The temperature dependence of entropy

This result of AS(totai) being positive helps explain how considering the entropy of a system s surroundings can obviate the apparent problems caused by only considering the processes occurring within a thermodynamic system. It also explains why crystallization is energetically feasible. 

The concept of a thermodynamic system is essentially macroscopic, and assumes the participation of large numbers of molecules. Indeed, the word system derives from the Greek sustema, meaning to set up, to stay together. 

As a new criterion for reaction spontaneity, we say AS(totai) must be positive. We must consider the surroundings if we are to understand how the overall extent of energetic disorder increases during a process. 

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As the temperature of a perfect crystal is increased, the random vibrational motions increase, and disorder increases within the crystal [see Fig. 10.11(b)]. Thus the entropy of a substance increases with temperature. Since S is zero for a perfect crystal at 0 K, the entropy value for a substance at a particular temperature can be calculated if we know the temperature dependence of entropy. 

For estimation of thermodynamic properties of dissolved species, one can use the Entropy Correspondence Principle ( ), where the entropy of an ion at a given temperature is regarded as a function of the charge, the dielectric constant, mass, radius, and other variables. The function depends mainly upon the choice of the standard state, solvent, and temperature. The temperature dependency of entropy was derived based on the above principles and experimental data. By conducting the a square regression on Criss-Cobble s data ( ), we obtained the following eqtiation for calculating the entropies of species in aqueous solution. 

For sohd and hquid substances, the influence of pressure on the entropy can be disregarded if there are no extreme changes in pressure. The temperature dependence of entropy can normally be determined from (4.18) assuming constant heat capacity Cp in the considered temperature range. If the temperature deviates by more than 100-200 K from the reference temperature 298.15 K, the temperature dependence of the heat capacity should be taken into consideration for accurate calculations. In such a case, the calculation includes integration of the expression (4.16) with Cp = Cp T). 

Figure 1.20 The temperature dependences of entropy change due to fluctuation free volume formation AS (1, 2) and partial decay of clusters (3, 4) for PC (1,...

NMR signals of the amino acid ligand that are induced by the ring current of the diamine ligand" ". From the temperature dependence of the stability constants of a number of ternary palladium complexes involving dipeptides and aromatic amines, the arene - arene interaction enthalpies and entropies have been determined" ". It turned out that the interaction is generally enthalpy-driven and counteracted by entropy. Yamauchi et al. hold a charge transfer interaction responsible for this effect. 

The temperature dependence of reaction rates permits evaluation of the enthalpy and entropy components of the free energy of activation. The terms in Eq. (4.4) corresponding to can be expressed as... 

The partial molar entropy of a component may be measured from the temperature dependence of the activity at constant composition the partial molar enthalpy is then determined as a difference between the partial molar Gibbs free energy and the product of temperature and partial molar entropy. As a consequence, entropy and enthalpy data derived from equilibrium measurements generally have much larger errors than do the data for the free energy. Calorimetric techniques should be used whenever possible to measure the enthalpy of solution. Such techniques are relatively easy for liquid metallic solutions, but decidedly difficult for solid solutions. The most accurate data on solid metallic solutions have been obtained by the indirect method of measuring the heats of dissolution of both the alloy and the mechanical mixture of the components into a liquid metal solvent.05... 

One of the more interesting results of these calculations is the contribution to the heat capacity. Figure 10.10 shows the temperature dependence of this contribution to the heat capacity for CH3-CCU as calculated from Pitzer s tabulation with 7r = 5.25 x 10-47 kg m2 and VQ/R — 1493 K. The heat capacity increases initially, reaches a maximum near the value expected for an anharmonic oscillator, but then decreases asymptotically to the value of / expected for a free rotator as kT increases above Vo. The total entropy calculated for this molecule at 286.53 K is 318.86 J K l-mol l, which compares very favorably with the value of 318.94T 0.6 TK-1-mol 1 calculated from Third Law measurements.7... 

Clearly, the temperature profile is linear. The activation parameters are the sums shown in general, a sum of entropies and enthalpies is the result when constants are multiplied. If values of AS% and Aare known independently, from the temperature dependence of Ka for example, one can then calculate AS and AH by difference. 

Equilibrium vapor pressures were measured in this study by means of a mass spectrometer/target collection apparatus. Analysis of the temperature dependence of the pressure of each intermetallic yielded heats and entropies of sublimation. Combination of these measured values with corresponding parameters for sublimation of elemental Pu enabled calculation of thermodynamic properties of formation of each condensed phase. Previ ly reported results on the subornation of the PuRu phase and the Pu-Pt and Pu-Ru systems are correlated with current research on the PuOs and Pulr compounds. Thermodynamic properties determined for these Pu-intermetallics are compared to analogous parameters of other actinide compounds in order to establish bonding trends and to test theoretical predictions. 

In addition to chemical reactions, the isokinetic relationship can be applied to various physical processes accompanied by enthalpy change. Correlations of this kind were found between enthalpies and entropies of solution (20, 83-92), vaporization (86, 91), sublimation (93, 94), desorption (95), and diffusion (96, 97) and between the two parameters characterizing the temperature dependence of thermochromic transitions (98). A kind of isokinetic relationship was claimed even for enthalpy and entropy of pure substances when relative values referred to those at 298° K are used (99). Enthalpies and entropies of intermolecular interaction were correlated for solutions, pure liquids, and crystals (6). Quite generally, for any temperature-dependent physical quantity, the activation parameters can be computed in a formal way, and correlations between them have been observed for dielectric absorption (100) and resistance of semiconductors (101-105) or fluidity (40, 106). On the other hand, the isokinetic relationship seems to hold in reactions of widely different kinds, starting from elementary processes in the gas phase (107) and including recombination reactions in the solid phase (108), polymerization reactions (109), and inorganic complex formation (110-112), up to such biochemical reactions as denaturation of proteins (113) and even such biological processes as hemolysis of erythrocytes (114). 

As to the computation of reaction enthalpies and entropies, AH and AS , the same arguments apply if they have been obtained from the temperature dependence of the equilibrium constant. A different situation arises vdien AH is determined directly from calorimetry, say with a constant relative error 6. The standard entropy AS then has the standard error... 

Hence the reduction in entropy (A5 > that results from loss of rotational and translational freedom leads to a more positive (unfavorable) value of AG. The enthaplic and entropic components of AGto, and AG, st can be determined from the temperature dependence of kcM and of kcJKs, respectively, from the Arrhenius equation... 

The simplicity and accuracy of such models for the hydration of small molecule solutes has been surprising, as well as extensively scrutinized (Pratt, 2002). In the context of biophysical applications, these models can be viewed as providing a basis for considering specific physical mechanisms that contribute to hydrophobicity in more complex systems. For example, a natural explanation of entropy convergence in the temperature dependence of hydrophobic hydration and the heat denaturation of proteins emerges from this model (Garde et al., 1996), as well as a mechanistic description of the pressure dependence of hydrophobic... 

We used the temperature dependence of the open circuit voltage (OCV) at constant composition x in LixC6 to measure the entropy variation AS(x) expressed by ... 

Harkins et al., 1940), where ne is the ESP, and Ae is the average area per molecule at the ESP as obtained from the 11/ 4 isotherm of the spread film. The temperature dependence of the ESP may then be used to calculate the excess surface entropies from (5) and enthalpies of spreading from (6). 

We start by introducing the concept of entropy S to explain why some reactions occur spontaneously, without needing additional energy, yet others do not. The sign of A 5 for a thermodynamic universe must be positive for spontaneity. We explore the temperature dependence of A5. 

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