Journal of Physical Chemistry A, Vol.102, No.45, 8860-8864, 1998
Temperatures of the maximum reaction rate and their relation to the equilibrium temperatures
This paper derives the relationship between the temperatures of maximum reaction rate and the equilibrium temperatures for exothermic reactions. For a reversible reaction described by Arrhenius type rate coefficients the relation is found to be (1/T-r,T- max) - (1/T-eq) (R/(E-2 - E-1)) ln(E-2/E-1), where R is the gas constant and E-1 and E-2 are the activation energies of the forward and backward reaction. The result implies that the operating Line of the maximum reaction rate will be parallel to the equilibrium line in a 1/T versus conversion diagram when the activation energies (or enthalpy change of reaction) are constant. For systems with constant pressure, the constant distance between the two curves is then equivalent to a constant driving force of the reaction, Delta G/T. Thus, we have shown that a recently developed principle for an energy efficient process design, called equipartition of forces, can be applied also near the maximum reaction rate for elementary, exothermic reactions with Arrhenius' type kinetics at constant pressure.
Keywords:OPTIMIZATION