A Course in Statistical Thermodynamics by Joseph Kestin

By Joseph Kestin

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The remaining laws of classical thermodynamics as well as the extremum principles emerge as natural generalizations of the statistical properties of large mechanical systems which are independent of the details of their structure. Beyond this, statistical thermodynamics leads to explicit expressions for the fundamental equation of state of every system whose mechanical model is known in sufficient detail. The first modern successful steps toward the development of statistical thermodynamics were taken by Ludwig Boltzmann (1844-1906), Josiah 29 30 2.

Hence, on the average, the repulsive forces between the particles increase, and thus balance the external force. Even the application of infinite compression does not cause matter to collapse because the repulsive force increases very fast at short range. When tension is applied the average distances between molecules increase and the external force is balanced by the accompanying decrease in the forces of repulsion or increase in the forces of attraction. However, the forces of attraction can only increase as long as the mean distance is less than r{.

It is known from mechanics that this number,/, is independent of the nature of the system of coordinates used for the description. The position of a monatomic molecule in the physical space is described by three independent coordinates, and for this reason the monatomic molecule is said to possess / = 3 degrees of freedom. Polyatomic molecules are assumed to move in a more complex fashion, as already mentioned. 7) degrees of freedom in the same way as a monatomic molecule. Secondly, the molecules perform rotations about axes passing through the center of mass.

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