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Remarks

This lecture has presented three distinct treatment of gas pressure, based respectively on ensemble averaging, thermodynamic manipulation of the partition function, and kinetic theory. All three approaches get the same answer. The third approach, which shows molecules as mobile points that transfer momenta via collisions, is a conventional treatment found in many texts. The second approach illustrates the fundamental links between statistical mechanics and thermodynamics, a theme that will be developed systematically in later chapters. The thermodynamic approach is very powerful, but requires that the partition function is known. The thermodynamic method only lets one determine those variables -- the thermodynamic variables -- that can be obtained from the free energy.

The first approach, not found in most other sources, illustrates the Gibbsian ensemble method in pure form. Unlike the kinetic theory, no reference was made to an elapsed time tex2html_wrap_inline571 . For an equilibrium quantity, no reference to the passage of time should required, because no time-dependent process is involved in an equilibrium quantity. To repeat an analogy proposed above, an ensemble may be viewed as a set of photographs, one of each possible state of the system. To calculate the ensemble average of an equilibrium quantity, it is adequate to examine individual snapshots, and make a calculation on each snapshot. An average over all possible photographs is then taken. In equilibrium calculations one need not inquire as to the dynamics -- the order in which one snapshot follows the next in a ``motion picture'' of the system.

All three approaches to P represent the ``kinetic model of the gas'', the kinetic model having as its primary assumption that the gas Hamiltonian depends only on kinetic energies and on the gas-wall potential. Each approach uses the same physical model for the system. The approaches differ in their lines of attack. Since Section 6.1 obtained P from a series of static pictures (Fig. 6.1) of atoms near walls, no atomic motion being exhibited during the calculation, why does the description of Section 6.1 merit the apellation ``kinetic model''? The answer is that the kinetic model of the ideal gas should be understood as the antithesis of the ``static model of the ideal gas'', in which nearly immobile gas atoms interact via a short-range springlike repulsive interaction. In a statistical-mechanical treatment of the errorneous static theory of gasses, the energy of the system would be dominated by harmonic potentials (with extremely large equilibrium lengths) between nearby gas molecules The static model of the gas had peak acceptance in the early tex2html_wrap_inline895 century, but is now nearly forgotten.


next up previous
Next: Problems Up: Chapter 6 Previous: P from the kinetic theory

Nicholas V Sushkin
Sun Jun 30 15:18:58 EDT 1996