Catalysis of the reaction of ozone with chloride ions by metal ions in an acidic medium

Леванов, А. В.; Kuskov, I. V.; Koiaidarova, K. B.; Zosimov, A. V.; Antipenko, E. E.; Лунин, В. В.

doi:10.1007/s10975-005-0021-z

Cited by 27 publications

(11 citation statements)

References 5 publications

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“…The products, the kinetics, and the mechanism of the reaction between ozone and chloride ions in aque ous solutions were studied most comprehensively in RUSSIAN [8][9][10][11][12][13][14][15][16][17]. In a reaction proceeding in an acidic medium, the final product is molecular chlorine (in aqueous solutions of chloride, molecular chlorine is present in the form of Cl 2 and Cl complex ions).…”

mentioning

confidence: 99%

Primary stage of the reaction between ozone and chloride ions in aqueous solution: Oxidation of chloride ions with ozone through the mechanism of oxygen atom transfer

Леванов

Antipenko

Лунин

2012

Russ. J. Phys. Chem.

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519Studying how ozone reacts with chloride ions in aqueous solutions is of immediate interest. This reac tion is possible in various manufacturing processes (e.g., water conditioning and purification) involving the use of ozone and in which the presence of Cl -ions is possible. Due to the presence of ozone in the Earth's atmosphere and the great abundance of chloride ions in nature, the reaction between О 3 and Cl -can con siderably affect the environment. The probability of the reaction between these two components must be taken into account when using ozonized saline solu tion in medicine.The question of the nature of the primary stage in the complex reaction between О 3 and Cl -(aq) is of great importance. A mechanism in which the oxida tion of chloride ions with ozone occurs via the transfer of an oxygen atom from the О 3 molecule to the Cl -ion has been recognized in all works devoted to studying the reaction between О 3 and Cl -(aq) since 1949. In 2010, however, a new mechanism for this reaction was proposed: it was claimed that the oxidation of chloride atoms is accompanied by the transfer of an electron from the Cl -ion to the О 3 molecule [2, 3] (see also [4]). The purpose of this work is to clarify via which mechanism the primary stage of the reaction between О 3 and Cl -(aq) actually proceeds.One feature of the complex reaction between О 3 and Cl -(aq) is that its primary stage is a slow process. At the same time, the substances produced during the primary stage are much more reactive than chloride ions and enter into rapid secondary reactions that lead to the formation of the final products. As a result, indi vidual primary reactions (without secondary reac tions) is virtually inaccessible to experimental studies. Consequently, any conclusions as to the nature of the primary stage should be based on information about the final products and the kinetic features of the com plex reaction between О 3 and Cl -(aq) as a whole.The kinetics of the reaction between О 3 and Cl -(aq) in an acid aqueous solution were studied for the first time in [1]. The reaction was found to be catalyzed by Н + ions, and the rate constants were determined to be 0 and 9.5°С. At higher temperatures, determination of the rate constants failed, since the results were dis torted appreciably by the decomposition of ozone. For the same reason, only the upper limit value of the rate constant was determined in [5] for the non catalytic reaction between О 3 and Cl -(aq) at 23°С, k < 3 × 10 -3 l/(mol s) (pH 2). In [6,7], the kinetics of the decomposition of ozone in an aqueous solution containing chloride ions was studied using the same method as in [5]. If we relate the constant of the decomposition of ozone found in the works men tioned above to the concentration of chloride ions, we obtain the upper limit values for the rate constant of the noncatalytic reaction between О 3 and Cl -. These estimates are in agreement with the following data [5]: k < 3 × 10 -3 l/(mol s) (рН 6, 20°С) [6]; k < 6 × 10 -3 l/(mol s) (pH 6, 20°С) [7].The produ...

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confidence: 99%

Primary stage of the reaction between ozone and chloride ions in aqueous solution: Oxidation of chloride ions with ozone through the mechanism of oxygen atom transfer

Леванов

Antipenko

Лунин

2012

Russ. J. Phys. Chem.

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“…More recent works confirm the second order rate constant for this reaction as well as the catalytic effect of the H + . [31][32][33] Levanov et al 32,33 proposed the mechanism indicated by reactions B-D for this system. Siddiqui suggested that hypochlorite could react with ozone generating chloride and chlorite ions.…”

Section: Reaction Between Chloride Ion and Ozonementioning

confidence: 89%

“…Siddiqui suggested that hypochlorite could react with ozone generating chloride and chlorite ions. In addition, chlorite ion could also react with O 3 and produces chlorate ion by pathway shown in reactions E to G. 34 Levanov et al 32,33 suggested that Cl 2 formation and its release into a gas phase result from a rapidly established equilibrium. Unfortunately it is very difficult to identify chlorine gas in the presence of the ozone, especially at low reactants concentration used.…”

Section: Reaction Between Chloride Ion and Ozonementioning

confidence: 99%

Ozonation of azo dye acid black 1 under the suppression effect by chloride ion

Paprocki¹,

Santos²,

Hammerschitt³

et al. 2010

J. Braz. Chem. Soc.

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O objetivo deste estudo é determinar a cinética degradação do corante Acid Black 1 por ação oxidante do ozônio e avaliar a influência da contaminação de íons cloreto na degradação deste corante. Foram observadas cinéticas de pseudo-primeira ordem, tanto para a degradação das estruturas cromóforas (620 nm), quanto das aromáticas (321 nm). A completa remoção da coloração foi verificada em 25 min ([corante] 0 = 1,8 × 10 -5 mol L -1 ), enquanto que as estruturas aromáticas foram degradadas com menor velocidade. A presença de íon cloreto, principal impureza do reagente sólido, influencia significantemente a velocidade de ozonização (-42%), mesmo em baixa concentração (5,6 × 10 -4 mol L -1 ). O mecanismo mais provável para o efeito supressor do íon cloreto envolve a direta reação entre O 3 e Cl -gerando HOCl, dentre outros subprodutos. Apesar deste aspecto, a ozonização pode ser um processo de degradação competitivo para este corante.The aim of this study is to determine the kinetics of the Acid Black 1 dye by oxidizing action of ozone and to evaluate the influence of chloride ion contamination on the dye degradation. Pseudofirst order kinetics was observed for both decolorization (620 nm) and aromatic structure (321 nm) degradations. A complete color removal was verified in 25 min ([dye] 0 = 1.8 × 10 -5 mol L -1 ), while aromatic structures degraded at slower rates. The presence of chloride ion, the principal impurity of the solid dye reagents, influences significantly the ozonation rate (-42%), even at low chloride concentration (5.6 × 10 -4 mol L -1 ). The most probable mechanism for the chloride suppression effect involves a direct reaction between O 3 and Cl -generating HOCl, among other by-products. In despite of that, ozonation could be a competitive degradation process for this dye.

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“…Although literature about the reaction between O 3 , NaCl, and silver is not available, it is known that O 3 can react with chloride ions in an aqueous solution to form Cl 2 , according to Reaction 1. 16 It is likely that the alkaline form of this reaction occurs in the humid environment where the concentration of H + is limited The rate of the reaction forming Cl 2 , Reaction 1 or 5, is dependent on the pH of the solution, the concentration of catalytic ions, 18 the temperature, 19 and the concentration of dissolved ozone. 20 The decomposition of aqueous ozone can generate some OH radicals, but they are not able to oxidize chloride ions unless the pH is very acidic.…”

Section: Discussionmentioning

confidence: 99%

“…Certain metal ions such as cobalt ions can have catalytic effects on this reaction as the release of Cl 2 gas was observed to increase with increasing concentration of cobalt ions. 18 Moreover, increasing temperature can also increase the reaction rate. 19 Besides Cl 2 , the generation of chlorate ions ͑ClO 3 − ͒ was observed in alkaline media, and the concentration of aqueous ozone decreased with increasing pH as a result of the increased rate in ozone decomposition.…”

Section: Hmentioning

confidence: 99%

Effects of Sodium Chloride Particles, Ozone, UV, and Relative Humidity on Atmospheric Corrosion of Silver

Liang

Allen²,

Frankel

et al. 2010

J. Electrochem. Soc.

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The corrosion of Ag contaminated with NaCl particles in gaseous environments containing humidity and ozone was investigated. In particular, the effects of relative humidity and UV light illumination were quantitatively analyzed using a coulometric reduction technique. The atmospheric corrosion of Ag was greatly accelerated in the presence of ozone and UV light. Unlike bare Ag ͑i.e., with no NaCl particles on the surface͒, Ag with NaCl exhibited fast corrosion even in the dark, with no UV in the presence of ozone. Samples exposed to different outdoor environments and samples exposed in a salt spray chamber were studied for comparison. Ag corroded at extremely low rates in a salt spray chamber partly because of the combined absence of light and oxidizing agents such as ozone. © 2010 The Electrochemical Society. ͓DOI: 10.1149/1.3310812͔ All rights reserved. Despite their widespread use, the results of accelerated atmospheric corrosion tests such as ASTM B117 often do not correlate well with field exposures.1 As shown below, silver is an example of this phenomenon as silver oxidizes readily during outdoor field exposure but is barely attacked in a salt spray chamber. Clearly, some controlling factors of the chemical and electrochemical reactions in the field exposures are not accurately reproduced in the salt spray chamber environment.Atmospheric corrosion of silver is affected by factors such as relative humidity ͑RH͒, 2-4 airborne pollutants, 5,6 and temperature. Traditional atmospheric corrosion studies of Ag have focused mainly on sulfidation 3,7-9 as silver reacts strongly with sulfurcontaining species. The absence of such species in the ASTM B117 test is one reason why silver is relatively inert in the salt spray environment. However, there has been little focus on the effects of chloride and photoassisted corrosion.In a previous paper, 10 the effects of ozone, UV radiation, and RH on the atmospheric corrosion of bare silver were studied. Atomic oxygen generated by the photolysis of ozone by UV radiation reacted quickly with bare silver to form silver oxide. However, 254 nm UV radiation or ozone alone did not cause any corrosion of Ag within the exposure period. The corrosion rate of bare silver was relatively independent of RH, and it was suggested that the initial chemisorption of atomic oxygen or OH radical under wet conditions is relatively unaffected by RH. The effects of chloride on these reactions are not known. Furthermore, the atmospheric corrosion rate of metals in the field is typically dependent on RH as a result of the interactions of water with salts on the surface. 11Sea-salt aerosols can play a critical role in the atmospheric corrosion process. Cole et al. described marine aerosol formation, chemistry, reaction with atmospheric gases, transport, deposition onto surfaces, and reaction with surface oxides.12 The small size of sea-salt aerosols allows them to be carried away by the wind to places far away from the sea.13 These aerosols are created by physical processes such as the bursting of air...

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Catalysis of the reaction of ozone with chloride ions by metal ions in an acidic medium

Cited by 27 publications

References 5 publications

Primary stage of the reaction between ozone and chloride ions in aqueous solution: Oxidation of chloride ions with ozone through the mechanism of oxygen atom transfer

Primary stage of the reaction between ozone and chloride ions in aqueous solution: Oxidation of chloride ions with ozone through the mechanism of oxygen atom transfer

Ozonation of azo dye acid black 1 under the suppression effect by chloride ion

Effects of Sodium Chloride Particles, Ozone, UV, and Relative Humidity on Atmospheric Corrosion of Silver

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