Statistical entropy interpretation

The principle of tire unattainability of absolute zero in no way limits one s ingenuity in trying to obtain lower and lower thennodynamic temperatures. The third law, in its statistical interpretation, essentially asserts that the ground quantum level of a system is ultimately non-degenerate, that some energy difference As must exist between states, so that at equilibrium at 0 K the system is certainly in that non-degenerate ground state with zero entropy. However, the As may be very small and temperatures of the order of As/Zr (where k is the Boltzmaim constant, the gas constant per molecule) may be obtainable. 

MSN.74. I. Prigogine, The statistical interpretation of nonequilibrium entropy, Acta Phys. Austriaca, Suppl. X, 401 50 (1973). 

Next, we review findings of educational research about the main areas of physical chemistry. Most of the work done was in the areas of basic thermodynamics and electrochemistry, and some work on quantum chemistry. Other areas, such as chemical kinetics, statistical thermodynamics, and spectroscopy, have not so far received attention (although the statistical interpretation of entropy is treated in studies on the concepts of thermodynamics). Because many of the basics of physical chemistry are included in first-year general and inorganic courses (and some even in senior high school), many of the investigations have been carried out at these levels. 

Entropy is interpreted as the number of microscopic arrangements included in the macroscopic definition of a system. The second law is then used to derive the distribution of molecules and systems over their states. This allows macroscopic state functions to be calculated from microscopic states by statistical methods. 

If we attempt to interpret the observations with regard to residual entropy in Frame 16, section 16.4 and those features that are not entirely in accord with the Third Law, we see that equation (17.1) represents a statistical interpretation of entropy which gives a reasonable account of these departures from the Third Law as well as giving an entirely consistent account of the Third Law itself. 

If we restrict ourselves to time intervals which are experimentally realizable, the statistical interpretation is equivalent to the requirement that the entropy of an isolated gas quantum should always increase.153 Beyond that, however, one can in fact defend two opposite points of view. 

Classical thermodynamics is based on a description of matter through such macroscopic properties as temperature and pressure. However, these properties are manifestations of the behavior of the countless microscopic particles, such as molecules, that make up a finite system. Evidently, one must seek an understanding of the fundamental nature of entropy in a microscopic description of matter. Because of the enormous number of particles contained in any system of interest, such a description must necessarily be statistical in nature. We present here a very brief indication of the statistical interpretation of entropy, t... 

Krug, R. R., W. G. Hunter, and R. A. Grieger, Statistical interpretation of enthalpy-entropy compensation. Nature, 261, 566-567 (1976). 

A comparison of expression (54) with the statistical interpretation of the adsorbate entropy provides additional insight to the significance of the different terms in this equation. The total partition function adsorbed molecules where M > N is (5, 8)... 

Provide a statistical interpretation of the change in entropy that occurs when a gas undergoes a volume change (Section 13.2, Problems 3-10). 

The third law of thermodynamics lacks the generality of the other laws, since it applies only to a special class of substances, namely pure, crystalline substances, and not to all substances. In spite of this restriction the third law is extremely useful. The reasons for exceptions to the law can be better understood after we have discussed the statistical interpretation of the entropy the entire matter of exceptions to the third law will be deferred until then. 

If the energy of the system is increased, the distribution can be broader the number of complexions and the entropy of the system goes up. This is a statistical interpretation of the fact illustrated by the fundamental equation (9.12) ... 

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