In the late Middle Ages, sulfuric acid was obtained in small quantities in glass vessels in which sulfur was burned with saltpeter in a moist atmosphere. Higher rates of production first became possible with the introduction of lead chambers as reaction vessels by ROEBUCK, in Birmingham, England, in 1746. The next major step forward came in 1793, when CLEMENT and DESORMES achieved better results by introducing supplemental air into the lead chamber process. They interpreted this as meaning that the nitrous gases were acting only as facilitators of the process, and that the oxidation itself was being effected by the air (i.e., oxygen).
In 1827, GAY-LUSSAC introduced a method for absorbing nitrogen oxides from the lead- chamber off-gases. With the further development by GLOVER in 1859 of a method for recovering nitrogen oxides from the newly formed acid by stripping with incoming hot gases, it became possible to make the nitrogen oxide- catalyzed process continuous.
As early as 1831, PHILLIPS, in Bristol, England, had patented the oxidation of sulfur dioxide to sulfur trioxide over a platinum catalyst at high temperature. Nevertheless, it was only after oleum demand for dye manufacture began to increase – from about 1872 onward – that this invention was adopted by industry, and intensive development of the contact process began. Better solid catalysts were then sought, and the chemistry and thermodynamics of the SO2/SO3 equilibrium were investigated. Systematic studies undertaken by KNIETSCH at BASF on the reaction equilibrium of SO2 oxidation over a platinum catalyst, published in 1901 [24] , formed an important basis for an understanding of thermodynamic principles.


[24] R. Knietsch, Ber. Dtsch. Chem. Ges. 34 (1901) 4069 – 4115.

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