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The kinetics and mechanism of the oxidation of formic acid by bromine in acid aqueous media

Brusa, M. A. and Colussi, A. J. (1980) The kinetics and mechanism of the oxidation of formic acid by bromine in acid aqueous media. International Journal of Chemical Kinetics, 12 (12). pp. 1013-1020. ISSN 0538-8066. doi:10.1002/kin.550121210. https://resolver.caltech.edu/CaltechAUTHORS:20150731-122050576

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Abstract

The reaction between formic acid and bromine in strongly acid aqueous media at 298 K Br_2 + HCOOH → 2Br^- + 2H^+CO_2 was studied by absorption spectrophotometry (λ = 447 nm). Reaction rates, expressed as R = -d[Br_2]/dt, depend on the concentrations of HCOOH (0.3–2.4M), Br_2[(2.7–13.6) × 10^(−3)M], H^+ (0.03–2.0M), and Br^− (up to 0.6M). The mechanism HCOO^- + Br_2 → 2Br^- + H^+ + CO_2 HCOOH ^2⇌_(-2) HCOO^- + H^+ Br^- + Br_2 ^3⇌_(-3) Br_3^- with k_1 = 20.2 ± 1.2 M^(−1) sec^(−1), pK_2 = 3.76, pK_3 = −1.20, accounts for all experimental observations. Br_3^− and HCOOH can be considered unreactive within experimental error. Apparent deviations from the basic mechanism at higher acidities can be quantitatively ascribed to the nonideality of ionic species.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1002/kin.550121210DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/kin.550121210/abstractPublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1980 John Wiley & Sons. Received April 14, 1980, Accepted June 11, 1980.
Issue or Number:12
DOI:10.1002/kin.550121210
Record Number:CaltechAUTHORS:20150731-122050576
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150731-122050576
Official Citation:Brusa, M. A. and Colussi, A. J. (1980), The kinetics and mechanism of the oxidation of formic acid by bromine in acid aqueous media. Int. J. Chem. Kinet., 12: 1013–1020. doi: 10.1002/kin.550121210
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59113
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:06 Aug 2015 20:38
Last Modified:10 Nov 2021 22:15

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