1. Temperature-Dependent Rate and Equilibrium Constants for Br<SUP>•</SUP>(aq) + Br<SUP>-</SUP>(aq) ↔ Br<INF>2</INF><SUP>-•</SUP>(aq)
- Author
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Liu, Y., Pimentel, A. S., Antoku, Y., Giles, B. J., and Barker, J. R.
- Abstract
Aqueous bromine atoms were produced by laser flash photolysis of 1,2-dibromoethane at 248 nm in solutions containing bromide ions. Forward and reverse rate constants of the title reaction were determined as functions of temperature. An analysis of potential sources of systematic errors shows that the measured forward and reverse rate constants have relative uncertainties (±σ
k /k) of ~10 and ~25%, respectively, over the temperature range from 10.5 to 50 °C. The Arrhenius parameters are (k f ± 10%) = 5.1 × 1012 exp (−1812/T) M-1 s-1 and (kr ± 25%) = 2.5 × 1010exp (−4068/T) s-1. The equilibrium constant is found from the ratio of kf /kr : (Keq ± 30%) = 2.0 × 102 exp (2256/T) M-1 or (3.9 ± 1.2) × 105 M-1 at 298 K. The reaction entropy and enthalpy are ΔSR ° = 44 ± 6 J mol-1 K-1 and ΔHR ° = −19 ± 2 kJ mol-1, respectively. The corresponding reaction reduction potential is ΔE° = 0.33 ± 0.01 V, in very good agreement with that calculated from half-cell potentials. In addition, preliminary rate constants for Br2 -• + Br2 -• → Br3 - + Br- and the hydrogen abstraction reaction (Br• + BrCH2 CH2 Br → •CBrH−CH2 −Br + H+ + Br-) are reported.- Published
- 2002
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