American Chemical Society, Journal of Chemical Education, 12(90), p. 1639-1644, 2013
DOI: 10.1021/ed300886j
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The dependence on the temperature of the population of the ith state, P-i, in the Boltzmann distribution is analyzed by studying its derivative with respect to the temperature, T. A simple expression is found, involving P-i, the energy of the state, E-i, and the average energy, < E >. This relation is completely general (it has the same form in all the thermodynamic ensembles), and it has a relevant didactic content, given that it predicts the qualitative variation of P-i with T even in complex systems. The derivation of this relation, the discussion of its properties, and its application to simple problems is appropriate for a statistical thermodynamics course in the chemistry curriculum.