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Example · Example 4

Q.Explain why the rate of most chemical reactions increases sharply with even a modest rise in temperature, although the average kinetic energy of the molecules rises only slightly over the same temperature range.

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Molecular kinetic energies in a sample are not all identical but are spread over a range described by the Maxwell-Boltzmann distribution. Only molecules whose energy exceeds the activation energy threshold, EaE_a, can react upon a suitably oriented collision. Raising the temperature shifts the whole energy distribution only slightly, since average kinetic energy is proportional to TT; but because the fraction of molecules above a fixed high threshold EaE_a is given by the exponential Boltzmann factor e−Ea/RTe^{-E_a/RT}, a small increase in TT can produce a disproportionately large increase in this fraction -- the high-energy 'tail' of the distribution that lies above EaE_a grows much faster than the distribution's average shifts. It is this exponential growth in the population of sufficiently energetic (and hence reaction-capable) molecules, not any large change in the bulk ave …

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