| Summary: | For a complex catalytic reaction with a single-route linear mechanism, a new, kinetico-thermodynamic form of the steady-state reaction rate is obtained, and we show how its symmetries in terms of the kinetic and thermodynamic parameters allow better discerning their influence on the result. Its reciprocal is equal to the sum of <i>n</i> terms (<i>n</i> is the number of complex reaction steps), each of which is the product of a kinetic factor multiplied by a thermodynamic factor. The kinetic factor is the reciprocal apparent kinetic coefficient of the <i>i</i>-th step. The thermodynamic factor is a function of the apparent equilibrium constants of the <i>i</i>-th equilibrium subsystem, which includes the <inline-formula><math display="inline"><semantics><mrow><mo stretchy="false">(</mo><mi>n</mi><mo>−</mo><mn>1</mn><mo stretchy="false">)</mo></mrow></semantics></math></inline-formula> other steps. This kinetico-thermodynamic form separates the kinetic and thermodynamic factors. The result is extended to the case of a buffer substance. It is promising for distinguishing the influence of kinetic and thermodynamic factors in the complex reaction rate. The developed theory is illustrated by examples taken from heterogeneous catalysis.
|
|---|