Nitrosothiosulphate Ion (S2O3NO-) as a Nitrosating Species

Article abstract of DOI:10.1039/P29860000193

Analysis of rate data obtained for the nitrosation of N-methylaniline in the presence of thiosulphate ion indicates that the nitrosothiosulphate ion is formed and that it acts as a nitrosating species.The bimolecular rate constant for reaction in water at 25 deg C is evaluated as 1.2E4 l mol^-1 s^-1 from the variation of the observed rate constant with and also as 1.2E4 l mol^-1 s^-1 from the variation of the observed rate constant with .Results are also reported, for comparison purposes, for the corresponding reactions of nitrosyl bromide and nitrosyl thiocyanate.Nitrosyl bromide (in its reaction with N-methylaniline) is more reactive than the nitrosothiosulphate ion by a factor of ca. 4E-5, and nitrosyl thocyanate is more reactive than the nitrosothiosulphate ion by a factor of ca.1.5E-4.There is also kinetic evidence of nitrosation by the nitrosothiosulphate ion of methanol, hydrazine, and a thiol.The decomposition of S2O3NO(-) follows the rate law -d/dt=k₁+k₂².This is interpreted in terms of two concurrent reaction pathways, the first involving the formation of the radical anion S2O3^-. in a rate-limiting homolysis (followed by rapid dimerisation) and the second a bimolecular reaction of two S2O3NO(-) ions homolysis (followed by rapid dimrisation) and the second a bimolecular reaction of two S2O3NO(-) ions with concurrent S-N bond fission and S-S bond formation yielding the tetrathionate ion S4O6(2-).

Full text of DOI:10.1039/P29860000193

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

View Article Online

View Article Online