✦ LIBER ✦

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

✍ Scribed by M. A. Brusa; A. J. Colussi

Publisher: John Wiley and Sons
Year: 1980
Tongue: English
Weight: 326 KB
Volume: 12
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550121210

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✦ Synopsis

The reaction between formic acid and bromine in strongly acid aqueous media at 298 K Brz + HCOOH -2 Br-+ 2 H+ + COz was studied by absorption spectrophotometry (A = 447 nm). Reaction rates, expressed as H = -d[Brz]/dt, depend on the concentrations of HCOOH (0.3-2.4M), Br2[(2.7-13.6) X 10-3M], H+ (0.03-2.OM), and Br-(up to 0.6M). The mechanism 1 HCOO-+ Brz -+ 2 Br-+ H+ + COz HCOOH + HCOO-+ H+ Br-+ Brz +Bigwith k l = 20.2 f 1.2 M-l sec-', pK2 = 3.76, pK3 = -1.20, accounts for all experimental observations. Br3-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.

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