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Excited state kinetics and stern-Volmer quenching plots in the photolysis of azoisopropane at 366 nm

✍ Scribed by G. O. Pritchard; F. M. Servedio

Publisher
John Wiley and Sons
Year
1975
Tongue
English
Weight
484 KB
Volume
7
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The photochemistry of azoisopropane is reinvestigated at 366 nm over an extended pressure range by using n‐butane as an added bath gas, and over a range of temperature from 277° to 180°C. The Stern‐Volmer type plot of the N~2~ product quantum yield is interpreted in terms of the decomposition of the vibrationally excited upper singlet and triplet states, with the onset of the dissociation of the vibrationally equilibrated triplet state as the temperature is increased. The energy barrier for the dissociation of the vibrationally equilibrated first triplet state is found to be 8.8 kcal/mole. Triplet sensitization experiments with biacetyl correlate with our observations, and it is suggested that the proposed mechanism is generally applicable to the photodissociation of acyclic azoalkanes at 366 nm, based on a comparison of our data with those of Wu and Rice on hexafluoroazomethane.

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