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 (IO₃⁻), 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 IO₃⁻ + 2 H⁺ + 4 H₂O

and the reduction of iodate back to iodine:

5 H₂O₂ + 2 IO₃⁻ + 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 IO₃⁻.

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. 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.

• Ludovit Treindl; Richard M. Noyes (1993). "new explanation of the oscillations in the Bray–Liebhafsky reaction". The Journal of Physical Chemistry. 97 (43): 11354. doi:10.1021/j1001.
• David. Edelson; Richard M. Noyes (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. Bibcode:1999PCCP....1.4605S. doi:10.1039/a904722k.
• Ivan Valent; L'ubica Adamčikova,; Peter Sevčik (1998). "Simulations of the Iodine Interphase Transport Effect on the Oscillating Bray−Liebhafsky Reaction". The Journal of Physical Chemistry A. 102 (39): 7576. doi:10.1021/jp982323b.
• Frank G. Buchholtz; Sebastian Broecker (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. doi:10.1021/jp973362a.
• Dragomir Stanisavljev; Nebojsa Begovic; Vladana Vukojevic (1998). "Influence of Heavy Water on the Bray−Liebhafsky Oscillating Reaction". The Journal of Physical Chemistry A. 102 (35): 6887. doi:10.1021/jp9808025.
• Jiménez-Prieto, Rafael; Silva, Manuel; Pérez-Bendito, Dolores (1998). "Critical ReviewApproaching the use of oscillating reactions for analytical monitoring". The Analyst. 123 (2): 1. Bibcode:1998Ana...123....1J. doi:10.1039/a703354k.