Many books cover the determination of rate constants under
different experimental conditions and different chemical
composition of the reaction mixture in their formal treatment of
thermal kinetics. However, most textbooks are limited to simple
mechanisms. In contrast, analogous treatment of photochemical
reactions is limited to the publication of special reactions and
investigations. Therefore, this book is aimed at providing an
overall description of formal photokinetics covering a wider scope
than the usual books on kinetics.
This volume attempts to provide a concise treatment of both
thermo- and photochemical reactions by means of generalised
differential equations, their set-up in matrix notation, and their
solution by a formalism using numerical integration. At a first
glance this approach might be surprising. However, apart from the
argument that the didactics of thermal reactions are easier to
handle than those of kinetics, the book provides additional reasons
in support of this approach. Therefore, the formalism derived
allows the evaluation of photochemical reactions, which are
superimposed thermal reactions taking into account that the amount
of light absorbed varies during the reaction. Because of this, any
approximation, either by using total absorbance or negligible
absorbance, will cause considerable errors even for simple
reactions. The approach chosen to transform the axis of the
radiation time into a new variable that includes the photokinetic
factor proves that formal kinetics can be applied to thermal and
photochemical reactions as well, and even allows the handling of
solutions that cannot be homogenised or solid samples in which the
concentration varies locally.By using this approach to introduce
partial photochemical quantum yields even complex mechanisms can be
determined quantitatively.
A large number of examples for different mechanisms and an
introduction to many spectroscopic and chromatographic methods
suitable for photokinetic analyses are provided to enable the
reader to carry out a step-by-step evaluation of his own
measurements. To reduce the number of formula in some chapters an
appendix has been included which contains a detailed description of
the calculus of some essential examples. For the convenience of the
reader the following has been included:
- A large number of examples describing the use of formula
- A detailed description of the procedure for applying
photokinetics to complex consecutive photoreactions
- An Internet address where the reader can find a tutorial for
this procedure:
http: //www.barolo.ipc.uni-tuebingen.de/tele/photokin/
- A simple macro to help in programming his own evaluation
procedure.
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