Abstract

It is commonly asserted that entropy tends towards a maximum at equilibrium in isolated systems. But entropy is only defined in equilibrium states, so in an isolated system the entropy is constant, if it is defined at all. The solution to this paradox is the existence of metastable equilibrium states, so common in mineralogy and petrology. Consideration of such states in a thermodynamic context also involves the concept of constraints and of the affinity, and because the affinity is a measure of the change in Gibbs energy in spontaneous reactions involving metastable phases, the entropy paradox and the overstepping of reactions in metamorphic rocks are closely related subjects.

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