Rate constant, variation

Reaction Reaction number Rate constant Variation in odd oxygen... 

M 1s 1 versus 0.037 M 1s 1 at 30C), but the measured rate constant varies somewhat from experiment to experiment. Considering the slowness of this proton transfer, the rate constant variation may reflect varying degrees of adventitious catalysis. 

Therefore the rate constant variation with pressure is given by... 

Several theoretical treatments have shown that in Eq. (1) should be an inverse function of the solvent relaxation time (usually the longitudinal relaxation time, tl e.g., see Refs. 16, 18, 24, and 25). This becomes especially important when Areorg is mostly (or entirely) a function of solvent contributions. The significance of the inferred contributions of Tl to I nu in regard to material in this section, is that the condition < 1 implies v x < 2i nu, so that variations in Tl should be inversely correlated with rate constant variations only for adiabatic... 

The arrangement of Chapters 1 to 5 of this Part of this Report by type of compound results in a dispersal of references dealing with the role of the solvent. To remedy this, some of these references have been collected together here, both to illustrate current approaches to determining the role of solvents in inorganic reaction mechanisms and the use of rate-constant variation with solvent composition trends as diagnostic tools. 

Examine the convergence of the computed rate constant at a series of pressures as the number of reactive grains is increased, and confirm that about 10-15 equally spaced grains are adequate. By a separate (hand ) calculation show that if only one grain is used, the rate constant variation with pressure is strict Lindemann. 

The importance of developing an appropriate theory became increasingly evident. Although theory only provides relatively inaccurate rate constants, it nevertheless predicts the range of the rate constant variation and/or its temperature dependence. This is often very helpful in the elucidation of the reaction mechanism. Equally important was the development of experimental methods of creating highly non-equilibrium conditions such as the shock tube technique, flash photolysis and various kinds of chemical activation. 

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