On the Mechanism of the Perborate Oxidation of Organic Sulfides in Glacial Acetic Acid

Abstract

Perborate solution in glacial acetic acid generates peracetic acid on aging, and the peracetic acid oxidation of organic sulfides is fast. The oxidation with fresh solutions of perbor-

One-Pot Preparations of Diaryliodonium Bromides from Iodoarenes and Arenes, with Sodium Perborate as the Oxidant

“…We have also observed that a preliminary period of stirring NaBO 3 ·H 2 O with acetic anhydride at 30 o C (preferably within 90 min) enhances considerably the oxidizing activity of this solution. Recently, Indian chemists [ 11 ] have observed the generation of peracetic acid on aging of NaBO 3 ·4H 2 O solutions in glacial acetic acid, confirmed by chemical tests.…”

One-Pot Preparations of Diaryliodonium Bromides from Iodoarenes and Arenes, with Sodium Perborate as the Oxidant

“…We have also observed that a preliminary period of stirring NaBO 3 ·H 2 O with acetic anhydride at 30 o C (preferably within 90 min) enhances considerably the oxidizing activity of this solution. Recently, Indian chemists [ 11 ] have observed the generation of peracetic acid on aging of NaBO 3 ·4H 2 O solutions in glacial acetic acid, confirmed by chemical tests.…”

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

“…The negative ρ-values -0.54, -0.48, and -0.46 at 20, 35, and 50 °C, respectively) point to an electron-deficient sulfur atom in the transition state. Further, the reaction constant (ρ) compares with those of (i) Mo(VI)-catalysed oxidation in aqueous acetic acid which is zero, first and second order in SPB, PMA and Mo(VI), respectively, 9 (ii) W(VI)-catalysed oxidation in aqueous acetic acid which is first order in SPB and exhibits Michaelis-Menten kinetics with respect to PMA and W(VI) 6 and (iii) uncatalysed second-order oxidation in glacial acetic acid 4 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 .…”

“…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 ], one of which is the reactive oxidant.…”

“…A possible explanation for the enhancement of Mo(VI)-catalysed oxidation rate by trichloroacetic acid is that [MoO 2 (O 2 )] is susceptible to protonation and the protonated species is a better oxidant than the unprotonated one. Although SPB generates peracetic acid on aging in acetic acid 4,5,11 the possibility of Mo(VI)-catalysed formation of peracetic acid and the oxidation turning to be peracetic acid oxidation is unlikely; the peracetic acid oxidation of DPS and PMA, under identical conditions, are almost instantaneous. 4…”

Decontamination of materials contaminated with Bacillus anthracis and Bacillus thuringiensis Al Hakam spores using PES-Solid, a solid source of peracetic acid

“…Interestingly, the mechanism of peracetic acid oxidation has specificity for organic sulfides in contrast to hypochlorite, which has general chemical reactivity (Karunakaran and Kamalam ). The test conditions here were also at near‐neutral pH, while hypochlorite is stored at high pH.…”

One-Pot Preparations of Diaryliodonium Bromides from Iodoarenes and Arenes, with Sodium Perborate as the Oxidant

“…We have also observed that a preliminary period of stirring NaBO 3 ·H 2 O with acetic anhydride at 30 o C (preferably within 90 min) enhances considerably the oxidizing activity of this solution. Recently, Indian chemists [ 11 ] have observed the generation of peracetic acid on aging of NaBO 3 ·4H 2 O solutions in glacial acetic acid, confirmed by chemical tests.…”

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

“…The negative ρ-values -0.54, -0.48, and -0.46 at 20, 35, and 50 °C, respectively) point to an electron-deficient sulfur atom in the transition state. Further, the reaction constant (ρ) compares with those of (i) Mo(VI)-catalysed oxidation in aqueous acetic acid which is zero, first and second order in SPB, PMA and Mo(VI), respectively, 9 (ii) W(VI)-catalysed oxidation in aqueous acetic acid which is first order in SPB and exhibits Michaelis-Menten kinetics with respect to PMA and W(VI) 6 and (iii) uncatalysed second-order oxidation in glacial acetic acid 4 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 .…”

“…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 ], one of which is the reactive oxidant.…”

“…A possible explanation for the enhancement of Mo(VI)-catalysed oxidation rate by trichloroacetic acid is that [MoO 2 (O 2 )] is susceptible to protonation and the protonated species is a better oxidant than the unprotonated one. Although SPB generates peracetic acid on aging in acetic acid 4,5,11 the possibility of Mo(VI)-catalysed formation of peracetic acid and the oxidation turning to be peracetic acid oxidation is unlikely; the peracetic acid oxidation of DPS and PMA, under identical conditions, are almost instantaneous. 4…”

Decontamination of materials contaminated with Bacillus anthracis and Bacillus thuringiensis Al Hakam spores using PES-Solid, a solid source of peracetic acid

“…Interestingly, the mechanism of peracetic acid oxidation has specificity for organic sulfides in contrast to hypochlorite, which has general chemical reactivity (Karunakaran and Kamalam ). The test conditions here were also at near‐neutral pH, while hypochlorite is stored at high pH.…”

One-Pot Preparations of Diaryliodonium Bromides from Iodoarenes and Arenes, with Sodium Perborate as the Oxidant

“…We have also observed that a preliminary period of stirring NaBO 3 ·H 2 O with acetic anhydride at 30 o C (preferably within 90 min) enhances considerably the oxidizing activity of this solution. Recently, Indian chemists [ 11 ] have observed the generation of peracetic acid on aging of NaBO 3 ·4H 2 O solutions in glacial acetic acid, confirmed by chemical tests.…”

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

“…The negative ρ-values -0.54, -0.48, and -0.46 at 20, 35, and 50 °C, respectively) point to an electron-deficient sulfur atom in the transition state. Further, the reaction constant (ρ) compares with those of (i) Mo(VI)-catalysed oxidation in aqueous acetic acid which is zero, first and second order in SPB, PMA and Mo(VI), respectively, 9 (ii) W(VI)-catalysed oxidation in aqueous acetic acid which is first order in SPB and exhibits Michaelis-Menten kinetics with respect to PMA and W(VI) 6 and (iii) uncatalysed second-order oxidation in glacial acetic acid 4 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 .…”

“…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 ], one of which is the reactive oxidant.…”

“…A possible explanation for the enhancement of Mo(VI)-catalysed oxidation rate by trichloroacetic acid is that [MoO 2 (O 2 )] is susceptible to protonation and the protonated species is a better oxidant than the unprotonated one. Although SPB generates peracetic acid on aging in acetic acid 4,5,11 the possibility of Mo(VI)-catalysed formation of peracetic acid and the oxidation turning to be peracetic acid oxidation is unlikely; the peracetic acid oxidation of DPS and PMA, under identical conditions, are almost instantaneous. 4…”

Decontamination of materials contaminated with Bacillus anthracis and Bacillus thuringiensis Al Hakam spores using PES-Solid, a solid source of peracetic acid

“…Interestingly, the mechanism of peracetic acid oxidation has specificity for organic sulfides in contrast to hypochlorite, which has general chemical reactivity (Karunakaran and Kamalam ). The test conditions here were also at near‐neutral pH, while hypochlorite is stored at high pH.…”