Chemical Technology

Subject Code: CH2001

Lecture 7

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 Sulfuric acid (oil of vitriol)
Properties
Chemical formula H2SO4
Molar mass 98.079 g/mol
Appearance Clear, colorless liquid
Odor Odorless
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Density 1.8302 g/cm , liquid
Melting point 10.31°C (50.56 °F; 283.46 K) Ball-and-stick model
Boiling point 337°C (639 °F; 610 K) When sulfuric acid is above 300 °C (572 °F; 573
length = 142.2 pm,
K), it gradually decomposes to SO3 + H2O
Solubility in water miscible, exothermic S-O bond length =
Vapor pressure 0.001 mmHg (20 °C) 157.4 pm,
Acidity (pKa) -2.8±0.5, 1.99
O-H bond length = 97
Conjugate base Hydrogen sulfate pm
Viscosity 26.7 cP (20 °C)

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 Grades of sulfuric acid
Mass fraction Density Concentration
Common name
H2SO4 (kg/L) (mol/L)
<29% 1.00-1.25 <4.2 diluted sulfuric acid
battery acid
29–32% 1.25–1.28 4.2–5.0
(used in lead–acid batteries)
chamber acid
62–70% 1.52–1.60 9.6–11.5
fertilizer acid
tower acid
78–80% 1.70–1.73 13.5–14.0
Glover acid
93.2% 1.83 17.4 66 °Bé ("66-degree Baumé") acid
98.3% 1.84 18.4 concentrated sulfuric acid

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Sulfuric production by contact process videos

• https://www.youtube.com/watch?reload=9&v=Bu3ns9Ii80M
• https://www.youtube.com/watch?v=xjLUJ-7m5v8
• https://www.youtube.com/watch?v=_zj3bMjFclA

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 Sulfuric acid production process
• Sulfuric acid is produced from sulfur, oxygen and water via the
conventional contact process (DCDA) or the wet sulfuric acid
process (WSA) and Lead chamber process.
• All processes are based on the SO2. chamber process was developed first
(1746) but produced acid of concentration less than 80%. Contact process
yields 98% h2so4 and higher which can be diluted, if necessary. Chamber
process is virtually obsolete.
• the Contact Process for the manufacture of sulphuric acid, which
goes on to explain the reasons for the conditions used in the process.
• Effect of proportions, temperature, pressure and catalyst on the
composition of the equilibrium mixture, the rate of the reaction and
the economics of the process.

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 Process
• In the first step, sulfur is burned to produce sulfur dioxide.
S (s) + O2 → SO2
• The sulfur dioxide is oxidized to sulfur trioxide by oxygen in the presence of a
vanadium(V) oxide catalyst. This reaction is reversible and the formation of the
sulfur trioxide is exothermic.
2 SO2 + O2 2 SO3
• The sulfur trioxide is absorbed into 97–98% H2SO4 to form oleum (H2S2O7), also
known as fuming sulfuric acid. The oleum is then diluted with water to form
concentrated sulfuric acid.
H2SO4 + SO3 → H2S2O7
H2S2O7 + H2O → 2 H2SO4
• Directly dissolving SO3 in water is not practiced.
• As this process is an exothermic reaction so the temperature should be as low as
possible. The yield has been found to be maximum at about 410 - 450° C.

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 Flow sheet of production process
• Purification of the air and sulfur
dioxide (SO2) is necessary to For, 1 Ton of H2SO4
avoid catalyst poisoning. SO2 = 0.67 ton
• Hot sulfur trioxide passes through Air = 1450-2200 Nm3
the heat exchanger and is
dissolved in concentrated H2SO4 in
the absorption tower to
form oleum:
• Oleum is reacted with water to
form concentrated H2SO4.

Catalyst
• Widely used catalyst is vanadium
pentoxide dispersed on a porous
carrier in the pellet form.
• Platinum catalyst was previously
used but suffers from easy poising,
fragility, rapid heat deactivation,
high initial investment.
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 Characteristics of catalysis
• Porous carrier
• Active catalytic agent
• Promoter

Advantages/disadvantages
• Relatively immune to poisons
• Low initial investments and only 5% replacement per year
• Requires only 10 kg catalyst mass containing 7-8%V2O5 per daily ton of 100%
acid.
• Must use dilute SO2 input (7-10%) as catalyst is less active and requires high
O2/SO2 to give economic conversion.
• Larger convertors and higher initial investment are necessary.

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 Process description
• Air-SO2 gas containing 7-10% SO2 and 11-14% O2 is preheated by convertor
gas, if necessary and sent to first stage of steel construction. This is the high
temperature (500-600 C) stage, contain 30% to the total catalyst and convert
about 80% of SO2.
• The convertor product is cooled by heat exchange at 300C and fed to a second
stage where total yield is increased to 97% by operating at 400-450C for
favourable equilibrium.
• High yields product gases are cooled to 150C by water and air heat exchangers
and absorbed in oleum fed at a rate to allow not over a 1% rise in acid strength.
Final scrubbing is done with a lower strength (97%) acid. Oleum concentration
up to 40% can be made by tower absorption. Higher strength oleum up to 65%
is prepared by distilling 20% oleum.