Order of photochemical kinetics for bistable photoswitchable systems

Mahato, Samyadeb (2018) Order of photochemical kinetics for bistable photoswitchable systems. Masters thesis, Indian Institute of Science Education and Research Kolkata.

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Abstract

The order of the photochemical reaction kinetics is a matter of debate and it is not well understood. There are two schools of thoughts on the matter. One school suggests that assigning a definite reaction order to a photochemical reaction has no sound basis and qualification should be done only with quantum yield whereas the other school states that the order of photochemical reaction is condition dependent. There has been a dearth of systematic experimental verification. In this thesis, we endeavoured to experimentally understand the kinetics in terms of reaction order for bidirectional (reversible) photochemical reactions of several photochromic systems namely 1) cis-trans photoisomerization of azobenzene 2) photochromism of spiropyran to merocyanin and 3) photoisomerization of benzodihydropyrene-cyclophanediene systems. It has been found that both the forward and reverse reactions in all three systems can be given a reaction order. The order can be zero, one or fractional, dependent upon conditions, mainly dictated by the concentration.

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