Dalton's disputed nitric oxide experiments and the origins of his atomic theory.

In 1808 John Dalton published his first general account of chemical atomic theory, a cornerstone of modern chemistry. The theory originated in his earlier studies of the properties of atmospheric gases. In 1803 Dalton discovered that oxygen combined with either one or two volumes of nitric oxide in closed vessels over water and this pioneering observation of integral multiple proportions provided important experimental evidence for his incipient atomic ideas. Previous attempts to reproduce Dalton's experiments have been unsuccessful and some commentators have concluded the results were fraudulent. We report a successful reconstruction of Dalton's experiments and provide an analysis exonerating him of any scientific misconduct. But we conclude that Dalton, already thinking atomistically, adjusted experimental conditions to obtain the integral combining proportions.

Atomic Theory and Multiple Combining Proportions: The Search for Whole Number Ratios.

John Dalton's atomic theory, with its postulate of compound formation through atom-to-atom combination, brought a new perspective to weight relationships in chemical reactions. A presumed one-to-one combination of atoms A and B to form a simple compound AB allowed Dalton to construct his first table of relative atomic weights from literature analyses of appropriate binary compounds. For such simple binary compounds, the atomic theory had little advantages over affinity theory as an explanation of fixed proportions by weight. For ternary compounds of the form AB2, however, atomic theory made quantitative predictions that were not deducible from affinity theory. Atomic theory required that the weight of B in the compound AB2 be exactly twice that in the compound AB. Dalton, Thomas Thomson and William Hyde Wollaston all published within a few years of each other experimental data that claimed to give the predicted results with the required accuracy. There are nonetheless several experimental barriers to obtaining the desired integral multiple proportions. In this paper I will discuss replication experiments which demonstrate that only Wollaston's results are experimentally reliable. It is likely that such replicability explains why Wollaston's experiments were so influential.

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.