By Michel Boudart
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Extra resources for Kinetics of Chemical Processes
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Sec. 4 Thermodynamic Formulation of Rates Thermodynamic Rates 41 Formulation of As a consequence of the fundamental assumption of equilibrium, everything happens as if transition states Z at concentration cz were in equilibrium with reactants A and B for an elementary step A + B —» Products. 2) where R is the gas constant, AGot is the change in standard Gibbs free energy for the reaction A + B —> Z while AHoi and Δ^* are the corresponding changes in standard enthalpy and standard entropy. The superscript 0 is used to denote standard states while superscript * denotes quantities pertaining to the formation of the transition state considered as a molecular species which is assumed to possess normal thermodynamic properties.
T h e transition state AB does not possess any vibrational entropy since its only vibrational mode is missing and, as remarked above, has been replaced by a translation along the collision coordinate. (Fig. 1). 1 Collision between two hard spheres A and B. 44 Chemical Kinetics of Elementary Steps Chap. 15) The second part of the problem now consists in the evaluation of the enthalpy of formation of AB from A and B. Since the system is a mixture of perfect gases, designation of a standard state for the enthalpy is superfluous so that superscripts zero can be omitted.
Changes of volume accompanying the reaction are negligible. 3 Consider a rate function of the form : dt W h a t is the relation between the second-order rate constant k and the half-life tll2? 4 Stirring gases is inconvenient and ineflicient at any scale. For the study of gas phase reactions catalyzed at the surface of a solid, the mechanical problem of setting u p a gas-solid stirred-flow reactor is a difficult one. If, however, a recirculation p u m p for gases is available, a stirred-flow reactor can be built readily for measuring the rate of a reaction catalyzed by a solid.