Efficiency of the Electrolytic Separation of Lithium Isotopes

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Abstract
The electrolytic separation coefficient, α, has been determined for the lithium isotope separation in the electrolysis of lithium chloride solutions at a mercury cathode. Its value was found to be 1.055± about 0.005 and, within limits of error, was independent of temperature, of the fraction electrolyzed and of the amount of back reaction at the cathode. The factor was the same for LiCl dissolved in absolute ethyl alcohol as for aqueous LiCl. Isotopic analyses were made by a densimetric method of relative atomic weight determination. Crystalline materials with densities reproducible to the fifth decimal place were prepared. The observed separation is markedly larger than would be given by the exchange equilibrium. It is therefore certain that a kinetic mechanism is operative, although partial approach to equilibrium may enter as a secondary process. The data do not warrant a distinction between the various mechanisms which have been proposed as rate determining steps. They are consistent with Bell's quantum‐mechanical explanation (α=1.12) or with a ``diffusion layer'' mechanism (α=1.08) if partial approach to equilibrium is assumed as a secondary step.

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