History of Chromatography - Precursors

Precursors

The earliest use of chromatography—passing a mixture through an inert material to create separation of the solution components based on differential adsorption—is sometimes attributed to German chemist Friedlieb Ferdinand Runge, who in 1855 described the use of paper to analyze dyes. Runge dropped spots of different inorganic chemicals onto circles of filter paper already impregnated with another chemical, and reactions between the different chemicals created unique color patterns. According to historical analysis of L. S. Ettre, however, Runge's work had "nothing to do with chromatography" (and instead should be considered a precursor of chemical spot tests such as the Schiff test).

In the 1860s, Christian Friedrich Schönbein and his student Friedrich Goppelsroeder published the first attempts to study the different rates at which different substances move through filter paper. Schönbein, who thought capillary action (rather than adsorption) was responsible for the movement, called the technique capillary analysis, and Goppelsroeder spent much of his career using capillary analysis to test the movement rates of a wide variety of substances. Unlike modern paper chromatography, capillary analysis used reservoirs of the substance being analyzed, creating overlapping zones of the solution components rather than separate points or bands.

Work on capillary analysis continued, but without much technical development, well into the 20th century. The first significant advances over Goppelsroeder's methods came with the work of Raphael E. Liesegang: in 1927, he placed filter strips in closed containers with atmospheres saturated by solvents, and in 1943 he began using discrete spots of sample adsorbed to filter paper, dipped in pure solvent to achieve separation. This method, essentially identical to modern paper chromatography, was published just before the independent—and far more influential—work of Archer Martin and his collaborators that inaugurated the widespread use of paper chromatography.