Micellar catalytic effects in the oxidation of methyl phenyl sulfide with hydrogen peroxide and the hydrogen peroxocarbonate anion

Vakhitova, L. N.; Zhil’tsova, S. V.; Skrypka, A. V.; Razumova, N. G.; Taran, N. A.; Savëlova, V. A.; Popov, A. F.

doi:10.1007/s11237-006-0055-y

Cited by 9 publications

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References 7 publications

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“…The observed pH dependences may be rationalized as follows (on a qualitative level): the oxidation process involves both neutral hydrogen peroxide and its anion HO 2 -; the concentration of the latter increases as pH rises, whereas its oxidizing power is weaker than that of neutral species [30,35]. Increase of pH also leads to reduction of the concentration of the active oxidant species as a result of dissociation of HCO 4 -ions to CO 4 2-; like HO 2 -, CO 4 2-is a weaker oxidant than its protonated form [32,36].…”

Section: Methodsmentioning

confidence: 99%

“…As model substrates we used diethyl 4-nitrophenyl phosphonate (I) (Paraoxon), which is a structural analog of organophosphorus neuroparalytic agents and pesticides [1,20,21,23], and methylsulfanylbenzene (II, thioanisole) as analog of HD in both reactivity and hydrophobic properties [17,[29][30][31][32][33][34]. As the main decontaminating agent we examined hydrogen peroxide which is a mild and ecologically safe oxidant toward HD analogs, and its anionic form HOO -shows supernucleophilic properties with respect to organophosphorus compounds.…”

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Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

et al. 2011

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The kinetics of oxidation of methylsulfanylbenzene and nucleophilic decomposition of diethyl 4-nitrophenyl phosphate with hydrogen peroxide in the presence of ammonium hydrogen carbonate or boric acid in aqueous, aqueous-alcoholic, micellar, and microemulsion media were studied. Quantitative parameters of the examined processes were determined, and the possibility of using hydrogen peroxide for the design of oxidative nucleophilic decontaminating systems was demonstrated.Taking into account huge worldwide stocks of chemical weapons [1-6], the problem implying utilization of highly toxic chemical agents has recently become especially important. The most common chemical weapons may be divided into three main groups: (1) phosphorus acid esters (neurotoxins and structurally similar pesticides, e.g., GB, GD, and Metaphos); (2) organosulfur compounds (blister agents, e.g., Yperite or HD); and (3) compounds with combined (neuroparalytic) action (VX).The optimal system for decontamination of toxic chemical agents should ensure their solubilization and simultaneously high rate of decomposition. Therefore, organized nanosize systems such as micellar solutions and microemulsions are promising from the viewpoint of development of ecologically safe decontaminating compositions [11,12,[15][16][17][18][19][20][21]; these systems provide increased reagent concentration at the phase boundary between micelles (oil drop) and water and create favorable conditions for nucleophilic attack on electrophilic centers of toxic substrates [21,22].While searching for chemically active components capable of rapidly and irreversibly decomposing toxic chemicals, specific attention is now given to the design of universal oxidative nucleophilic systems for degradation of chemical agents of different natures. For example, nucleophilic reagents are efficient toward phosphorus acid esters and halides (GB) [23,24], dialkyl sulfides like HD are decomposed by the action of oxidants [16,25,26], whereas oxidative nucleophilic systems containing an HOX-OX -couple (X = OH, Hlg, etc.) are preferred for decontamination of chemical agents like VX or mixtures of compounds belonging to the above three types (GB, HD, VX) [20,27]. In this respect, hydrogen peroxide due to its dual nature (it is an effective oxidant toward HD analogs [15,25] and reactive α-nucleophile toward phosphorus acid esters [1,24,28]) may be regarded as universal agent in the design of mild and ecologically safe decontami-

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confidence: 99%

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confidence: 99%

Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

et al. 2011

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“…Paraoxon was selected as the model substrate because it is an analog of organophosphorus pesticides and military poison gases (GB and VX) and has been studied in detail in nucleophilic reactions involving the hydroperoxide anion HOO -[1, 2,8]. Micellar, microemulsion (ME), and water-ethanol solutions, shown in our previous work [1, 8,9] to have a high solubilizing effect on paraoxon, were used as the reaction media.…”

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confidence: 99%

“…Nevertheless, Persol holds special interest as a decontaminating agent relative to optimization of the acidic properties of oxidative nucleophilic systems. In previous work [2,9], we found that the limiting pH value, at which the 226 (1) ________ *Here and henceforward, the hydrogen peroxide concentration [H 2 O 2 ] 0 indicates the initial concentrations of hydrogen peroxide within peroxysolvates I and II.…”

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confidence: 99%

“…The decrease in the micelle effect using peroxysolvate II as the source of HOO -anion (compare the values of (k obs /k w ) max for samples 3 and 1, Table 2) with increasing value of K S is predicted and understood considering the effect of electrolytic additives on micellar catalytic reactions [9] and is also confirmed by independent data for the reaction in the H 2 O 2 /HO -/CTAB system with added NH 4 HCO 3 (sample 4, Table 2). A logical explanation for the decrease in the micellar increase in rate in the reaction with peroxysolvate II (sample 3, Table 2) is competitive adsorption of HOO -and CO 3 2-on the micelle surface, which leads to a decrease in the concentration of the HOOanion [2]. Evaluation of the micellar catalytic effects using Eq.…”

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Peroxysolvates of carbamide and sodium carbonate in the nucleophilic decomposition of paraoxon

et al. 2011

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The nucleophilic decomposition of paraoxon (4-nitrophenyl ester of diethylphosphoric acid) by the HOOanion generated from peroxysolvates of sodium carbamide and carbonate in aqueous, micellar, microemulsion, and water-ethanol media was studied. Feasibility was demonstrated for the use of solid sources of hydrogen peroxide in decontaminating nucleophilic systems.Key words: nucleophilic substitution, kinetics, hydrogen peroxide, carbamide peroxysolvate, sodium carbonate peroxysolvate, 4-nitrophenyl ester of diethylphosphoric acid, chemical decontaminating systems.Hydrogen peroxide (H 2 O 2 ) as a decontaminating agent meets the major requirements of systems for the elimination of chemical contaminants in the environment [1]. In the form of H 2 O 2 , HOO -anions, and peroxo anions, hydrogen peroxide has high and broad activity relative to the major types of ecotoxicant substrates, namely, yperite analogs [2, 3] and pentavalent phosphorus compounds [1,4], and meets the major requirements of green technology. However, the use of concentrated aqueous solutions of H 2 O 2 entails additional risks in storage, transport, and use at temperatures below 0°C [5]. Thus, solid nonaqueous reagents such as peroxysolvates of carbamide (hydroperite, CO(NH 2 ) 2 ·H 2 O 2 (I)) and sodium carbonate (Persol, Na 2 CO 3 ·1.5H 2 O 2 (II)) should be used as alternative sources of H 2 O 2 . Peroxysolvates I and II are crystalline nontoxic industrial chemicals, which are stable upon storage [6]. Hydroperite and Persol are used in large quantities as efficient oxidizing agents and components of household chemicals [6]. These compounds have also been used for the oxidation of yperite analogs [5,7]. Hence, it was of interest to study the nucleophilic reactivity of peroxysolvates I and II relative to organophosphorus esters to determine the feasibility of their use as alternative sources of H 2 O 2 in oxidative nucleophilic decontamination systems.In the present work, we studied the kinetics of the decomposition of 4-nitrophenyl ester of diethylphosphoric acid (paraoxon (III)) by the peroxysolvates of carbamide and sodium carbonate in aqueous, micellar, microemulsion, and water-ethanol media. 0040-5760/11/4704-0225

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Efficient decolorization of typical azo dyes using low-frequency ultrasound in presence of carbonate and hydrogen peroxide

Zhao

Tai

et al. 2018

Journal of Hazardous Materials

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Micellar catalytic effects in the oxidation of methyl phenyl sulfide with hydrogen peroxide and the hydrogen peroxocarbonate anion

Cited by 9 publications

References 7 publications

Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

Peroxysolvates of carbamide and sodium carbonate in the nucleophilic decomposition of paraoxon

Efficient decolorization of typical azo dyes using low-frequency ultrasound in presence of carbonate and hydrogen peroxide

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