Progress in Reaction Kinetics and Mechanism

The influence of micellar media upon the transnitrosation reaction between N-methyl-N-nitroso-p-toluensulfonamide (MNTS) and three linear alkylamines (n-octylamine (OA), N-methyl-n-octylamine (MOA) and N,N-dimethyl-n-octylamine (DMOA)) in micelles of Cetyltrimethylammonium Chloride (CTACl) has been studied. The rate constants were obtained and the pseudophase model allowed us to obtain the intrinsic reactivity constants in the aqueous pseudophase and in the micellar pseudophase (kⁱ₂ and k^w₂) and the binding constant of the amines to the micellar phase (K_a).

Radio-labelled free radicals were formed by the addition of muonium-a radioactive hydrogen atom with a positive muon as its nucleus-to benzaldehyde, as adsorbed in cation-exchanged zeolite X. PhCHOMu• radicals were the major species formed and the activation parameters associated with their reorientational motion were measured using longitudinal-field muon spin relaxation (LF-MuSRx). Two distinct adsorbed fractions were detected in each of the samples containing Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺ and Ba²⁺ cations, believed to be from (1) an effectively bulk benzaldehyde component with an almost common activation energy for molecular reorientation of ca 3kJ/mol, and (2) benzaldehyde adsorbed inside the zeolite supercages. MgX showed only the supercage fraction clearly.

Radiolabelled free radicals were formed by the addition of muonium-a radioactive hydrogen atom with a positive muon as its nucleus-to α-pinene, β-pinene, dihydrocarvone, dihydrocarveol and dipentene, each as adsorbed in porous carbon. The radicals were identified using transverse-field muon spin rotation (TF-MuSR) and the activation parameters associated with their reorientational motion were measured using longitudinal-field muon spin relaxation (LF-MuSRx). Two distinct adsorbed fractions were detected in each sample, characterised by activation energies in the range 2-6 kJ/mol and 12-16 J/mol respectively.