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MEASUREMENT OF INDUCTION PERIODS IN INHIBITED FREE‐RADICAL OXIDATION BY INFRARED CHEMILUMINESCENCE AT 1270 nm
Author(s) -
Lee S. H.,
Niu Q.,
Sheng X. C.,
Mendenhall G. D.
Publication year - 1989
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1989.tb04156.x
Subject(s) - chemiluminescence , chemistry , amine gas treating , quenching (fluorescence) , decomposition , radical , solvent , photochemistry , oxygen , luminescence , induction period , hydrocarbon , medicinal chemistry , organic chemistry , fluorescence , catalysis , physics , optoelectronics , quantum mechanics
Abstract— Infrared chemiluminescence at 1.27 µ. appears after the consumption of phenolic inhibitors in solutions of 1‐tetralyl hydroperoxide in tert ‐butylbenzene (BPh), initiated with di‐ tert ‐butyl hyponitrite (BHN) at 68 o C. The induction periods with phenols were in excellent agreement with ones calculated from rates of decomposition of the initiator. Di‐(2,2,6,6‐tetramethyl‐4‐piperidinyl) sebacate, benzhyd‐rol, a derivative of benzhydrol, and di‐rerr‐butyl ketoxime under these conditions showed no inhibition or a weak effect. Initiated solutions 2.5 mM in p,p′‐di‐ tert ‐octyldiphenylamine showed no detectable emission at 1270 nm because of efficient quenching of 1 O 2 by diaryl nitroxides formed from the amine, and because the oxidation products of the amine are peroxy scavengers (Thomas, J. R. 1960, J. Amer. Chem. Soc. 82, 5955). The relative yields of IR luminescence from several alkyl hydroperoxides and oxygen‐hydrocarbon mixtures, initiated in each case by BHN, were found to vary substantially with the structure of the hydrocarbon and with the solvent.