Liebig's alkaloid analyses: the uncertain route from content to molecular formulae

Liebig's 1831 paper that describes a new apparatus for the analysis of organic compounds and the results of several analyses using the apparatus is a justly famous contribution to the evolution of modern chemistry. In this paper, I look at the three separate components of Liebig's combustion apparatus that collect the water, carbon dioxide and nitrogen released by the combustion of six alkaloids. Gravimetric data included in the paper reveal that very accurate results could be obtained for water by absorption in a calcium chloride tube, and even better results for carbon dioxide resulted from use of the Kaliapparat. Volumetric measurement of nitrogen gave very poor results despite Liebig's efforts to improve it. Inaccuracies in nitrogen measurement made consistent construction of accurate molecular formulae for nitrogenous substances impossible, and only fortuitous decisions intended to bring molecular formulae into agreement with measured combining weights gave formulae in agreement with modern ones, as in the case for quinine.