Conclusion
The principle of microscopic reversibility is one of the few generalising principles used in organic chemistry which have their roots in the fundamental laws of thermodynamics. It has, therefore, been highly popular.
However, although the principle has some important uses, its general application is not without pitfalls. The principle is easy to misunderstand and to misapply: indeed, some of its formulations are semantically dubious. The principle is most dangerous when used as a charm, for it is more subtle than some of its formulations suggest.
But above all, the principle may not be used for deducing or disproving the mechanism of a reaction, except when the mechanism in the reverse direction is known independently. For, such use is, perhaps, the deadliest misapplication.
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Chandrasekhar, S. The principle of microscopic reversibility in organic chemistry - a critique. Res Chem Intermed 17, 173–209 (1992). https://doi.org/10.1163/156856792X00128
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DOI: https://doi.org/10.1163/156856792X00128