Carbonium Ion Salts. I. Tropenium and Trityl Bromoborates<sup>1</sup>

Harmon, Kenneth M.; Harmon, Ann B.

doi:10.1021/ja01465a031

Cited by 21 publications

(4 citation statements)

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“…The time-current relationship at constant current for an electrode process with semi-infinite linear diffusion control has been shown to be (10) iorl/S --1/2 nFD1/2 ~i/~ C [1] where io is current density (amp cm-2), r is the transition time (sec), C is the concentration of the reducible ion (moles cm-a), D is the diffusion coefficient (cm 2 sec-1), and the remaining terms have their usual significance. From this equation it is seen that if the reaction is diffusion controlled the product, iov 1/2, remains constant for a given concentration as the current is varied, and that D can be obtained from the slope of a plot of the product vs. concentration.…”

Section: Resultsmentioning

confidence: 99%

“…Uranyl(VI) in molten chloride salt solutions can be electrolytically or chemically reduced to UO2. The electrolytic reduction is under investigation at this laboratory for use in a process to reclaim uranium and plutonium from UO2-based nuclear fuels (1) and as a method of preparing high quality crystalline UO2 (2). Part of this research program has been a study of the mechanism and the thermodynamic properties of the reduction.…”

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confidence: 99%

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Studies on the Electroreduction of Uranyl (VI) in Molten Equimolar KCl-NaCl by Chronopotentiometric and Electrode Impedance Measurements

Stromatt

1963

J. Electrochem. Soc.

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The reduction of UO2(VI) to UO2 in molten KCI-NaCI salt at 716~ has been shown by chronopotentiometry to be diffusion controlled at a platinum electrode. Furthermore, the potential-time curves indicated that the reaction occurred in two steps at nearly the same potential. This observation was verified by measuring the pseudo capacity of the polarized cathode as a function of its potential for which a plot of the data shows two peaks in capacity. The first was found to be symmetric with a concentration-independent potential, which is indicative of an electrode reaction producing a soluble product. The second peak was asymmetric with a concentration-dependent potential, which is indicative of an electrode reaction producing an insoluble product. These observations suggested that the electrode reaction proceeds by a reduction of UO2(VI) to UO2(V) followed by the reduction of the UO2(V) to UO2(s) Additional verification of this mechanism was provided by the reduction of UO2 (VI) by UO2 to yield a stable solution of UO2 (V). The heterogeneous rate constant for the reduction of UO2(VI) to UO2(V) was estimated to be 2 cm sec -I, but a value for the reduction of UO2(V) could not be determined because of the solid UO2 deposit. The diffusion coefficient was estimated from the chronopotentiometric data to be 2.2 x 10 -5 em 2 sec -I.Uranyl(VI) in molten chloride salt solutions can be electrolytically or chemically reduced to UO2. The electrolytic reduction is under investigation at this laboratory for use in a process to reclaim uranium and plutonium from UO2-based nuclear fuels (1) and as a method of preparing high quality crystalline UO2 (2). Part of this research program has been a study of the mechanism and the thermodynamic properties of the reduction.The electrolytic reduction of UO2C12 to UO2 was first described by Hampe in 1888 (3). More recently, Smirnov and Ivanovsky (4) studied the anodic behavior of the UO2 electrode in the eutectic LiC1-KC1 melt. They found only hexavalent uranium in the melt after anodization and determined that the reaction proceeded by direct electron loss rather than through dissolution by anodic chlorine. Their estimate of the oxidation potential of UO2, compared to a chlorine electrode, was 0.57v. Hill, Perano, and Osteryoung conducted a polarographic investigation of the UO2(VI) reduction, also in the eutectic LiC1-KC1 melt (5). They found that the polarographic wave did not conform to a reversible twoelectron process, but that there was a linear relationship between wave height and UO2(VI) concentration. They plated UO2 on the microelectrode and measured the open-circuit potential as a function of concentration. The data obtained in this fashion did suggest a reversible two-electron transfer process, and their estimate of the emf for the reaction was close to that obtained by Smirnov and Ivanovsky. Wilks (6) reported a study of the reactions occurring in the UO2C12-KC1-NaC1 melt which would result in stoichiometric and nonstoichiometric UO2 deposits on electrolysis. He suggested the pres...

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Studies on the Electroreduction of Uranyl (VI) in Molten Equimolar KCl-NaCl by Chronopotentiometric and Electrode Impedance Measurements

Stromatt

1963

J. Electrochem. Soc.

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“…against the ionization potential of the halide ions15 gives a straight line, (4) the separation of the two bands of the tropenium iodide complex is in agreement with that expected16 for the different electron affinities of the Py2 and By, states of iodine atom as observed in other16•17 charge-transfer complexes of halide ion, (5) X-ray data18 on solid tropenium iodide gives evidence for a weak charge-transfer bond between the iodide ion and the tropenium ion, which might be expected to persist in ion-pairs.…”

Section: Sirmentioning

confidence: 99%

Carbonium Ion Salts. III. Spectra and Decomposition of Tropenium Halides in Methylene Chloride

Harmon¹,

Cummings²,

Davis³

et al. 1962

J. Am. Chem. Soc.

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“…PhsCBB^was too sensitive to moisture to carry out elemental analysis, and its purity was confirmed from the yield of triphenylcarbinol formed upon hydrolysis. 6 Ir spectra were measured as Nujol mulls. Except for the case of PhsCBCU and PhsCBBr» (which decomposed very quickly in the air), all the spectra showed essentially the same pattern and possessed a peak at 1360 cm-1 which has been assigned to uc-ph °f the triphenylmethyl cation.7 NMR spectra were obtained in ethylene dichloride.…”

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confidence: 99%

Preparations of Triphenylmethyl Salts and Their Use in the Cationic Polymerization of α-Methylstyrene. Counteranion and Polymer Structure

Kunitake¹,

Tsugawa²

1975

Macromolecules

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Carbonium Ion Salts. I. Tropenium and Trityl Bromoborates¹

Cited by 21 publications

References 3 publications

Studies on the Electroreduction of Uranyl (VI) in Molten Equimolar KCl-NaCl by Chronopotentiometric and Electrode Impedance Measurements

Studies on the Electroreduction of Uranyl (VI) in Molten Equimolar KCl-NaCl by Chronopotentiometric and Electrode Impedance Measurements

Carbonium Ion Salts. III. Spectra and Decomposition of Tropenium Halides in Methylene Chloride

Preparations of Triphenylmethyl Salts and Their Use in the Cationic Polymerization of α-Methylstyrene. Counteranion and Polymer Structure

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Carbonium Ion Salts. I. Tropenium and Trityl Bromoborates1

Cited by 21 publications

References 3 publications

Studies on the Electroreduction of Uranyl (VI) in Molten Equimolar KCl-NaCl by Chronopotentiometric and Electrode Impedance Measurements

Studies on the Electroreduction of Uranyl (VI) in Molten Equimolar KCl-NaCl by Chronopotentiometric and Electrode Impedance Measurements

Carbonium Ion Salts. III. Spectra and Decomposition of Tropenium Halides in Methylene Chloride

Preparations of Triphenylmethyl Salts and Their Use in the Cationic Polymerization of α-Methylstyrene. Counteranion and Polymer Structure

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Carbonium Ion Salts. I. Tropenium and Trityl Bromoborates¹