Solvent Effects on Gas-Phase Reaction Rates

Effect of Pressure on Gas-Phase Reaction Rate Coefficients. Decomposition of Hydrogen Iodide

“…correlated the experimental rate data for the HI decomposition well. These values of critical properties are in good agreement with the values based on the molecular structure discussed by Mills and Eckert (1968) for the transition state complex.…”

Solvent Design for Chemical Reactions

“…The applicability of Equation 3 was first demonstrated in the study of ionic reactions in dilute aqueous solutions using the Debye-Hückel treatment. It has been applied to gas-phase reactions (Eckert and Boudart, 1963;Mills and Eckert, 1968) in terms of valid equations of state. For liquid-phase reactions a number of different approaches can be used (Eckert, 1967) for obtaining the activity coefficients in Equation 3-various expressions for excess Gibbs energies of mixtures-or when available, experimental data are preferable.…”

Ionic Recation Design. Solvent and Salt Effects

“…(2) Although Brfinsted and Bjerrum originally developed Equation 2 for application to ionic reactions in very dilute solution, using the theory of Debye and Htickel (1923) to calculate y, recent applications of the theory to solvent design have been primarily for nonionic reactions. It was applied to gas-phase reactions (Mills and Eckert, 1968), and by the use of regular solution theory Scott, 1962, 1964), to nonpolar reactions in solution (Glasstone et al, 1941;Wong and Eckert, 1969). The Kirkwood (1934) approach for predicting activities of polar molecules has been used often for nonionic but polar reactions-some recent examples of this are given by Hartmann et al (1965) and Heydtmann et al (1966).…”