Molybdenum(VI) catalysis of perborate or hydrogen peroxide oxidation of iodide ion

Karunakaran, C.; Muthukumaran, B.

doi:10.1007/bf00141517

Cited by 37 publications

(16 citation statements)

References 6 publications

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“…In aqueous and partly aqueous solution it affords hydrogen peroxide which acts as the oxidizing agent (1)(2)(3)(4)(5)(6). It oxidizes morpholine and N -methylmorpholine to the corresponding hydroxylamine and N -oxide, respectively (6).…”

Section: Introductionmentioning

confidence: 99%

FORMATION OF PERACETIC ACID ON AGING OF PERBORATE SOLUTIONS IN ACETIC ACID: KINETICS OF THE OXIDATION OF MORPHOLINE ANDN-METHYLMORPHOLINE

Karunakaran

Kamalam

2001

Synthesis and Reactivity in Inorganic and Metal-Organic Chemist

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Perborate solutions in glacial acetic acid generate peracetic acid on aging and the peracetic acid oxidation of morpholine and N -methylmorpholine is fast. But perborate dissolved in ethylene glycol or propylene glycol does not show the aging effect and the oxidation is smooth. The smooth oxidation exhibits Michalis-Menten dependence on [morpholines] and is of apparent zero order in the oxidizing agent but the rate increases linearly with [perborate] 0 . The mechanism of oxidation is discussed and the rate law derived.

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Section: Introductionmentioning

confidence: 99%

FORMATION OF PERACETIC ACID ON AGING OF PERBORATE SOLUTIONS IN ACETIC ACID: KINETICS OF THE OXIDATION OF MORPHOLINE ANDN-METHYLMORPHOLINE

Karunakaran

Kamalam

2001

Synthesis and Reactivity in Inorganic and Metal-Organic Chemist

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“…Sodium perborate is an environmentally friendly, cheap, nontoxic, large scale industrial chemical used primarily in detergents and as a mild oxidant. Sodium perborate is a true peroxo salt and is a convenient source of hydrogen peroxide [6,7].…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Oxidation of Hydrazine in Membraneless Fuel Cells

Durga

Ponmani

Kiruthika

et al. 2014

Journal of Electrochemical Science and Technology

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This paper describes the continuous flow operation of membraneless sodium perborate fuel cell using acid/alkaline bipolar electrolyte. Here, hydrazine is used as a fuel and sodium perborate is used as an oxidant under Alkaline-acid media configuration. Sodium perborate affords hydrogen peroxide in aqueous medium. In our operation, the laminar flow based microfluidic membranleless fuel cell achieved a maximum power density of 27.2 mW cm −2 when using alkaline hydrazine as the anolyte and acidic perborate as the catholyte at room temperature with a fuel mixture flow rate of 0.3 mL min -1. The simple planar structured membraneless sodium perborate fuel cell enables high design flexibility and easy integration of the microscale fuel cell into actual microfluidic systems and portable power applications.

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“…and in acetic acid-ethylene glycol with SPB dissolved in ethylene glycol (excluding p-nitro-Sphenylmercaptoacetic acid which follows different kinetics)10 (-0.98 at 45 °C, -0.55 at 55 °C, -0.83 to -0.77 at 45-65 °C and -0.80 to -0.72 at 50-60 °C, respectively).SPB on dissolution in glacial acetic acid yields equivalent amount of H 2 O 2 , and on aging peracetic acid is generated at the expense of H 2 O 2 4,5,11. In acetic acid, Na 2 MoO 4 exists as MoO 3 , the coordinated water molecule omitted 12. With H 2 O 2 , MoO 3 forms two peroxo species, dioxoperoxomolybdenum (VI) [MoO 2 (O 2 )] and oxodiperoxomolybdenum(VI) [MoO (O 2 ) 2 ], one of which is the reactive oxidant.…”

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confidence: 99%

Mo(Vi)-Catalysis of Perborate Oxidation of Aryl Sulfides in Acetic Acid

Karunakaran

2006

Journal of Chemical Research

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Molybdenum(VI) catalyses effectively the sodium perborate oxidation of aryl sulfides to sulfoxides in glacial acetic acid. The catalysed oxidations of diphenyl sulfide and S-phenylmercaptoacetic acids are zero order with respect to the oxidant and first order with respect to the sulfides and Mo(VI). Trichloroacetic acid enhances the oxidation. Glacial acetic acid is a suitable solvent; methanol or ethylene glycol suppresses the reaction. The kinetic results reveal dioxoperoxomolybdenum(VI) as the reactive oxidant.Economic and environmental constraints necessitate replacement of oxidation procedures requiring large amounts of heavy metals by catalytic alternatives using clean oxidants. Particularly of interest are procedures that use readily available catalysts and cheap oxygen sources. Sodium perborate (NaBO 3 .4H 2 O), a peroxo salt of anionic formula [B 2 (O 2 ) 2 (OH) 4 ] 2-, is an inexpensive, innocuous, easily handled, stable, large-scale industrial chemical primarily used in detergents. It is an effective reagent in organic synthesis, acetic acid is the solvent of choice 1-3 and we reported recently the mechanisms of oxidation of organic sulfides and anilines in glacial acetic acid. 4,5 In aqueous acetic acid perborate behaves as H 2 O 2 and metal ion catalysis is that of H 2 O 2 oxidation; 6,7 presence of water reduces the efficiency and is of little synthetic utility. 1 So far there is no report on metal ioncatalysed perborate oxidation in glacial acetic acid, hence this work. Muzart 8 reports Cr(VI)-assistance of perborate oxidation in benzene-water (1:1) under phase transfer conditions. Results and discussionSodium perborate (SPB) is insoluble in organic solvents like methanol, ethanol, 2-propanol, t-butanol, dimethylformamide, dioxane, acetonitrile, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypentan-2,3-diol and glycerol but readily dissolves in acetic acid and less so in ethylene glycol. In acetic acid, with catalytic amount of Na 2 MoO 4 , SPB effectively oxidises diphenyl sulfide to diphenyl sulfoxide, identified by its IR spectrum (1034 cm -1 ) and melting point (69 °C; lit. 70 °C); the yield is 75%. S-Phenylmercaptoacetic acid is oxidised to phenylsulfinylacetic acid, identified by its IR spectrum; 1078 (SO), 1724 (C = O), 3423, 3227, 3023 (OH) cm -1 . 3 .9H 2 O) are insoluble in glacial acetic acid and could not be employed as catalysts. Oxoacids of transition metals (vanadic, molybdic and tungstic acids) and phosphomolybdic and phosphotungstic acids also do not dissolve in glacial acetic acid. Although Zr(IV) catalyses the oxidation the catalytic efficiency is only about one-half of Mo(VI) and the kinetic results lack reproducibility; ZrOCl 2 .8H 2 O was the salt used.

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Molybdenum(VI) catalysis of perborate or hydrogen peroxide oxidation of iodide ion

Abstract: Perborate in aqueous solution generates H202; in its presence the molybdenum(VI) catalysed oxidation of iodide ion is first order with respect to the oxidant and catalyst, and is independent of [I-] and [H +]. Kinetic studies point to peroxymolybdenum(VI) species as the oxidizing species.

Cited by 37 publications

References 6 publications

FORMATION OF PERACETIC ACID ON AGING OF PERBORATE SOLUTIONS IN ACETIC ACID: KINETICS OF THE OXIDATION OF MORPHOLINE ANDN-METHYLMORPHOLINE

FORMATION OF PERACETIC ACID ON AGING OF PERBORATE SOLUTIONS IN ACETIC ACID: KINETICS OF THE OXIDATION OF MORPHOLINE ANDN-METHYLMORPHOLINE

Electrochemical Oxidation of Hydrazine in Membraneless Fuel Cells

Mo(Vi)-Catalysis of Perborate Oxidation of Aryl Sulfides in Acetic Acid

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