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In 1871, Josef Stefan established the theoretical framework which allowed the design of his diffusion column. It consisted of a volatile liquid A overlaid with gases A and B. A steady gas B sweep flowed at the top, maintaining the concentration of gas A close to zero at that location. Binary gas diffusion coefficients, whose magnitudes are crucial in many mass transfer operations, were estimated with this device. This line of work was continued uninterruptedly by many research groups around the world for over eight decades. However, in the 1950s inaccuracies in the diffusivity estimates were detected mainly due to column end effects such as gas turbulence/eddy formation resulting from the sweeping stream as well as interfacial curvature. The latter affects the transport area and the path length of gas A to the top. Studies departing from the traditional Stefan column role of binary diffusivity estimation were promptly initiated to attain a better understanding of transport phenomena within the column. These efforts, which endure to this day, applied fundamental chemical engineering principles to determine the source of the diffusivity inaccuracies, the dimensionality of gas transport, the importance of interfacial curvature and nonisothermal column operation, and how liquid-phase events such as mixing affect device performance. These research initiatives have led to an in-depth description of transport phenomena within the Stefan column. Historical references are thoroughly analyzed, chemical engineering contributions to this field are highlighted, and perspectives for future theoretical and experimental work along these lines are presented.

Chemical engineering contributions resulting in an improved understanding of the Stefan diffusion column: A 150-year perspective