Entropy changes, thermodynamic temperature

Both kinetic and thermodynamic approaches have been used to measure and explain the abrupt change in properties as a polymer changes from a glassy to a leathery state. These involve the coefficient of expansion, the compressibility, the index of refraction, and the specific heat values. In the thermodynamic approach used by Gibbs and DiMarzio, the process is considered to be related to conformational entropy changes with temperature and is related to a second-order transition. There is also an abrupt change from the solid crystalline to the liquid state at the first-order transition or melting point Tm. 

An important question for chemists, and particularly for biochemists, is, Will the reaction proceed in the direction written J. Willard Gibbs, one of the founders of thermodynamics, realized that the answer to this question lay in a comparison of the enthalpy change and the entropy change for a reaction at a given temperature. The Gibbs free energy, G, is defined as... 

The second law of thermodynamics also consists of two parts. The first part is used to define a new thermodynamic variable called entropy, denoted by S. Entropy is the measure of a system s energy that is unavailable for work.The first part of the second law says that if a reversible process i f takes place in a system, then the entropy change of the system can be found by adding up the heat added to the system divided by the absolute temperature of the system when each small amount of heat is added ... 

Why Do We Need to Know This Material The second law of thermodynamics is the key to understanding why one chemical reaction has a natural tendency to occur bur another one does not. We apply the second law by using the very important concepts of entropy and Gibbs free energy. The third law of thermodynamics is the basis of the numerical values of these two quantities. The second and third laws jointly provide a way to predict the effects of changes in temperature and pressure on physical and chemical processes. They also lay the thermodynamic foundations for discussing chemical equilibrium, which the following chapters explore in detail. 

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. 

A reversible adiabatic expansion of an ideal gas has a zero entropy change, and an irreversible adiabatic expansion of the same gas from the same initial state to the same final volume has a positive entropy change. This statement may seem to be inconsistent with the statement that 5 is a thermodynamic property. The resolution of the discrepancy is that the two changes do not constitute the same change of state the final temperature of the reversible adiabatic expansion is lower than the final temperature of the irreversible adiabatic expansion (as in path 2 in Fig. 6.7). 

Innate Thermodynamic Quantities. Certain components of the total change in AG° are innate, because such parameters have nonzero values, even when extrapolated to 0 K. Other components change with temperature e.g., at r = 0 K, TA = 0). Because A = U - TS and G = H - TS - then = Go°) = (Ao° = Uo°) at absolute zero. Except for entropy, the residual values of these quantities are the same at absolute zero, and they describe the innate thermodynamic behavior of the system. 

Although endothermic, these reactions are thermodynamically spontaneous at high temperature due to the favorable entropy change associated with the formation of random gaseous products from solid starting materials. 

The very low water adsorption by Graphon precludes reliable calculations of thermodynamic quantities from isotherms at two temperatures. By combining one adsorption isotherm with measurements of the heats of immersion, however, it is possible to calculate both the isosteric heat and entropy change on adsorption with Equations (9) and (10). If the surface is assumed to be unperturbed by the adsorption, the absolute entropy of the water in the adsorbed state can be calculated. The isosteric heat values are much less than the heat of liquefaction with a minimum of 6 kcal./mole near the B.E.T. the entropy values are much greater than for liquid water. The formation of a two-dimensional gaseous film could account for the high entropy and low heat values, but the total evidence 22) indicates that water molecules adsorb on isolated sites (1 in 1,500), so that patch-wise adsorption takes place. 

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