The p Block

15th-Group Elements 7. The oxides of the type E2O3 of nitrogen and phosphorus are
Nitrogen Family purely acidic, that of arsenic and antinomy are amphoteric
1. Nitrogen and phosphorus are non-metals, arsenic and and those of bismuth are predominantly basic.
antinomy are metalloids and bismuth is a typical metal. PH3 < AsH3 < NH3 < SbH3 < BiH3 → Boiling Point
2. Except nitrogen, all the elements show allotropy. PH3 < AsH3 < SbH3 < NH3 → Melting Point
3. Bismuth hardly forms any compound in –3 oxidation state. NH3 > PH3 > AsH3 > SbH3 → Bond Energy
4. The only well characterissed Bi (V) compound is BiF5.
⇒ Pentaoxide of 15th group element is acidic. N2O3, P2O3
5. In the case of nitrogen, all oxidation states from +1 to +4 tend
are acidic, As­2O3, Sb2O3 are amphoteric with Bi2O3 is
to disproportionate in acid solution. For example,
basic.
(i) 3HNO2 → HNO3 + H2O + 2NO
⇒ Trihalide of 15th group elements are covalent except
6. In case of phosphorus, nearly all intermediate oxidation states
disproportionate into +5 and –3 both in alkali and acid. BiF3.

Structure of Oxides of Nitrogen

Oxide of Nitrogen Oxide State Physical Appearance Structure

N2O nitrous oxide +1 Colourless gas N≡N→O
NO Nitric oxide +2 Colourless gas N=O
O O
N2O3 Dinitrogen trioxide +3 Blue colour solid N–N
O

O O
N2O4 Dinitrogen tetraoxide +4 Colourless solid O
N–N
O

N
NO2 Nitrogen dioxide +4 Brown gas O O

O O O
N2O5 Dinitrogen pentaoxide +5 Colourless solid O
N N
O

Oxides of Nitrogen
Name Formula Oxidation state Common methods of preparation Physical appearance
of nitrogen and chemical nature
Dinitrogen oxide N2O +1 NH4NO3 Heat
 → N2O + 2H2O Colourless gas, neutral
[Nitrogen oxide]
Nitrogen monoxide NO +2 2NaNO2 + 2FeSO4 + 3H2SO4 → Fe2(SO4)3 Colourless gas, neutral
[Nitrogen (II) oxide] + 2NaHSO4 + 2H2O + 2NO
Dinitrogen trioxide N2O3 +3 2NO + N2O4 250 K
 → 2N2O3 Blue solid, acid blue
[Nitrogen (III) oxide] liquid (–30°C)
 Nitrogen dioxide NO2 +4 2Pb(NO3)2 673 K
 → 4NO2 + 2PbO + O2 Brown gas, acidic
[Nitrogen (IV) oxide]
Dinitrogen tetroxide N2O4 +4 2NO2
Cool

 
 N2O4 Colourless solid/liquid,
Heat
[Nitrogen (IV) oxide] acidic
Dinitrogen pentaoxide N2O5 +5 4HNO3 + P4O10 → 4HPO3 + 2N2O5 Colourless solid, acidic
[Nitrogen (V) oxide]

Preparation 4NH3 + 3O2  N2 + 6H2O

(i) 2NH4Cl + Ca(OH)2  4NH3 + 5O2
Pt/Rh
4NO + 6H2O
CaCl2 + 2NH3 + 2H2O 1100K
MOP Properties Ostwald’s
NH33 process
(ii) Mg3N2 + HOH 8NH3 + 3Cl2  6NH4Cl + N2
Mg(OH)2 + 2NH3 excess

Manufacturing NH3 + 3Cl2  NCl3 + 3HCl

Haber Process excess

Fe + Mo
N2 + 3H2 2NH3 + 24KCal
750 K
200-300 atm

Concentration of nitric acid Metal Main products

Mg, Mn H2+ metal nitrate
Very Dilute HNO3 Fe, Zn, Sn NH4NO3 + metal nitrate
Cu, Ag, Hg No reaction
Fe, Zn N2O + metal nitrate
Dilute HNO3
Pb, Cu, Ag NO + metal nitrate
NO2 + H2SnO3
Conc. HNO3 Sn
(Metastannic acid)
Conc. HNO3 Fe, Co, Ni, Cr, Al Rendered passive

Oxoacids of Phosphorus
Name Formula Oxidation state of Characteristic bonds and Preparation
nitrogen their number
Hypophosphorus H3PO2 +1 One P — OH white P4 + alkali
(Phosphinic)
Orthophosphorous H3PO3 +3 Two P — OH P2O3 + H2O
(Phosphonic) One P — H
One P = O
Pyrophosphorous H4P2O5 +3 Two P — OH PCl3 + H3PO3
Two P — H
Two P = O
Hypophosphoric H4P2O6 +4 Four P — OH red P4 + alkali
Two P = O
One P — P
Orthophosphoric H3PO4 +5 Three P — OH P4O10 + H2O
One P = O

P The p-Block Elements 19

W
 Name Formula Oxidation state of Characteristic bonds and Preparation
nitrogen their number
Pyrophosphoric H4P2O7 +5 Four P — OH heat phosporic acid
Two P = O
One P — O — P

Metaphosphoric* (HPO3)n +5 Three P — OH phosphorous acid + Br2, heat

Three P = O in a sealed tube
Three P — O — P

PCl3
Cl2 dry 3H2O
P4 H3PO3 + 3HCl

R–COOH
PCl3 RCOCl + H3PO3
Colourless
+SOCl2 oily liquid R–OH
P4 R–Cl + H3PO3
–SO2, –S2Cl2

PCl5

dry Cl2 (ex) H2O

P4 POCl3 + 2HCl
4H2O (Partial Hydrolysis)
H3PO4 + 5HCl
PCl3 R–OH
Yellowish RCl / RCOCl + POCl3 + HCl
+SO2Cl2 R–COOH
P4 white AgCl/SnCl4 + PCl3
–SO2 Ag/Sn
powder

16th-Group Elements
Oxygen Family

1. Oxygen is the most abundant of all the elements on earth crust.

2. Oxygen and sulphur are non-metals, selenium and tellurium are metalloids, whereas polonium is a metal.
3. Polonium hardly shows –2 oxidation state.
4. Reducing property of dioxide decreases from SO2 to TeO2, SO2 is reducing while TeO2 is an oxidising agent.
5. Sulphur hexafluoride, SF6 is an exceptionally stable for steric reasons.
6. The well known monohalides are dimeric in nature. Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2.
Ozone
PbS
PbSO2
–
I , H2O –
I2 + OH + O2

Oxidizing MS
MSO4 + O2
3O Property ) Pb/Cu/Zn/ Ca(
O3
2 2 endothermic
process ic form of
moist parent
S/P/As oxy acid
Pale Violet Hg2O + O2
Blue black Hg
Dark
Gas Solid Peroxide
blue
Oxide + O2
liquid

20 NEET (XII) Module-2 PW

* Fishy odour, Highly toxic. 7. Flourine forms two oxides OF2 and O2F2. However, only OF2
is thermally stable at 298 K.
Gases Absorbent
These oxides are essentially oxygen fluoride because of the
O3 Turpentine Oil/Oil of cinnamon.
higher electronegativity of fluorine than oxygen. Both are
NO FeSO4
strong fluorinating agents.
SO2 NaOH
CO Cu2Cl2 8. O2F2 oxidises plutonium to PuF6 and the reaction is issued in
O2 Pyrogallol removing plutonium as PuF6 from spent nuclear fuel.
Metal above 9. A combination of kinetic and thermodynamic factors lead to
H2
Metal Sulphate + H2 the generally decreasing order of stability of oxides formed
In reactivity by halogens, I > Cl > Br.
Series
dil. H2SO4
Class A 10. I2O5 is a very good oxidising agent and is used in the
(Non-oxidizing acid)
Sub gp - I estimation of carbon monoxide.
Volatile Product
acidic radical 18th–Group Elements
Acid
NH3 + H2SO4  (NH4)2SO4 + H2O
1. Relative Abundance:
Dehydration
eg: HCOOH  CO + H2O Ar > Ne > Kr > He > Xe > Rn
agent
Conc. H2SO4 H2C2O4  CO2 + CO + H2O
Oxidizing 2. Melting and Boiling point:
eg: Br–/I–  Br2/I2
Nature
s/c  CO2 /SO2 + H2 O Rn > Xe > Kr > Ar > Ne > He
Metal Metal sulphate + SO2 3. He has the lowest boiling point among all elements.
(Except Au. Pt) Zn + 2H2SO4  ZnSO4 + SO 2 + 2H 2O
4. Noble gases are monoatomic, colourless, odourless, sparingly
17th–Group Elements soluble in water and diffusing through most commonly used
1. The electron affinity values (in KJ mol–1) for 17 group laboratory materials.
element are given below: 5. O2[PtF6] is the first noble gas compound.
F Cl Br  
I 6. Ar, Kr and Xe from clathrate compounds when pass in ice
333 349 325 296 with high pressure.
2. All halogens are coloured. For example, F2 has yellow gas, A·  6H2O (A = Ar/Kr/Xe)
Cl2 greenish yellow gas, Br2 red liquid and I2 violet coloured
Preparation of Xe-Fluoride
solid.
F2, 673 K, 1 bar
3. They react with metals and non-metals to form halides and XeF2
the reactivity of the halogens decreases down the group.
2F2, 873 K, 7 bar O2F2
i.e. the order is F2 > Cl2 > Br2 > I2. Xe XeF4 143K XeF6 + O2
4. In general, a halogen oxidises halide ions of higher atomic 3F2, 573 K, 70 bar
XeF6
number.
Properties
F2 + 2X– → 2F– + X2 (X = Cl, Br or I)
Fluoride donor: Eg.
Cl2 + 2X– → 2Cl– + X2 (X = Br or I)
Br2 + 2I– → 2Br– + I2 XeF2 + MF 5 → [XeF4 ]+ [MF6 ]−
(M = As/Sb/ P)

5. Reaction with water:

Fluoride acceptor: Eg.
2F2(g) + H2O(l) → 4H+ (aq) + 4F–(aq) + O2(g)
XeF6 + MF → M + [XeF7 ]−
X2(g) + H2O(l) → HX (aq) + HOX (aq) (M = Na / K / Rb/ Cs)

(where X = Cl or Br) Fluoride agents: Eg.

SF4 / Pt
4I– (aq) + 4H+ (aq) + O2(g) → 2I2(s) + 2H2O(l) XeF4  → PtF4 /SF6 + Xe
6. Halogens form many oxides with oxygen but most of them Reaction with SiO2: Eg.
are unstable. 2XeF6 + SiO2 → SiF4 + XeOF4

P The p-Block Elements 21

W
Hydrolysis
H2O 1
Xe + 2HF + O
2 2
XeF2
+SOCl2 – 1
– Xe + 2F + H2O + O
2OH 2 2

6XeF4 + 12H2O → 4Xe + 2XeO3 + 24HF + 3O2

Mixture of noble gases (He, Ne, Ar, Kr, Xe)

in contact with coconut charcoal at 173 K

Unadsorbed Adsorbed
(He, Ne) (Ar, Kr, Xe)
in contact with in contact with another
charcoal at 93 K charcoal at liquid air
temperature

Adsorbed Unadsorbed
Ne He

In the first charcoal Second charcoal

Kr, Xe. Temp. Ar
raised to 183 K

Evolved Kr Remained adsorbed Xe

22 NEET (XII) Module-2 PW