CaltechAUTHORS
  A Caltech Library Service

A kinetic study of pyrophosphate and peroxodiphosphate complexation of oxovanadium(IV) ion

Hoffmann, M. R. and Stern, R. A. and Rieger, P. H. and Edwards, J. O. (1976) A kinetic study of pyrophosphate and peroxodiphosphate complexation of oxovanadium(IV) ion. Inorganica Chimica Acta, 19 . pp. 181-187. ISSN 0020-1693. https://resolver.caltech.edu/CaltechAUTHORS:20151215-112214021

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20151215-112214021

Abstract

The formation constant of the vanadyl pyrophosphate complex, VO(H_2P_2O_7), determined spectrophotometrically in acidic 1.0 M NaClO_4 solution, is logK = 4.4±0.1 at 25°C. The kinetics of the complexation of vanadyl ion by pyrophosphate and peroxodiphosphate were studied at pH 2.0 using stopped-flow spectrophotometry. The reactions are first-order in ligand and in vanadyl ion with rate constants k_2 = 2.3×10^4 and 7.5×10^3 M^(−1) sec^(−1) at 12°C for H_2P_2O_7^(2−) and H_2P_2O_8^(2−), respectively. The complexation reactions were followed by slower secondary processes which are attributed to polymerization. The results for the complexation reactions are consistent with an interchange mechanism for the formation of a monodentate complex, followed by rapid closure of the chelate ring. Peroxodisulfate, studied under similar conditions, showed no evidence of innersphere complexation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/S0020-1693(00)91092-2DOIArticle
http://www.sciencedirect.com/science/article/pii/S0020169300910922PublisherArticle
ORCID:
AuthorORCID
Hoffmann, M. R.0000-0001-6495-1946
Additional Information:© 1976 Elsevier. Received February 24, 1976. Taken in part from the Ph.D. Thesis of M. R. H., Brown University, 1973. Stimulating discussions with M. W. Kendig and N. D. Chasteen are gratefully acknowledged. This work was supported in part by FMC Corporation and the Air Force Office of Scientific Research.
Funders:
Funding AgencyGrant Number
FMC CorporationUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Record Number:CaltechAUTHORS:20151215-112214021
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151215-112214021
Official Citation:M.R. Hoffmann, R.A. Stern, P.H. Rieger, J.O. Edwards, A kinetic study of pyrophosphate and peroxodiphosphate complexation of oxovanadium(IV) ion, Inorganica Chimica Acta, Volume 19, 1976, Pages 181-187, ISSN 0020-1693, http://dx.doi.org/10.1016/S0020-1693(00)91092-2. (http://www.sciencedirect.com/science/article/pii/S0020169300910922)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:62942
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:15 Dec 2015 20:43
Last Modified:03 Mar 2020 13:01

Repository Staff Only: item control page