CHEMILUMINESCENCE FROM ALKYL HYPONITRITES IN VISCOUS-LIQUID MEDIA

We have studied the effect of dissolved polymers and mineral oil on th e chemiluminescence from tert-butylbenzene solutions of trans-di-2-pro pyl hyponitrite (IPHN), trans-di-1-phenylethyl hyponitrite (PEHN) and 3,3,4,4-tetramethyl-1,2-dioxetane (TMD) in the presence of a fluoresce nt species (2-tert-butyl-9,10-dibromoanthracene). It was found that th e addition of polymers (poly(alpha-methylstyrene) and others) to solut ions of the hyponitrites or TMD decreased their chemiluminescence. In contrast, addition of mineral oil decreased the luminescence from TMD but increased the luminescence from the hyponitrites. The decrease in luminescence was ascribed to the expected reduced rates of energy tran sfer to the fluorescent species in competition with decay of the carbo nyl triplets. The increase in luminescence on addition of mineral oil was too large to be accounted for by larger cage effects in the case o f PEHN. The increase was tentatively ascribed to higher excited state formation efficiencies from alkoxyl radical dismutation in more viscou s media.