Group 15 - Nitrogen family :

N P As Sb Bi

non-metal metalloid metal

General e-conf [] (n-2) f14 (n-1)d10 ns2 np3

Variations in Group 15
Variations of group 15 :
size : N < P < As < Sb < Bi
IE : N > P > As > Sb > Bi
EA : N < P < As < Sb < Bi
Eneg : N > P > As > Sb ≈ Bi
Melting Point :
N P As Sb Bi

exist as Network metal

N2 and P4 solid

As > Sb > Bi > P > N

Metallic character - N < P < As < Sb < Bi

Oxidation state :

General OS = +5 , +3, -3
N also shows +1, +2, +4 with oxygen
ex . N2O, NO , NO2 because of multiple bond formation
Stability of +5 and -3 decreases and +3 increases down the group
Anomalous behavior of N
Anomalous Behavior of Nitrogen :
- Small size
- High eneg.
- High BDE
- Absence of vacant orbital
- Multiple bond formation tendency.
Chemical properties of N
Chemical properties :
A. Reaction with Hydrogen

E + H2 ⟶ EH3

- Δ Hf : NH3 > PH3 > AsH3 > SbH3

endo exo

BE : NH3 > PH3 > AsH3 > SbH3

BA : NH3 > PH3 > AsH3 > SbH3

Lewis Base : NH3 > PH3 > AsH3 > SbH3

Reducing Nature : NH3 < PH3 < AsH3 < SbH3 < BiH3
Reaction with oxygen :
They form E2O3 and E2O5 type oxide

E2O5 ⟶ all acidic

E2O3 ⟶ N and P - acidic

As and Sb - amphoteric
Bi - basic
Reaction with Halogens :
- They form EX3 and EX5
- N only forms EX3
- Stability order : NF3 > NCl3 > NBr3 > NI3

explosive
- Except BiF3 all trihalides are covalent
Preparation of dinitrogen
Dinitrogen (N2) Preparation :
Δ
1. (NH4)2 Cr2O7 N2 + H2O + Cr2O3

2. NH4NO2 Δ N2 + H2O

3. NH4Cl + HNO2 N2 + H2O + HCl

4. C2H5NH2 + HNO2 N2 + C2H5OH

5. NaN3 Δ Na(s) + N2(↑)

6. Ba(N3)2 Δ Ba(s) + N2(↑)

7. Excess NH3 + Cl2 N2 + NH4Cl

7. NH3 + excess Cl2 NCl3 + HCl

Properties of N2 :

1. Colourless, tasteless, non-toxic, very low solubility in water

2. Due to high BDE, it directly reacts with only few metals

Li + N2 ⟶ Li3N

Mg + N2 ⟶ Mg3N2
2000k
3. N2 + O2 ⟶ NO (lightening)
Ammonia Preparation :
1. Any ammonium salt + Base ⟶ NH3
NH4+Cl- + NaOH ⟶ NH3 + NaCl + H2O

1. Heating of ammonium salt having non/weak oxidising anion.

NH4Cl ⟶ NH3 (↑) + HCl (↑)
1. Metal nitride + H2O ⟶
Mg3N2 + H2O ⟶ Mg(OH)2 + NH3
Ammonia Preparation :

1. Zn/Al + NO2- / NO3- + NaOH ⟶ NH3 + NaAlO2 / Na2ZnO2

2. Urea + H2O ⟶ NH3 + CO2
3. Haber’s process N2 + 3H2 ⟶ 2NH3 cat : Iron oxide/ Al2O3/K2O
Temp 700K
Press 20MPa
Properties of ammonia :
- Colourless
- Pungent smell
- Diamagnetic
- Polar
- Water soluble
- Basic
- Liquid NH3 + alkali metal ⟶ powerful reducing agent
Nitrous acid
Nitrous acid Preparation & properties :
1. metal nitrite ⟶ HNO2
2. N2O3 + H2O ⟶ HNO2

Properties :

1. Colourless liquid
2. Unstable at RT
HNO2 ⟶ HNO3 + NO
Oxidising Property of HNO2

Itself changes from HNO2 ⟶ NO

SO2 ⟶ SO2-4
H2S ⟶ S
Fe2+ ⟶ Fe3+
Sn2+ ⟶ Sn4+
AsO33- ⟶ AsO43-
I - ⟶ I2
Reducing Property of HNO2

Itself changes from HNO2 ⟶ HNO3

KMnO4 / H+ ⟶ Mn2+
K2Cr2O7 / H+ ⟶ Cr3+
Cl2 ⟶ Cl-
H2O2 ⟶ H2O
Nitric acid
Nitric Acid Preparation :
conc H2SO4
1. NaNO3 HNO3 + NaHSO4

2. KNO3 conc H2SO4 HNO3 + KHSO4

3. Ostwald Process

RT
Step 1 : NH3 + O2 NO + H2O
Δ
Step 2 : NO+ O2 NO2

Step 3 : NO2 +H2O HNO2 + HNO3

also
HNO2 HNO3 + NO
Chemical properties of Nitric acid
Chemical properties of HNO3 :
1. Acid - base reaction
CaO + HNO3 ⟶ Ca(NO3)2 + H2O
Na2CO3 + HNO3 ⟶ NaNO3 + CO2 + H2O

2. Reaction with non-metal

Conc HNO3 is strong OA
itself HNO3 ⟶ NO2

P4 ⟶ H3PO4
I2 ⟶ HIO3
S ⟶ H2SO4
Reaction with metals
Metals with reactivity more than H except Pb

M + case HNO3 (70%) ⟶ NO2

M + dil HNO3 (20%) ⟶ N2O
M + v dil HNO3 (6%) ⟶ NH4NO3

M + conc HNO3 ⟶ NO2

M + dil HNO3 ⟶ NO
M + v v dil HNO3 ⟶ x

2% HNO3 can react only with Mg and Mn

Cu + 45% HNO3 ⟶ Cu(NO3)2 + N2O3
Brown Ring Test :
FeSO4 + H2SO4 + NO2-/NO3- ⟶ Brown ring complex

NO2- + dil/conc H2SO4 + Fe2+ ⟶ Fe3+ + NO

NO + FeSO4 ⟶ [Fe(H2O)5NO]SO4

NO3- + dil H2SO4 ⟶ x

Fe2+ + NO3- + conc H2SO4 ⟶ Fe3+ + NO

NO + FeSO4 ⟶ [Fe(H2O)5NO]SO4
Aqua Regia :
HNO3 + HCl ⟶ [Cl] + NO
1:3
Used to dissolve Au and Pt
Al + HNO3 + HCl ⟶ H[AuCl4] + NO
Pt + HNO3 + HCl ⟶ H2[PtCl6] + NO
Preparation and properties of N oxides :

1. N2O Colourless
a. NH4NO3 ⟶ N2O + H2O diamagnetic neutral

b. Zn + dil HNO3 ⟶ N2O + H2O laughing gas

c. HNO2 + NH2OH ⟶ N2O + H2O

2. NO
Colourless neutral
a. FeSO4 + NaNO2 + dil H2SO4 ⟶ Fe3+ + NO paramagnetic
b. Cu + dil HNO3 ⟶ Cu2t + NO
c. N2 + O2 ⟶ NO
Preparation and properties of N oxides

3. N2O3
Blue colour liquid
NO + NO2 ⟶ N2O3 diamagnetic
Cu + 45 % HNO3 ⟶ N2O3

4. NO2
Paramagnetic
Pb[NO3]2 ⟶ PbO + NO2
acidic reddish
Cu/Zn + conc HNO3 ⟶ Cu2t /Zn2 + NO2
brown
Preparation and properties of N oxides:

N2O4 Colourless liquid

cool acidic
NO2 N2O
heat
4

N2O5
Colourless solid
HNO3 + P4O10 HPO3 + N2O5 acidic
Phosphorous :
P4 + H2O ⟶ x
P4 + limited O2 ⟶ P4O6
P4 + excess O2 ⟶ P4O10
P4 + NaOH ⟶ PH3 + NaH2PO2

P4 + lin Cl2 ⟶ PCl3

P4 + excess Cl2 ⟶ PCl5
Phosphorus :
Δ Δ
P4 RedP Black P

white

Low T, high pressure

 White P Red P

- Insoluble in water - Insoluble in water

- Soluble in CS2. - Insoluble in CS2

- Glows in dark - Dosen’t glow in dark

- poisonous - Non - poisonous

PH3 : Phosphine

Δ
White P4 + NaOH PH3 + NaH2PO2

H3PO3 Δ H3PO4 + PH3

Δ
H3PO2 H3PO4 + PH3
H2O
Ca3P2 Ca(OH)2 + PH3
Properties of PH3

- Rotten fish smell

- Strong reducing agent because of weak P-H bonds

hv
- Aq PH3 ⟶ Red P + H2
Chlorides of P

P4 + limited Cl2 ⟶ PCl3

P4 + excess Cl2 ⟶ PCl5

P4 + SO2Cl2 ⟶ PCl5 + SO2

P4 + SOCl2 ⟶ PCl3 + SO2 + S2Cl2

PCl5 + Ag ⟶ AgCl + PCl3

PCl5 + SnCl2 ⟶ SnCl4 + PCl3

PCl3 + H2O ⟶ H3PO3 + HCl

PCl5 + H2O ⟶ POCl3 ⟶ H3PO4 + HCl

Oxoacids of P

H3PO2. - Hypophosphorous acid

or Phosphinic acid

White P4 + NaOH ⟶ PH3(↑) + NaH2PO2

H3PO2
Oxoacids of P

H3PO3 Phosphorous acid

Or
Phosphonic acid

P2O3 + H2O ⟶ H3PO3

PCl3 + H2O ⟶ H3PO3 + HCl

H3PO3 ⟶ H3PO4 + PH3

Pyro / diphosphorous acid

PCl3 + H3PO3 ⟶ H4P2O5 + HCl

Hypophosphonic acid H4P2O6

Red P + NaOH ⟶ Na4P2O6 + P2H4

H3O+

H4P2O6
Orthophosphoric acid
Di/ pyrophosphoric acid
Metaphosphroic acid HPO3

Sealed tube
H3PO3 + Br2 ⟶ HBr + HPO3
Δ
Reactivity towards Hydrogen :
E + H2 ⟶ EH2

1. Bond length of hydrides :

Increases down the group
2. Bond energy decreases down the group
3. Thermal stability decreases.
4. Acidic natures increases
5. Bond angle decreases
6. Melting / Boiling point
H2O > H2Te > H2Se > H2S
Reactivity towards Oxygen :
- They form EO2 and EO3 type oxides
- Reducing property : SO2 > SeO2 > TeO2
- All oxides EO2 and EO3 are acidic in nature.
Reactivity towards Halogens :
- The form EX2 and EX4 and EX6
- Reactivity : SF6 < SeF6 < TeF6
- Among tetra fluroides
SF4(g) SeF4(l) TeF4(s)
- Rate of hydrolysis
SF6 < SeF6 < TeF6
- They also form monohalide which exist in dimer form
which disproportionate on heating
Δ Se + SeCl
Se Cl ⟶
2 2 4
Preparation of oxygen :
A. Heating of

KClO3 Δ KCl + O2
KMnO4 Δ K2MnO4 + MnO2 + O2
K2Cr2O7 Δ K2CrO4 + O2 + Cr2O3
Preparation of oxygen :
B. Heating of H2O2 Δ H2O + O2

C. Heating of higher oxides

PbO2 Δ PbO + O2
Pb2O3 Δ PbO + O2
Pb3O4 Δ PbO + O2

Mn2O7 Δ MnO2 + O2

CrO3 Δ Cr2O3 + O2
Preparation of oxygen :
Industrial Method :
Liquefaction of air followed by fractional distillation
Properties of Oxygen
Properties of O2 :
- Colourless gas
- Pale blue liquid
- Dark blue solid
- Odourless
- Slightly soluble in water
- paramagnetic
Ozone and its preparation :
- Allotropic form of oxygen
Silent electric
O2 ⇌ O3

discharge
Properties of ozone :
O3 - pale blue gas
Dark blue liquid
Violet black solid.
- Odourless , harmful in large concentration.
Estimation of ozone

KI + O3 -------------> I2 + K2O
I2 + Na2S2O3 -----------> Na2S4O6 + NaI
Oxidising property of ozone :
Cl- Cl2
Br- Br2

I- I2

NO2 NO3
- -

SO32- SO42-

S2O32- SO42-

AsO33 AsO43-
-
Oxidising property of ozone :
S H2SO4
P H3PO4

I2 HIO3

K2MnO4 KMnO4

K4[Fe(CN)6] K3[Fe(CN)6]
Sulphur & its compounds
Allotropes of sulphur :

Crystalline Amorphous
α - sulphur Colloid sulphur
β - sulphur Plastic sulphur
Allotropes of sulphur :
369 k β - sulphur
α - sulphur
Rhombic Monoclinic

- Both α and β are Ss

- Both are in soluble in water
- Both are soluble in CS2
- Density α > β
- Melting point β > α
Hydrogen sulphide :
Properties
- Colourless gas
- Rotten egg smell
- Diamagnetic
- Reducing gas
(CH3COO)2Pb + H2S ⟶ PbS (black ppt)
Reducing nature of H2S:
O3 O2

KMnO4/H+ Mn2+
K2Cr2O7/H+ Cr3+

Cl2/Br2/I2 Cl-/Br/I-
SO2 S

H2O2 H2O
Preparation of SO2:
S + O2 SO2 (↑)

Roasting of sulphide are

SO32- + H+ H2SO3 H2O + SO2 (9)

(unstable)
Preparation of SO2:

1. Colourless

2. Pungent suffocating smell

3. Acidic nature

NaOH + SO2 ⟶ Na2SO3

Ca(OH)2 + SO
VO2 ⟶ CaSO3 (↓) ⟶SO2 ⟶ Ca(HSO3)2
2 5

1. SO2 + O2 ⟶ SO3

2. SO2 acts as temporary bleaching agent.

Reducing action of sulphur dioxide
SO2 + KMnO4 / H+ Mn2+ + SO42-

SO2 + K2Cr2O7 / H+ Cr3+ + SO42-

Fe3 + SO2 Fe2+ + SO42-

Preparation of H2SO4 :

Contact process:

FeS2 + O2 ⟶ FeO + SO2

V2O5

SO2 + O2 ⟶ SO3

SO3 + H2SO4 ⟶ H2S2O7

H2S2O7 + H2O ⟶ H2SO4

 H2SO4

dil H2SO4 Conc. H2SO4

Acts as Can act as

acid only - Acid
- OA
- Dehydrating agent
Reactions of H2SO4 :
- metal + H2SO4 ⟶

Zn + dil H2SO4 ⟶ ZnSO4 + H2 (↑)

Cu + dil H2SO4 ⟶ x

Zn + conc. H2SO4 ⟶ ZnSO4 + SO2 + H2O

Cu + Conc. H2SO4 ⟶ CuSO4 + SO2 + H2O
Reactions of H2SO4 :
non-metal + H2SO4 ⟶

conc

P4 + H2SO4 ⟶ H3PO4 + SO2

I2 + H3SO4 ⟶ HIO3 + SO2

C + H2SO4 ⟶ H2O + CO2 + SO2

B + H2SO4 ⟶ H3BO3 + SO2

Si + H2SO4 ⟶ H4SiO4 + SO2
S8 + H2SO4 ⟶ SO2 + H2O
Hypo
Preparation of Hypo :
- S8 + NaOH ⟶ Na2S2O3 + Na2S
- Na2CO3 + SO2 ⟶ Na2SO3 + CO2
SO2 + H2S ⟶ S + H2O
Finally Na2SO3 + S ⟶ Na2S2O3
Properties of Hypo :
S2O32- + Strong OA SO42-

(cl2 , Br2 , etc)

S2O32- + weak OA S4O62-

(Cu2+ , Fe3t , I2)

Oxyacids of Sulphur
Oxyacids of Sulphur
Oxyacids of Sulphur