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Chemical Thermodynamics by J. Rajaram

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Chapter 7

Statistical Thermodynamics

7.a.  The Statistical Method

In thermodynamics the equilibrium properties of macroscopic systems are defined in terms of observable parameters like pressure, volume, etc. These properties can be experimentally determined by suitable measurements on macroscopic systems. However, the observable properties of a macroscopic system (the properties of the total bulk or bulk properties) are the result of the contributions of its microscopic constituents, atoms, molecules or ions.

It should be possible to calculate macroscopic properties of a system from a suitable summation of the properties of microscopic constituents. This is precisely the aim of statistical mechanics. Statistical thermodynamics is concerned with ...

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