Abstract
It is shown on the basis of (1) conservation of mass, (2) positive concentrations, and (3) the principle of detail balancing that periodic reactions cannot occur in a closed system described bylinear differential equations. The matrix,A, of the rate equations must be such that |A|=0,aij>0 fori≠j,aii<0, andVAV−1=B, whereV is diagonal andB is symmetric. These properties ofA imply that the latent roots are real and non-positive and that neither catalysis nor inhibition can be described bylinear equations. It is further shown that periodic reactions cannot occur in anopen system for which the matrix associated with the chemical reactions has the above properties and in which thesimple law of diffusion is obeyed. The relation of these results to Onsager's reciprocal relations and to previous work on periodic and cyclic chemical reactions is discussed. The utility of certain of these results for the treatment of isotope kinetics is indicated.
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