The First Organic Catalytic Reaction: Constantin Kirchhoff’s Experiments and Their Place in the History of Catalysis

This essay concerns Constantin Kirchhoff (1764-1833), a Russian chemist of German origin working at the Imperial Court Apothecary in St. Petersburg. In 1811, a quarter century before Berzelius coined "catalysis," Kirchhoff converted starch to grape sugar (glucose) with vitriolic (sulfuric) acid and established that a charge of acid far too small to have combined with the starch nevertheless converted all of it, that reducing the acid lengthened the process without altering the product, and that the acid remained, to be neutralized, at the end. The practical result-crystalline sugar from potato starch-was promptly recognized and rewarded. The finding beneath it was not: Berzelius credited the discovery to Kirchhoff and stated that the acid was recovered unchanged, but the notice did not take, and Kirchhoff was remembered for the sugar. What he set down was a protocol of unusual completeness for its date-the proportions, the four runs, and the times-made at manufacturing scale before Academy witnesses, and he claimed nothing beyond what he had weighed. On this evidence, Kirchhoff was the first to record what would later be recognized as a homogeneous catalytic reaction in organic chemistry, in a year that had neither the concept nor a word for it.