Bray–Liebhafsky reaction

The Bray–Liebhafsky reaction is a chemical clock first described by William C. Bray in 1921 and the first oscillating reaction in a stirred homogeneous solution.[1] He investigated the role of the iodate (IO−
3), the anion of iodic acid, in the catalytic conversion of hydrogen peroxide to oxygen and water by the iodate. He observed that the concentration of iodine molecules oscillated periodically and that hydrogen peroxide was consumed during the reaction.

An increase in temperature reduces the cycle in the range of hours. This oscillating reaction consisting of free radical on non-radical steps was investigated further by his student Herman A. Liebhafsky,[2] hence the name Bray–Liebhafsky reaction. During this period, most chemists rejected the phenomenon and tried to explain the oscillation by invoking heterogeneous impurities.

A fundamental property of this system is that hydrogen peroxide has a redox potential which enables the simultaneous oxidation of iodine to iodate:

5 H2O2 + I2 → 2 IO−
3 + 2 H+ + 4 H2O

and the reduction of iodate back to iodine:

5 H2O2 + 2 IO−
3 + 2 H+ → I2 + 5 O2 + 6 H2O

Between these two reactions the system oscillates causing a concentration jump of the iodide and the oxygen production. The net reaction is:

2 H2O2 → 2 H2O + O2

necessitating a catalyst and IO−
3.

References
  1. Bray, William C. (1921). "A periodic reaction in homogeneous solution and its relation to catalysis". Journal of the American Chemical Society. 43 (6): 1262–1267. doi:10.1021/ja01439a007.
  2. Bray, William C.; Liebhafsky, Herman A. (1931). "Reactions involving hydrogen peroxide, iodine and iodate ion. I. Introduction". Journal of the American Chemical Society. 53: 38–44. doi:10.1021/ja01352a006.

Further reading
  • Treindl, Ludovit; Noyes, Richard M. (1993). "A new explanation of the oscillations in the Bray–Liebhafsky reaction". The Journal of Physical Chemistry. 97 (43): 11354. doi:10.1021/j100145a039.
  • Edelson, David; Noyes, Richard M. (1979). "Detailed calculations modeling the oscillatory Bray–Liebhafsky reaction". The Journal of Physical Chemistry. 83 (2): 212. doi:10.1021/j100465a002.
  • Schmitz, Guy (1999). "Effects of oxygen on the Bray–Liebhafsky reaction". Physical Chemistry Chemical Physics. 1 (19): 4605–4608. Bibcode:1999PCCP....1.4605S. doi:10.1039/a904722k.
  • Valent, Ivan; Adamčikova, Ľubica; Sevčik, Peter (1998). "Simulations of the Iodine Interphase Transport Effect on the Oscillating Bray−Liebhafsky Reaction". The Journal of Physical Chemistry A. 102 (39): 7576. Bibcode:1998JPCA..102.7576V. doi:10.1021/jp982323b.
  • Buchholtz, Frank G.; Broecker, Sebastian (1998). "Oscillations of the Bray–Liebhafsky Reaction at Low Flow Rates in a Continuous Flow Stirred Tank Reactor". The Journal of Physical Chemistry A. 102 (9): 1556. Bibcode:1998JPCA..102.1556B. doi:10.1021/jp973362a.
  • Stanisavljev, Dragomir; Begović, Nebojša; Vukojević, Vladana (1998). "Influence of Heavy Water on the Bray−Liebhafsky Oscillating Reaction". The Journal of Physical Chemistry A. 102 (35): 6887. Bibcode:1998JPCA..102.6887S. doi:10.1021/jp9808025.
  • Jiménez Prieto, Rafael; Silva, Manuel; Pérez Bendito, Dolores (1998). "Critical Review: Approaching the use of oscillating reactions for analytical monitoring". The Analyst. 123 (2): 1. Bibcode:1998Ana...123....1J. doi:10.1039/a703354k.
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