Driving force for a catalyzed reaction derived from a reaction rate spectrum

作者：Yasuda Yusuke^*

来源：Bulletin of the Chemical Society of Japan, 2007, 80(11): 2137-2144.

DOI：10.1246/bcsj.80.2137

Based on the acceleration of Gibbs free energy, -d(2)G/dt(2), a kinetic (or falls) model for a catalyzed CO oxidation was developed. Since G(T)(t) of the system inevitably decreases during a reaction, it may be regarded as the height of water in the model; -d(2)GT/dt(2) FT corresponding to gravity, may be regarded as the driving force for the reaction to occur. The reaction mechanism for CO(X) + (1/2)O-2(y) -> CO2(Z) can be divided into two parallel transformations, X <-> A(X) <-> B-X <-> Zx and Y <-> A(Y) <-> B-Y <-> Z(Y), which are composed of the three elementary steps accompanied by intermediate A and B. The driving force F-X for A(X) and B-X to proceed and also F-Y for A(Y) and B-Y were determined separately. Because F-T (=F-X + F-Y), F-X, and F-Y were independent of t in a definite period, they (instead of G(t)) are useful for describing coupling among the elementary steps and correlations among the intermediates. The reaction can be written X + Y + @ -> Z* + @, where Z* means that Z leaving catalysts has hyperthermal energy and @ denotes the active site where By (assigned to subsurface oxygen) is located. The present dissipative structure is supported by FT, not by any autocatalytic reaction.

• 出版日期2007-11-15