Microscopic reversibility principle

Michaelis-Menten equation, 35, 90-94 Microscopic reversibility, principle of, 172-175... 

The figure below (from Rimstidt and Barnes, 1980) shows the energy profiles in the dissolution (forward direction) and precipitation (reverse direction) reactions of amorphous Si02 and quartz, Q -Si02. Use the concept of detailed balancing (microscopic reversibility principle) to explain why the dissolution rate constant is directly proportional to the solubility of the Si02 solid phase. 

Here Cl. is the extent of water saturation with the mineral / and tj are empiric dimensionless constants taking into account violation of microscopic reversibility principle for each of three rates. When water saturation state by the mineral tends to zero, value of the sum also tends to some max value ... 

In keeping with the microscopic reversibility principle this problem is also concerned with the routes of decomposition of a-complexes (routes a and c, b). 

It should be noted that, in virtue of the microscopic reversibility principle, the above-described rule also regulates the type of approach of the attacking nucleophile to the carbonyl group, in other words, the exact conformation of the axially nonsymmetrical nucleophile at the stage of the formation of the tetrahedral intermediate. 

Contrary to the previous ones, mechanism IV is not a linear mechanism but a cyclic one. Therefore, it exists a relation between the microscopic rate constants derived from the microscopic reversibility principle ... 

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