Organic Polarography

Wawzonek, S.

doi:10.1021/ac60061a008

Cited by 9 publications

(6 citation statements)

References 78 publications

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“…The dominant product of those reactions is 10-monohydromirex (Figure 1), with photomirex formed as only a minor product (23). The formation of 10-monohydromirex as the dominant product of electron transfer reactions is somewhat expected because these reactions have been shown to be largely controlled by redox potentials (44), and geminal dihalides typically are more easily reduced than isolated halides (45,46). Nevertheless, the formation of photomirex as the product of the DOM-mediated reaction of mirex could be expected of an electron transfer reaction from DOM to mirex.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Implications of the Intrahumic Dechlorination of Mirex

Burns

Hassett

Rossi

1997

Environ. Sci. Technol.

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The hydrophobic chlorocarbon mirex readily binds to aqueous humic acids (HAs). In HA solutions irradiated at sunlight wavelengths (λ g 290 nm), mirex molecules bound to HAs are transformed to photomirex by dechlorination. The mechanism of this intrahumic dechlorination was investigated both in HA solutions and in model systems simulating select photochemical capabilities of HAs. In HA solution, the reaction was unaffected by methanol and pentanol; was accelerated by hydroxide; and was inhibited by oxygen, 2-chloroethanol, nitrate, and hydrogen ion, all four of which can scavenge hydrated electron. Additional experiments probing for involvement of hydrated electron were consistent with it as the reactant. In irradiated N,N-dimethylaniline solution, a model system for generating hydrated electron, mirex was dechlorinated to form photomirex, the same product that is found in HA solution. Relative rate experiments in HA solution, while inconsistent with the reaction with hydrated electron in homogeneous solution, were consistent with reaction with a purely intrahumic hydrated electron. However, other humic-generated reductants cannot be eliminated as possible reactants. The potential confounding influence of hydrophobic partitioning to HAs on investigations using molecular probes is evaluated in terms of current data and previous reports.

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Section: Resultsmentioning

confidence: 99%

Mechanistic Implications of the Intrahumic Dechlorination of Mirex

Burns

Hassett

Rossi

1997

Environ. Sci. Technol.

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“…Ar--NH----N -b e -> Ar--NH~N[:], is [5] 2Ar~NH--N[~ -> Ar--NH--NH--Ar q-N2 [6] Ar~NH--N[~ -b 2H + ~-Ar--NH----NH2 2+ [7] Ar--NH:NH2 2+ -~ 2e-> Ar--NH--NH2 i4 [8] Ar--NH--NH2 -~ H + ~_ Ar--NII--NH3 + [9] Thus the present paper demonstrates formation of a primary hydrazine derivative by a direct electrochemical reduction of the corresponding diazonium fluoborate.…”

Section: Resultsmentioning

confidence: 99%

“…In particular, Wawzonek (8) proposed that the first reduction wave corresponds to the formation of a free radical, with consecutive formation of diphenylmercury and phenylmercuric chloride. The limiting current of the second wave was found to be four times higher than that of the first one.…”

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confidence: 99%

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Electrochemical Reduction of Aromatic Diazonium Salts: I . Electrochemical Behavior of p‐Tolyl‐ and p‐Anisyldiazonium Fluoborates at a Mercury Cathode: Evidence for the Corresponding Hydrazines Formation

Orange

Elfakir‐Hamet

Caullet

1981

J. Electrochem. Soc.

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Reduction of p-methyl and p-methoxyphenyldiazonium fluobora~e in aqueous solutions at mercury micro and macroelectrodes results in formation of a primary hydrazine ArNH-NH2. The radical ArN -----N' formed in the first electrochemical step forms Ar-Hg-Ar; the product of the two electrons reduction forms Ar-NH-NH-Ar in competitive chemical reactions. Low temperature (4~ and moderate stirring enable minimizing of these side reactions.* Electrochemical Society Active Member.

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“…It is well known that anions such as CC13can eliminate chloride ion and form carbenes in the absence of protons:9 CCL(' -+ :CC& + C1- ( 8 ) Wawzonek10 was able to trap the dichlorocarbene with tetramethylethylene in an electrolytic reduction of carbon tetrachloride in acetonitrile.…”

Section: Discussionmentioning

confidence: 99%

Preparation of poly‐p‐xylylenes by electrolysis

Gilch¹

1966

J. Polym. Sci. A‐1 Polym. Chem.

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Poly‐p‐xylylenes were prepared by electrolytic reduction of α,α′‐dihalo‐p‐xylenes at controlled cathode potentials (c.p.). Polymers and halides are formed at the cathode; at the anode the halide is oxidized to halogen. Poly‐p‐xylylene was prepared from α,α′‐dichloro‐p‐xylene (c.p. −1.2 v.) and α,α′‐dibromo‐p‐xylene (c.p. −1.2 v.); poly‐p‐2‐chloroxylylene from α,α′,2‐trichloro‐p‐xylene (c.p. −1.4 v.) and α,α′‐dibromo‐2‐chloro‐p‐xylene (c.p. −1.2 v.); poly‐α,α,α′,α′‐tetrachloro‐p‐xylylene from α,α,α,α′,α′,α′‐hexachloro‐p‐xylene (c.p. −0.7 v.), and poly‐α,α,α′,α′‐tetrafluoro‐p‐xylylene from α,α′‐dibromo‐α,α,α′,α′‐tetrafluoro‐p‐xylene (c.p. −1.1 v.). The cathode potentials were measured and controlled with respect to a saturated calomel electrode. Current efficiencies up to 96% were observed. α,α,α′,α′‐Tetrachloro‐p‐xylylene was identified as an intermediate in the reduction of α,α,α,α′,α′,α′‐hexachloro‐p‐xylene. A general mechanism for these reactions is suggested and discussed. It involves elimination of halide by a two‐electron charge transfer with formation of a xylyl anion, followed by an elimination of halide in α′‐position yielding xylylenes which then polymerize.

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Organic Polarography

Cited by 9 publications

References 78 publications

Mechanistic Implications of the Intrahumic Dechlorination of Mirex

Mechanistic Implications of the Intrahumic Dechlorination of Mirex

Electrochemical Reduction of Aromatic Diazonium Salts: I . Electrochemical Behavior of p‐Tolyl‐ and p‐Anisyldiazonium Fluoborates at a Mercury Cathode: Evidence for the Corresponding Hydrazines Formation

Preparation of poly‐p‐xylylenes by electrolysis

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