Entropy absolute zero

If the entropy of each element in some crystalline state be taken as zero at the absolute zero of temperature, every substance has a finite positive entropy, but at the absolute zero of temperature the entropy may become zero, and does so become in the case of perfect crystalline substances. 

Figure A2.1.10. The impossibility of reaching absolute zero, a) Both states a and p in complete internal equilibrium. Reversible and irreversible paths (dashed) are shown, b) State P not m internal equilibrium and with residual entropy . The true equilibrium situation for p is shown dotted.

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. 

Deals with the concept of entropy, which serves as a means of determining whether or not a process is possible. Defines the zero entropy state for any substance in a single, pure quantum state as the absolute zero of temperature. 

Thermodynamics is concerned with the relationship between heat energy and work and is based on two general laws, the 1st and 2nd laws of thermodynamics, which both deal with the interconversion of the different forms of energy. The 3rd law states that at the absolute zero of temperature the entropy of a perfect crystal is zero, and thus provides a method of determining absolute entropies. 

Loss of motivity (dissipation of energy) is therefore accompanied by increase of entropy, but the two changes are not wholly co-extensive, because the former is less the lower the temperature T0 of the auxiliary medium, whilst the latter is independent of T0, and depends only on the temperature of the parts of the system. If T0 = 0, i.e., the temperature of the surroundings is absolute zero, there is no loss of motivity, whilst the entropy goes on increasing without limit as the heat is gradually conducted to colder bodies. 

The theorem of Nernst applies only to chemically homogeneous condensed phases the entropy of a condensed solution phase has at absolute zero a finite value, owing to the mutual presence of the different components. 

It may reasonably be assumed that the terms in the expression for the entropy which depend on the temperature diminish, like the entropy of a chemically homogeneous condensed phase, to zero when T approaches zero, and the entropy of a condensed solution phase at absolute zero is equal to that part of the expression for the entropy which is independent of temperature, and depends on the composition (Planck, Thennodynamik, 3 Aufi., 279). 

As with the first and second laws, the Third Law is based on experimental measurements, not deduction. It is easy, however, to rationalize such a law. In a perfectly ordered3 crystal, every atom is in its proper place in the crystal lattice. At T— 0 Kelvin, all molecules are in their lowest energy state. Such a configuration would have perfect order and since entropy is a measure of the disorder in a system, perfect order would result in an entropy of zero.b Thus, the Third Law gives us an absolute reference point and enables us to assign values to S and not just to AS as we have been restricted to do with U, H, A, and G. 

Figure 4.12 Entropy of liquid helium near absolute zero.

G. E. Gibson and W. F. Giauque. "The Third Law of Thermodynamics. Evidence from the Specific Heats of Glycerol that the Entropy of a Glass Exceeds that of a Crystal at the Absolute Zero". J. Am. Chem. Soc.. 45. 93-104 (1923). 

FIGURE 7.11 The experimental determination of entropy, (a) The heat capacity at constant pressure in this instance) of the substance is determined from close to absolute zero up to the temperature of interest, (b) The area under the plot of CP/T against T is determined up to the temperature of interest. 

We may now use Equations 7 and 12 for the vapor pressure of crystal and glass to calculate the change in entropy when we pass from crystal to glass at temperatures near the absolute zero. 

The difference per mole in the entropy of a given substance at the absolute zero in the form of a glass and crystal can be given by an equation of the form SgisLSS — 5crystai = R log a, where a is a small number increasing with the complexity of the molecule. 

The entropy of a perfect crystal at the absolute zero is not dependent on the complexity of the unit of crystal structure. 

We have already stated that some defects are related to the entropy of the solid, and that a perfeet solid would violate the second law of thermodynamics. The 2nd law states that zero entropy is only possible at absolute zero temperature. However, most solids exist at temperatures far above absolute zero. Thus, most of the solids that we eneounter are defeet-solids. The defects are usually "point defeets", which are atomlstie... 

This is an expression of Nernst s postulate which may be stated as the entropy change in a reaction at absolute zero is zero. The above relationships were established on the basis of measurements on reactions involving completely ordered crystalline substances only. Extending Nernst s result, Planck stated that the entropy, S0, of any perfectly ordered crystalline substance at absolute zero should be zero. This is the statement of the third law of thermodynamics. The third law, therefore, provides a means of calculating the absolute value of the entropy of a substance at any temperature. The statement of the third law is confined to pure crystalline solids simply because it has been observed that entropies of solutions and supercooled liquids do not approach a value of zero on being cooled. 

The third law of thermodynamics states that the entropy of a perfect crystal is zero at a temperature of absolute zero. Although this law appears to have limited use for polymer scientists, it is the basis for our understanding of temperature. At absolute zero (-273.14 °C = 0 K), there is no disorder or molecular movement in a perfect crystal. One caveat must be introduced for the purist - there is atomic movement at absolute zero due to vibrational motion across the bonds - a situation mandated by quantum mechanical laws. Any disorder creates a temperature higher than absolute zero in the system under consideration. This is why absolute zero is so hard to reach experimentally ... 

The third law of thermodynamics, one version of which is as a system approaches absolute zero of temperature, all processes cease and the entropy of the system approaches a minimum value , is of little importance for biogenesis. It means that it is impossible to cool a system down to absolute zero (even via an infinite number of steps). 

This means that all substances have some entropy (dispersal of energy and/or matter, i.e. disorder) except when the substance is a pure, perfect, motionless, vibrationless crystal at absolute zero Kelvin. This also implies that the entropy of a substance can be expressed on an absolute basis. 

In a perfect crystal at 0 K all atoms are ordered in a regular uniform way and the translational symmetry is therefore perfect. The entropy is thus zero. In order to become perfectly crystalline at absolute zero, the system in question must be able to explore its entire phase space the system must be in internal thermodynamic equilibrium. Thus the third law of thermodynamics does not apply to substances that are not in internal thermodynamic equilibrium, such as glasses and glassy crystals. Such non-ergodic states do have a finite entropy at the absolute zero, called zero-point entropy or residual entropy at 0 K. 

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