The Anodic Oxidation of Zinc and a Method of Altering the Characteristics of the Anodic Films

Fry, H. Christopher; Whitaker, M. C.

doi:10.1149/1.2427446

Cited by 29 publications

(14 citation statements)

References 9 publications

(13 reference statements)

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“…Although the Δ E 12 ° value is quite large in the gas phase (e.g., over 4 V for anthracene), the calculated value in acetonitrile using DFT reduced to 843 mV compared well to the experimental value of 670 mV. This value was further reduced to 802 mV when ion pairing with the electrolyte was included . Further computational studies of the ion pairing between BMIm + and the dianion of dinitrobenzene (DNB 2– ) in the gas phase were reported .…”

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confidence: 62%

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Electrochemistry and Spectroelectrochemistry of 1,4-Dinitrobenzene in Acetonitrile and Room-Temperature Ionic Liquids: Ion-Pairing Effects in Mixed Solvents

Atifi

2014

Anal. Chem.

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Room-temperature ionic liquids (RTILs) have been shown to have a significant effect on the redox potentials of compounds such as 1,4-dinitrobenzene (DNB), which can be reduced in two one-electron steps. The most noticeable effect is that the two one-electron waves in acetonitrile collapsed to a single two-electron wave in a RTIL such as butylmethyl imidazolium-BF4 (BMImBF4). In order to probe this effect over a wider range of mixed-molecular-solvent/RTIL solutions, the reduction process was studied using UV–vis spectroelectrochemistry. With the use of spectroelectrochemistry, it was possible to calculate readily the difference in E°’s between the first and second electron transfer (ΔE 12° = E 1° – E 2°) even when the two one-electron waves collapsed into a single two-electron wave. The spectra of the radical anion and dianion in BMImPF6 were obtained using evolving factor analysis (EFA). Using these spectra, the concentrations of DNB, DNB–•, and DNB2– were calculated, and from these concentrations, the ΔE 12° values were calculated. Significant differences were observed when the bis(trifluoromethylsulfonyl)imide (NTf2) anion replaced the PF6 – anion, leading to an irreversible reduction of DNB in BMImNTf2. The results were consistent with the protonation of DNB2–, most likely by an ion pair between DNB2– and BMIm+, which has been proposed by Minami and Fry. The differences in reactivity between the PF6 – and NTf2 – ionic liquids were interpreted in terms of the tight versus loose ion pairing in RTILs. The results indicated that nanostructural domains of RTILs were present in a mixed-solvent system.

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confidence: 62%

“…This value was further reduced to 802 mV when ion pairing with the electrolyte was included. 8 Further computational studies of the ion pairing between BMIm + and the dianion of dinitrobenzene (DNB 2-) in the gas phase were reported. 1 DFT calculations show that the dianion of DNB interacts with BMIm + in a very unusual manner.…”

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confidence: 99%

Electrochemistry and Spectroelectrochemistry of 1,4-Dinitrobenzene in Acetonitrile and Room-Temperature Ionic Liquids: Ion-Pairing Effects in Mixed Solvents

Atifi

2014

Anal. Chem.

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“…37 Such anomalies due to the presence of IL electrolytes are usually ascribed to the strong ion-pairing in ILs. In a series of computational studies, Fry et al 38 have examined and reported the interactions between solvent, electrolytic ions, and electroactive species, indicating that the redox potentials can be lowered when ion-pairing with the electrolyte was included. We hypothesize that similar shifts in the oxidation mechanisms of the analytes (i.e.…”

Section: Resultsmentioning

confidence: 99%

2,4-Toluene diisocyanate detection in liquid and gas environments through electrochemical oxidation in an ionic liquid

Lü

Rehman

Chi

et al. 2016

Analyst

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The electrochemical oxidation of 2,4-toluene diisocyanate (2,4-TDI) in an ionic liquid (IL) has been systematically characterized to determine plausible electrochemical and chemical reaction mechanisms and to define the optimal detection methods for such a highly significant analyte. It has been found that the use of an IL as the electrolyte allows the oxidation of 2,4-TDI to occur at a less positive anodic potential with no side reactions as compared to traditional acetonitrile based electrolytes. UV-Vis, FT-IR, Cyclic Voltammetry and Electrochemical Impedance Spectroscopy (EIS) studies have revealed the unique mechanisms of dimerization of 2,4-TDI at the electrode interface by self-addition reactions, which can be utilized to improve the selectivity of detection. The study of 2,4-TDI redox chemistry further facilitates the development of a robust amperometric sensing methodology by selecting a hydrophobic IL ([C4mpy][NTf2]) and by restricting the potential window to only include the oxidation process. Thus, this innovative electrochemical sensor is capable of avoiding the two most ubiquitous interferents in ambient conditions (i.e. humidity and oxygen), thereby enhancing the sensor performance and reliability for real world applications. The method was established to detect 2,4–TDI in both liquid and gas phases. The limits of detection (LOD) values were 130.2 ppm and 0.7862 ppm, respectively, for the two phases, and are comparable to the safety standards reported by NIOSH. The as-developed 2.4-TDI amperometric sensor exhibits a sensitivity of 1.939 μA/ppm. Moreover, due to the simplicity of design and the use of an IL both as a solvent and non-volatile electrolyte, the sensor has the potential to be miniaturized for smart sensing protocols in distributed sensor applications.

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“…From the results of Ref. [37], the oxide formation seems to be greater on grains of Zn with a mainly exposed basal plane (0001). The grains have high packing density closer to that of the basal plane.…”

Section: The Models 231 Zn Surfacementioning

confidence: 97%

Theoretical and experimental study of the interaction of O2 and H2O with metallic zinc—discussion of the initial step of oxide formation

Alimenti¹,

Gschaider²,

Bazán

et al. 2004

Journal of Colloid and Interface Science

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The Anodic Oxidation of Zinc and a Method of Altering the Characteristics of the Anodic Films

Cited by 29 publications

References 9 publications

Electrochemistry and Spectroelectrochemistry of 1,4-Dinitrobenzene in Acetonitrile and Room-Temperature Ionic Liquids: Ion-Pairing Effects in Mixed Solvents

Electrochemistry and Spectroelectrochemistry of 1,4-Dinitrobenzene in Acetonitrile and Room-Temperature Ionic Liquids: Ion-Pairing Effects in Mixed Solvents

2,4-Toluene diisocyanate detection in liquid and gas environments through electrochemical oxidation in an ionic liquid

Theoretical and experimental study of the interaction of O2 and H2O with metallic zinc—discussion of the initial step of oxide formation

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