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Flash photolysis of s ‐trinitrobenzene solutions
Author(s) -
Capellos C.,
Suryanarayanan K.
Publication year - 1973
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550050212
Subject(s) - chemistry , flash photolysis , photochemistry , ultrafast laser spectroscopy , solvent , absorption (acoustics) , oxygen , proton , ion , organic chemistry , reaction rate constant , kinetics , laser , physics , quantum mechanics , acoustics , optics
Flash photolysis of s ‐trinitrobenzene (TNB) aerated solutions in alcohols generates a transient species with absorption maxima at 430 and 510 nm. The yield of the transient is a function of oxygen concentration, and its rate of formation is viscosity dependent. In deaerated solutions instead of the transient, a brown permanent product, identified as a charge transfer (CT) complex with absorption maxima at 470 and 550 nm, is produced. These species are formed only in polar solvents with relatively high proton affinity. The data suggest an intermolecular proton transfer, from electronically excited TNB to the solvent forming the anionThe anion thereby produced interacts with oxygen in aerated alcohols to form the transient attributed to CT complexwhile in deaerated alcohols the anion reacts with the solvent to produce RO − , which leads to the CT complex RO… − TNB. This mechanism is supported by detailed kinetic and spectroscopic studies.