The contact process

 Converts raw sulphur, oxygen, and water to sulphuric acid.

 Knietsh in Germany developed this method.
 Basically, it involves the catalytic combination of sulphur dioxide and
oxygen to form sulphur trioxide, which is then dissolved to form sulphuric
acid.

a. Preparation of sulphur dioxide

 Sulphur dioxide is obtained by burning sulphur in dry air.
 S(s) + O2(g) → SO2(g)

b. Purification of gases and drying

 The sulphur dioxide is then mixed with excess air and passed through an
electric chamber to remove impurities and dust which might poison the
catalyst.
 The gas mixture is then passed through concentrated sulphuric acid to dry
it before it is delivered to the contact tower.

c. Conversion to sulphur trioxide

 In this chamber, the sulphur dioxide combines with oxygen in the presence
of finely divided vanadium (V) oxide to yield sulphur trioxide.
V2O5 400-450°C
 2SO2(g) + O2(g) 2SO 3(g)

d. Conversion to oleum
 The sulphur trioxide is cooled and passed into an absorption tower where
it dissolves in concentrated sulphuric acid to produce a very thick liquid
called oleum, H₂S207.
 The oxide is not dissolved directly in water because the heat evolved
causes the solution to boil, producing a mist of acid droplets, which would
pervade the factory.
 SO3(l) + H2SO4(l)→ H2S2O7(aq)

e. Dilution
 The oleum is then diluted with appropriate amounts of water to produces
the 98% sulphuric acid commonly used in the laboratory, and other
desired concentrations.
  H2S2O7(aq) + H2O (l) → 2H2SO4(l)

Sulphur trioxide, SO3

Physical Properties
 It is also known as sulphuric anhydride, is an acidic oxide.
 It is a non-polar molecule.
 It has three common physical states: solid, liquid and gas.
 It exists at room temperature as white needle-shaped crystals. Pungent
smell.
 It has a low melting point (16.8°C) and boiling point (45°C), therefore it is
readily vapourized on heating.
 Sulphur trioxide gas is a serious pollutant and one of the main sources of
acid rain.

Chemical Properties
 It is anhydride of sulphuric acid. It combines exothermically with water to
form sulphuric acid and release a lot of heat.
 SO3(l) + H2O (l)→ H2SO4(aq)
 Reacts with sulfur dichloride to produce the useful reagent thionyl
chloride.
 SO3+ SCl2 →SOCl2 + SO2
 Reacts with alkalis to produce salt and water.
 Eg: SO3(l) +2NaOH(aq) → Na2SO4 (s) +H2O(l)
 Dissolves in concentrated sulphuric acid to form oleum or fuming sulphuric
acid.
 SO3(l) + H2SO4(l)→ H2S2O7(aq)

Preparation
 Sulphur dioxide does not combine appreciatively with oxygen to form
sulphur trioxide under normal conditions.
 Good yield of sulphur trioxide requires the presence of a catalyst like
vanadium (V) oxide, a slight high presence, and a temperature of 400-
450°C.
 Contact process:
V2O5 400-450°C
 2SO2(g) + O2(g) 2SO 3(g)

Sulphuric (VI) acid, H2SO4

Preparation
 Contact process
1. SO3(l) + H2SO4(l) → H2S2O7(aq)
2. H2S2O7 (aq) + H2O (l) → 2H2SO4(l)
Physical Properties
 Concentrated sulphuric acid is a colourless, odourless, oily liquid having a
boiling point of 338°C.
 The mass percentage concentration of commercially available
concentrated sulfuric acid is 98.3%.
 It has a density of 1840kg/m3.
 It is corrosive and causes severe burns if it comes in contact with the skin.
 It is sour to the taste.
 Concentrated sulphuric acid and water can dissolve each other in any
proportion and release a lot of heat at the same time.

When diluting concentrated sulfuric acid, slowly pour it into water and stir it
continuously with a glass rod so that the heat generated can escape in time when
concentrated sulfuric acid dissolves in water to prevent water from boiling and
spewing out.

Chemical Properties
1. As an acid (dilute)
Dilute sulphuric acid is a strong diprotic acid, which ionizes in two stages to
release 2 moles of H+ ions.
 React with metals
Metals + acid → salt + hydrogen gas (simple displacement reaction),Eg:
 Zn (s) + H2SO4(aq) → ZnSO4(aq) + H2(g)
 Fe (s) + H2SO4(aq) → FeSO4(aq) + H2(g)
 React with bases
Alkali + acid → salt of hydrogen sulphate/salt of sulphate + water,Eg:
 NaOH (aq) + H2SO4(aq) → NaHSO4 (aq) + H2O (l)
[excess] [acidic salt]

 2NaOH (aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O (l)

*Copper sulphate, used for electroplating or making fungicides, is obtained
from the neutralization reaction of sulfuric acid and copper oxide.
 CuO(s) + H2SO4(aq)→ CuSO4(aq) + H2O (l)

 React with carbonates and hydrogen carbonates

Carbonate/hydrogencarbonate + acid → salt of sulphate + carbon
dioxide,Eg:
 Na2CO3 (s) + H2SO4(aq)→ Na2SO4(aq) + H2O (l) + CO2(g)
 2NaHCO3(s) + H2SO4(aq)→ 2Na2SO4(aq) + 2H2O (l) + 2CO2(g)

2. As an oxidizing agent (concentrate)

The hot concentrated sulphuric acid exhibits oxidizing properties by
accepting electronsfrom reducing agents. The acid itself is reduced to
sulphur dioxide.
 2H2SO4(l) + 2e-→ SO42- (aq) + 2H2O (l) + SO2(g)
As an oxidizing agent, conc. H2SO4 could reacts with the following
substances:

 React with metals

 The concentrated acid oxidizes metals to produce the corresponding
metallic sulphate and sulphur dioxide.Eg:
 2H2SO4(l) + Zn (s) → ZnSO4(aq) + 2H2O (l) + SO2(g)
 6H2SO4(l) + 2Fe (s) → Fe2(SO4)3(aq) + 6H2O (l) + 3SO2(g)

* At room temperature, conc. H2SO4 do not react with Al and Fe metals. It

is because a protective oxide layer formed which prevent the acid to
further react with the metal. As a result, Fe and Al vessel could be used to
fill cold, concentrated H2SO4 .

 React with non-metals

The hot concentrated acid oxidizes non-metals to produce their
corresponding oxides and sulphur dioxide. Eg:
 2H2SO4(l) + C (s) → CO2(g) + 2H2O (l) + 2SO2(g)
 2H2SO4(l) + S (s) → 2H2O (l) + 3SO2(g)

 React with hydrogen sulphide

Sulphuric acid oxidizes hydrogen sulphide to sulphur. The reaction takes
place readily when hydrogen sulphide is bubbled into hot or cold
concentrated sulphuric acid.
 H2SO4(l) + H2S (g) → 2H2O (l) + SO2(g) + S (s)

3. As a dehydrating agent
 As a result of its affinity for water, concentrated sulfuric acid is able to
remove, in the form of water, the hydrogen and oxygen from compounds
like sugar, ethanol, methanoic acid and oxalic acid, thus decomposing
them.
 This process is known as dehydration and the acid is known as
dehydrating agent.
 Dehydration reactions account for the corrosive action of the acid on cloth,
paper, wood, and even the skin.
 In another form of dehydration, the water of crystallisation is removed
from a compound so that the compound becomes anhydrous.
 Example:
conc. H2SO4
 CuSO4·5H2O (s) CuSO4(s) + 5H2O (l)
blue white

conc. H2SO4
 C12H22O11(s) (sugar) 12C (s) (soot) + 11H2O (l)
white black solid

conc. H2SO4
 HOOCCOOH (s) CO (g) + CO2(g) + H2O (l)
oxalic acid

conc. H2SO4
 C2H5OH (l) C 2H4(g) + H2O (l)
Alcohol ethene

4. As a drying agent
 Concentrated sulphuric acid is able to absorb a large amount of water
because of its high affinity for water.
 H2SO4(l) + H2O (l)→ H3O+ + HSO4-(aq) (highly exothermic)
  Concentrated sulphuric acid is used as drying agent for many gases but
not for alkali gases such as ammonia or gases that are reducing agent
such as H2S.

5. As a non-volatile acid: displacement of volatile acid

 Due to its high boiling point (335°C), it is able to displace other acids of
lower boiling point from their salts to give an acid salt of sulphuric acid
and the volatile acid. Eg:
 NaCl (s) + conc. H2SO4(l) → NaHSO4(aq) + HCl (g)
 NaNO3(s) + conc. H2SO4(l) → NaHSO4(aq) + HNO3(g)

Uses of sulphuric acid

1. Fertilizers
 About one quarter of the sulphuric acid produced in the world is used
for the production of the two fertilizers: calcium dihydrogen
phosphate(V), CaH4P2O8 and ammonium sulphate, (NH4)2SO4.

2. Pigments
 Large amounts of the acid are used in the manufacture of pigments,
e.g. TiO2 and BaSO4.

3. Cleaning metals
 The acid is used to clean or pickle metals before electroplating or
enamelling.

4. Dehydrating agent
 It is used as a dehydrating agent in the nitration of compounds from
which explosives are made.

5. Electrolyte
 It is used as an electrolyte in lead accumulators and batteries and in
the refining of metals by electrolysis.

6. Manufacture of certain chemicals

 It is used in the preparation of many important chemical compounds,
e.g.hydrochloric acid, nitric acid, metallic sulphates and many others.

Sulphites , SO32-

Chemical properties
1. React with acids
 When sulphites compounds are heated with dilute acid, sulphur dioxide
is evolved. Eg:
 CaSO3 (s) +2HCl (aq) → CaCl2 (aq) + H2O (l)+ SO2 (g)
2. Reaction with air
 A sulphite is oxidized to the sulphate slowly by air, and rapidly by many
oxidizing agents.
3. As a reducing agent
 Sulphite in dilute acidified solution have the same reducing powers,
reduced oxidizing agent as sulphuric acid.
Tests
1. On warming with a dilute acid
 Warm some of the unknown substance with a dilute acid. If sulphur
dioxide is evolved, then sulphite is present.
 SO32-(aq) + 2H+(aq) → H2O (l) + SO2(g)
2. With barium nitrate(V)
 Add some barium nitrate(V) solution to a solution of the unknown
substance.
 A white precipitate of barium sulphite will be formed in the presence
of a sulphite.
 This precipitate will dissolve in dilute nitric acid with the evolution of
sulphur dioxide.
 Ba2+(aq) + SO32-(aq)→BaSO3(s)
 BaSO3(s) + 2HNO3(aq) → Ba(NO3)2(aq) +H2O(l)+ SO2(g)
(compare: BaSO4 white solid, not soluble in dil. acid)

Sulphates, SO42-
Properties
 The sulphates of sodium, potassium and calcium are stable to
heat.
 However, the sulphates of metals lower down in the electrochemical
series tend to decompose on heating. Eg:
heat

 2FeSO4(s) Fe2O3(s) + SO2(g) + SO3(g)

Tests
 Take some of the unknown solution in a test-tube and acidify it with dilute
hydrochloric acid. Then add a few drops of barium chloride solution.
 A white precipitate of barium sulphate is formed if the unknown solution
contains the sulphate ions.
 This precipitate should be insoluble in an excess of the dilute acid.
 Ba2+(aq) + SO42-(aq) → BaSO4(s)
 The acidification process is necessary to prevent the precipitation of other
insoluble barium compounds like barium carbonate or barium sulphate ,
which however are soluble in an acidic solution unlike the sulphate salt.

Some common sulphates

1. Ammonium sulphate, (NH4)2SO4
 Ammonium sulphate is popularly referred to as sulphate of ammonia. It
is extensively used as a fertilizer and, in more concentrated form, as a
weed killer.

2. Potassium sulphate,K2SO4
 It is used as a fertilizer.

3. Calcium sulphate, CaSO4

  Calcium sulphate is found naturally in the anhydrous form, CaSO4, or
the dihydrate form, CaSO4· 2H2O, commonly known as gypsum.
 Gypsum is used for the manufacture of plaster of Paris, CaSO4.
1/2H2O, on heating thedihydrate at about 100°C, some water of
crystallisation is lost and plaster of Paris, the hemihydrate, is formed.
 When mixed with water and left standing. Plaster of Paris sets to a very
hard mass.Plaster of Paris is widely used for making plaster casts,
moulds, cements, wall-plasters, andin surgery to keep a broken limb
rigid.
 2(CaSO4· 2H2O)(s) →(CaSO4)2· H2O(s)+3H2O(l)
plaster of Paris

4. Aluminium sulphate, Al2(SO4)3

 It forms double salts (alums) with other sulphates and is used in the
treatment of water and sewage, and in papermaking.
 Alums:
 The alums are double sulphates which ionize in solution to yield a
monovalent cation (usually Na+, K+ , or NH4+), a trivalent cation
(usually Fe3+ , Al3+ or Cr3+ ) and sulphate ions.
 Example: Potash alum, aluminium potassium sulphate, KAl(SO4) ·
12H2O, is one of the most commonest alums known. It is usually
used as a mordant in dyeing, i.e. it combines with and fixes the
dyestuff onto the fibre in cases where the fibre cannot by dyed
directly. It is also commonly used as a coagulant in water
purification for removing colloidal suspension particles.

5. Magnesium sulphate, MgSO4

 It is commonly known as Epsom salt. It is found naturally in some
springs and used as a mild purgative.

6. Iron (II) sulphate, FeSO4

 It is a good reducing agent. It is used in making inks, pigments and
tonics.

7. Barium sulphate, BaSO4

 A “barium cocktail” used in medicine as a contrast medium for
stomach and intestinal X-rays.

8. Copper (II) sulphate, CuSO4

 It is used mainly as a fungicide for spraying vines, citrus trees and
potatoes.
 It is also used in electroplating, as a timber preservative, in dyeing and
in the preparation of other copper compounds.