Random chiral asymmetry generation by chiral autocatalysis in a far-from-equilibrium reaction system

Citation
K. Asakura et al., Random chiral asymmetry generation by chiral autocatalysis in a far-from-equilibrium reaction system, J PHYS CH A, 104(12), 2000, pp. 2689-2694
Citations number
28
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
10895639 → ACNP
Volume
104
Issue
12
Year of publication
2000
Pages
2689 - 2694
Database
ISI
SICI code
1089-5639(20000330)104:12<2689:RCAGBC>2.0.ZU;2-T
Abstract
If the growth in a local concentration due to an autocatalytic process over comes diffusion, a concentration fluctuation in a small volume will grow. I n a chirally autocatalytic system, this phenomenon could produce a large va riation in the enantiomeric excess (ee). Here we report kinetic studies tha t 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 d eterministic kinetics that are usually encountered in chemistry; in these s ystems random fluctuations play an important role in determining the produc t distribution. In the present case we find large random fluctuations in th e ee.