OXYACIDS OF SULPHUR

 Oxyacids of sulphur are compounds

of sulphur with oxygen and hydrogen.

oxidation state : +2,+3 & +6

 sulphur exhibits a tetrahedral structure

when coordinated to oxygen.
 Generally, these contain at least
• one S=O bond &
• one S-OH bond.

 In addition to S=O and S-OH.

• Terminal peroxide groups,
• terminal S=S,
• terminal and bridging oxygen atoms and chains of (-S-)n are also observed.
 CLASSIFICATION

CLASS EXAMPLE

Normal oxyacids H2SO3 , H2SO4

Pyroacids H2S2O5 , H2S2O7

Thionic acids H2SnO6

Peroxyacids H2S2O8
 NORMAL OXYACIDS

SULPHUROUS ACID, H2SO3

 Do not exit in solution phase but can be isolated in the gaseous phase.
 Prepared by dissolving sulfur dioxide in water
 SO2 + H2O H2SO3

 Diprotic acid & ionizes in two steps:

 H2SO3 H+ + HSO-3
 HSO-3 SO2-3 + H+

 Any sulphite or bisulphite salt will evolve SO2 gas

when acidified.
 PROPERTIES

Density 1.03 g/ml at 25 °C(lit.)

Vapour density 2.3 ( air)
pKa 1.92(at 25℃)
Form Liquid
Colour Colourless
Water solubility Soluble
Sensitive Air sensitive
Stability Stable.
 SULPHURIC ACID, H2SO4

 Most important industrail chemical.

 Battery acid.

 Not found naturally.

 Total world production :

50,000,000 tons/years.
 MANUFACTURING

Raw materials
• Sulphur
• Water
• Air

Manufactured by either process

• Contact process
• The lead chamber process
 CONTACT PROCESS

 Three steps
• Production of SO2
• Conversion of SO2 into SO3
• Conversion of SO3 into H2SO4
 LEAD CHAMBER PROCESS

 Produces relatively dilute acid (62-78%)

 Lead chamber plant consists of

• 1 Pyrites burners
• 2 Nitre ports
• 3 Glover’s tower
• 4 Lead chambers
• 5 Gay-Lussac tower
• 6 Coolers
 PROPERTIES & USES

 As a raw material for HCl, H3PO4 , HNO3 .

 Manufacture of ammonium sulfate and aluminum sulfate.

 Acidic drain cleaners

Colourless oily
 Lead-acid batteries(electrochemistry) liquid
FP : 10.4 ̊C
BP : 290-317 ̊C
 Petroleum refining

 Medicine
 PYROACIDS

 Formed by condensation reactions of normal oxyacids.

 2H2SO3 H2S2O5 + H2O
 2H2SO4 H2S2O7 + H2O

Disulfurous acid Disulfuric acid

 THIONIC ACIDS

 Acids containing two sulphonic groups (-SO2OH) linked either directly or

through sulphur atom(s).

 General formula : H2SnO6 (n > 2)

 On the basis of no of S-atom present these can be

• Dithionoc acids &
• Polythionic acids

 Only occur in solution & as salts (thionates).

 DITHIONIC ACID (H2S2O6 )

 These are obtained by oxidizing a sulfite, but on a larger scale they are
made by oxidizing a cooled aqueous solution of sulfur dioxide with
manganese dioxide:

 2MnO2 + 3SO2 → MnS2O6 + MnSO4

 The manganese dithionate solution formed can then be converted to

dithionate salts of other metals by metathesis reactions:

 Ba2+(aq) + MnS2O6(aq) + MnSO4(aq) → BaSO4(s)↓ + BaS2O6·2H2O(aq)

 DITHIONIC ACID (H2S2O6 )

 Concentrated solutions of dithionic acid can subsequently be obtained

treating a barium dithionate solution with sulfuric acid:

 BaS2O6(aq) + H2SO4(aq) → H2S2O6(aq) + BaSO4(s)↓

 It is also formed when sulphurous acid is oxidized by KMnO4

 2H2SO3 + O H2S2O6 + H2O

 PROPERTIES

 It is unstable & decomposes as follows

• H2S2O6 H2SO4 + SO2

 Its salts with alkali & alkaline earth metal are stable in boiling
aqueous solution

 Its other salts decompose as follows

• S2O2-6 SO2-4 + SO2
 POLYTHIONIC ACIDS

 Polythionic acid is an oxoacid which has a straight chain

of sulfur atoms.

 The chemical formula H2SnO6 (n > 2).

 Preparation Methods

 By the action of Sulphur chlorides on sulphites and

thiosulphates in ether solution.
• SCl2 + 2SO2-3 S3O2-6 + 2Cl-
• SCl2 + 2S2O2-3 S5O2-6 + 2Cl-
• S2Cl2 + 2SO2-3 S4O2-6 + 2Cl-
• S2Cl2 + 2S2O2-3 S6O2-6 + 2Cl-

Diprotic Acids
Water Soluble
Alkali salts are
Stable than Alkaline
metal salts
 PEROXY ACIDS

 Sulphur has two peroxy acids with peroxide linkage (-O-O-)

• 1 peroxymonosulphuric acid (Caro's acid)

• 2 Peroxydisulphuric acid (Marshall's acid)

 PEROXYMONOSULPHURIC ACID

 This is prepared by the action of conc. H2O2 on sulphuric acid

or chlorosulphuric acid.

• H2O2 + H2SO4 ⇌ H2SO5 + H2O

• H2O2 + ClSO2OH ⇌ H2SO5 + HCl
 PROPERTIES & USES

 Exists as hygroscopic white crystalline solid

 Soluble in many aliphatic solvents

 Behaves as monoprotic acid in aqueous solution

 Disinfectant and cleaning agent e.g., swimming pool

treatment and denture cleaning.

 Alkali metal salts helps in delignification of wood.

 PEROXYDISULPHURIC ACID

 Chemical formula :H2S2O8

 The acid is prepared by the reaction of chlorosulfuric acid
with hydrogen peroxide.

• 2ClSO3H + H2O2 → H2S2O8 + 2 HCl

 PROPERTIES

 Called Marshall's acid after its inventor Prof Hugh Marshall.

 It contains sulfur in its +6 oxidation state and a peroxide group.

 Its salts(persulfates),are industrially important as powerful oxidizing

agents.

 It decomposes into SO3,O2 and H2SO4 on heating .

 2H2S2O8 2H2SO4 + 2SO3 + O2

 It undergoes hydrolysis giving Caro's acid

 H2S2O8 +H2O H2SO5 + H2SO4