Reversible attachment-detachment reactions

Mozumder (1996) has discussed the thermodynamics of electron trapping and solvation, as well as that of reversible attachment-detachment reactions, within the context of the quasi-ballistic model of electron transport. In this model, as in the usual trapping model, the electron reacts with the solute mostly in the quasi-free state, in which it has an overwhelmingly high rate of reaction, even though it resides mostly in the trapped state (Allen and Holroyd, 1974 Allen et ah, 1975 Mozumder, 1995b). Overall equilibrium for the reversible reaction with a solute A is then represented as... 

TABLE 10.6 Thermodynamic Functions for Reversible Attachment-Detachment Reactions in Hydrocarbon Liquids... 

Electron attachment to solutes in nonpolar liquids has been studied by such techniques as pulse radiolysis, pulse conductivity, microwave absorption, and flash (laser) photolysis. A considerable amount of data is now available on how rates depend on temperature, pressure, and other factors. Although further work is needed, some recent experimental and theoretical studies have provided new insight into the mechanism of these reactions. To begin, we consider those reactions that show reversible attachment-detachment equilibria and therefore provide both free energy and volume change information. 

Similarly, the reverse reaction step can be seen as the attachment/detachment of the Br- anion on an active site S+OAc, that is. 

This is the reverse process with respect to the dissociative attachment (2-66) and therefore it can also be illnstrated by Fig. 2-7. The associative detachment is a non-adiabatic process, which occnrs via intersection of electroiuc terms of a complex negative ion A -B and corresponding molecnle AB. Rate coefficients of the non-adiabatic reactions are qnite high, typically kd = 10 °-10 cm /s. The kinetic data and enthalpy of some associative detachment processes are presented in Table 2-7. 

The binding of oxygen to hemoglobin is a reversible reaction. The oxygen molecule must attach to the hemoglobin (Hb) and then later detach. The equilibrium equation for this reaction can be written ... 

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