Conversion of Cobalt(II) Acetate into Cobalt(III) Acetate by Autoxidizing Benzaldehyde

Nemecek, Antonio M.; Hendriks, Ch.F.; Beek, H. C. A. van; Bruyn, Michiel A. de; Kerckhoffs, Eugene J. M.

doi:10.1021/i360066a009

Cited by 9 publications

(3 citation statements)

References 7 publications

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“…The rate of this autocatalytic reaction decreases at increasing rate of stirring of the solution. In a previous paper the course of the reaction in non-or slowly stirred solutions was discussed (Nemecek et al, 1978). In this paper experiments will be described which were carried out under such vigorous stirring conditions that higher stirring rates did not result in a further decrease of the reaction rate.…”

Section: Introductionmentioning

confidence: 99%

The Kinetics of the Autoxidation of Aldehydes in the Presence of Cobalt(II) and Cobalt(III) Acetate in Acetic Acid Solution

Hendriks¹,

Beek²,

Heertjes³

1978

Ind. Eng. Chem. Prod. Res. Dev.

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The mechanism of the autoxidation of several aldehydes in the presence of Co11 and Co111 acetate was investigated in rapidly stirred acetic acid solutions. The kinetic parameters were determined. In the presence of Co" acetate the autoxidation of an aldehyde is inhibited by reduction of the chain carrying acylperoxy radicals by Co", while Co111 acetate, formed by this reaction, contributes to the initiation by oxidation of the aldehyde to acyl radicals. These combined effects explain the autocatalytic conversion of Co" into Co"1 acetate. In the absence of Co" acetate, the corresponding peracid is formed as the first stable product of the aldehyde autoxidation. Co1" acetate catalyzes the decomposition of these peracids with formation of acylperoxy radicals, which initiate a very fast autocatalytic oxidation of the aldehyde. At high concentrations Co1" acetate also participates in chain termination by oxidizing acyl radicals.

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Section: Introductionmentioning

confidence: 99%

The Kinetics of the Autoxidation of Aldehydes in the Presence of Cobalt(II) and Cobalt(III) Acetate in Acetic Acid Solution

Hendriks¹,

Beek²,

Heertjes³

1978

Ind. Eng. Chem. Prod. Res. Dev.

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“…An analogous stirring effect has been described in detail for the oxidation of cobalt(II) acetate in aerobic acetic acid solutions of aldehydes. The experiments and model calculations concerned were presented in a previous paper (Nemecek et al, 1978). It follows from Figure 1 that the initial reaction stage, e.g., the oxidation of cobalt(II) naphthenate by autoxidizing methyl linoleate, continues until ~95% conversion of Co11 is reached.…”

Section: Resultsmentioning

confidence: 96%

The Autoxidation of Methyl Linoleate and Methyl Linolenate in the Presence of Cobalt(II) and Cobalt(III) Naphthanate in n-Heptane Solution

Hendriks¹,

Heertjes²,

Beek³

1979

Ind. Eng. Chem. Prod. Res. Dev.

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Co11 and Co111 therefore leads to an autocatalytic conversion of Co" into Co111, the rate of which increases strongly with decreasing stirring rates. The second stage starts after 90-95% conversion of Con. The Com/Co" concentration ratio then reaches a constant value. In this stage the methyl esters are mainly converted into the corresponding hydroperoxides, while the corresponding hydroxy and keto compounds are formed as secondary products. In the third stage fragmentation products are formed and Co111 is converted into an inactive Co" complex. For the first two stages a reaction scheme is proposed which provides an adequate description of the results obtained. Conclusions are drawn for the processes taking place in drying paint films containing cobalt(II) naphthenate.

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“…/Co 2? and the 4-carboxyl benzolperoxy chain radicals concentration [18] at the different concentration of Co(OAc) 2 .…”

Section: Effect Of Co(oac) 2 Concentrationmentioning

confidence: 99%

Aerobic Oxidation of p-Toluic Acid to Terephthalic Acid over T(p-Cl)PPMnCl/Co(OAc)2 Under Moderate Conditions

et al. 2009

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The aerobic oxidation of p-toluic acid to terephthalic acid over tetra(p-chlorophenylporphinato)manganese (T(p-Cl)PPMnCl)/cobalt acetate was reported for the first time. The co-catalysis of T(p-Cl)PPMnCl/Co(OAc) 2 was also studied. The studies indicated that the PTA oxidation was influenced by the catalyst composition, catalyst concentrations and reaction conditions. A preliminary mechanism of this co-catalyzed oxidation reaction was proposed based on experimental observations.

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Conversion of Cobalt(II) Acetate into Cobalt(III) Acetate by Autoxidizing Benzaldehyde

Abstract: for providing a crude monomer of 4-vinylpyridine and valuable suggestions for the present work. They also acknowledge Dr. Tadatoshi Ota of Tokushima University for his stimulating discussions on the vinyl polymerization. The SEM observations were made by courtesy of the staff

Cited by 9 publications

References 7 publications

The Kinetics of the Autoxidation of Aldehydes in the Presence of Cobalt(II) and Cobalt(III) Acetate in Acetic Acid Solution

The Kinetics of the Autoxidation of Aldehydes in the Presence of Cobalt(II) and Cobalt(III) Acetate in Acetic Acid Solution

The Autoxidation of Methyl Linoleate and Methyl Linolenate in the Presence of Cobalt(II) and Cobalt(III) Naphthanate in n-Heptane Solution

Aerobic Oxidation of p-Toluic Acid to Terephthalic Acid over T(p-Cl)PPMnCl/Co(OAc)2 Under Moderate Conditions

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