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Relation to thermodynamic entropy

In thermodynamics, the change in entropy in a reversible process which transforms the system from state 1 to state 2 is

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where tex2html_wrap_inline607 is the heat absorbed in the process. We can now ask if the entropy obtained starting from the microscopic description agrees with the standard thermodynamic definition. We will consider two types of processes as described below:

I.
Isothermal expansion/compression of the system from volume, tex2html_wrap_inline609 to tex2html_wrap_inline611 . In an isothermal process, the temperature, T, does not change. Thus, the entropy relation can be integrated immediately to yield

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where tex2html_wrap_inline615 is the heat absorbed as the state changes from 1 to 2. Now, from the first law of thermodynamics, the change in total internal energy of the system is

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where tex2html_wrap_inline617 is the work done on the system. Since, for the ideal gas,

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and tex2html_wrap_inline619 , tex2html_wrap_inline621 and

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The expansion/compression of the system gives rise to a change in pressure such that tex2html_wrap_inline623 , where P(V) = NkT/V, is given by the equation of state (ideal gas law). Thus, the total work done on the system is

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Thus,

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and

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If we now use the statistical definition of entropy

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the change in entropy is

eqnarray245

where tex2html_wrap_inline627 . Thus, we see that the two agree exactly.

II.
Isochoric heating/cooling from temperature tex2html_wrap_inline629 to tex2html_wrap_inline631 . In an isochoric process, the volume remains constant. Hence,

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and, from the first law,

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However, for the ideal gas

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Thus, the change in entropy is

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From the statistical definition:

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which agrees exactly with the thermodynamic entropy change.

These two examples illustrate that the statistical approach agrees exactly with the standard thermodynamic definition of entropy.



Mark Tuckerman
Thu Feb 20 00:47:55 EST 2003