Photolytic and radiolytic studies of SO4•− in neat organic solvents
Abstract
A study of SO4•− in neat organic solvents by laser photolytic and pulse radiolytic methods has been described for the first time. The sulfate radical was produced in neat CH3CN and CHCl3 by laser photolysis of (CTA)2S2O8 (CTA = cetyltrimethylammonium), or in CH3CN ia reduction of (CTA)2S2O8 with a reducing species produced from pulse radiolysis. The quantum yield of SO4•− in CH3CN was 30% higher than in water, based on our experimental results. The SO4•− reacts slowly with CH3CN, but rapidly with CHCl3 to form •CCl3 which is further converted into CCl3O2• in the presence of oxygen. Rate constants for hydrogen abstraction from alkanols by SO4•− were lower by 1–2 orders of magnitude in CH3CN than in aqueous solutions.