REVERSIBLE OXYGENarm pressure results in the formation of a gold oxide with a stable potential of 1.236v. That this is not the reversible oxygen potential is shown by Fig. 8 which shows the effect of partial pressure changes. The potential changes do not follow the Nernst equation. It therefore appears unlikely that a reversible oxygen electrode can be established on gold or gold oxide substrates.We thank Professor J. O'M. Bockris and Miss W. Visscher for discussions. One of us (N.W.) wishes to thank the Council of Kyoto University for leave of absence.
A sensitive electrochemical technique, which permits the recording of the instantaneous rate of permeation of electrolytic hydrogen through palladium, is described. Results were obtained under conditions required by theory for the diffusion of hydrogen with the use of electronic potentiostats. Analysis of the results shows the validity of the equations previously deduced for the diffusion of hydrogen. No anomalies in the diffusion have been found under these conditions. Thus the diffusion constant is found to be independent of thickness in the range 0·0035 to 0·054 cm. The permeation has been found to be inversely proportional to thickness as required by theory. The diffusion constant for a hydrogen poor α-palladium has been found to be 1·30 ± 0·20 x 10
-7
cm
2
s
-1
at room temperature. Reasons for permeation anomalies reported in the literature for diffusion of hydrogen from the gas phase are discussed. Attention is drawn to errors in the classical time lag determination which unless corrected, can give rise to spurious thickness and temperature dependence of the diffusion constant.
A simple electrochemical technique is described for measuring the quantity of hydrogen permeating a thin membrane of iron or steel during cathodic charging or electroplating. For cadmium electroplating, the quantity is small when this metal is deposited from a fluoborate or a DL‐α‐amino‐n‐butyrate bath, but comparatively high when a cyanide bath is used. The mechanism which governs hydrogen permeation in alkaline solutions containing capillary active anionic species is discussed, and the remarkable similarity between hydrogen permeation and hydrogen induced brittle fracture of high strength steel is demonstrated.
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