Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction
The bromate-bromide reaction was investigated in an acidity range not studied yet. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm). It was observed a first-order behavior for bromate and bromide ions and a second-order behavior for H+ ion that results in the rate law nu = k[BrO3-][Br- ][H+]². This rate law suggests a mechanism involving two successive protonation of bromate followed by the interaction of the intermediate species H2BrO3+ with bromide. These results disagree with the obtained by other authors who observed a second-order behavior for the bromide and first-order for H+, and have proposed intermediate species like H2Br2O3 and HBr2O3-. The second-order for [H+] observed in the range 0.005 <= [H+] <= 2.77 mol L-1 sets down that the pKa of bromic acid, HBrO3, must be lower than -0.5 (T = 25 °C), different from all other values for this pKa proposed in the literature.
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Sociedade Brasileira de Química
2001
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oai:scielo:S0103-505320010006000142002-04-15Revisiting the Kinetics and Mechanism of Bromate-Bromide ReactionCôrtes,Carlos Eduardo S.Faria,Roberto B. bromic acid pKa bromate bromide kinetics The bromate-bromide reaction was investigated in an acidity range not studied yet. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm). It was observed a first-order behavior for bromate and bromide ions and a second-order behavior for H+ ion that results in the rate law nu = k[BrO3-][Br- ][H+]². This rate law suggests a mechanism involving two successive protonation of bromate followed by the interaction of the intermediate species H2BrO3+ with bromide. These results disagree with the obtained by other authors who observed a second-order behavior for the bromide and first-order for H+, and have proposed intermediate species like H2Br2O3 and HBr2O3-. The second-order for [H+] observed in the range 0.005 <= [H+] <= 2.77 mol L-1 sets down that the pKa of bromic acid, HBrO3, must be lower than -0.5 (T = 25 °C), different from all other values for this pKa proposed in the literature.info:eu-repo/semantics/openAccessSociedade Brasileira de QuímicaJournal of the Brazilian Chemical Society v.12 n.6 20012001-12-01info:eu-repo/semantics/articletext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532001000600014en10.1590/S0103-50532001000600014 |
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Côrtes,Carlos Eduardo S. Faria,Roberto B. |
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Côrtes,Carlos Eduardo S. Faria,Roberto B. Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction |
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Côrtes,Carlos Eduardo S. Faria,Roberto B. |
author_sort |
Côrtes,Carlos Eduardo S. |
title |
Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction |
title_short |
Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction |
title_full |
Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction |
title_fullStr |
Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction |
title_full_unstemmed |
Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction |
title_sort |
revisiting the kinetics and mechanism of bromate-bromide reaction |
description |
The bromate-bromide reaction was investigated in an acidity range not studied yet. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm). It was observed a first-order behavior for bromate and bromide ions and a second-order behavior for H+ ion that results in the rate law nu = k[BrO3-][Br- ][H+]². This rate law suggests a mechanism involving two successive protonation of bromate followed by the interaction of the intermediate species H2BrO3+ with bromide. These results disagree with the obtained by other authors who observed a second-order behavior for the bromide and first-order for H+, and have proposed intermediate species like H2Br2O3 and HBr2O3-. The second-order for [H+] observed in the range 0.005 <= [H+] <= 2.77 mol L-1 sets down that the pKa of bromic acid, HBrO3, must be lower than -0.5 (T = 25 °C), different from all other values for this pKa proposed in the literature. |
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Sociedade Brasileira de Química |
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2001 |
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http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532001000600014 |
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AT cortescarloseduardos revisitingthekineticsandmechanismofbromatebromidereaction AT fariarobertob revisitingthekineticsandmechanismofbromatebromidereaction |
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