Catalytic oxidation of thiocyanates in an acid medium

Батоева, А. А.; Tsybikova, B. A.; Ryazantsev, A. V.

doi:10.1134/s1070427210060121

Cited by 4 publications

(3 citation statements)

References 11 publications

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“…. The oxidizing agents of choice are usually hydrogen peroxide (H 2 O 2 ) 21 and ozone (O 3 ) 23 in order to avoid the formation of any hazardous side products.…”

Section: −mentioning

confidence: 99%

“…Technologically feasible processes for SCN – removal almost exclusively utilize oxidative degradation approaches . The fundamental reactions of these processes are catalytic, − photocatalytic, , and also biological oxidations. , The universal goal is to convert SCN – quantitatively into environmentally more tolerable cyanate ion (OCN – ) [or carbonate ion (CO 3 2– ) and nitrogen (N 2 )] and SO 4 2– . The oxidizing agents of choice are usually hydrogen peroxide (H 2 O 2 ) and ozone (O 3 ) in order to avoid the formation of any hazardous side products.…”

Section: Introductionmentioning

confidence: 99%

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Detailed Kinetics and Mechanism of the Oxidation of Thiocyanate Ion (SCN^–) by Peroxomonosulfate Ion (HSO₅^–). Formation and Subsequent Oxidation of Hypothiocyanite Ion (OSCN^–)

2013

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The haloperoxidase-catalyzed in vivo oxidation of thiocyanate ion (SCN(-)) by H(2)O(2) is important for generation of the antimicrobial hypothiocyanite ion (OSCN(-)), which is also susceptible to oxidation by strong in vivo oxidizing agents (i.e., H(2)O(2), OCl(-), OBr(-)). We report a detailed mechanistic investigation on the multistep oxidation of excess SCN(-) with peroxomonosulfate ion (HSO(5)(-) in the form of Oxone) in the range from pH 6.5 to 13.5. OSCN(-) was detected to be the intermediate of this reaction under the above conditions, and a kinetic model is proposed. Furthermore, by kinetic separation of the consecutive reaction steps, the rate constant of the direct oxidation of OSCN(-) by HSO(5)(-) was determined: k(2) = (1.6 ± 0.1) × 10(2) M(-1) s(-1) at pH 13.5 and k(2)(H) = (3.3 ± 0.1) × 10(3) M(-1) s(-1) at pH 6.89. A critical evaluation of the estimated activation parameters of the elementary steps revealed that the oxidations of SCN(-) as well as the consecutive OSCN(-) by HSO(5)(-) are more likely to proceed via 2e(-)-transfer steps rather than 1e(-) transfer.

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“…. The oxidizing agents of choice are usually hydrogen peroxide (H 2 O 2 ) 21 and ozone (O 3 ) 23 in order to avoid the formation of any hazardous side products.…”

Section: −mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Detailed Kinetics and Mechanism of the Oxidation of Thiocyanate Ion (SCN^–) by Peroxomonosulfate Ion (HSO₅^–). Formation and Subsequent Oxidation of Hypothiocyanite Ion (OSCN^–)

2013

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“…3 The rate of SCN − oxidation by H 2 O 2 is slow 4 in the absence of peroxidases, however, other oxidants like HOCl, 5 HOBr, 6 ClO 2 7 and HSO 5 − 8 effect SCN − oxidation efficiently resulting in the formation of putative hypothiocyanite ions. Apart from biological significance, the oxidation of thiocyanate is important in regard to its removal from industrial waste water, 9 and thiocyanation of various organic compounds in synthetic organic chemistry. 10,11 The mechanism of oxidation of thiocyanate is quite complex because of the formation of various fleeting intermediates, however, the biological significance of hypothiocyanite (two-electron oxidation product of thiocyanate) has been well documented in a very recent review article.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of thiocyanate with H2O2 catalyzed by [RuIII(edta)(H2O)]−

2013

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The [Ru(III)(edta)(H2O)](-) (edta(4-) = ethylenediaminetetraacetate) complex is shown to catalyze the oxidation of thiocyanate (SCN(-)) with H2O2 mimicking the action of peroxidases. The kinetics of the catalytic oxidation process was studied by using stopped-flow and rapid scan spectrophotometry as a function of [Ru(III)(edta)], [H2O2], [SCN(-)], pH (3.2-9.1) and temperature (15-30 °C). Spectral analyses and kinetic data are suggestive of a catalytic pathway in which hydrogen peroxide reacts directly with thiocyanate coordinated to the Ru(III)(edta) complex. Catalytic intermediates such as [Ru(III)(edta)(OOH)](2-) and [Ru(V)(edta)(O)](-) were found to be non-reactive in the oxidation process under the specified conditions. Formation of SO4(2-) and OCN(-) was identified as oxidation products in ESI-MS experiments. A detailed mechanism in agreement with the spectral and kinetic data is presented.

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A critical review on destruction of thiocyanate in mining effluents

Gould

King

Mohapatra

et al. 2012

Minerals Engineering

119

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Catalytic oxidation of thiocyanates in an acid medium

Cited by 4 publications

References 11 publications

Detailed Kinetics and Mechanism of the Oxidation of Thiocyanate Ion (SCN^–) by Peroxomonosulfate Ion (HSO₅^–). Formation and Subsequent Oxidation of Hypothiocyanite Ion (OSCN^–)

Detailed Kinetics and Mechanism of the Oxidation of Thiocyanate Ion (SCN^–) by Peroxomonosulfate Ion (HSO₅^–). Formation and Subsequent Oxidation of Hypothiocyanite Ion (OSCN^–)

Oxidation of thiocyanate with H2O2 catalyzed by [RuIII(edta)(H2O)]−

A critical review on destruction of thiocyanate in mining effluents

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Catalytic oxidation of thiocyanates in an acid medium

Cited by 4 publications

References 11 publications

Detailed Kinetics and Mechanism of the Oxidation of Thiocyanate Ion (SCN–) by Peroxomonosulfate Ion (HSO5–). Formation and Subsequent Oxidation of Hypothiocyanite Ion (OSCN–)

Detailed Kinetics and Mechanism of the Oxidation of Thiocyanate Ion (SCN–) by Peroxomonosulfate Ion (HSO5–). Formation and Subsequent Oxidation of Hypothiocyanite Ion (OSCN–)

Oxidation of thiocyanate with H2O2 catalyzed by [RuIII(edta)(H2O)]−

A critical review on destruction of thiocyanate in mining effluents

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Product

Resources

About

Detailed Kinetics and Mechanism of the Oxidation of Thiocyanate Ion (SCN^–) by Peroxomonosulfate Ion (HSO₅^–). Formation and Subsequent Oxidation of Hypothiocyanite Ion (OSCN^–)

Detailed Kinetics and Mechanism of the Oxidation of Thiocyanate Ion (SCN^–) by Peroxomonosulfate Ion (HSO₅^–). Formation and Subsequent Oxidation of Hypothiocyanite Ion (OSCN^–)