The Oxidation of Pinacol by Ceric Sulfate

Mino, G.; Kaizerman, S.; Rasmussen, Elisabeth

doi:10.1021/ja01515a053

Cited by 136 publications

(32 citation statements)

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“…If our conjectures are correct, the results with glucose mean that in this case the reaction [8] is not suppressed by the presence of the monomer, even t l~o~i g h the rate of polymerization is increased by the presence of the glucose. It must be borne in mind For personal use only.…”

Section: Glz~cosementioning

confidence: 67%

“…Can Some attempts were lllade to determine the alllount of acetone formed, using the spectrophotometric method of Behre and Benedict (10). In analogy with the oxidation by ceric ions (8), it was hoped that the principal reaction ~vould be followed, perhaps, by further oxidation (to acetone) of the radical formed. If this were correct, the amount of acetone produced for every mole of persulphate cleconlposed would be a t .least 2 mole.…”

Section: Pinacolmentioning

confidence: 99%

“…This argument can be given in more quantitative terms, as follows. If we add the termination step P. + P. --t poly~ller; rate constant kt, (81 the liinetics are supposed to be fully described by the reactions [I]- [8]. Of these reactions, [3] is suppressed by the presence of the monomer and will therefore be omitted.…”

Section: Glz~cosementioning

confidence: 99%

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Studies on the Mechanism of Persulphate-Initiated Grafting Onto Cellulose

Sankalia¹,

Chaudhuri²,

Hermans³

1962

Can. J. Chem.

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When the polymerization of vinyl acetate or acrylonitrile is initiated by persulphate in the presence of cellophane, grafting onto the cellulosic baclcbone occurs. This is proved by comparing the graft with a physical mixture of cellulose and homopolymer.Sotne aspects of the mechanism of this grafting are studied by means of model cornpou~lds, in particular pinacol. I t is found that the rate of polymerization of acrylonitrile initiated b y persulphate is increased by the addition of pinacol, but decreases on addition of more pinacol. This may be explained by assuming that the radicals formed from the pinacol can terminate each other and that this reaction competes with the reaction between these radicals and the monomer. The amount of acetone formed by the persulphate oxidation of pinacol a t low pinacol concentrations is about 0.5 nlole per mole persulphate and decreases with increasing pinacol concentration. This indicates complexities that do not exist in the ceric ion oxidation of pinacol.

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Section: Glz~cosementioning

confidence: 67%

Section: Pinacolmentioning

confidence: 99%

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Studies on the Mechanism of Persulphate-Initiated Grafting Onto Cellulose

Sankalia¹,

Chaudhuri²,

Hermans³

1962

Can. J. Chem.

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“…The oxidation of some organic substrates by Ce(IV), believed to occur by direct attack of the ceric species on the substrate, appears to proceed by electron abstraction [1][2][3], while in some cases the reaction goes through an intermediate complex [4][5][6]. Ammonium ceric nitrate gives more intense colours with hydroxy compounds than does ceric sulfate, mostly due to the complex formation with them and the subsequent liberation of a free radical by the decomposition of the complex.…”

Section: Introductionmentioning

confidence: 99%

Aqueous polymerization of methyl acrylate initiated by ceric ion-reducing agent systems in nitric acid medium

Reddy¹,

Srinivasan²

2000

Designed Monomers and Polymers

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Abstract-A kinetic study of the aqueous polymerization of methyl acrylate (MA) was carried out at 30 • C in nitric acid medium by employing ammonium ceric nitrate (ACN)-methyl cellosolve (MC) and ACN-ethyl cellosolve (EC) as the redox initiator systems. The ceric ion consumption was found to be first order with respect to the ceric ion concentration with both initiator systems. The formation of complexes between Ce(IV) and reducing agents was observed. The orders with respect to Ce(IV), the reducing agents, and the monomer were evaluated for the aqueous polymerization of MA by Ce(IV)-reducing agent (RA) initiator systems. The overall activation energies, E overall , for the aqueous polymerization of MA were evaluated in the temperature range 27-40 • C. The effect of constant nitrate ion in the reaction medium was studied. A kinetic mechanism for the aqueous polymerization of MA initiated by redox initiator systems is presented.

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“…lMino et al 2 have shown that during oxidation of alcohols, such as pinacol with ceric salts, the ceric ions are responsible for generation as well as termination of free radical sites.…”

mentioning

confidence: 99%