Constrained entropy

This is a law about the equilibrium state, when macroscopic change has ceased it is the state, according to the law, of maximum entropy. It is not really a law about nonequilibrium per se, not in any quantitative sense, although the law does introduce the notion of a nonequilibrium state constrained with respect to structure. By implication, entropy is perfectly well defined in such a nonequilibrium macrostate (otherwise, how could it increase ), and this constrained entropy is less than the equilibrium entropy. Entropy itself is left undefined by the Second Law, and it was only later that Boltzmann provided the physical interpretation of entropy as the number of molecular configurations in a macrostate. This gave birth to his probability distribution and hence to equilibrium statistical mechanics. 

The equilibrium state, which is denoted x, is by definition both the most likely state, p(x E) > p(x E), and the state of maximum constrained entropy, iS,(T (x /ij > iS 0(x j. This is the statistical mechanical justification for much of the import of the Second Law of Equilibrium Thermodynamics. The unconstrained entropy, as a sum of positive terms, is strictly greater than the maximal constrained entropy, which is the largest term, S HE) >. S(1 (x j. However, in the thermodynamic limit when fluctuations are relatively negligible, these may be equated with relatively little error, S HE) . S(1 (x j. 

The remaining condition for the constrained entropy to be a maximum is that the second derivatives of S must all be negative ... 

Let us now attempt to re-express the Gibbs criterion of equilibrium in alternative analytical and graphical forms that are more closely related to Clausius-like statements of the second law. For this purpose, we write the constrained entropy function S in terms of its... 

The essential feature of isolation constraints is constancy with respect to any form of energy exchange, which can be denoted by subscript U. The variations of constrained entropy Su with respect to variations of X about an equilibrium position Xeq are schematically depicted in the Su X diagram of Fig. 5.1a. As shown in the diagram, Su is a... 

Figure 5.1 Schematic plots of (a) constrained entropy Sjj and (b) unconstrained entropy S as functions of a general extensive property X near equilibrium, Xeq. In each case, the negative curvature of the entropy function (constrained or unconstrained) carries it below its equilibrium tangent (dashed line).

Briscoe WH, Attard P (2002) Counterion-only electric double layer a constrained entropy approach. J Chem Phys 117 5452-5464... 

W. H. Briscoe and P. Attard, J. Chem. Phys., 117, 5452 (2002). Counterion-Only Electrical Double Layer A Constrained Entropy Approach. 

The actual amount and stmcture of this "bound" water has been the subject of debate (83), but the key factor is that in water, PVP and related polymers are water stmcture organi2ers, which is a lower entropy situation (84). Therefore, it is not unexpected that water would play a significant role in the homopolymeri2ation of VP, because the polymer and its reactive terminus are more rigidly constrained in this solvent and termination k is reduced... 

Keck, J. C. (1978). Rate-controlled constrained equilibrium method for treating reactions in complex systems. In Maximum Entropy Formalism" (R. D. Levine and M. Tribus, eds). M.I.T. Press, Cambridge, MA. 

If peptide residues are converted to peptoid residues, the conformational heterogeneity of the polymer backbone is likely to increase due to cis/trans isomerization at amide bonds. This will lead to an enhanced loss of conformational entropy upon peptoid/protein association, which could adversely affect binding thermodynamics. A potential solution is the judicious placement of bulky peptoid side chains that constrain backbone dihedral angles. 

The details of the derivation are complicated, but the essence of this equation is that the more possible descriptions the system has, the greater is its entropy. The equation states that entropy increases in proportion to the natural logarithm of W, the proportionality being given by the Boltzmann constant, k — 1.3 806 x lO V/r. Equation also establishes a starting point for entropy. If there is only one way to describe the system, it is fully constrained and W — 1. Because ln(l)=0,S = 0 when W — 1. 

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. 

One important feature not revealed directly by Table 14-2 is that binding atoms into molecules always constrains the atoms and reduces total entropy. As illustrated in Figure 14-13. a sample containing 2 mol He has considerably more entropy (252 J/K) than 1 mol H2 (131 J/K), even though both samples contain the same total number of... 

The substance in the more constrained phase has the lower entropy. For substances that are otherwise similar, liquid S gas. ... 

The decomposition of N2 O4 requires a bond to break. This is the reason why the decomposition has a positive A 77 °. At the same time, the number of molecules doubles during decomposition, which is the reason AS° has a positive value. The positive enthalpy change means that energy Is removed from the surroundings and constrained, whereas the positive entropy change means that matter is dispersed. At temperatures below 315 K, the enthalpy term dominates and decomposition is not spontaneous, but at temperatures above 315 K, the entropy term dominates and decomposition is spontaneous. 

By the same reasoning, a negative AS ° and a positive AH ° oppose spontaneity, so a reaction in which the system becomes constrained and energy is absorbed is nonspontaneous regardless of temperature. The system and its surroundings both would experience decreases in entropy if such a process were to occur, and this would violate the second law of thermod3mamics. 

Phase changes, which convert a substance from one phase to another, have characteristic thermodynamic properties Any change from a more constrained phase to a less constrained phase increases both the enthalpy and the entropy of the substance. Recall from our description of phase changes in Chapter 11 that enthalpy increases because energy must be provided to overcome the intermolecular forces that hold the molecules in the more constrained phase. Entropy increases because the molecules are more dispersed in the less constrained phase. Thus, when a solid melts or sublimes or a liquid vaporizes, both A H and A S are positive. Figure 14-18 summarizes these features. 

Schematic view of the three phase changes leading from more constrained to less constrained phases, illustrated by the phase changes for water. Each is accompanied by positive enthalpy and entropy changes for the substance.

As described in Section 14-1. when AR and ZlS have the same sign, the spontaneous direction of a process depends on T. For a phase change, enthalpy dominates AG at low temperature, and the formation of the more constrained phase is spontaneous, hi contrast, entropy dominates AG at high temperature, and the formation of the less constrained phase is spontaneous. At one characteristic temperature, A G = 0, and the phase change proceeds in both directions at the same rate. The two phases coexist, and the system is in a state of d Tiamic equilibrium. 

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