Steady-State Studies by EPR on the Photodissociation of Some Alkyl Hydroperoxides

Abstract

A new steady-state method for studying dynamic photochemical processes by EPR is discussed. The EPR spectra of some photolysed alkyl hydroperoxides are obtained and the free radical intermediates identified as alkoxy radicals. Recombination rate constants of ∼105 liters/mole sec were obtained with activation energies of ∼4 kcal. A new EPR spectrometer with improved sensitivity capable of photoirradiation in situ and variable temperatures is discussed.

EPR at work: Part 1

“…The "multipurpose" cavity resonator had a grid that permitted in situ ultraviolet irradiation of the sample. Sample temperature was controlled by a nitrogen flow system that has changed only slightly over the next few decades (the article cited as "in press" is Piette and Landgraf) (27). EPR is a major contributor to the study of various steps in photosynthesis because many of the species created during photosynthesis have unpaired electrons (28 -30).…”

Epr at Varian: 1954-1974

“…The article describes experiments with the new 100 kc EPR spectrometer with multipurpose cavity and sample control equipment. Reference was made to a paper by L. H. Piette and W. C. Landgraf (5).…”