Oscillations in chemical systems. IX. Reactions of cerium(IV) with malonic acid and its derivatives

Jwo, Jing‐Jer; Noyes, Richard M.

doi:10.1021/ja00852a017

Cited by 82 publications

(39 citation statements)

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“…Within the experimental error their consumption ratios are about 7, with essentially no dependence on the malonic acid concentration. For comparison of our data to previous measurements we also include the value of 5.9 (square in Figure 1) reported by Jwo and Noyes, 4 which can be seen to fall into a reasonable interval of the present data under aerobic conditions. The presented results reveal a complex dependence of the overall stoichiometry on the initial malonic acid and oxygen concentration.…”

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confidence: 76%

Stoichiometric Fingerprinting as an Aid in Understanding Complex Reactions: The Oxidation of Malonic Acid by Cerium(IV)

et al. 1997

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The stoichiometry of the Ce(IV) oxidation of malonic acid (MA) under aerobic and anaerobic conditions was investigated. The Ce(IV)/MA consumption ratio is found to vary from about 3.5 to 7, depending nonlinearly on the initial concentration of malonic acid as well as dissolved oxygen. The observed data can be quantitatively explained by a model that employs the characteristic structure of branching pathways in the overall mechanism and does not require the exact knowledge of the rate constants. It is concluded that a systematic study of consumption ratios provides an important aid for elucidating mechanisms of complex reactions.

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confidence: 76%

Stoichiometric Fingerprinting as an Aid in Understanding Complex Reactions: The Oxidation of Malonic Acid by Cerium(IV)

et al. 1997

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“…; Table I). Consequently, this result suggest that the stable fragments Q i cannot be tartronic acid (HC(OH)(COOH) 2 ) and mesoxalic acid (CO(COOH) 2 ), since in this case one would find . In the framework of R7b, f ϭ q ϭ 0 however, it seems reasonable to conclude that either tartronic acid and glyoxylic acid (HCOCOOH) or mesoxalic acid and hydroxyacetic acid (H 2 C (OH)COOH) are produced, because both product pairs correspond to a q value of 1 (i.e.…”

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confidence: 90%

“…: HCOOH ϩ 6 Ce(III) ϩ 2 CO ϩ 6 H . (R1) 2 While measurements of the overall CO 2 stoichiometry are fairly frequent in the literature [9], we are not aware of systematic data on the CO 2 production from oxidation experiments with large excess organic acid in which dissolved oxygen is explicitly considered. Under reaction conditions in which the organic acid is in excess, it can be assumed that only a small number of intermediates are formed.…”

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confidence: 99%

“…In other words, the relevant reaction mechanism is minimized to a few "starting" reactions of the complex overall mechanism. Most oxidation reactions between an organic acid RH and a metal ion M ϩn (e.g., Ce(IV) start with the formation of an organic radical Rؒ (e.g., the malonyl radical) [1,2,7]: conditions. Cerium(IV) is used as the oxidizing agent.…”

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confidence: 99%

“…In the case of the aerobic oxidation of malonic acid an increase of the stoichiometry from about zero to approximately 0.5 is observed. This change can be explained in terms of the following two reactions, which are a subset of standard autooxidation mechanisms [1,2]:…”

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confidence: 99%

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Carbon dioxide production in the oxidation of organic acids by Cerium(IV) under aerobic and anaerobic conditions

Butler

Steinbock

et al. 1998

Int. J. Chem. Kinet.

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The stoichiometry of CO 2 production during the ceric oxidation of various organic acids is measured under conditions with organic acid excess. Measurements utilize a photometric methodology. For anaerobic conditions stoichiometries [CO 2 ] produced : [Ce(IV)] reduced of about 0 (malonic acid), 0.5 (e.g., glyoxylic acid), and 1.0 (oxalic acid) are found. Oxalic acid showed an oxygen-induced decrease of CO 2 production, while other compounds such as malonic acid increased the amount of produced CO 2 or showed no changes (e.g., tartronic acid). In the case of mesoxalic acid the stoichiometry is increased from about 0.5 to 2.0 due to the presence of molecular oxygen. The results are discussed on the basis of simple reaction mechanisms demonstrating that useful information on reaction pathways and intermediates can be extracted from these simple measurements.

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Kinetics and mechanism of the oxidation of some carboxylates by a nickel (III) oxime-imine complex

Saha

Dutta

Gangopadhyay

et al. 1997

Int. J. Chem. Kinet.

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(where HL 1 ϭ 15-amino-3-methyl-4,7,10,13-tetraazapentadec-3-en-2-one oxime) were carried out over the regions pH 3.0 -5.75, 2.80 -5.50, and 2.50 -7.58, respectively, at constant ionic strength and temperature 40ЊC. All the reactions are overall second-order with first-order on both the oxidant and reductant. A general rate law is given as], where k d is the auto-decomposition rate constant of the complex, k s is the electron transfer rate constant, n is the stoichiometric factor, and R is either formate, oxalate, or malonate. The reactivity of all the reacting species of the reductants in solution were evaluated choosing suitable pH regions. The reactivity orders are:for the oxidation of formate, oxalate, and malonate, respectively, and these trends were explained considering the effect of hydrogen bonded adduct formation and thermodynamic potential.

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Oscillations in chemical systems. IX. Reactions of cerium(IV) with malonic acid and its derivatives

Cited by 82 publications

References 5 publications

Stoichiometric Fingerprinting as an Aid in Understanding Complex Reactions: The Oxidation of Malonic Acid by Cerium(IV)

Stoichiometric Fingerprinting as an Aid in Understanding Complex Reactions: The Oxidation of Malonic Acid by Cerium(IV)

Carbon dioxide production in the oxidation of organic acids by Cerium(IV) under aerobic and anaerobic conditions

Kinetics and mechanism of the oxidation of some carboxylates by a nickel (III) oxime-imine complex

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