Abstract
The influence of OH − concentration, in the solvent medium dioxane-water 40:60 at 25·0, on the oxidation rates of diphenylphosphine oxide (DPPO) by t-BuOOH, H 2O 2 and p-nitroperoxybenzoic acid, and of bis- p-tolylphosphine oxide by t-BuOOH has been investigated. For the oxidation of the phosphorus substrates by the hydroperoxides above, the rate law found (R = k 2″[Ar 2PHO] [ROO −]) differs from the rate law confirmed to hold for the oxidation of DPPO by peroxyacids in alkaline media, i.e.: R = (k 2″ + k 3[OH−])[Ar 2PHO] [RCO 3 −]. This is interpreted on the basis of one common reaction mechanism involving formation of an intermediate of similar structure, wherein a change in the rate controlling step is likely to occur on passing from p-O 2N·C 6H 4CO 3 − to t-BuOO −. In the same solvent medium, pK a′ values for t-BuOOH and H 2O 2 have been estimated.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
