Entropy significance

In general, it seems more reasonable to suppose that in chemisorption specific sites are involved and that therefore definite potential barriers to lateral motion should be present. The adsorption should therefore obey the statistical thermodynamics of a localized state. On the other hand, the kinetics of adsorption and of catalytic processes will depend greatly on the frequency and nature of such surface jumps as do occur. A film can be fairly mobile in this kinetic sense and yet not be expected to show any significant deviation from the configurational entropy of a localized state. 

B2.4.2). The slope of the line gives AH, and the intercept at 1/J= 0 is related to A imimolecular reaction, such as many cases of exchange, might be expected to have a very small entropy change on gomg to the transition state. However, several systems have shown significant entropy contributions—entropy can make up more than 10% of the barrier. It is therefore important to measure the rates over as wide a range of temperatures as possible to obtain reliable thennodynamic data on the transition state. 

However, reaction 7 suffers other shortcomings, eg, entropy problems. Other proposals range from trace peroxidic contaminants to ionic mechanisms for generating peroxides (1) to cosmic rays (17). In any event, the initiating reactions are significant only during the induction period (18). 

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... 

When a process is completely reversible, the equahty holds, and the lost work is zero. For irreversible processes the inequality holds, and the lost work, that is, the energy that becomes unavailable for work, is positive. The engineering significance of this result is clear The greater the irreversibility of a process, the greater the rate of entropy production and the greater the amount of energy that becomes unavailable for work. Thus, every irreversibility carries with it a price. 

The fact that shock waves continue to steepen until dissipative mechanisms take over means that entropy is generated by the conversion of mechanical energy to heat, so the process is irreversible. By contrast, in a fluid, rarefactions do not usually involve significant energy dissipation, so they can be regarded as reversible, or isentropic, processes. There are circumstances, however, such as in materials with elastic-plastic response, in which plastic deformation during the release process dissipates energy in an irreversible fashion, and the expansion wave is therefore not isentropic. 

Both types of mutations have been made in T4 lysozyme. The chosen mutations were Gly 77-Ala, which caused an increase in Tm of 1 °C, and Ala 82-Pro, which increased Tm by 2 °C. The three-dimensional structures of these mutant enzymes were also determined the Ala 82-Pro mutant had a structure essentially identical to the wild type except for the side chain of residue 82 this strongly indicates that the effect on Tm of Ala 82-Pro is indeed due to entropy changes. Such effects are expected to be additive, so even though each mutation makes only a small contribution to increased stability, the combined effect of a number of such mutations should significantly increase a protein s stability. 

The one-pot synthesis of 9 described above appears to afford only modest yields of azacrowns. One might wonder why any crown at all would be formed under non-high dilution conditions intended to yield only open-chained material. Vogtle suggests that this can be explained in terms of template, steric and entropy effects . These factors are of doubtless significance, but it is interesting to note that in the synthesis of poly-azamacrocycles, Richman and Atkins found that there was no significant template effect observed. The question of the template effect in Ihe syntheses of 9 has recently been addressed by Kulstad and Malmsten They conclude that the formation of 9 is assisted by the presence of alkali metal cations. 

Clearly, proximity and orientation play a role in enzyme catalysis, but there is a problem with each of the above comparisons. In both cases, it is impossible to separate true proximity and orientation effects from the effects of entropy loss when molecules are brought together (described the Section 16.4). The actual rate accelerations afforded by proximity and orientation effects in Figures 16.14 and 16.15, respectively, are much smaller than the values given in these figures. Simple theories based on probability and nearest-neighbor models, for example, predict that proximity effects may actually provide rate increases of only 5- to 10-fold. For any real case of enzymatic catalysis, it is nonetheless important to remember that proximity and orientation effects are significant. 

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