P-BLOCK ELEMENTS

Inorganic Chemistry

BY – SAGAR VARJATIA SIR

The P-Block Elements
Sture
 P-Block Elements

Conceptual Part Compound of p-Block

Back Bonding Allotropes
Inert pair effect bridge bonding
Hydrolysis Oxyacids

BACK Back Bonding: Coordinate type -bond. If Condition for formation of back bonding:
BONDING coordinate type  bond get form between central • One species must have lone pair.
atom and bonded atom of a molecule it is known as • Another species must have vacant orbital
back bonding • Size of atom should be small

Eg.1 Back Bonding in Boron Trihalide Eg.2 Exhibit resonance in Back bond
X X X X
X X = F, Cl, Br, I
P - P X → Contain lp …………..donar
Back
B → Contain vacant orbital - acceptor B B B B
B Bonding
X X X X X X X X
X X Resonance
hybrid

Extent of back bond BF3 > BCl3 > BBr3 > BI3 Lewis acid strength BF3 < BCl3 < BBr3 < BI3
2p-2p 2p-3p 2p-4p 2p-5p
 Few more examples of back bonding

1. Shape of trimethyl amine pyramidal while 3. Lewis base strength 3. Bond angle of (CH3)2O is very less than
shape of trisillyl amine is triangular planar. (SiH3)2O
⚫⚫ ⚫⚫

SiH3 N(CH3)3 > N(SiH3)3

pyramidal lp involve in
Back bond O
N
back bonding O
B
CH3 CH3 CH3 CH3 SiH3 SiH3
CH3 SiH3 SiH3 No back bonding Back bond effect of lp 
C : No vacant orbital Bond angle 

INERT Some heavy metallic elements of P-block exhibit Electron pair of s-subshell of valence shell is reluctant
higher stability in lower oxidation state in Tl > Tl
+1 +3
PAIR to participate during chemical combination, it is
comparisons of their group oxidation state it is due Pb > Pb
+2 +4
EFFECT known as inert pair and this effect is known as inert
to inert pair effect Bi+3 > Bi+5 pair effect

It is due to higher amount of energy required for this electron pair removal which is not compensated by bond
formation energy.
Generally in oxide and fluorides inert pair effect becomes non-effective [due to higher bond energy]
Order of stability of oxidation state
TlCl exist but not TlCl3
Due to inert pair B+3 > Al+3 > Ga+3 > In++3 > Tl+3
PbI2 exist but not PbI4
effect B+ < Al+ < Ga+ < In+ < Tl+
BiCl3 exist but not BiCl5
C2+ < Si2+ < Gu2+ < Sn2+ < Pb2+
DIMERIZATION/POLYMERIZATION:-
 Hydrolysis
Break down of a molecule through water and formation of new product is known as hydrolysis
Hydro – water
• It is nucleophilic substitution reaction.
Lysis –break
down HOH + MX → H – O – M – X → M – OH + HX
|
H
molecule Intermediate product

Extent of Hydrolysis  Covalent character . 15th group Halides

BeCl2 + 2HOH → Be(OH)2 + 2HCl BF3 + 3HOH → B(OH)3 + 3HF
Ordinary
BCl3 + 3HOH → B(OH)3 + 3HCl 3BF3 + 3HF → 3H [BF4] NF3 + HOH Conditions No hydrolysis
AlCl3 + 3HOH → Al(OH)3 + 3HCl 4BF3+ 3H2O → 3H[BF4]
SiCl4 + 4HOH → Si(OH)4 + 4HCl (partially hydrolysis) NCl3 + HOH → NH3 + 3HOCI
SF6 + H2O → No hydrolysis Similarly PCl3 + HOH → H3PO3 + 3HCI
due to crowding SiF4 + 4HOH → SI(OH)4 + 4HF AsCl3 + HOH → As(OH)3 + 3HCl
2SiF4 + 4HF → H2+[SIF6]2– SbCl3 + HOH → SbOCl + 2HCI
Ordinary
CCl4 + HOH ConditionsNo hydrolysis Hydrolysis followed by (partial hydrolysis)
Lewis acid-base reaction. BiCl3 + HOH → BiOCl + 2HCl
Carbon → No vacant orbital. (Partial Hydrolysis)
PCl5 + HOH → POCl3 → H3PO4
partial completely
 Hydrolysis of higher covalent character Hydrolysis of Interhalogen compounds
containing salt
AX + HOH → HX + HOA
Be2C + 4HOH → 2Be(OH)2 + CH4 HX Hydrophalic acid
Mg2C3 + 4HOH → 2Mg(OH)2 + C3H4 AX3 + HOH → 3HX + HAO2 HOA, HAO2, HAO3 HAO4
CaC2 + 2HOH → Ca(OH)2 + C2H2 AX5 + HOH → 5HX HAO3 Oxyacid of halogen
Al4C3 + 12 HOH → 4Al(OH)3 + 3CH4
Mg3N2 + 6HOH → 3Mg (OH)2 + 2NH3 AX7 + HOH → 7HX + HAO4
AlN + 3HOH → Al(OH)3 + NH3
Ca3P2 + 6HOH → 3Ca(OH)2 + 2PH3 Hydrolysis of Xe
LiH + HOH → LiOH + H2
HOH
CaH2 + 2HOH → Ca(OH)2 + H2 XeF2 Xe + 2HF + O2
HOH
6XeF4 4Xe + 2XeO3 + 24HF + 3O2
HOH HOH
XeF6 2HF + XeFO4 HOH 2HF + XeO2F2 2HF + XeO3
Partial partial complete
Oxy-Acids
Element Oxide Oxyacid Basicity

1. Boron B2O3 B(OH)3 boric acid Not protonic

acid mono-
➢ Mainly oxy-acids are hydroxide of Non-metal oxides. basic lewis
➢ No. of H+ ion furnish by an oxyacid is known as their acid
basicity. Oxyacid obtained by dissolving non-metal oxide
2. Carbon CO2 H2CO3 TWO
in water. Carbonic acid
Eg. CO2 + HOH → H2CO3 or OC(OH)2
3. Nitrogen H2N2O2
Here: CO2 → Non metal oxide ■ Anhydride of carbonic
Hyponitrous acid
acid OC(OH)2 → Oxyacid HNO2
➢ N2O4 → Mixed anhydride Nitrous acid
➢ It gives → HNO2 and HNO3 HNO3
Nitric acid
Oxide Acid HNO4
➢ N2O3 → HNO2 — Nitrous acid Pernitric acid
➢ N2O5 → HNO3 — Nitric acid 4. Phosphorus H3PO2
➢ P4O14 → H3PO4 — Phosphoric acid Hypophosphorus acid
➢ SO2 → H2SO3 — Sulphurous acid H3PO3
➢ SO3 → H2SO4 — Sulphuric acid Phosphorus acid
➢ Cl2O7 → HClO4 — Perchloric acid H3PO4
Ortho phosphorus acid
➢ Oxyacids of different elements HNO3
meta phosphorus acid
H4P2O5
Pyrophosphorus acid
H4P2O7
Order of acidic strength Pyrophosphoric acid
H3PO2 > H3PO3 > H3PO4 H4P2O6
Reducing nature Hypophosphoric acid
H3PO2 > H3PO3 > H3PO4
 OXYACIDS OF SULPHUR
1. Sulphurous acid – H2SO3
2. Sulphuric acid – H2SO4
3. Thiosulphuric acid – H2S2O3
4. Peroxymonosulphuric (Caro’s acid) – H2SO5 (Peroxide bond)
5. Peroxydisulphuric acid (Marshal’s acid) – H2S2O8 (Peroxide bond)
6. Pyrosulphuroous acid – H2S2O5 (S – S linkage)
7. Pyrosulphuric acid – H2S2O7 (S – O – S linkage)
8. Thionus acid – H2S2O4
9. Thionic acid – H2S2O6
10. Polythionus acid – H2(S)nO4 (S-S linkage)
11. Polythionic acid – H2(S)nO6 (S-S linkage)

OXYACIDS OF HALOGEN(Cl)

1. Hypochlorous acid – HClO

2. Chlorous acid – HClO2
3. Chloric acid – HClO3
4. Perchloric acid – HClO4

Order of acidic strength

HClO < HClO2 < HClO3 < HClO4

Oxidising nature
HClO > HClO2 > HClO3 > HClO4
ALLOTROPY • Those substance which are made up of same elements but having different bonding
arrangement are known as allotropes and this phenomenon known as allotropy.
• Those elements which exhibit higher tendency of catenation exhibit higher tendency of
allotropy.
• Therefore carbon, phosphorus and sulphur exhibit maximum allotropy.

ALLOTROPES OF CARBON

DIAMOND GRAPHITE FULLERENE

C-sp3, tetrahexral structure Hexagonal layer structure Latest discovered allotrope of carbon it is
C-C bond length 1.54 Å All sp2 hybrid carbon found in chimney sooty particle
Compact 3 dimensional Unhybrid orbital electron form It contain C60 – C320 ; sp2 hybrid
structure -bond. This -bond exhibit Contain pentagon and hexagonal structure
Hardest substance resonance and due to C60: Buckminster fullerene soccer ball
Very high map (~3400°C) resonance there is mobility of (football) or buckey ball.
Very high density electrons and it becomes C60 : 20 hexagon rings
Non conductor conductor of electricity 12 pentagon rings
Very high refractive index Purest form of carbon
Exhibit total internal reflection No dangling bond
Shines brighty in light
 ALLOTROPES OF PHOSPHOROUS

(a) White Phosporous (b) Red Phosphorous (c) Black Phosphorous

White Phosphorous Red Phosphorous

Waxy solid Brittle powder

Poisonous Non poisonous

Soluble in CS2 Insoluble in water Insoluble in water and CS2

Monomer of P4 Polymer of P4

Highly reactive due to bond angle strain More stable than white phosphorous

It glows in dark due to slow oxidation (phosphorescence) It does not glow in dark

It gives phosphine (PH3) on reaction with NaOH It gives hypo phosphoric acid on reaction with NaOH

Order of stability or MP or density → White < red < black

803 K
Red Phosphorous ⎯⎯⎯⎯⎯→ -Black Phosphorous
high P

573 K Inert
medium

473 K
White Phosphorous ⎯⎯⎯⎯⎯→ -Black Phosphorous
high P
 ALLOTROPES OF SULPHUR
S
Crystalline Amorphous

Rhombic sulphur (-S) Milk of sulphur (-S)

most stable form Plastic sulphur (-S)
Monoclinic sulphur (-S) Colloidal sulphur
>95.6°C
-S -S H2S + 2HNO3 ⎯⎯⎯→ S + 2NO2 + 2H2O
<95°, 6°C Redox
RA OA
95.6°C = transition temp.
Both are soluble in CS2 but
insoluble in water

(a) density of S > S (b) Both are puckered crown shape having S8 units
(c) S2 is paramagnetic sulphur which exist in vapour form at high temperature
(d) S6 is chair form of S

EFFECT OF 95.5°C 119°C 130-200°C >200°C

TEMPERATURE S8() ⎯⎯⎯→ S8() ⎯⎯⎯→ S(liq.) ⎯⎯⎯⎯⎯→ Viscosity of ⎯⎯⎯→ Viscosity
liquid increase decrease
 13 Group : Boron Family
Borox (Na2B1O7.10H2O)

Hydrolysis of borox
Na2B4O7 + 7H2O  2NaOH + 4H3BO3
Alkaline solution
……………………………………………………………………

Borax bead test for transition metal cations

form Colored transition metal meta borate

 740C
Na 2 B4O7 .10H 2O ⎯⎯⎯⎯→ Na 2O4O7 ⎯⎯⎯→ NaBO2 + B2O3
−10H 2O
Transparent borax glassy mass

Cr Mn Fe Co Ni Cu NaBO2 + B2O3 + Cu +2 → Cu(BO 2 )2

Green Pink Green Blue Brown Blue Transition Copper meta
metal cation borate blue color
Diborane (B2H6)

H PO
(i) 3Mg + 2B → Mg3B2 ⎯⎯⎯⎯ →2 6
3 4 B H

(ii) B2O3 + 3H2 + 2Al 150C(MOP)

⎯⎯⎯⎯⎯→
B2H 6 + Al2P3
(iii) 2BF3 + 6NaH B2H6 + 6NaF
180C
⎯⎯⎯→
(iv) NaBH4 + I2 B2H6 + 2NaI + H2
ether
⎯⎯⎯→

Borazole
Or Borazine
B3N3H6 Isoelectronic and Isostructural with benzene
Inorganic  It is called as Inorganic Benzene
Benzene
Orthoboric acid [H3BO3 or B(OH)3]
Alums [Me2SO4,M2'(SO4)3.24H 2O] [Me2SO4,M2'(SO4)3.24H2O]
Alums

Carbon monoxide
[CO]
 PHOSPHINE (PH3)
Physical properties :
Preparation Colourless gas having smell of galic or rotten fish, slightly soluble in water and
slightly heavier than air.
(i) Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3
(ii) PH4I + NaOH → NaI + H2O + PH3 Chemical properties :

Laboratory preparation : (i) 2PH3 + 4O2 → P2O3 + 3H2O

P4 + 3NaOH + 3H2O → 3NaH2PO2 + PH3 713 𝐾
(ii) 4PH3 P4 + 6H2
Uses : (iii) PH3 + 4Cl2 PCl5 + 3HCl
As Holme’s signals in deep seas and oceans.
For the production of smoke screens.

PHOSPHORUS HALIDES
Preparation :
P4 + 10Cl2(g) → 4PCl5(s)
Phosphorus form two types of halides, phosphorus trihalides,
PCl3 + Cl2(g) → PCl5(s)
PCl5 Structure :
PX3 and phosphorus pentahalides, PX5 (X = F, Cl, Br).
P4 + 10SO2Cl2 → 4PCl3 + 10SO2 Cl
Preparation Structure : Cl

P4 + 6Cl2 → 4PCl3 Properties :

Pale yellow crystalline solid. Cl P 120°
Properties : P In solid state it exists as [PCl4]+[PCl6]–.
PCl3 + 3H2O → H3PO3 + 3HCl 240 pm
It sublimes on heating.
Cl Cl Cl
2PCl3 + O2 → 2POCl3 Cl PCl5
heat
PCl3 + Cl2
Cl
PCl3 + Cl2 → PCl5
Partial
hydrolysis H2O
PCl5 + H6O POCl3 + 2HCl H3PO4 + 5HCl
 SULPHURIC ACID (H2SO4)

It is also known as oil of vitriol and king of chemicals. • SO3 is absorbed by conc. H2SO4 and then water is added
❑ Manufacture of sulphuric acid: to produce the acid of desired concentration.
➢ Lead chamber process: H2SO4 + SO3 ⎯→ H2S2O7
The various steps involved are: H2S2O7 + H2O ⎯→ 2H2SO4
• Production of SO2 : By burning S or iron pyrites.
S + O2 ⎯→ SO2 ❑ Properties: Its specific gravity is 1.8 and it is 98% by
4FeS2 + 11O2 ⎯→ 2Fe2O3 + 8SO2 weight.
• Production of catalyst : Oxides of nitrogen. ➢ It is strong dibasic acid.
2NaNO3 + H2SO4 ⎯→ Na2SO4 + 2HNO3 H2SO4  2H+ + SO42–
2HNO3 ⎯→ H2O + NO + NO2 + O2 ➢ It acts as an oxidising agent
• Reaction in lead chamber H2SO4 ⎯→ H2O + SO2 + O
SO2 + NO2 ⎯→ SO3 + NO ➢ Non metals are oxidized to their oxides and metals to
SO3 + H2O ⎯→ H2SO4 the corresponding sulphates.
2NO + O2 ⎯→ 2NO2 (Used again) C + 2O ⎯→ CO2
➢ Dehydrating agent: It is strongly dehydrating in
➢ Contact process: nature.
H2SO4
The steps involved are: C12H22O11 ⎯⎯⎯⎯→ 12C + 11H2O
• Production of SO2: it is produced by burning sulphur or (Charring of sugar)
iron pyrites are purified by treating with steam to remove
dust particles. ❑ Uses:
• Conversion of SO2 to SO3: It is does not container or • In lead storage batteries.
catalyst chamber after being pre-heated to 450°C.
2SO2 + O2  2SO3 + x cal • In manufacture of paints and pigments.
Catalyst: Formerly, platinized asbestos was used which is • In metallurgy for electrolytic refining of metals.
costly and easily poisoned. These days V2O5 is used.
HYDRIDES OF GROUP 15, 16, 17
INTERHALOGEN COMPOUNDS:

DECREASING OXIDISING POWER:

Thank
You