88344-47-2Relevant academic research and scientific papers
Thermal Dissociation of Thiuram Disulfides in Solution; an Electron Spin Resonance and Kinetic Study
Nichols, Peter J.,Grant, Michael W.
, p. 1379 - 1386 (2007/10/02)
Tetraisopropylthiuram disulfide dissociates reversibly in solution to form dithiocarbamate thio radicals which can be detected by e.s.r. (g 2.015).The termodynamics of the dissociation has been examined in decalin by quantitative e.s.r. and a dissociation enthalpy of 104+/-2 kJ mol-1 and an entropy of dissociation of 57+/-5 J K-1 mol-1 has been obtained.Replacing the isopropyl group by other alkyl groups significantly affects the extent of dissociation which decreases in the sequence isopropyl ca. cyclohexyl > ethyl ca. methyl > benzyl as the alkyl group is changed.Studies of the kinetics of dissociation of the thiuram disulfides are consistent with the e.s.r. observations and indicate that thio radical recombination occurs at a near diffusion-controlled rate.
