PROBABILITY-DISTRIBUTION OF THE CHEMICAL-STATES OF A CLOSED-SYSTEM AND THERMODYNAMIC LAW OF MASS-ACTION FROM KINETICS - THE RNA EXAMPLE

We show some thermodynamic results concerning chemical kinetics, eithe r from statistical physics, under the strong assumption (EXS) of the s tatistical exponential distribution of the physical states, or from ki netics. In that frame, the reaction rates are modeled according to the stochastic activation collision theory, under the weaker assumption ( EXW) of the statistical exponential distribution not on the whole spac e but only within each structure; moreover a symmetry condition (SY) c oncerning the local properties of the rate constants is assumed. The B oltzmann distribution and an extension of the more general result of t he thermodynamic law of mass action are proved. Moreover, we show that the assumptions (EXS) and (EXW) are equivalent, under (SY). At last, we deal with the stochastic example of the RNA structure for which we calculate the temporal probabilities of the structures by means of a j ump process. (C) 1997 American Institute of Physics.