Triangular wave cyclic voltammetry. I

Galus, Zb́igniew; Lee, H.Y.; Adams, Ralph N.

doi:10.1016/0022-0728(63)80087-x

Cited by 23 publications

(6 citation statements)

References 10 publications

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“…Electrochemical reversibility was not investigated directly, but if the oxidations are reversible in the electrochemical sense, the Ep values will be related to classical half-wave potentials by an additive constant.10 Chemical irreversibility does not necessarily exclude the possibility that the electrode process may be reversible, e.g., the reduction of 2,4,6trinitroterphenyl, vide infra. (5) 1.03 66 2.4 2-Nitroterphenyl (6) 1.88 1.30 80 2.4 3-Nitroterphenyl (7) 1.78 0.98 80 2.9 4-Nitroterphenyl (8) 1.76 ± O.OF 1.14 70 2.2 2,4-Dinitroterphenyl (9) 1.86 0.81 60 2.9 2,6-Dinitroterphenyl (10) 1.76 1.04s 72 2.3 4,4' '-Dinitroterphenyl (11) 2.06 1.02 66 2.4 2,4,6-Trinit roterphenyl (12) Benzene( 13) Biphenyl (14) p-Terphenyl (15) 2.00 2.43* 1.9V 1.78 0.67 52 1.9 " In MeCN-TBAP. 6 In DMF-TBAP. "…”

Section: Resultsmentioning

confidence: 99%

Nitro-p-terphenyls. II. The Relation between Charge-Transfer Properties and Polarographic Oxidation and Reduction Potentials

Hansen¹,

Toren²,

Young³

1966

J. Phys. Chem.

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Section: Resultsmentioning

confidence: 99%

Nitro-p-terphenyls. II. The Relation between Charge-Transfer Properties and Polarographic Oxidation and Reduction Potentials

Hansen¹,

Toren²,

Young³

1966

J. Phys. Chem.

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“…We have studied proton effects in the nonaqueous electrochemistry of the Q/QH2 system (11) and have characterized the oxidation of QH2 in acetonitrile (12) using electrochemical techniques over a wide time scale. The products and an intermediate have been detected by cyclic voltammetry (13).…”

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confidence: 99%

Proton Effects in the Electrochemistry of the Quinone Hydroquinone System in Aprotic Solvents

Eggins¹,

Chambers²

1970

J. Electrochem. Soc.

183

118

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Electrochemical and spectroscopic techniques have been used to study the benzo‐, duro‐, tetrachloro‐, and p‐xyloquinone‐hydroquinone couples in nonaqueous solvents. The proton transfer reactions which are coupled to the electron transfer steps are elucidated. Oxidation of the hydroquinone leads to the protonated quinone species, while reduction of the quinones in the presence of a proton source gives mixtures of the corresponding hydroquinone, its conjugate base, and the free semiquinone, depending on the amount and strength of the proton donor used. Oxidation of the hydroquinones is postulated to proceed via a dimer of the one‐electron intermediate. Preliminary results are reported on the electrochemical behavior of solutions containing the quinhydrone charge‐transfer complex.

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“…According to the j p -v 1/2 plot, we believe that the electrode processes at p 1 and p 2 are controlled by diffusion, while the control step at p 3 is as yet uncertain. The electrode reaction at p 4 must be controlled by charge transfer, which has been reported by Nicolas et al 16 Moreover, the mechanism of the electrode reaction can be reflected by plotting I p /v 1/2 vs. v. 23,24 This correlation was demonstrated in detail by Nicholson, and was reported to be most useful for the qualitative characterization of systems in which preceding, following, or catalytic chemical reactions are coupled with reversible or irreversible charge transfers. 24 In each of the kinetic cases, the effect of the chemical reaction depended on its rate, as compared with the time required to perform the experiment.…”

Section: Resultsmentioning

confidence: 93%

“…Single charge transfer step : 4C + 4F − − 4e − → 4CF [23] Whole charge transfer step : 4n C + 4n F − − 4n e − → (CF) n [24] where the reactant F − is a simple F − anion, "Graphite" represents the graphite electrode, "F − -Graphite" represents the phase of graphite intercalated by F − , and n' is the number of the unit cell of graphite. (CF) n is graphite fluoride, which has a structure composed of chair-type cyclohexane rings axially bound to fluorine atoms 31 and decomposes at temperatures of 573-873 K. 21,[32][33][34] Thus, the chemical reaction of this electrode process is attributed to (CF) n decomposition expressed by Reaction 12.…”

Section: Resultsmentioning

confidence: 99%

Mechanism of Graphite Electrode Fluorinated in 2.4NaF/AlF₃–Al₂O₃Melt at 1373 K

Gong

Shi

Wang

et al. 2014

J. Electrochem. Soc.

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The electrochemical behavior of a graphite anode in 2.4NaF/AlF 3 -0.05wt%Al 2 O 3 molten salt was investigated via cyclic voltammetry (CV) and chrono-electrochemical techniques. Four oxidation current peaks, located at 1.42, 2.5, 3.1, and 3.94 V vs. Al/Al 3+ , were observed in CV curves, which may be attributed to the formation of CO 2 , CF 4 , graphite fluoride ((CF) n ), and F 2 , respectively. The anode effect occurred when the potential exceeded 3.5 V. Meanwhile, the mechanism of the electrode reaction of CO 2 and (CF) n formation was confirmed to be irreversible charge transfer followed by a chemical reaction. Therefore, we confirmed that the passivation of the graphite anode was due to the formation of (CF) n on the electrode surface, blocking the mass transfer. According to the number of the charge transfer and the characteristics of the electrode reactions, we discuss detailed reaction pathways for CF 4 and (CF) n formation. In addition, the presence of the small quantity of C 2 F 6 in the anode gas is discussed.In the primary aluminum production by the Hall-Héroult process, cryolite-alumina molten salt and a carbon anode are employed. The cell reaction under normal conditions isThe exit gas from the electrolysis cell consists of a mixture of CO 2 and CO, and the secondary reactions between CO 2 and aluminum yield CO. 1 However, a cell malfunction, known as the anode effect (AE), can easily occur when the alumina content in the electrolyte is less than 1 wt%. The anode effect results in not only the generation of perfluorocarbons (PFCs) CF 4 and C 2 F 6 but also a high consumption of energy for a higher cell voltage. 2 Owing to the high global warming potentials of CF 4 and C 2 F 6 3 and the fact that the primary aluminum industry is the major anthropogenic source of CF 4 and C 2 F 6 , 4 the Environmental Protection Agency and the primary aluminum producers have established the Voluntary Aluminum Industrial Partnership (VAIP) with the goal of substantially reducing PFC emission. 5 To gain a better understanding of the mechanism of CF 4 and C 2 F 6 generation, the anodic behaviors of carbonaceous electrodes have been widely studied in recent decades. The traditional view mentioned that fluorine ions react with carbon anodes to directly generate CF 4 and C 2 F 6 during the anode effect. 2,6,7 The formation of CF 4 and C 2 F 6 can be expressed by the following reactions:Moreover, CF 4 and C 2 F 6 coming from the decomposition of COF 2 has been suggested. 8-11 COF 2 is considered an intermediate product prior to the anode effect, then, it decomposes to form CF 4 and C 2 F 6 . The reactions are described as 2Na 3 AlF 6 + Al 2 O 3 + 3C = 3COF 2 + 6NaF + 4Al E 1373K = 1.81 V [4] 2COF 2 = CO 2 + CF 4 lg K 1373K = −0.176 [5] 3COF 2 + 2C = 3CO + C 2 F 6 lg K 1373K = −1.351 [6]

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Triangular wave cyclic voltammetry. I

Cited by 23 publications

References 10 publications

Nitro-p-terphenyls. II. The Relation between Charge-Transfer Properties and Polarographic Oxidation and Reduction Potentials

Nitro-p-terphenyls. II. The Relation between Charge-Transfer Properties and Polarographic Oxidation and Reduction Potentials

Proton Effects in the Electrochemistry of the Quinone Hydroquinone System in Aprotic Solvents

Mechanism of Graphite Electrode Fluorinated in 2.4NaF/AlF₃–Al₂O₃Melt at 1373 K

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Triangular wave cyclic voltammetry. I

Cited by 23 publications

References 10 publications

Nitro-p-terphenyls. II. The Relation between Charge-Transfer Properties and Polarographic Oxidation and Reduction Potentials

Nitro-p-terphenyls. II. The Relation between Charge-Transfer Properties and Polarographic Oxidation and Reduction Potentials

Proton Effects in the Electrochemistry of the Quinone Hydroquinone System in Aprotic Solvents

Mechanism of Graphite Electrode Fluorinated in 2.4NaF/AlF3–Al2O3Melt at 1373 K

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Mechanism of Graphite Electrode Fluorinated in 2.4NaF/AlF₃–Al₂O₃Melt at 1373 K