Apparent Reaction Kinetics 49 which has the interesting property of approaching infinity as the magnitudes of r, and ry become the same. Physically this means an explosion, so r, = ry defines an explosion limit for the branching chain reaction. The branching chain theory has been used to interpret explosions in the low-pressure region for reactions such as HO, and CO-O;. This sort of explosion is different from the normal thermal explosion in which the heat evolved in a reaction cannot be removed from the system, leading to increasing temperatures, rates of reaction, heat evolution, noise, and a puff of greasy blue smoke. After you finish Chapter 3 come back here and show me how the chain-growth polymerization and the Fischer-Tropsch synthesis add up to about the same in terms of product distribution 1.7 Chemical Equilibrium The logical joining point between the study of chemical kinetics and chemical ther- modynamics is the point, in an elementary step, where the rate of the forward reaction is equal to the rate of the reverse reaction. This is the point of chemical equilibrium and is implied in the relationships of equations (1-22) and (1-23). While we cannot conduct a short course here on the thermodynamics of chemical equili- brium, some review will be useful. The reader may also wish to refer to a favorite text on thermodynamics for amplification of our condensed presentation. 171 Equi ium in Single-Phase Systems The criterion for chemical equilibrium in a single-phase, single-reaction system is stated in terms of the minimization of the free energy of the system. In terms of the reaction, then Loe, (1-138) where v; are the stoichiometric coefficients written in the same way as for equation (1-49), positive for products and negative for reactants, and G; are partial molar free energies. Following Sandler (8.1. Sandler, Chemical Engineering Thermodynamics, John Wiley, New York, 1989), let us follow the development for a typical reaction CO; + Hy + CO+H0 occurring in a closed system (in the thermodynamic sense) at constant pressure and some suitable temperature. If the pressure is low enough to permit the assumption of