Lead chamber process

The lead chamber process was an industrial method ide in the presence of a catalyst. The recovery and reuse
used to produce sulfuric acid in large quantities. It has of oxides of nitrogen was an important economic consid-
been largely supplanted by the contact process. eration in the operation of a chamber process plant.
In 1746 in Birmingham, England, John Roebuck began In the reaction chambers, nitric oxide reacts with oxy-
producing sulfuric acid in lead-lined chambers, which gen to produce nitrogen dioxide. Liquid from the bottom
were stronger, were less expensive, and could be made of the chambers is diluted and pumped to the top of the
much larger than the glass containers which had been chamber and sprayed downwards in a ne mist. Sulfur
used previously. This allowed the eective industrial- dioxide and nitrogen dioxide are absorbed in the liquid
ization of sulfuric acid production and, with several re- and react to form sulfuric acid and nitric oxide. The lib-
nements, this process remained the standard method of erated nitric oxide is sparingly soluble in water and re-
production for almost two centuries. So robust was the turns to the gas in the chamber where it reacts with oxy-
process that as late as 1946, the chamber process still ac- gen in the air to reform nitrogen dioxide. Some percent-
counted for 25% of sulfuric acid manufactured.[1] age of the nitrogen oxides are sequestered in the reaction
liquor as nitrosylsulfuric acid and as nitric acid, so fresh
nitric oxide must be added as the process proceeds. Later
versions of chamber plants included a high-temperature
1 Process Glover tower to recover the nitrogen oxides from the
chamber liquor, while concentrating the chamber acid to
Sulfur dioxide is introduced with steam and nitrogen ox- as much as 78% H2 SO4 . Exhaust gases from the cham-
ide into large chambers lined with sheet lead where the bers are scrubbed by passing into a tower through which
gases are sprayed down with water and chamber acid. The some of the Glover acid ows over broken tile. Nitrogen
sulfur dioxide and nitrogen dioxide dissolve and over a oxides are absorbed to form nitrosylsulfuric acid, which
period of approximately 30 minutes the sulfur dioxide is is then returned to the Glover tower to reclaim the oxides
oxidized to sulfuric acid. The presence of nitrogen diox- of nitrogen.
ide is necessary for the reaction to proceed at a reasonable
Sulfuric acid produced in the reaction chambers is lim-
rate. The process is highly exothermic, and a major con- ited to about 35% concentration. At higher concentra-
sideration of the design of the chambers was to provide a tions, nitrosylsulfuric acid precipitates on the lead walls
way to dissipate the heat formed in the reactions. as chamber crystals and is no longer able to catalyze the
Early plants used very large lead-lined wooden rectangu- oxidation reactions.[2]
lar chambers (Faulding box chambers) that were cooled
by ambient air. The internal lead sheathing served to con-
tain the corrosive sulfuric acid and to render the wooden 2 Chemistry
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 Sulfur dioxide is generated by burning elemental sulfur or
a kilogram of burned sulfur. In the mid-19th century, by roasting pyritic ore in a current of air:
French chemist Gay-Lussac redesigned the chambers as
stoneware packed masonry cylinders. In the 20th cen- S8 + 8 O2 8 SO2
tury, plants using Mills-Packard chambers supplanted the
earlier designs. These chambers were tall tapered cylin- 4 FeS2 + 11 O2 2 Fe2 O3 + 8 SO2
ders that were externally cooled by water owing down
the outside surface of the chamber. Nitrogen oxides are produced by decomposition of
Sulfur dioxide for the process was provided by burning niter in the presence of sulfuric acid or hydrolysis of
elemental sulfur or by the roasting of sulfur-containing nitrosylsulfuric acid:
metal ores in a stream of air in a furnace. During the
early period of manufacture, nitrogen oxides were pro-
2 NaNO3 + H2 SO4 Na2 SO4 + H2 O + NO
duced by the decomposition of niter at high temperature
+ NO2 + O2
in the presence of acid, but this process was gradually
supplanted by the air oxidation of ammonia to nitric ox- 2 NOHSO4 + H2 O 2 H2 SO4 + NO + NO2

1
2 5 EXTERNAL LINKS

In the reaction chambers, sulfur dioxide and nitrogen

dioxide dissolve in the reaction liquor. Nitrogen diox-
ide is hydrated to produce nitrous acid which then oxi-
dizes the sulfur dioxide to sulfuric acid and nitric oxide.
The reactions are not well characterized but it is known
that nitrosylsulfuric acid is an intermediate in at least one
pathway. The major overall reactions are:

2 NO2 + H2 O HNO2 + HNO3

SO2 (aq) + HNO3 NOHSO4
NOHSO4 + HNO2 H2 SO4 + NO2 + NO
SO2 (aq) + 2 HNO2 H2 SO4 + 2 NO

Nitric oxide escapes from the reaction liquor and is sub-

sequently reoxidized by molecular oxygen to nitrogen
dioxide. This is the overall rate determining step in the
process:[3]

2 NO + O2 2 NO2

Nitrogen oxides are absorbed and regenerated in the pro-

cess, and thus serve as a catalyst for the overall reaction:

2 SO2 + 2 H2 O + O2 2 H2 SO4

3 References
[1] Edward M. Jones, Chamber Process Manufacture of Sul-
furic Acid, Industrial and Engineering Chemistry, Nov
1950, Vol 42, No. 11, pp 220810.

[2] F. A. Gooch and C. F. Walker, Outlines of Inorganic

Chemistry, MacMillan, London, 1905, pp 274.

[3] Jones, pp 2209.

4 Further reading
Derry, Thomas Kingston; Williams, Trevor I.
(1993). A Short History of Technology: From the
Earliest Times to A.D. 1900. New York: Dover.

Kiefer, David M. (2001). Sulfuric Acid: Pumping

Up the Volume. American Chemical Society. Re-
trieved 2008-04-21.

5 External links
Process ow sheet of sulphuric acid manufacturing
by lead chamber process
 3

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