PINEGROVE

EDUCATIONAL INSTITUTIONS
Snehitha Hills, Peeran Cheru, Hyderabad, [Link] - 500091

OZONE
Ozone is an allotropic form of oxygen. It is formed from atmospheric

oxygen in the presence of sunlight. This ozone layer protects the earth’s

surface from an excessive concentration of ultraviolet (UV) radiations.

Preparation
When a slow dry stream of oxygen is passed through a silent electrical

discharge, conversion of oxygen to ozone (10%) occurs. The product is

known as ozonised oxygen.

3O2 → 2O3 ΔH = +142 kJ mol–1

Since the formation of ozone from oxygen is an endothermic process, it is

necessary to use a silent electrical discharge in its preparation to prevent its

decomposition.

Physical Properties
Ozone has a characteristic smell, if concentration rises above 100 ppm

breathing becomes uncomfortable and it causes headache.

(i) When pure, it is a pale blue gas; liquid ozone is darker blue and solid
ozone is violet black.

(ii) It is heavier than air.

(iii) It is slightly soluble in water but more soluble in turpentine oil, glacial
acetic acid or carbon tetrachloride.

(iv) It is diamagnetic and endothermic.

Decomposition

Ozone is thermodynamically unstable with respect to oxygen, since its

decomposition into oxygen results in the liberation of heat (ΔH is negative)

and an increase in entropy, resulting in a large negative free energy change

(ΔG) for its conversion into oxygen.

2O3 ⎯⎯
→ 3O2, ΔH = 284 kJ mol–1

Oxidizing Properties

Ozone is the fourth strongest oxidizing agent. The others are fluorine,

atomic oxygen and oxygen fluoride OF2.

The oxidation reactions of O3 can be divided into two categories.

(A) Reactions in which oxygen is evolved, i.e., one oxygen atom per ozone

molecule is utilized.

(B) No oxygen is evolved, i.e., all the oxygen atoms in ozone are consumed.

(A) Examples of O3 reactions in which O2 is liberated

(i) Black lead sulphide is oxidized to white lead sulphate

PbS + 4O3 → PbSO4 + 4O2

(ii) Iodine is liberated from potassium iodide solution.

2KI + H2O + O3 → 2KOH + I2 + O2

(iii) Alkaline KI is oxidized to potassium iodate and periodate.

KI + 3O3 → KIO3 + 3O2

KI + 4O3 → KIO4 + 4O2

(iv) Halogen acids are oxidized to the corresponding halogens,

2HCl + O3 → Cl2 + H2O + O2

NaNO2 + O3 → NaNO3 + O2

(vi) Ferrous sulphate is oxidized to ferric sulphate.

2FeSO4 + H2SO4 + O3 → Fe2(SO4)3 + H2O + O2

(vii) Sodium sulphite is oxidized to sodium sulphate.

Na2SO3 + O3 → Na2SO4 + O2

(viii) Sodium arsenite is oxidized to sodium arsenate.

Na3AsO3 + O3 → Na3AsO4 + O2

(ix) Potassium ferrocyanide is oxidized to potassium ferricyanide.

2K4[Fe(CN)6] + H2O + O3 → 2K3[Fe(CN)6] + 2KOH + O2

(x) Green potassium manganate is oxidized to purple permanganate.

2K2MnO4 + H2O + O3 → 2KMnO4 + 2KOH + O2

(xi) H2S is oxidized to sulphur.

H2S + O3 → H2O + S + O2

(xii) When O3 is passed over solid KOH at high pressure orange red solid

potassium ozonoxide is formed

2KOH + 5O3 → 2KO3 + H2O + 5O2

Oxidation of Non-metals

Most non-metals, like iodine, sulphur, phosphorous and arsenic are

oxidized to their corresponding-ic acids

S + H2O + 3O3 → H2SO4 + 3O2

P4 + 6H2O + 10 O3 → 4H3PO4 +10 O2

I2 + H2O + 5O3 → 2HIO3 + 5O2

Dry iodine is oxidized to yellow powder I4O9

2I2 + 9 O3 → I4O9 + 9O2.

Oxidation of Metals Silver metal gets blackened in ozone due to alternate

oxidation of the metal and reduction of the metal oxide.

2Ag + O3 → Ag2O + O2

Ag2O + O3 → 2Ag + 2 O2

Tailing of mercury

When ozone is passed into mercury, it oxidizes it to mercurous oxide which

dissolves in mercury. Then mercury loses its upper meniscus and non

sticking nature to the glass

2Hg + O3 → Hg2O + O2

The loss of metallic lustre and the meniscus of mercury metal in the

presence of ozone and as a result making mercury sticking to the glass

surface is called tailing of mercury.

(B) Examples of reactions where O3 is completely consumed

(i) SO2 is oxidized to SO3

3SO2 + O3 → 3SO3

(ii) SnCl2 is oxidized to SnCl4 in the presence of HCl

3SnCl2 + 6HCl + O3 → 3SnCl4 + 3H2O

With unsaturated organic compounds containing double bonds, it forms

addition compounds called ozonides. The ozonides get decomposed by water

or dilute acids forming carbonyl compounds. The total reaction is called

ozonolysis.
 Reactions with peroxides:

Ozone reacts with barium peroxide and hydrogen peroxide to liberate

oxygen

BaO2 + O3 → BaO + 2O2

H2O2 + O3 → H2O + 2 O2

Ozone reduces Ag2O to silver

Ag2O + O3 → 2Ag + 2 O2

The reactions of ozone with peroxides and silver oxide are examples of

mutual reduction reactions. These are called so because ozone as well as the

reactant (H2O2, BaO2, Ag2O) lose one oxygen atom each. Thus both the

reactants are reduced as loss of oxygen is reduction.

Bleaching Property

It is a good bleaching agent (dry) on account of its oxidizing action on

organic matter like rubber, cork, oil, ivory, starch, waxes, wood pulp etc.

Estimation of O3

When ozone reacts with an excess of potassium iodide solution buffered with

a borate buffer (pH 9.2), iodine is liberated which can be titrated against a

standard solution of sodium thiosulphate. This is a quantitative method for

estimating O3 gas

Uses

(i) Ozone is used as germicide and disinfectant for sterilization of water and for

improving the atmosphere of crowded places like underground railways,

mines, cinema halls etc.

(iii) It is used to identify the position of unsaturation and number of double

bonds or triple bonds.

(iv) It is used in the manufacture of potassium permanganate by oxidation of

potassium manganate.

Tests for Ozone

(i) It can be detected by its characteristic rotten fishy smell.

(ii) It turns the starch iodide paper blue.

(iii) It can be identified by its tailing effect of mercury.

(iv) It turns the white shining silver to black.

(v) It converts the benzidine paper to brown and tetramethyl or ethyl base

paper to violet.

Structure

ozone is a bent molecule (similar to the water molecule).

The O – O distances are 127.2 pm (1.272 Å). The angle is 116.78°.

The central atom is sp² hybridized with one lone pair.

Ozone is a polar molecule with a dipole moment of 0.53 D.

The molecule can be represented as a resonance hybrid with two contributing

structures, each with a single bond on one side and double bond on the other.

The arrangement possesses an overall bond order of 1.5 for both sides.