The polarography of beryllium

Abstract

The polarography of beryllium in 0.5M lithium chloride has been investigated in some detail, using several polarographic and coulometric techniques. Current-time curves, microscopic examination and cinematography of the mercury drop, and the effect of complexing agents, aided in elucidating the electrode process. The experimental data show that the polarographic step for the tetraquoberyllium ion is diffusion-controlled but irreversible, and results from the reduction of two protons liberated from the coordinated water molecules, yielding beryllium hydroxide and hydrogen. The evidence suggests that this reduction takes place in a stepwise process, with a soluble beryllium hydroxy complex as an intermediate. The polarographic results can be correlated with published potentiometric data on the composition and stabilities of hydrolysed beryllium species in aqueous media. The number of electrons involved in the electrode reaction depends on the number of hydroxyl groups per beryllium atom in the beryllium complex. Beryllium oxalate and salicylate complexes also give a reduction step, but only if the complex contains coordinated water molecules. The diffusion coefficient of the tetraquoberyllium ion was found to be 6.2 ± 0.3 x 10^-6 cm² sec^-1 at 30°.