In the book Physical Chemistry, a Molecular Approach by Simon and McQuarrie, the have used the Maxwell–Boltzmann distribution for velocity of molecules to estimate the the rate constant of a reaction. However, the distribution is valid only for systems in equilibrium, so, how is this approach justifiable?

Snapshot of the derivation

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    $\begingroup$ Equilibrium does not exclude reactants from being converted to products, and vice versa. It just means that there is a steady state or balance between forward and reverse processes. $\endgroup$ – Night Writer Feb 7 at 14:34
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    $\begingroup$ Also implied is that the Boltzmann distribution is not affected by the reaction, i.e. even though reaction may occur ever so rapidly the 'system' or 'heat' bath' always provides energy to restore the distribution. $\endgroup$ – porphyrin Feb 7 at 15:39

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