The Consistency of Certain Kinetic and Equilibrium Expressions

This condition must define the same surface in (c, Z)-space as does the equilibrium condition 

We wish to show that this is the only function for which the relation is true the proofs given elsewhere [9,10] are in error since they assume too large a number of degrees of freedom.  

By the phase rule of Gibbs the system has s degrees of freedom so that, if the two thermodynamic variables are chosen, only s — 2 of the remaining concentrations may be selected, and the other two are fixed by (9) and 

Now if the same manifold is defined by both equations (8) and (9), and therefore also by (16) and (20), we should be able to solve (16) for c1 and, on substituting it in the left side of (20), find that the resulting expression was independent of y. This will be so if d(k/k )ldy = 0 when dclldy is calculated from (16). But, differentiating the two equations logarithmically, we have 

One of the less satisfactory features of P was its tentative treatment of reaction mechanism. It was confined to the case of a single overall reaction and did not make clear the nature of the degeneracy in the differential equations for the concentrations. 

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