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Is mixing a thermodynamic process?

 

作者: A. Ben‐Naim,  

 

期刊: American Journal of Physics  (AIP Available online 1987)
卷期: Volume 55, issue 8  

页码: 725-733

 

ISSN:0002-9505

 

年代: 1987

 

DOI:10.1119/1.15064

 

出版商: American Association of Physics Teachers

 

关键词: THERMODYNAMICS;MIXING;ENTROPY;FREE ENERGY;IRREVERSIBLE PROCESSES;CHEMICAL POTENTIAL;STATISTICAL MECHANICS;GASES

 

数据来源: AIP

 

摘要:

Mixing processes exist with positive entropy change and negative free energy change. However, the idea that theirreversibilityof the mixing processes is responsible for the so‐called free energy and entropy of mixing is faulty. The mixing, as well as the demixing processes may be associated with either reversible or irreversible phenomena, depending on the particular conditions. For ideal gases, the word ‘‘mixing’’ in the terms ‘‘mixing entropy’’ and ‘‘mixing free energy’’ may sometimes be useddescriptivelybut nevercausatively. The quantity −∑NiR ln Xi, usually referred to as ‘‘mixing entropy,’’ has nothing to do with the mixing phenomenon. Therefore the terms ‘‘mixing entropy’’ and ‘‘mixing free energy’’ are essentially misconceptions. In fact, it is shown that the process of mixing of ideal gases has, by itself, no relevance to any thermodynamic quantity. Therefore, in a thermodynamical sense, it is a nonprocess. The concepts of assimilation and deassimilation are introduced. It is shown that the ‘‘deassimilation process is essentially irreversible.’’ This should replace the traditional principle that ‘‘the mixing process is essentially irreversible.’’

 

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