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- W2093296782 abstract "In the study of chemical kinetics, great importance attaches to the manner in which the velocity coefficient, k , varies with the temperature, T . Their relation is generally expressed by the differential equation ( d ln k )/ dT = E A / RT 2 , (1) where E A is now by common consent referred to as the apparent energy of activation. Integrating on the assumption that E A is a constant, independent of temperature, we obtain the well-known equation of Arrhenius, In k = B - E A / RT . (2) Having regard to the accuracy usually ascribable to experimental velocity coefficients, the assumption is a valid one. In recent years, however, precise work on certain selected reactions has shown that the supposition is ill founded. The newer data are in better agreement with the differential equation ( d ln k )/ dT = E / RT 2 + J / RT . (3) Integrating on the assumption that E and J are independent of temperature, we have the more general relation In k = C + ( J/R )ln T - E/RT , (4) which reduces to the simpler formula when J is zero. This equation, though not wholly satisfactory, is to be regarded as an improvement on equation (2) because (1) it is in better accordance with experiment, and (2) it is not restricted to systems wherein the average energy of reactive molecules and the average energy of normal molecules respond identically to temperature. Very few reactions have been examined with sufficient precision to allow of an evaluation of the constants in equation (4), and it is with the object of increasing their number that the present investigation was undertaken." @default.
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- W2093296782 date "1940-03-28" @default.
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- W2093296782 title "The kinetics of decarboxylation in solution" @default.
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- W2093296782 doi "https://doi.org/10.1098/rspa.1940.0048" @default.
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