 2H2O; (NH4)2S + H2S (excess)  (NH4)2 Sx+1 + xH2
yellow ammonium sulphide
TESTS FOR H2S :
(i) Turns acidified lead acetate paper black
(ii) Gives violet or purple colouration with sodium nitropruside solution.
USES:
(i) As a laboratory reagent for the detection of basic radicals in qualitative analysis.
(ii) As reducing agnet.
(E) Sodium thiosulphate (Na2S2O3 . 5 H2O, hypo) :

Preparation :
(i) Na2CO3 + H2O + 2 SO2 (excess)  2 NaHSO3 + CO2
NaHSO3 + Na2CO3  2 Na2S2O3 + H2O + CO2
heat
Na2SO3 + S (finely divided)   Na2S2O3 .
(ii) 2 NaHS + 4 NaHSO3  3 Na2S2O3 + 3 H2O
(iii) Na2S + Na2SO3 + I2  Na2S2O3 + 2 NaI
(iv) 2 Na2S (aq) + 3 SO2 (g)  S  + Na2S2O3 (aq)

(v) 2Na2S3 + 3O2 (from air)  2Na2S2O3 + 2S
Physical Properties :
(i) It is a colourless crystalline substance which loses water of crystallisation on strong heating.
(ii) It is soluble in water.
(1) As antichlor :
The fibre to be coloured is passed through a bleaching powder tank to bleach the surface but in this process
some chlorine is attached to the fibre which must be removed before dying , for this purpose fibre is passed
through a solution of hypo which removes the chlorine from the surface of fibre according to following reaction:
Na2S2O3 + 4Cl2 + 5H2O  2NaHSO4 + 8 HCl
Therefore, it is known as antichlor.
(2) Reaction with HCl :

Na2S2O3 + 2 HCl + H2O  2 NaCl + SO2 + S + H2O
Used as a test for distinguishing SO32– (only SO2 is formed) and S2O32– (SO2 and S are formed)
(3) Complex formation reactions :

(i) With Ag – salts (AgNO3 or AgCl, AgBr, AgI )
If Na2S2O3 is not in excess :

Na2S2O3 + 2 AgNO3 Ag2S2O3 + 2 NaNO3
white ppt
H2O
H2SO4 + Ag2S (Black)

If Na2S2O3 is in excess :
2 Na2S2O3 + AgNO3  Na3 [Ag(S2O3)2] + NaNO3 (most common reaction written in maximum text
books)
(soluble complex)
 AgBr (s) + 3 S2O32– (aq)  [Ag(S2O3)3]5– + Br– (Refrence : J.D. Lee and cotton wilkinson)
This reaction is utilized in photography where hypo is used as Fixer.
(ii) With FeCl3 :
With FeCl3 solution hypo developes a pink or violet colour which soon vanishes according to following
reaction
Fe3+ + 2 S2O3–2  [Fe(S2O3)2]–
The violet colour disappears quickly due to the reduction of ferric chloride by thiosulphate
[Fe(S2O3)2]– + Fe+3  2 Fe+2 + S4O6–2
(iii) With AuCl3(soluble in water) :
AuCl 3 + 2Na2S2O3  AuCl  + Na2S4O6 + 2NaCl

reducing agent
AuCl + 2Na2S2O3  Na3 [Au(S2O3)2] + NaCl

soluble complex
(iv) With CuCl2 :
2CuCl2 + 2Na2S2O3  2CuCl  (white) + Na2S4O6 + 2NaCl
2CuCl + Na2S2O3  Cu2S2O3 + 2NaCl
3Cu2S2O3 + 2Na2S2O3  Na4 [Cu6 (S2O3)5]

Soluble complex
(v) With Bi3+ ions :

Bi+3 + 3Na2S2O3 Na3[Bi(S2O3)3] + 3Na+
Soluble complex
But it soon decomposes to give black ppt of Bi2S3

(4) Reaction with HgCl2 :
Na2S2O3 + HgCl2  HgS2O3 + 2NaCl
HgS2O3 + H2O  HgS  (black) + H2SO4
HgCl2+ 2HgS  HgCl2.2HgS  (Black)
(5) As reducing agent :

In Iodometric titration
(i) I2 + 2S2O32–  S4O62– + 2I– (decolourises the colour of iodine)
(ii) 2KMnO4 + Na2S2O3  Na2SO4 + K2SO4 + Mn2O3
(6) 215 º C
Na2S2O3.5H2O   Na2S2O3 + 5H2O
4Na2S2O3   220 º C
 3Na2SO4 + Na2S5
 Moderate reducing character of S2O32–
2 S2O32– + I2  S4O62– + 2 I–
 2 S2O32– + 4 H2O2  S3O62– + SO42– + 4 H2O

cold saturated solution

Et O
 Na2S2O3 + 2 HCl 20
 H2S2O3 . 2 Et2O + 2 NaCl
– 78 C
No solvent
 HSO3Cl + H2S  0   H S O + HCl
2 2 3
10 C
 Solution of dithionite are not very stable and decompose according to the stoichiometry :
2 S2O42– + H2O  S2O32– + 2HSO3–
(7) Structure :
O
O
O
O S O
S
Que. How will you distinguish b/w thiosulphate and sulphite.
Sol. Thiosulphate ion reacts with Ag+ ions to forms a white precipitate which is unstable and changes into black
ppt. on shaking with water .
S2 O3-2 + 2Ag +  Ag2S2O3  
H2 O
 Ag2S  + H2SO4
Similarly, S2O3-2 + Pb+2  PbS2O3 (white)


PbS2O3 is soluble in excess of S2O3-2 but when PbS2O3 is boiled with water black precipitate of PbS is
formed.
List of Question from VIth group

1. H2O2 is not stored in glass containers why?
2. Why ozone make mercury viscous ?
3. O3 is dimagnetic but O3(-) is paramagnetic. Explain.
4. Hypo gives pink colour with FeCl3 which rapidly disappears.
5. For drying H2S gas conc. H2SO4 can not be used why.?
Ans. H2S + H2SO4 Conc SO2 + S  + 2H2O
Therefore for drying H2S either anyhydrous CaCl2 or P2O5 is used
6. On heating rhombic sulphur it melts but viscosity of liquid increases up to 200oC & beyond that it decrease
why ?
S S
S
S Viscosity
S 
S

o 
Ans. 250 C
S S Viscosity
On heating S8 ring are broken and long chain polymers are formed up to 200oC the colour of the liquid
becomes dark yellow. Thus due to polymerisation liquid becomes viscous but beyound 200oC long chains
are broken into shorter chains & ultimately S2 molecules are formed in the vapour phase which is a dark- red
coloured gas. When this molten sulphur is poured in to water we get plastic sulphur which is insoluble in CS2
7. SF6 is formed but OF6 is not known why?
8. Sulphur dioxide is a more powerful reducing agent in alkaline medium than in the basic medium.
Ans. In acidic medium
2H2O + SO2 SO42– + 4H+ + 2e–
+
If H conc increases, equilibrium shift in back ward direction
In basic medium.
SO2 + 4OH- SO4-2 + 2H2O + 2e-
Equilibrium shift in forward direction.

9. HNO3 can not be used for the preparation of H2S. Why ?
Ans. H2 S is prepared by action of dil H2SO4 on FeS.
FeS + H2SO4 (dil) FeSO4 + H2S (g)
If we use HNO3 , no doubt H2S will be formed , but it will be immediately oxidised into sulpur
H2S + [O]  H2O + S

[HNO3]
10. H2O should not be added to conc. H2SO4 why ? Then how to make it dilute.
Ans. When water is added to conc. H2SO4 , larger amount of heat is evolved, tempt. of solution rises and solution
may bump out which is hazardous therefore conc. H2SO4 must be added to the water slowly.
11. NH4Cl is better than NaCl for reaction with conc. H2SO4 so as to produce HCl why ?
Ans. NaCl + H2SO4 (conc.)150oC  NaHSO4 + HCl

Salt cake (insoluble)
due to deposition of NaHSO4 on the surface of solution (reaction mix), reaction stops.
However if we increase the temp up to 550oC or more then further reaction takes place.
NaH SO4 + NaCl   Na2SO4 + HCl.
But no such problem arises with NH4Cl because NH4HSO4 is a soluble compound (no salt cake is formed)
therefore following reaction take place completely at low tempt.
2 NH4Cl + H2SO4  (NH4)2 SO4 + 2HCl (g)
12. It is not possible to produce HBr or HI by action of conc H2SO4 on sodium bromide or sodium iodide although
HCl can be prepared why? Then how to prepare these compounds.
Ans. No doubt, HBr and HI will be produced by action of conc H2SO4 on NaBr or NaI but conc. H2 SO4 is an
oxidising agent also, therefore, it immediately oxidises HBr in to Br2
13. Give the chemistry of :

(i) Etching of glass by HF :
Sol. The glass surface is coated with wax and marking is done with a pointed substance with the help of 40- 60%
aq. HF. The marking becomes permanent on glass surface due to following reaction :
Na2SiO3 + HF  2NaF + SiF4 + 3H2O
CaSiO3 + 6HF  CaF2 + SiF4 + H2O
(ii) Destruction of ozone layer by freons :

Ans. Chloro-fluoro carbons like CFCl3 , CF2Cl 2 etc. are known as FREONS. They are mainly used as cooling
gases in refrigerators and in air conditioners But their use now a days is discouraged due to their attack on
the ozone layer according to following scheme:
 
Photolysis O3
Freons    O2 + Cl O
 C l 
rapid
 
slowly
Cl O   C l + O
 
O3 + C l  O2 + Cl O & so on
 
O + Cl O  C l + O2

CHEMISTRY LECTURE NOTES
COURSE : (JP & JF)
(LECTURE No. 1 TO 8)
TOPIC :
p-Block Elements
(Nitrogen and oxygen family)

(2099) Lecture Notes P Block 15 16 E.pdf - TMP

Загружено:

Сведения о документе

Исходное описание:

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

(2099) Lecture Notes P Block 15 16 E.pdf - TMP

Загружено:

Авторское право:

Доступные форматы

Lecture # 1

Atomic and Ionic Radii :

RESONANCE p-Block Elements (Group 15 & 16) - 1

3 HNO2  HNO3 + H2O + 2 NO

Anomalous properties of nitrogen :

Properties of Hydrides of Group 15 Elements

Property NH 3 PH3 AsH3 SbH3 BiH3

Melting point / K 195.2 139.5 156.7 185 –

(ii) Reactivity towards oxygen :

RESONANCE p-Block Elements (Group 15 & 16) - 2

(iv) Reactivity towards metals :

Laboratory method of preparation :

Common methods of preparation :

(iii) By heating ammonium dichromate:

(iv) By oxidation of ammonia

(B) At higher temperature.

(a) By passing ammonia over heated cupric oxide:

(b) By heating urea with a nitrite in presence of dilute H2SO4:

RESONANCE p-Block Elements (Group 15 & 16) - 3

(ii) Chemical properites :

N2 (g) + 3 H2 (g) 2 NH3 (g) ; fH– = – 46.1 kJ mol–1

(iii) On a large scale , ammonia is manufactured by Haber’s process.

RESONANCE p-Block Elements (Group 15 & 16) - 4

 NiCl2 (aq.) + 2NH4OH (aq.)  Ni(OH)2(green) + 2NH4Cl

Cu2+ (aq) + 4 NH3 (aq) [Cu(NH3)4]2+ (aq)

Ag+ (aq) + Cl–1 (aq) AgCl (s)

AgCl (s) + 2 NH3 (aq)  [Ag (NH3)2]Cl (aq)

Cd2+ + 4NH3(aq)  [Cd(NH3)4]2+ (aq)

(iii) Na + NH3 

RESONANCE p-Block Elements (Group 15 & 16) - 5

(vi) M(NO3)2 + 2NH4OH  M(OH)2 (white) + 2NH4NO3

(vii) Mercuric salts, NH4OH forms a white precipitate

Tests of ammonia/ammonium salts :

(ii) Ammonium salts gives yellow ppt. with H2PtCl6

(iii) Turmeric paper turns brown when exposed to ammonia gas.

 NH3 burns in dioxygen with a pale yellow flame.

RESONANCE p-Block Elements (Group 15 & 16) - 6

N2H4 + 2I2 4HI + N2

 N2H4.HCl (aq) + HNO2 HN3 + HCl + 2H2O

  CO – [NH – (CH2 )5 – CO]n – NH  

2HN3  3N2 + H2

 NaN3 + H2S + H2 O  NH3 + N2 + S + NaOH.

RESONANCE p-Block Elements (Group 15 & 16) - 7

(2) Oxides of nitrogen :

Table : Oxides of Nitrogen

Nitrous oxided (N2O) :

Nitric Oxide (NO) :

It is not an acid anhydride.

4NO + O2 (in appropriate amount)   2N2 O3

RESONANCE p-Block Elements (Group 15 & 16) - 8

2 HNO3 + As2O3 + 2 H2O  NO + NO2 + 2 H3AsO4

It is the anhydride of nitrous acid.

Nitrogen dioxide and dinitrogen tetraoxide (N2O4) :

N2O4 + H2O  HNO3 + HNO2

NO2 + H2O  HNO3 + HNO2

SO2 + H2O + NO2  H2SO4 + NO

 Dinitrogen pentoxide (N2O5) :

RESONANCE p-Block Elements (Group 15 & 16) - 9

NaNO3 + H2SO4  NaHSO4 + HNO3

4 NH3 (g) + 5 O2 (g) (from air) 4 NO (g) + 6 H2O (g)

Nitric oxide thus formed combines with oxygen giving NO2.

3 NO2 (g) + H2O (1)  2 HNO3 (aq) + NO (g)