Flash photolysis study for reactions of NO3· with sulfur compounds in acetonitrile solution

✍ Scribed by Seiji Akiho; Osamu Ito; Masashi Iino

• Publisher: John Wiley and Sons
• Year: 1989
• Tongue: English
• Weight: 454 KB
• Volume: 21
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550210806

✦ Synopsis

The rate constants for the reaction of NO3' with sulfur compounds in acetonitrile have been determined by the flash photolysis method. The rate constant for dimethyl sulfone (2.7 x lo4 M-'s-' a t -10°C) is larger than that of the deuterium derivative, indicating that NO; abstracts the hydrogen atom from dimethyl sulfone. In the case of dimethyl sulfide, the rate constant was evaluated to be 1.5 x lo9 M-' s-' at -10°C; the transient absorption band attributable to the cation radical was observed after the decay of NO3', suggesting the electron transfer reaction from the sulfide to NO3'. For diphenyl sulfide and dimethyl disulfide, the electron transfer reactions were also confirmed. For dimethyl sulfoxide, the reaction rate constant of 1.2 x lo9 M-' s-l (at -10°C) was not practically affected by the deuterium substitution, suggesting that NO3' adds to sulfur atom forming (CH3)2S(0)-ON02. On the other hand, for diphenyl sulfoxide, the electron transfer reaction occurs. By the comparison of these rate constants in acetonitrile solution with the reported rate constants in the gas phase, the change of the reaction paths was revealed.