A peroxy-radical of chlorine, Cl·O·O

Eachus, R. S.; Edwards, P.; Subramanian, S.; Symons, Martyn C. R.

doi:10.1039/c19670001036

Cited by 6 publications

(7 citation statements)

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“…This “chlorine peroxide” of ref.32 was generated from KClO 4 by irradiating with γ-rays at 195 K; however, the reported value, g 0 = 2.009, was similar to that of the superoxide anion (O 2 ●− ). As a result, we believe the value reported by Eachus et al [ 32 ] is for an oxygen radical (O ● ). On the other hand, g 0 = 2.0043 is close to g 0 = 2.000, the value for a chlorine radical (Cl ● ), rather than g = 2.0114.…”

Section: Resultsmentioning

confidence: 71%

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Identifying the chloroperoxyl radical in acidified sodium chlorite solution

Kawata¹,

Kohno

Nukina³

et al. 2021

PLoS ONE

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The present study identified the active radical species in acidic sodium chlorite and investigated the feasibility of quantifying these species with the diethylphenylenediamine (DPD) method. Electron spin resonance (ESR) spectroscopy was used to identify the active species generated in solutions containing sodium chlorite (NaClO2). The ESR signal was directly observed in an acidified sodium chlorite (ASC) aqueous solution at room temperature. This ESR signal was very long-lived, indicating that the radical was thermodynamically stable. The ESR parameters of this signal did not coincide with previously reported values of the chlorine radical (Cl●) or chlorine dioxide radical (O = Cl●-O and O = Cl-O●). We refer to this signal as being from the chloroperoxyl radical (Cl-O-O●). Quantum chemical calculations revealed that the optimal structure of the chloroperoxyl radical is much more thermodynamically stable than that of the chlorine dioxide radical. The UV-visible spectrum of the chloroperoxyl radical showed maximum absorbance at 354 nm. This absorbance had a linear relationship with the chloroperoxyl radical ESR signal intensity. Quantifying the free chlorine concentration by the DPD method also revealed a linear relationship with the maximum absorbance at 354 nm, which in turn showed a linear relationship with the chloroperoxyl radical ESR signal intensity. These linear relationships suggest that the DPD method can quantify chloroperoxyl radicals, which this study considers to be the active species in ASC aqueous solution.

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Section: Resultsmentioning

confidence: 71%

“…In the case of Eachus et al [ 32 ], the ESR parameters reported were g x = 1.9983 and α x = 0.53 mT, g y = 2.0017 and α y = 0.72 mT, and g z = 2.0130 and α z = 1.49 mT for “chlorine peroxide, Cl-O-O”. The g 0 value was g 0 = ( g z + g x + g y )/3 = 2.0043 and α 0 = (α z +α x +α y )/3 = 0.913 mT.…”

Section: Resultsmentioning

confidence: 99%

Identifying the chloroperoxyl radical in acidified sodium chlorite solution

Kawata¹,

Kohno

Nukina³

et al. 2021

PLoS ONE

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“…During the course of the study, it became apparent that there remained disagreement between different investigators of the low pressure region for the reaction, 2CIO~Cl 2 +0 2 • Porter [6] was the first to report the existence of the ClO radical in a mixture of chlorine and oxygen after flash photolysis by observing intense vibronic bands from 3100 to 2577 A.· Since its discovery, ClO has been observed in the same ultraviolet region by many investigators, [5,[7][8][9][10][11][12][13][14][15] with various methods of production. The electron spin resonance of the radical has been observed both in rigid solution [16] and in the gas phase [17,18]. Infrared study by the method of matrix iso'lation [19] has identified the dimer, Cl 2 0 2 , but not the radical, ClO.…”

Section: Discussionmentioning

confidence: 94%

“…Other indirect evidence has been presented for the existence of CIOO; [20] however, direct evidence of the existence of ClOO has been obtained only recently. Cole [21] detected an electron spin resonance ascribed to ClOO in an irradiated perchlorate single crystal, and another electron spin resonance was tentatively ascribed to it [16]. In a matrix isolation study, Rochkind and Pimentel [19] assigned a pair of infrared absorption bands to ClOO; and a positive identification of ClOO in an argon matrix was made by Arkell and Schwager [22] in an infrared study.…”

Section: Discussionmentioning

confidence: 99%

“…The phase-shift method extracts the fundamental component of this complex function and express it as C = (Cs/2) [1+1Xsin(2nt/T+¢)] (16) where ¢ is the phase-shift between exciting light and radical species, and IX is the r(/.tio of the modulation amplitude em to the steady-state amplitude c, of the radical. If the function (16) is substituted into the defining equations (13) and (14) for Z 1 and Z 2 , we obtain (23) it is seen that the complete, digital method expressed as plane polar coordinates gives identical results as the phase-shift method for phase ¢ and relative amplitude, IX.…”

Section: )mentioning

confidence: 99%

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Molecular Modulation Mass Spectrometry Kinetic Study of the ClO Free Radical

Johnston

1972

Bulletin des Soc Chimique

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In complex photochemical reactions the effective mechanism may be different at low and at high light intensities, since the ratio of radicals to reactants may approach unity at high light intensities and may be 10−4 or less at low light intensities (such as sunlight). The method of flash photolysis has been highly successful in measuring the spectra and kinetics of free radicals in systems of high light intensities. In this laboratory a method named “molecular modulation spectrometry” has been developed, which measures the spectra and lifetimes of free‐radicals in lowintensity photochemical systems. Previous versions have utilized infrared and ultraviolet spectrometry. In this article the method is extended to ion‐counting mass spectrometry. The molecular‐modulation mass spectrometer was used to re‐investigate the kinetics of the CIO radical at low pressure and at low light intensities. Studies by flash photolysis have shown that the CIO radical decays by simple, second‐order kinetics This study confirms the previous result found in low intensity photolysis of CI2 and O2 that the decay process is complex and dependent on inert gas The change in rate law between high and low light intensities and trends exhibited by the parameters, k′ and k″, show that we still do not have a complete understanding of the mechanism of this reaction.

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Part 3

Morton¹,

Preston²

Atoms, Inorganic Radicals, and Radicals in Metal Complexes

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A peroxy-radical of chlorine, Cl·O·O

Abstract: Technology and to the Science Research Council for their support of this work.

Cited by 6 publications

References 0 publications

Identifying the chloroperoxyl radical in acidified sodium chlorite solution

Identifying the chloroperoxyl radical in acidified sodium chlorite solution

Molecular Modulation Mass Spectrometry Kinetic Study of the ClO Free Radical

Part 3

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