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Kinetics and Mechanism for Oxidation of Tetracyanoplatinate(II) by Chlorine and Hypochlorous Acid and for Hydrolysis of Chlorine in Aqueous Solution

Drougge, Lise and Elding, Lars Ivar LU (1985) In Inorganic Chemistry 24(14). p.2292-2297
Abstract
Oxidation of Pt(CN)42- in aqueous solutions of chlorine has been followed by stopped-flow spectrophotometry. For pH less than ca. 7, the reaction takes place by two parallel paths with Cl2 and HOCl as oxidants. Rate law determined. In unbuffered solutions of chlorine in aqueous NaClO4, the slow HOCl path is predominant, whereas in weakly acidic solutions buffered with HCl, oxidation takes place via the five orders of magnitude faster Cl2 path. For certain conditions, the displacement of the hydrolysis equilibrium of chlorine becomes rate-determining for the oxidation of Pt(CN)42- by chlorine, which then appears to be zero order in complex. Equilibrium and rate constants determined. Oxidation by HOCl gives primarily trans-Pt(CN)4(OH)22-,... (More)
Oxidation of Pt(CN)42- in aqueous solutions of chlorine has been followed by stopped-flow spectrophotometry. For pH less than ca. 7, the reaction takes place by two parallel paths with Cl2 and HOCl as oxidants. Rate law determined. In unbuffered solutions of chlorine in aqueous NaClO4, the slow HOCl path is predominant, whereas in weakly acidic solutions buffered with HCl, oxidation takes place via the five orders of magnitude faster Cl2 path. For certain conditions, the displacement of the hydrolysis equilibrium of chlorine becomes rate-determining for the oxidation of Pt(CN)42- by chlorine, which then appears to be zero order in complex. Equilibrium and rate constants determined. Oxidation by HOCl gives primarily trans-Pt(CN)4(OH)22-, which rapidly reacts with a second molecule of HOCl to form a stable hypochlorite complex. Oxidations with HOCl and ClO- are inner-sphere two-electron transfers with the oxygen of the hypochlorite as bridging atom. (Less)
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publication status
published
subject
keywords
Tetracyanoplatinate(II), Chlorine, Hypochlorous acid, Oxidation, Hydrolysis, Tetracyanoplatinate(II), Chlorine, Hypochlorous acid, Oxidation, Reaction mechanism, Hypochlorite complex, Chlorine hydrolysis, Stopped-flow spectrophotometry
in
Inorganic Chemistry
volume
24
issue
14
pages
6 pages
publisher
The American Chemical Society
external identifiers
  • scopus:0009760426
ISSN
1520-510X
DOI
10.1021/ic00208a033
language
English
LU publication?
yes
id
871e8e0a-9d39-4cb0-940c-25c04e2bb22b
date added to LUP
2017-02-07 18:54:08
date last changed
2017-07-30 05:21:15
@article{871e8e0a-9d39-4cb0-940c-25c04e2bb22b,
  abstract     = {Oxidation of Pt(CN)42-  in aqueous solutions of chlorine has been followed by stopped-flow spectrophotometry. For pH less than ca. 7, the reaction takes place by two parallel paths with Cl2 and HOCl as oxidants.  Rate law determined. In unbuffered solutions of chlorine in aqueous NaClO4, the slow HOCl path is predominant, whereas in weakly acidic solutions buffered with HCl, oxidation takes place via the five orders of magnitude faster Cl2 path. For certain conditions, the displacement of the hydrolysis equilibrium of chlorine becomes rate-determining for the oxidation of Pt(CN)42- by chlorine, which then appears to be zero order in complex. Equilibrium and rate constants determined. Oxidation by HOCl gives primarily trans-Pt(CN)4(OH)22-, which rapidly reacts with a second molecule of HOCl to form a stable hypochlorite complex. Oxidations with HOCl and ClO- are inner-sphere two-electron transfers with the oxygen of the hypochlorite as bridging atom. },
  author       = {Drougge, Lise and Elding, Lars Ivar},
  issn         = {1520-510X},
  keyword      = {Tetracyanoplatinate(II),Chlorine,Hypochlorous acid,Oxidation,Hydrolysis,Tetracyanoplatinate(II),Chlorine,Hypochlorous acid,Oxidation,Reaction mechanism,Hypochlorite complex,Chlorine hydrolysis,Stopped-flow spectrophotometry},
  language     = {eng},
  month        = {07},
  number       = {14},
  pages        = {2292--2297},
  publisher    = {The American Chemical Society},
  series       = {Inorganic Chemistry},
  title        = {Kinetics and Mechanism for Oxidation of Tetracyanoplatinate(II) by Chlorine and Hypochlorous Acid and for Hydrolysis of Chlorine in Aqueous Solution},
  url          = {http://dx.doi.org/10.1021/ic00208a033},
  volume       = {24},
  year         = {1985},
}