Relaxation times, rate constants, and cidep for transient alcohol radicals in the photoreduction of 1,4-naphthoquinone by microsecond time resolved ESR

Autor:	S. Frydkjaer, L.T. Muus
Rok vydání:	1981
Předmět:	Propanol Microsecond chemistry.chemical_compound Reaction rate constant chemistry Radical Analytical chemistry General Physics and Astronomy Relaxation (physics) Alcohol 1 4-Naphthoquinone Physical and Theoretical Chemistry Microscopic theory
Zdroj:	Chemical Physics. 59:365-371
ISSN:	0301-0104
DOI:	10.1016/0301-0104(81)85178-6
Popis:	The photoreduction of 1,4-naphthoquinone in 2-propanol and 2-methyl-1-propanol at −23°C was studied with a new microsecond time resolving ESR spectrometer system. The transient alcohol radicals were identified and their relaxation times measured. The 2-propyl-2-ol radical derived from 2-propanol was found to have T 1 = 1.50 μs and T 2 = 1.01 μs. For the 2-methyl-1-propyl-1-ol radical derived from 2-methyl-1- propanol T 1 was determined to 3.19 μs whereas T 2 could not be found. The rate constants for the reaction of alcohol radicals with unexcited 1,4-naphthoquinone was measured to 6.7 × 10 8 l s −1 mol −1 for 2-propanol and 3.2 × 10 8 l −1 mol −1 for 2-methyl-1-propanol. The initial RPM polarisation for the alcohol radicals was measured and compared with values calculated from the microscopic theory. The calculated values were too small by a factor of two.
Databáze:	OpenAIRE
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