Abstract
The saturation recovery method has been used to measure the electron spin relaxation times of short‐lived free radicals in solution. The radicals were produced by continuous in situ radiolysis with a 2.8 MeV electron beam (except for two cases where stable radicals were formed by air oxidation). The ESR spectrometer used broad‐band amplification of the detected ESR signal (time constant of 100 ns) and signal averaging by means of a transient recorder and minicomputer. The magnetic field was stepped off the ESR line for alternate saturating pulses; the phase of the microwave saturating pulse could be changed by 180 ° to allow separation of the saturation recovery and free induction decay. The sensitivity was such that T1 values greater than 1 ms could be determined for samples of 1014 spins (i.e., 3×10−6 M radical in 50 ml) if the ESR linewidth was 100 mG and transient curves from 40 000 saturating pulses were averaged. Somewhat smaller values of T1 could be determined with higher radical concentrations. T...
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