Kinetic Relationships between Reactions in the Gas Phase and in Solution

Abstract

r) cio2 + 3~0~ -NO,CI t N ? O~

Reactions in the gas and liquid phases: Comparison of kinetic and thermodynamic data

“…The entropies of vaporization of the transition state and reactant are also likely to be nearly equal (as in the general case for Z V B = 0). This implies the near equality of rate coefficients and Arhenius factors for unimolecular reactions in the two phases, and this is supported by experimental evidence that is frequently cited (2,4] and also by recent evidence relating to the isomerization of cyclobutenes [ 181.…”

“…As a contribution to the second of these methods of approach to the problem, we will examine the relationships between kinetic or thermodynamic data for a reaction carried out in the gas and liquid phases. Although such comparisons have been discussed [2,3,4], certain features have not been fully appreciated.…”

Chemical Reaction Dynamics in Solution

“…Literature reviews seem to indicate that this is the case (95,96); an often-quoted example is the dimerization of cyclopentadiene. Literature reviews seem to indicate that this is the case (95,96); an often-quoted example is the dimerization of cyclopentadiene.…”

“…There are very few measurements of ksoln/kgas for atom transfers available for comparison, but those that exist suggest that ksoln/kgas � 10 (95,96). Even fo r a hard-sphere solvent, high density solvent "pressure" effects should stabilize (in free-energy terms) a compact transition state compared to the separated reactants.…”

Radiation‐induced dechlorination of carbon tetrachloride. II. The kinetics of liquid‐phase reactions of trichloromethyl radicals in n‐hexane solutions

“…The equality in E3 values in the gas and liquid phases, which results from the assignment of activation energies of diffusion to Eq values both in n-hexane and c yclohexane, can be understood in terms of the following thermodynamic arguments. The difference between reaction enthalpies of a system whose behavior is thermodynamically ideal in both phases is given [7] by (8) AHOR,, -AH OR,^ = ZAHo,(products) -2AHo,(reactants) where AHOR,, and AH'RJ are reaction enthalpies in the gas and liquid phase, respectively, and AH' , represents heats of vaporization. Consequently the difference between the gas-and liquid-phase activation energies of such a thermodynamically ideal system is given by (a) I t is assumed that reaction (4) is not diffusion controlled.…”