Teil eines Buches,
The Deviations from the Law of Mass Action for Simple Bimolecular Reaction: Molecular Dynamics Study
Abstract Book of the XXIII IUPAP International Conference on Statistical Physics, Genova, Italy, (9-13 July 2007)
Zusammenfassung
The influence of concentrations of reagents on the rate of irreversible reaction: A + B -> C + B has been investigated by performing large scale computer simulations on identical soft sphere systems. The problem has been analyzed both for deterministic systems (gas, liquid) and for the stochastic ones where the spheres are immersed in the Brownian medium. Significant deviations from the law of mass action are presented. The deviations result not only from fluctuations in concentrations of reagents. For the Brownian systems the simulations have given a positive value of the excess in the rate coefficient, which contradicts with general expectations. The effect is strictly correlated with direct interactions between B particles. For the considered Brownian systems, the effect dominates over the fluctuations effect. The B - B interactions influence also the reaction rate for the deterministic systems, but here the effect is weaker and for long times the excess in the rate coefficient has been always negative due to the fluctuations in concentrations of reagents.
