The determination of absolute electron affinities of chlorobenzenes, chloronaphthalenes and chlorinated biphenyls from reduction potentials

Wiley, J.R.; Chen, E.C.M.; Chen, E.S.D.; Richardson, PG; Reed, W. R.; Wentworth, W. E.

doi:10.1016/0022-0728(91)85546-2

Cited by 30 publications

(8 citation statements)

References 10 publications

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“…From the onset of the first cathodic potential of C 6 Cl 6 and the commonly assumed potential of the Fc +/0 couple in vacuum (−4.8 eV), [21,22] the LUMO energy of C 6 Cl 6 can be estimated as −2.7 eV. Assuming linear relationship between the first reduction potential and the gas‐phase EA a value in related arenes with comparable solvation energy, EA a of C 6 Cl 6 can be estimated as 1.0±0.1 eV (see Figure S1 in the Supporting Information) in good agreement with the electrochemical estimates provided in the literature (0.98–1.09 eV) [17] …”

Section: Resultssupporting

confidence: 86%

“…Considering perchlorobenzene (C 6 Cl 6 ), several experimental EA a measurements have been reported to date: 0.91 eV using ion/molecule equilibria [10] and 0.98 and 1.09 eV based on the electrochemical data. [17] They are in a good agreement with the available theoretical estimates at the DFT-D, CCSD(T)-F12, and CBS-QB3 levels that fall within the 0.80-1.35 eV range. [18,19] In the present work, we revisit C 6 Cl 6 with the use of the DEA spectroscopy technique that offers a more comprehensive picture of various competing channels of evolution/dissociation of the initially forming molecular anions.…”

Section: Introductionsupporting

confidence: 85%

“…Electrochemical reduction of perhalobenzenes in aprotic solvents proceeds via abstraction of halide anions, and subsequent recombination of the aryl radicals leads to assembly of halogenated polyaromatic networks on the surface of a gold electrode. Considering perchlorobenzene (C 6 Cl 6 ), several experimental EA a measurements have been reported to date: 0.91 eV using ion/molecule equilibria [10] and 0.98 and 1.09 eV based on the electrochemical data [17] . They are in a good agreement with the available theoretical estimates at the DFT‐D, CCSD(T)‐F12, and CBS‐QB3 levels that fall within the 0.80–1.35 eV range [18,19] .…”

Section: Introductionsupporting

confidence: 72%

“…Assuming linear relationship between the first reduction potential and the gas-phase EA a value in related arenes with comparable solvation energy, EA a of C 6 Cl 6 can be estimated as 1.0 � 0.1 eV (see Figure S1 in the Supporting Information) in good agreement with the electrochemical estimates provided in the literature (0.98-1.09 eV). [17] DEA spectra for C 6 Cl 6 are shown in left panel of Figure 2. Right panel in Figure 2 represents molecular anion lifetime as a function of incident electron energy.…”

Section: Resultsmentioning

confidence: 99%

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Dissociative Electron Attachment to Hexachlorobenzene

et al. 2022

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Gas phase molecules of hexachlorobenzene (C 6 Cl 6 ) were investigated by means of dissociative electron attachment spectroscopy (DEAS). Three channels of molecular negative ions decay have been identified: abstraction of Cl À and Cl 2 À as well as electron detachment (τ a ~250 μs at 343 K). All three channels exhibit temperature dependence. The adiabatic electron affinity estimated using a simple but typically accurate Arrhenius model (EA a = 1.6-1.9 eV) turns out to be much higher than the quantum-chemical predictions (EA a = 0.9-1.0 eV). We discuss the possible reasons behind the observed discrepancy.

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Section: Resultssupporting

confidence: 86%

Section: Introductionsupporting

confidence: 85%

Section: Introductionsupporting

confidence: 72%

Section: Resultsmentioning

confidence: 99%

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Dissociative Electron Attachment to Hexachlorobenzene

et al. 2022

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“…It is no doubt that the reduction potential of chlorinated benzene increases with the chlorination level. The electron affinities of 1,2-DCB, PeCB, and HCB were estimated to be 0.09, 0.73, and 1.0 eV, respectively [16][17][18]. As the reduction potential of polychlorinated aromatic compound increases with the increase of chlorination, the oxidative destruction of chlorinated compound by V 2 O 5 /TiO 2 is unfavorable.…”

Section: Sv ¼ Flow Rate=volume Of Catalystmentioning

confidence: 99%

Catalytic Conversions of Polychlorinated Benzenes and Dioxins with Low-chlorine Using V2O5/TiO2

Lee

Jurng

2007

Catal Lett

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Chlorinated benzene, especially 1,2-dichlorobenzene (1,2-DCB), has been widely used as one of surrogate compounds of dioxin to find the noble methods to control dioxin. However, the relationship between the catalytic activity of dioxin surrogate compound and dioxin has not been understood quite well. In this work, we used a vanadium based catalyst (V 2 O 5 /TiO 2 ) to compare catalytic activity of chlorinated benzenes and dibenzo-p-dioxins with low-chlorine content using the lab-scale system. We investigated the catalytic conversions of low-chlorinated dioxins, [2-monochlorodibenzo-p-dioxin (2-MCDD), 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD)] and polychlorinated benzenes [1,2-DCB, 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB), pentachlorobenzene (PeCB), hexachlorobenzene (HCB)] using a V 2 O 5 /TiO 2 catalyst to understand quantitative relationship between dioxin and benzene with the chlorination level. The catalytic decomposition of chlorinated aromatic compounds was following 1,2-DCB > 1,2,3,4-TeCB > 2-MCDD > PeCB ≥ 2,3-DCDD > HCB. It might be more reasonable that PeCB or HCB should be used as the dioxin surrogate compound rather than 1,2-DCB. Also, we investigated the effect of both O 2 content and space velocity (SV) on the catalytic decomposition of 1,2-DCB in the presence of V 2 O 5 /TiO 2 catalyst because these factors should be considered significantly in combustion facilities to control various pollutants. The decomposition of 1,2-DCB shows dependency on the SV while the effect of oxygen content on the catalytic decomposition is negligible in the range of 5-20%.

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Spectroscopic and electrochemical properties of 1,3-diketonatoboron derivatives

Chow

Johansson

Zhang

et al. 1996

J. Phys. Org. Chem.

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A series of tetracoordinated boron complexes derived from various 1,j-diketones and bidentate ligands (oxalato, malonato, catecholato and difluoro) were prepared. Their absorption, fluorescence and phosphorescence spectra, a t ambient temperature and 77 K, and cyclic voltammmetry in acetonitrile were studied. The boron complexes exhibited high molar absorptivity and fluorescence intensities as compared with the parent diketones; the phenomena are in agreement with the lowest singlet excited state possessing the z, z,* configuration with a rigid chelate structure. The redox potential differences correlate linearly with the lowest singlet (E,) as well as the triplet (ET) excited state energy with slopes lower than unity. These linear correlations re-state that the electron exchange and Coulombic integral also vary proportionally to the potential differences. From these correlations, it is possible to determine E , and E , of those boron complexes that do not give fluorescence and phosphorescence.

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The determination of absolute electron affinities of chlorobenzenes, chloronaphthalenes and chlorinated biphenyls from reduction potentials

Cited by 30 publications

References 10 publications

Dissociative Electron Attachment to Hexachlorobenzene

Dissociative Electron Attachment to Hexachlorobenzene

Catalytic Conversions of Polychlorinated Benzenes and Dioxins with Low-chlorine Using V2O5/TiO2

Spectroscopic and electrochemical properties of 1,3-diketonatoboron derivatives

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