Kinetics of the simultaneous oxidation of nickel(II) and sulfur(IV) by oxygen in alkaline medium in Ni(II)–sulfur(IV)–O<sub>2</sub> system

Sharma, Anil Kumar; Mudgal, Punit K.; Bansal, Seema; Gupta, K. C.

doi:10.1002/kin.20496

Cited by 6 publications

(2 citation statements)

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“…S(IV), were studied by following the decrease in the concentration of S(IV). This procedure was the same as that described by Brodizinsky et al [42] and subsequently used by us [43][44][45][46]. The reactions were conducted in 0.15 L Erlenmeyer flasks open to air, to allow the passage of atmospheric oxygen.…”

Section: Methodsmentioning

confidence: 99%

Inhibition of Atmospheric Aqueous Phase Autoxidation of Sulphur Dioxide by Volatile Organic Compounds: Mono-, di- and Tri-Substituted Benzenes and Benzoic Acids

Meena

Dhayal

Rathore

et al. 2017

Progress in Reaction Kinetics and Mechanism

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Like many other volatile organic compounds (VOCs), the methoxy derivatives of benzene and benzoic acid are found in the atmosphere and, therefore, looking to their possible intervention in aqueous phase atmospheric oxidation of the major acid rain precursor, SO2, by oxygen, the kinetics of SO2 [hereafter referred to as S(IV)] autoxidation have been studied in the presence of methoxybenzene (anisole) and disubstituted 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and 1,4-dimethoxybenzene. The effects of benzoic acid and its 2,6-dimethoxy, 3,4-dimethoxy, 2,3,4-trimethoxy and 2,4,5-trimethoxy derivatives have also been examined, as have the influences of 4-hydroxybenzoic acid, benzanilide and o-sulfobenzimide. As the methoxy group is known to influence the reaction SO4–· + organics [Formula: see text] SO42– + non-chain products, to understand the degree of influence of the methoxy group on the inhibition of this reaction, this series of methoxy compounds was selected. The kinetics were first-order in S(IV). Most of the VOCs inhibited S(IV) autoxidation, except benzanilide and o-sulfobenzimide, in accordance with kobs = k0/(1 + B [Inh]), where kobs and k0 are the first-order rate constants in the presence and absence of VOCs respectively and B is the inhibition parameter. The most interesting feature of this work is that, despite the high kinh values, the B values are unexpectedly quite low and benzanilide and o-sulfobenzimide showed no effect. The B values appear to be independent of kinh, which is opposite to that found in the case of a series of hydroxyl compounds. It appears probable that additional steps involving peroxy intermediates are involved.

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Section: Methodsmentioning

confidence: 99%

Inhibition of Atmospheric Aqueous Phase Autoxidation of Sulphur Dioxide by Volatile Organic Compounds: Mono-, di- and Tri-Substituted Benzenes and Benzoic Acids

Meena

Dhayal

Rathore

et al. 2017

Progress in Reaction Kinetics and Mechanism

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“…The experimental procedure, which was exactly the same as described earlier by Brodzinsky et al [37] and subsequently used by us [18,38], is briefly given here. The reactions were conducted in 0.15 L Erlenmeyer flasks, open to air to allow the passage of atmospheric oxygen.…”

Section: Methodsmentioning

confidence: 99%

Kinetics of copper(II)‐catalyzed oxidation of S(IV) by atmospheric oxygen in ammonia buffered solutions

Sharma

Singh

Mehta

et al. 2011

Int J of Chemical Kinetics

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To understand the chemistry of Cu(II)-NH 3 -S(IV)-O 2 system, the kinetics of the oxidation of sulfur(IV) catalyzed by amminecopper(II) complexes has been studied in the ammonia-buffered solutions. Sulfur(IV) is oxidized to sulfate. The complexes, Cu(NH 3 ) 2+ , Cu(NH 3 ) 2+ 2 , and Cu(NH 3 ) 2+ 3 appear to be equally reactive and Cu(NH 3 ) 2+ 4 appears to be unreactive. The kinetics obey the rate law: 2+ 3 complexes, which appear to be equally reactive. The values of α 1 and γ 1 were found to be (1.32 ± 0.21) × 10 6 L 2 mol −2 s −1 (1.74 ± 0.40) × 10 9 L 3 mol −3 s −1 respectively at 30 • C. The reaction rate is not influenced by the presence of ethanol-a free radical scavenger, so a nonradical mechanism has been proposed. The results of this study are useful in understanding the atmospheric chemistry of aqueous phase autoxidation of dissolved sulfur dioxide in copper(II)-ammonia-sulfur(IV)-oxygen system at high pH. C

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Inhibition of Aquated Sulfur Dioxide Autoxidation by Aliphatic, Acyclic, Aromatic, and Heterocyclic Volatile Organic Compounds

Meena

Dhayal

Rathore

et al. 2017

Int J of Chemical Kinetics

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The oxidation of dissolved sulfur dioxide, sulfur(IV), by oxygen proceeds through the involvement of sulfoxy radicals among which sulfate radical anion is the main chain carrier. When organics are present, they inhibit the oxidation of sulfur(IV) via scavenging of SO4− radicals. In contrast to previous studies, which were limited mostly to aliphatic compounds, this paper presents the results of the effect of 13 new volatile organic compounds (VOCs) including aromatic and heterocyclic on uncatalyzed sulfur(IV) autoxidation at pH 8.2 and 25°C. In all cases, the kinetics was first order in the presence and absence of VOCs and experimental rate law was Eq. (1). trueright−d[normalSfalse( IV false)]/normaldt=k obs []normalSfalse( IV false)=ko[]normalSfalse( IV false)/{}1+Bfalse[ Inh false]where −d[S(IV)]/dt is the rate of sulfur(IV) disappearance, kobs is the first‐order rate constant in the presence of inhibitor, ko is the first‐order rate constant in the absence of inhibitor, [S(IV)] is concentration of sulfur(IV) at time, t, and B is an inhibition parameter. VOCs cause inhibition by scavenging sulfate radical anions, which propagate the autoxidation chain. An analysis of B (Eq. (1)) and kinh (Eq. (2)) values for 21 aliphatic, aromatic, acyclic, and heterocyclic organic compounds showed that these to be related by Eq. (3) for a subgroup and Eq. (4) for b subgroup. trueright SO 4−+ VOC 0.33em⟶k inh 0.33em SO 42−+ VOC a subgroup (benzamide, 2,2‐dimethyl‐1‐propanol, 1‐hexanol, methanol, ethanol, 1‐propanol, 2‐ propanol, 1‐butanol, 2‐butanol, ethylene glycol, rebaudioside A) truerightB=()0.87±0.21×10−30.16emk inh b subgroup (o‐toluic acid, m‐toluic acid, p‐toluic acid, 4‐hydroxybenzoic acid, 1‐heptanol, glycerol, sucralose, acesuifame K, glycine, 3‐pentanol) truerightB=()1.2±0.3×10−30.16emk inh

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Kinetics of the simultaneous oxidation of nickel(II) and sulfur(IV) by oxygen in alkaline medium in Ni(II)–sulfur(IV)–O₂ system

Cited by 6 publications

References 44 publications

Inhibition of Atmospheric Aqueous Phase Autoxidation of Sulphur Dioxide by Volatile Organic Compounds: Mono-, di- and Tri-Substituted Benzenes and Benzoic Acids

Inhibition of Atmospheric Aqueous Phase Autoxidation of Sulphur Dioxide by Volatile Organic Compounds: Mono-, di- and Tri-Substituted Benzenes and Benzoic Acids

Kinetics of copper(II)‐catalyzed oxidation of S(IV) by atmospheric oxygen in ammonia buffered solutions

Inhibition of Aquated Sulfur Dioxide Autoxidation by Aliphatic, Acyclic, Aromatic, and Heterocyclic Volatile Organic Compounds

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Kinetics of the simultaneous oxidation of nickel(II) and sulfur(IV) by oxygen in alkaline medium in Ni(II)–sulfur(IV)–O2 system

Cited by 6 publications

References 44 publications

Inhibition of Atmospheric Aqueous Phase Autoxidation of Sulphur Dioxide by Volatile Organic Compounds: Mono-, di- and Tri-Substituted Benzenes and Benzoic Acids

Inhibition of Atmospheric Aqueous Phase Autoxidation of Sulphur Dioxide by Volatile Organic Compounds: Mono-, di- and Tri-Substituted Benzenes and Benzoic Acids

Kinetics of copper(II)‐catalyzed oxidation of S(IV) by atmospheric oxygen in ammonia buffered solutions

Inhibition of Aquated Sulfur Dioxide Autoxidation by Aliphatic, Acyclic, Aromatic, and Heterocyclic Volatile Organic Compounds

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Kinetics of the simultaneous oxidation of nickel(II) and sulfur(IV) by oxygen in alkaline medium in Ni(II)–sulfur(IV)–O₂ system