Thermodynamics changes during thermodynamic

Next we consider the same reaction system, but now we do not assume that the first reaction is in thermodynamic equilibrium but rather that the concentration of the intermediate species B does not change during the reaction or that dCs/dt = 0,... 

All of the stereoselective transformations described so far originate from kinetic control. Therefore, the ratio of stereoisomers obtained does not reflect their relative energies and, provided that the reaction conditions allow a subsequent equilibration, this ratio may change during prolonged reaction periods. The two principal possibilities arising from thermodynamically controlled (equilibrating) conditions and are shown below. 

The second law of thermodynamics denies the possibility of processes in which the only change is transfer of heat from a higher to a lower temperature. The zeroth law deals with thermal equilibrium and thus, by implication, the direction of heat transfer. However, the zeroth law applies only to heat transfer at a single interface, whereas the second law can deal with processes in which devices accomplish the heat transfer. These devices can have multiple interfaces with the heat reservoirs and can change during the process, as long as their change is cyclic. 

Equation (1.14b) is advantageous when E, q, or w is expressed as a variable function, changing during a process. Some illustrations of the first law of thermodynamics are given as follows ... 

Table 1 clearly shows high thermodynamic stability of all the mixed-valence states involved. Since the solvational change during redox processes would affect the redox potentials, Kcom values which is the function of the difference in two successive redox potentials would also be affected by solvational change. Electronic stmeture of the mixed-valence states would be more important, however, in determining A com values (vide infra). Electronic structures of all the complexes except 7 have been interpreted in terms of molecular orbital consideration. Simplified qualitative molecular orbital schemes are given in Figure 2. 

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