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Time‐resolved photoacoustic calorimetry as a tool to determine rate constants of hydrogen‐abstraction reactions
Author(s) -
Nunes Paulo M.,
Correia Catarina F.,
Borges Dos Santos Rui M.,
Martinho Simões José A.
Publication year - 2006
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.20173
Subject(s) - chemistry , hydrogen atom abstraction , calorimetry , reaction rate constant , benzene , flash photolysis , solvent , calorimeter (particle physics) , photoacoustic imaging in biomedicine , acetonitrile , analytical chemistry (journal) , phenol , atmospheric temperature range , kinetics , hydrogen , photochemistry , organic chemistry , thermodynamics , physics , optics , quantum mechanics , detector , electrical engineering , engineering
The hydrogen‐abstraction reaction from phenol by tert ‐butoxyl radical was used to test time‐resolved photoacoustic calorimetry (TR‐PAC) as a method to obtain kinetic data. Absolute rate constants for this reaction were determined in benzene and in the 298–312 K temperature range, using a temperature‐controlled photoacoustic calorimeter, yielding an average value of 3.5 × 10 8 M −1 s −1 . This is in good agreement with the literature results obtained by laser flash photolysis (LFP). Kinetic solvent effects (KSE) in the same reaction were also studied using acetonitrile, carbon tetrachloride, and ethyl acetate as solvents. The results obtained by TR‐PAC are close to those derived by LFP (using the cumyloxyl radical as the abstracting species) and follow the expected trend based on the KSE. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 357–363, 2006