Transcription of thermodynamics 2: applications - USTC
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thermodynamics 2: applications - USTC
Statisticalthermodynamics 2:applicationsIn this chapter we apply the concepts of statistical thermodynamics to the calculation ofchemically significant quantities. First, we establish the relations between thermodynamicfunctions and partition functions. Next, we show that the molecular partition function can befactorized into contributions from each mode of motion and establish the formulas for thepartition functions for translational, rotational, and vibrational modes of motion and the con-tribution of electronic excitation. These contributions can be calculated from spectroscopicdata. Finally, we turn to specific applications , which include the mean energies of modes ofmotion, the heat capacities of substances, and residual entropies.
590 17 STATISTICAL THERMODYNAMICS 2: APPLICATIONS (a) The Helmholtz energy The Helmholtz energy, A, is defined as A =U −TS.This relation implies that A(0) = U(0), so substitution for U and S by using eqn 17.1 leads to the very simple expression A −A(0) =−kT ln Q (17.2) (b) The pressure By an argument like that leading to eqn 3.31, it follows from A = U − TS …
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