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 | |||||||||
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| 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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