The potential of saturated α-palladium in hydrogen-stirred solution compared to a Pt/H2 electrode in the same solution is 0.0495±0.0005 v. The potential-determining reaction on α-palladium is independent of hydrogen pressure. The potential-determining equilibrium is postulated to be, H++e= lim Pd(Pd−H)α. Pure palladium spontaneously absorbs hydrogen in hydrogen-stirred solution until the saturation limit of the α phase is reached. This limiting atomic ratio of H/Pd=0.025±0.005. Between a H/Pd atomic ratio of 0.03 to 0.36 both the α and β phases coexist and the mixed potential is determined by that of the α domains. In the H/Pd region 0.36 to 0.6, the potential is a function of the hydrogen content of the palladium.

A simple formalism is developed in which the determinantal equation for the reciprocal relaxation times of a reaction mechanism can be written down immediately from an inspection of the elementary chemical reactions in the mechanism. The reactions in the mechanism may be of any order; parallel reaction paths may be included. The determinantal equation can be solved for the relaxation times using the simple formalism and the expressions in terms of rate constants and equilibrium concentrations obtained at the end of the procedure. If the reactions are not thermodynamically independent then the order of the determinantal equation can be reduced directly in a simple way to that corresponding to the number of thermodynamically independent reactions. The procedure and the various approximational techniques are illustrated by a number of detailed examples. A number of general results are derived. It is pointed out that for kinetically elementary reactions, the matrix of Onsager coefficients is diagonal. The diagonal element is proportional to the exchange rate of the elementary reaction. It is shown that the transformation to normal coordinates can be done by using a product of a diagonal matrix and an orthogonal matrix. This simplifies the inversion of the transformation considerably. For systems with thermodynamically dependent reactions the explicit form of the time independent coordinates is derived. Some general relations between the elements of the transformation matrix are also derived.

Heat of Solution of Hydrogen in a Two-phase Pd-H Alloy 1123 in the introduction depended on the observed first power dependence of the uranium extraction coefficients, [U]

In recent years the application of relaxation techniques to the study of fast reactions has received considerable attention. Eigen and deMaeyer2 have developed the theory and experimental techniques for studying such reactions. However, little attention has been Contribution from Monsanto Chemical Company,