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摘要
En 中文
A homogeneous many-reaction system close to equilibrium is considered, in which it is postulated that the stoichiometric equations for the real reactions are linearly independent and that the rate of each reaction is proportional to its affinity and independent of all other affinities. It is shown that the symmetric (but non-diagonal) matrix that relates the rates to the affinities of a linearly independent but fictitious set of reactions can be made to display the identity of the real reactions if one can independently modify the real equilibration velocities. Formal diagonalization of a nondiagonal phenomenological matrix is shown to be an improper procedure for finding the real reactions; moreover, the set of equations found by this method loses its diagonality when the real equilibration velocities are modified. By contrast, the matrix relating the rates of the real reactions to their affinities retains its diagonality throughout all modifications of the equilibration velocities. This stronger diagonality condition is suggested as a criterion for real independent reactions. The results should be applicable to nonequilibrium thermodynamics.
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