Statistical Thermodynamics in Chemical Kinetics

Abstract

The dog-flea model illustrates an equilibrium distribution with the maximal states. If all fleas are on dog A, each might jump to dog B with some characteristic time. Independent jumps by fleas in either direction eventually lead to an equilibrium state. Even then, random jumps create a dynamic equilibrium. Even though fleas continue to jump between dogs, the 50–50 distribution is stable. Fleas continue to jump and although the system can fluctuate from this equilibrium, the 50–50 equilibrium is observed predominantly. For equal energy isomers, an initial state of only A isomers leads, in time, to the 50–50 A–B distribution.