The Third Law of Thermodynamics and Absolute Entropies

Finally, we calculate the change in entropy for cooling the vapor from 100°C to 25°C (usingeqn2.2again,butnowwithdatafor the vapor from Table 1.1)  

This enormously important expression will lie at the heart of our discussion of bioenergetics and the structural consequences of the Second Law. We see that it is consistent with common sense if the process is exothermic, AH is negative and therefore ASjur is positive. The entropy of the surroundings increases if heat is released into them. If the process is endothermic (AH 0), then the entropy of the surroundings decreases. 

The enthalpy of vaporization of water at 20°C is 44 kj mol . When 10 cm of water (corresponding to 10 g or 0.55 mol HjO) in an open vessel evaporates at that temperature, the change in entropy of the surroundings is 

The entropy of the surroundings decreases because heat flows out of them into the water. 

To calculate the entropy changes associated with bioiogicai processes, we need to see how to compile tables that list the values of the entropies of substances. 

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The symbol 9 is called the characteristic temperamre and can be calculated from an experimental determination of the heat capacity at a low temperature. This equation has been very useful in the extrapolation of measured heat capacities [16] down to OK, particularly in connection with calculations of entropies from the third law of thermodynamics (see Chapter 11). Strictly speaking, the Debye equation was derived only for an isotropic elementary substance nevertheless, it is applicable to most compounds, particularly in the region close to absolute zero [17]. 

The third law of thermodynamics states that the entropy of any crystalline, perfectly ordered substance must approach zero as the temperature approaches 0 K, and at T = 0 K entropy is exactly zero. Based on this, it is possible to establish a quantitative, absolute entropy scale for any substance as... 

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). 

The third law of thermodynamics establishes a starting point for entropies. At 0 K, any pure perfect crystal is completely constrained and has S = 0 J / K. At any higher temperature, the substance has a positive entropy that depends on the conditions. The molar entropies of many pure substances have been measured at standard thermodynamic conditions, P ° = 1 bar. The same thermodynamic tables that list standard enthalpies of formation usually also list standard molar entropies, designated S °, fbr T — 298 K. Table 14-2 lists representative values of S to give you an idea of the magnitudes of absolute entropies. Appendix D contains a more extensive list. 

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, 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). 

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. 

Statistical mechanics affords an accurate method to evaluate ArSP, provided that the necessary structural and spectroscopic parameters (moments of inertia, vibrational frequencies, electronic levels, and degeneracies) are known [1], As this computation implicitly assumes that the entropy of a perfect crystal is zero at the absolute zero, and this is one of the statements of the third law of thermodynamics, the procedure is called the third law method. 

Lewis and Gibson [3] also emphasized the positive entropy of solutions at 0 K and pointed out that supercooled liquids, such as glasses, even when composed of a single element (such as sulfur), probably retain a positive entropy as the temperamre approaches absolute zero. For these reasons Lewis and Randall [4] proposed the following statement of the third law of thermodynamics ... 

It is more problematical to define the third law of thermodynamics compared to the first and second laws. Experimental work by Richards (1902) and Nemst (1906) led Nemst to postulate that, as the temperature approached absolute zero, the entropy of the system would also approach zero. This led to a definition for the third law of thermodynamics that at a temperature of absolute zero the entropy of a condensed system would also be zero. This was further refined by Planck (1911) who suggested this be reworded as the entropy of a pure element or substance in a perfect crystalline form is zero at absolute zero. 

The third law of thermodynamics states that, for a perfect crystal at absolute zero temperature, the value of entropy is zero. The entropy of a molecule at other temperatures can be computed from the heat capacities and heats of phase changes using... 

So far, we have been able to calculate only changes in the entropy of a substance. Can we determine the absolute value of the entropy of a substance We have seen that it is not possible to determine absolute values of the enthalpy. However, entropy is a measure of disorder, and it is possible to imagine a perfectly orderly state of matter with no disorder at all, corresponding to zero entropy an absolute zero of entropy. This idea is summarized by the third law of thermodynamics ... 

The third law of thermodynamics, by which absolute values of the entropy can be determined, permits the calculation of the change of values of the Gibbs and Helmholtz energies with temperature. This subject is discussed in Chapter 15. 

The energy and entropy functions have been defined in terms of differential quantities, with the result that the absolute values could not be known. We have used the difference in the values of the thermodynamic functions between two states and, in determining these differences, the process of integration between limits has been used. In so doing we have avoided the use or requirement of integration constants. The many studies concerning the possible determination of these constants have culminated in the third law of thermodynamics. 

The Third Law of Thermodynamics postulates that the entropy of a perfect crystal is zero at 0 K. Given the heat capacity and the enthalpies of phase changes, Eq. (12-3) allows the calculation of the standard absolute entropy of a substance, S° = AS for the increase in temperature from 0 K to 298 K. Some absolute entropies for substances in thermodynamic standard states are listed in Table 12-1. 

Equation (16-2) allows the calculations of changes in the entropy of a substance, specifically by measuring the heat capacities at different temperatures and the enthalpies of phase changes. If the absolute value of the entropy were known at any one temperature, the measurements of changes in entropy in going from that temperature to another temperature would allow the determination of the absolute value of the entropy at the other temperature. The third law of thermodynamics provides the basis for establishing absolute entropies. The law states that the entropy of any perfect crystal is zero (0) at the temperature of absolute zero (OK or -273.15°C). This is understandable in terms of the molecular interpretation of entropy. In a perfect crystal, every atom is fixed in position, and, at absolute zero, every form of internal energy (such as atomic vibrations) has its lowest possible value. 

Figure 3.6 shows schematically the molar entropy of a pure substance as a function of temperature. If a structural transformation occurs in the solid state, an additional increase in the molar entropy comes from the heat of the transformations. As shown in the figure, the molar entropy of a pure substance increases with increasing temperature. In chemical handbooks we see the tabulated numerical values of the molar entropy calculated for a number of pure substances in the standard state at temperature 298 K and pressure 101.3 kPa. A few of them will be listed as the standard molar entropy, s , in Table 5.1. Note that the molar entropy thus calculated based on the third law of thermodynamics is occasionally called absolute entropy. 

Normally, the coefficient of thermal expansion a of a solid approaches a certain constant value at high temperatures and falls steeply as the temperature is lowered. This follows from (dV/dT)p = (dS/dp)T obtained by the differentiation of Vand -S in Eq. 3.37. The third law of thermodynamics assumes that the entropy S falls toward zero as the temperature approaches zero in the absolute temperature scale, and hence both (dSfdp)T and (dV/dT)p must be close to zero at sufficiently low temperatures. 

Temperature relates heat to entropy. As a body is heated and raised to a higher temperature, its particles move more violently, as in boiling water, and there is more disorder, more entropy. Conversely, as a body is cooled, temperature and entropy both decrease. There is a theoretical minimum temperature, — 273°C, known as absolute zero, where the parts (e.g., atoms) of a body are at perfect rest and perfectly ordered, so that entropy is at its theoretical minimum. The third law of thermodynamics states that as a body is cooled and approaches absolute zero, the further extraction of heat (energy) becomes harder and harder, so that however close one gets, it is impossible to reach absolute... 

The hydration entropy can also be deduced experimentally (Latimer 18) as the difference between the standard entropy of the hydrated ions (deduced from measurements of the specific heat on the basis of Nernst s Heat Theorem or the Third Law of Thermodynamics) and the theoretically calculated absolute entropy of the gaseous ion, both reckoned per unit volume at constant concentration. This entropy can also be calculated (Eley and Evans18). 

At absolute zero all the thermal motions of the atoms of the lattice of a crystal will have ceased and the solid will have no disorder and hence a zero entropy. This conclusion forms the basis of the third law of thermodynamics, which states that the entropy of a perfectly crystalline material is zero when T = 0. 

The third law of thermodynamics states that the entropy of any pure substance in equilibrium approaches zero at the absolute zero of temperature. Consequently, the entropy of every pure substance has a fixed value at each temperature and pressure, which can be calculated by starting with the low-temperature values and adding the results of all phase transitions that occur at intervening temperatures. This leads to tabulations of standard molar entropy S° at 298.15 K and 1 atm pressure, which can be used to calculate entropy changes for chemical reactions in which the reactants and products are in these standard states. 

The unattainabiiity formulation of the Third Law of Thermodynamics is briefly reviewed in Sect. 2.1. It puts limitations of the quest for absolute zero, and in its strongest mode forbids the attainment of absolute zero by any method whatsoever. But typically it is stated principally with respect to thermal-entropy-reduction refrigeration (TSRR). TSRR entails reduction of a refrigerated system s thermal entropy, i.e., its localization in the momentum part of phase space (in momentum space for short). The possibility or impossibility of overcoming these limitations via TSRR is considered, in Sects. 2.2. and 2.3. with respect to standard TSRR, and in Sect. 2.4. with respect to absorption TSRR. (In standard TSRR, refrigeration is achieved at the expense of work input in absorption TSRR, at the expense of high-temperature heat input.)... 

The third law of thermodynamics assigns by convention a zero entropy value to any pure substance (either an element or a compound) at absolute zero and in internal equilibrium. At absolute zero, atoms have very little motion. Absolute zero temperature is unattainable. 

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