Abstract

The particular set of reactivities of nitrogen donors and of peroxodisulfate that make their interactions mechanistically complicated are discussed. Two reactions of this class have been studied experimentally. In the oxidation of nitrite ion by peroxodisulfate, the nitrogeneous product is nitrate. The rate law: −d[S 2O 8 2−] dt = k 1[S 2O 8 2−] + k 2[S 2O 8 2−] [NO 2 −] has been found. A significant change in rate on addition of allyl alcohol to the system indicates the presence of free radicals to an extent greater than can be ascribed to the k 1 term alone. The possible intervention of NO 2 as an intermediate has been investigated. Mechanisms for the two oxidation paths are proposed. The reaction of peroxodisulfate with ammonia and ammonium ion gives dinitrogen. Radical (but not chain) paths were found as indicated by rate law (first order in peroxodisulfate and zero order in reductant), rate constants, and activation parameters. Copper(II) catalysis by a free radical chain process occurs in the ammonia oxidation.

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 call

Disclaimer: 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.