Qualitatively, entropy is simple. What it is, why it is useful in understanding the behavior of macro systems or of molecular systems is easy to state: Entropy increase from a macro viewpoint is a measure of the dispersal of energy from localized to spread out at a temperature T. The conventional q in q
rev/T is the energy dispersed to or from a substance or a system. On a molecular basis, entropy increase means that a system changes from having fewer accessible microstates to having a larger number of accessible microstates. Fundamentally based on statistical and quantum mechanics, this approach is superior to the non-fundamental "disorder" as a descriptor of entropy change.The foregoing in no way denies the subtlety or the difficulty presented by entropy in thermodynamics—to first-year students or to professionals. However, as an aid to beginners in their quantitative study of thermodynamics, the qualitative conclusions in this article give students the advantage of a clear bird’s-eye view of why entropy increases in a wide variety of basic cases: a substance going from 0 K to T, phase change, gas expansion, mixing of ideal gases or liquids, colligative effects, and the Gibbs equation.
Entropy change is categorized in some prominent general chemistry textbooks as being either positional (configurational) or thermal. In those texts, the accompanying emphasis on the dispersal of matter—independent of energy considerations and thus in discord with kinetic molecular theory—is most troubling. This article shows that the variants of entropy can be treated from a unified viewpoint and argues that to decrease students' confusion about the nature of entropy change these variants of entropy should be merged. Molecular energy dispersal in space is implicit but unfortunately tacit in the cell models of statistical mechanics that develop the configurational entropy change in gas expansion, fluids mixing, or the addition of a non-volatile solute to a solvent. Two factors are necessary for entropy change in chemistry. An increase in thermodynamic entropy is enabled in a process by the motional energy of molecules (that, in chemical reactions, can arise from the energy released from a bond energy change). However, entropy increase is only actualized if the process results in a larger number of arrangements for the system's energy, that is, a final state that involves the most probable distribution for that energy under the new constraints. Positional entropy should be eliminated from general chemistry instruction and, especially benefiting "concrete minded" students, it should be replaced by emphasis on the motional energy of molecules as enabling entropy change.
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