Ch.

19 Sulfuric Acid
 CONTENTS
Concept Map
History of manufacture development
Manufacture of sulphuric acid
Difference between laboratory and
Industrial method
Uses
Summary
Video
Evaluation
 CONCEPT MAP
SULPHUR
MANUFACTURE
TRIOXIDE
OF
USING
SULPHURIC ACID
V2O5
AS
SULPHUR CATALYST
USES

SULPHUR ACID
DIOXIDE RAIN
 HISTORY
One of the oldest industrially applied processes. Discovered by a Muslim
alchemist Jabir Ibn Hayyan in the tenth century.
In 17th century Johan Glauber manufactured sulphuric acid in the
laboratory by mixing Saltpeter and sulfur in a glass container and
burned in a moist atmosphere. Acid was collected from the condensed
vapors.
In England, 1746, the lead chamber reactor was invented. This invention
allowed for higher production rates (<78%).
In England, 1831, Peregrine Phillips patented the contact process that
described the oxidation of sulfur dioxide over a platinum catalyst. This
new process increased yields of reaction from 70 to above 95%.
 STRUCTURE
Sulphuric Acid may be represented as:

OR
 STRUCTERE
The Hydrogen bonding in the acid may be
illustrated as:
 DIFFERENCE BETWEEN
LABORATORY METHOD INDUSTRIAL METHOD
 MANUFACTURE OF SULPHURIC ACID
There are two methods for the manufacture of
sulphuric acid. They are:

Lead Chamber Process

Contact process
The Lead Chamber process is generally no
longer used .Hence the process will be
discussed.
 LEAD CHAMBER PROCESS
lead chamber process was an
industrial method used to produce
sulfuric acid in large quantities.
In 1746 in Birmingham, England, John
Roebuck began producing sulfuric acid
in lead-lined chambers, which were
stronger, less expensive, and could be
made much larger than the glass
containers which had been used
previously.
 LEAD CHAMBER PROCESS

This allowed the effective

industrialization of sulfuric acid
production and with several
refinements, this process remained
the standard method of production for
almost two centuries. So robust was
the process that as late as 1946, the
chamber process accounted for 25%
of sulfuric acid manufactured
 LEAD CHAMBER PROCESS
The Process:
1) Sulfur dioxide is introduced with
steam and oxides of nitrogen into
large chambers lined with sheet
lead where the gases are sprayed
down with water and chamber acid.
2) The sulfur dioxide and nitrogen
dioxide dissolve and over a period
of approximately 30 minutes the
sulfur dioxide is oxidized to sulfuric
acid. reactions.
 LEAD CHAMBER PROCESS
The Process:

3) The presence of nitrogen dioxide is

necessary for the reaction to
proceed. The process is highly
exothermic, and a major
consideration of the design of the
chambers was to provide a way to
dissipate the heat formed in the
reactions
 LEAD CHAMBER PROCESS
Process History:

4) Early plants used very large lead-lined wooden

rectangular chambers (Faulding box
chambers) that were cooled by ambient air.
The internal lead sheathing served to contain
the corrosive sulfuric acid and to render the
wooden chambers waterproof. Around the turn
of the nineteenth century, such plants required
about half a cubic meter of volume to process
the sulfur dioxide equivalent of a kilogram of
burned sulfur. In the mid 19th century
 LEAD CHAMBER PROCESS
Process History:

5) French chemist Gay-Lussac redesigned

the chambers as stoneware packed
masonry cylinders. In the 20th century,
plants using Mills-Packard chambers
supplanted the earlier designs. These
chambers were tall tapered cylinders
that were externally cooled by water
flowing down the outside surface of the
chamber.
 LEAD CHAMBER PROCESS
Process :
6) Sulfur dioxide for the process was provided by
burning elemental sulfur or by the roasting of
sulfur containing metal ores in a stream of air
in a furnace. During the early period of
manufacture, nitrogen oxides were produced
by the decomposition of niter (Potassium
Nitrate) at high temperature in the presence of
acid, but this process was gradually
supplanted by the air oxidation of ammonia to
nitric oxide in the presence of a catalyst. The
recovery and reuse of oxides of nitrogen was
an important economic consideration in the
operation of a chamber process plant.
 LEAD CHAMBER PROCESS
Process :

7) In the reaction chambers, nitric oxide (Nitrous

Oxide) reacts with oxygen to produce nitrogen
dioxide. Liquid from the bottom of the
chambers is diluted and pumped to the top of
the chamber and sprayed downwards in a fine
mist.
8) Sulfur dioxide and nitrogen dioxide are
absorbed in the liquid and react to form sulfuric
acid and nitric oxide. The liberated nitric oxide
is sparingly soluble in water and returns to the
gas in the chamber where it reacts with
oxygen in the air to reform nitrogen dioxide
 LEAD CHAMBER PROCESS
Process :

9) Some percentage of the nitrogen oxides

are sequestered in the reaction liquor as
nitrosylsulfuric acid (NOHSO4) and as
nitric acid, so fresh nitric oxide must be
added as the process proceeds.
10)Later versions of chamber plants
included a high temperature Glover
tower to recover the nitrogen oxides
from the chamber liquor, while
concentrating the chamber acid to as
much as 78% H2SO4
 LEAD CHAMBER PROCESS
Process :

11)Exhaust gases from the chambers are

scrubbed by passing into a tower through which
some of the Glover acid flows over broken tile.
Nitrogen oxides are absorbed to form
nitrosylsulfuric acid which is then returned to
the Glover tower to reclaim the oxides of
nitrogen.
12)Sulfuric acid produced in the reaction chambers
is limited to about 35% concentration. At higher
concentrations, nitrosylsulfuric acid precipitates
on the lead walls as chamber crystals and is no
longer able to catalyze the oxidation
reactions.[2]
 LEAD CHAMBER PROCESS
Chemistry :

1. Sulfur dioxide is generated by burning elemental sulfur or by

roasting pyritic ore in a current of air:

S8 + 8 O2 8 SO24
FeS2 + 11 O2 2 Fe2O3 + 8 SO2

2. Nitrogen oxides are produced by decomposition of niter in the

presence of sulfuric acid or hydrolysis of nitrosylsulfuric acid:

2 NaNO3 + H2SO4 Na2SO4 + H2O + NO + NO2 + O2

2 NOHSO4 + H2O 2 H2SO4 + NO + NO2
 LEAD CHAMBER PROCESS
Chemistry :

3. In the reaction chambers, sulfur dioxide and

nitrogen dioxide dissolve in the reaction liquor.
4. Nitrogen dioxide is hydrated to produce nitrous
acid which then oxidizes the sulfur dioxide to
sulfuric acid and nitric oxide.
5. The reactions are not well characterized but it
is known that nitrosylsulfuric acid is an
intermediate in at least one pathway.
 LEAD CHAMBER PROCESS
Chemistry :

The major overall reactions are:

2 NO2 + H2O HNO2 + HNO3

SO2 (aq) + HNO3 NOHSO4
NOHSO4 + HNO2 H2SO4 + NO2 + NO

SO2 (aq) + 2 HNO2 H2SO4 + 2NO

 LEAD CHAMBER PROCESS
Chemistry :
6. Nitric oxide escapes from the reaction liquor
and is subsequently reoxidized by molecular
oxygen to nitrogen dioxide. This is the overall
rate determining step in the process:
2 NO + O2 2 NO2
7. Nitrogen oxides are absorbed and
regenerated in the process, and thus serve as
a catalyst for the overall reaction:
2 SO2 + 2 H2O + O2 2 H2SO4
CONTACT PROCESS

RAW MATERIAL:
 CONTACT PROCESS
The process involves the following steps:

Production of sulfur dioxide

Purification of sulfur dioxide
Conversion of SO2 to SO3
Oleum formation
Formation of H2SO4
 CONTACT PROCESS
Production of sulfur dioxide 2
1. By burning sulfur:

2. By roasting Iron Pyrite:

Sulfur dioxide is purified to remove the impurities.

 PURIFICATION UNIT

This unit is an assembly of various

parts like.

a. Dust Precipitator
b. Scrubber
c. Drying Tower
d. Arsenic Purifier

http://www.contentshoppe.com/im
ages/eLearning/sample2.swf (click
on this site to see the purification
unit)
FLOW DIAGRAM OF PROCESS
 V2O5

2
Oxidation of sulphur dioxide

Catalytic Oxidation:
Catalytic Oxidation:
CONDITIONS:

Temperature (400-450C)
Pressure ( 1.5 2 atm )
Catalyst ( V 2 O5 )
Excess of Oxygen
 400-450C
V2O5

1.5-2 atm

Conversion of SO2 to SO3

Oleum formation

Sulfur trioxide is not readily soluble

in water and a mist is produced,
therefore it is first absorbed in con.
Sulfuric acid.
Formation of sulphuric acid

Dilution of oleum
Contact Process Flow diagram
LABORATORY USE USES INDUSTRIAL USE

SULPHURIC ACID

RESEARCH LABS

GENERAL USE
SUMMARY
 SUMMARY
USES INDUSTRY

SULPHURIC
RESEARCH LABS
ACID

GENERAL