Random Chiral Asymmetry Generation by Chiral Autocatalysis in a Far-from-equilibrium Reaction System

If the growth in a local concentration due to an autocatalytic process overcomes diffusion, a concentration fluctuation in a small volume will grow. In a chirally autocatalytic system, this phenomenon could produce a large variation in the enantiomeric excess (ee). Here we report kinetic studies that show such stochastic behavior in the synthesis of an autocatalytic chiral cobalt complex. The established values of the kinetic parameters indicate that temperature inhomogeneities in the form of local hot spots can have a significant effect on the progress of the reaction as well as the ee of the final product. Stochastic kinetics of this type are in stark contrast to deterministic kinetics that are usually encountered in chemistry; in these systems random fluctuations play an important role in determining the product distribution. In the present case we find large random fluctuations in the ee.