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Kinetics and mechanism of the reaction between hypochlorous acid and tetrathionate ion

✍ Scribed by Attila K. Horváth; István Nagypál

Publisher
John Wiley and Sons
Year
2000
Tongue
English
Weight
250 KB
Volume
32
Category
Article
ISSN
0538-8066

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✦ Synopsis

The reaction has been studied spectrophotometrically monitoring the absorbance in the wavelength range. The spectra of the reactants, intermediates, and prod-240-400 nm ucts in this system are overlapping; thus special programs [1,2] have been used (and tested) to unravel the kinetics and mechanism of the reaction. The stoichiometry of the reaction in excess hypochlorous acid is Various ex-

4 6 2 4 periments are presented to show that-in excess tetrathionate-the reaction produces a light-absorbing intermediate identified as The intermediate slowly hydrolyzes into Ϫ S O Cl . 2 3 sulfur and sulfate and it yields pentathionate in excess tetrathionate. The rate-determining steps and their rate constants are k 1 2Ϫ Ϫ 2Ϫ ϩ Ϫ 1 Ϫ1 S O ϩ HOCl 9 9 : S O Cl ϩ S O ϩ H ; k ϭ 32.4 M s 4 6 2 3 2 4 1 k 2 Ϫ 2Ϫ Ϫ ϩ Ϫ 1 Ϫ1 S O Cl ϩ HOCl ϩ 2H O 9 9 : 2SO ϩ 2Cl ϩ 5H ; k ϭ 7.7 M s 2 3 2 3 2

The further oxidation of and by HOCl to sulfate are fast processes.

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