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Although it is commonly omitted from undergraduate physical chemistry texts, the thermodynamics of mixing real gases can be approached in the same way as that of mixing ideal gases. This is done for mixtures of slightly imperfect gases, which are defined by a truncated virial equation of state Z = 1 + Bp/RT. An expression for the Gibbs energy of mixing is the fundamental result and, from this, expressions for excess entropy, enthalpy, and volume easily follow. Predicted variations in these excess thermodynamic functions with composition, temperature, and pressure are discussed in comparison with experimental data for binary systems that range from nearly to far from ideal. The excess second virial coefficient, which has both microscopic and macroscopic significance, is key to understanding slightly imperfect gas mixtures.
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