Absolute Reaction Rate Theory For Diffusion In Metals

UNDERSTANDING of the diffusion problem has recently been furthered by the analysis of Birchenall and Mehl.1 They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,2 Jost,3 Dehlinger,4 and Darken,' who assumed the net flux of dif¬fusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's' activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Hargreaves.7 The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinski10 in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitutional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitutional alloys were analyzed on the basis of the concepts of the chemical rate theory. CHEMICAL RATE THEORY According to the theory of absolute reaction rates8 the reaction [A,+A2+ ... +.A;->X,+X2 +...+X; EqI] is viewed as taking place in two steps. First the reactants A1, A2, . . . A[i] combine to form an activated complex M with which they are in equilibrium; [A, + A2 + .. . + Ai = M. Eq 2] Second the activated complex decomposes to give the products X1, X2. . .. X[j]; [M->X1+X2+ ... +.X;. Eq3] It has been shown8 that the number of activated complexes decomposing per unit volume per unit time is given by the expression† [kT]