Quantitative Determination of Phosgene

Olsen, John C.; Ferguson, George E.; Sabetta, V. J.; Scheflan, Leopold

doi:10.1021/ac50074a031

Cited by 17 publications

(8 citation statements)

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“…A parallel analysis for phosgene was conducted by adding an aliquot from the photolysate to a 3.00 mL solution of approximately 0.01 M Bu 4 NI in CHCl 3 from which ethanol had been removed. After 2 min, the absorbance at 365 nm was used to determine the concentration of

I_{3}^{-}

, arising from the reaction

{COCl}_{2} + 2 I^{-} \to CO(g) + I_{2} + 2 {Cl}^{-}

…”

Section: Methodsmentioning

confidence: 99%

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Photocatalysis of Chloroform Decomposition by Tetrachlorocuprate (II) on Dowex 2‐X8

Harvey

Hoggard

2014

Photochem & Photobiology

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Heterogenized on a polystyrene anion exchange resin and in the presence of oxygen, CuCl 2À 4 catalyzes the photodecomposition of chloroform at wavelengths above 345 nm with greater efficiency than an equivalent amount in homogeneous solution. The reaction is proposed to proceed in two stages, the first stage yielding CCl 4 and HO À 2 as products, the second consisting of a chain reaction resulting from the CuCl 2À 4 -catalyzed photodissociation of CCl 4 , yielding phosgene with CCl 3 radicals as chain carriers. Photodecomposition is retarded by added Cl À , CH 3 CN, C 6 H 12 or C 2 H 5 OH, which is ascribed to the displacement of CHCl 3 molecules from the vicinity of the copper by attraction to the polystyrene matrix or to the alkylammonium cation sites.

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I_{3}^{-}

, arising from the reaction

{COCl}_{2} + 2 I^{-} \to CO(g) + I_{2} + 2 {Cl}^{-}

…”

Section: Methodsmentioning

confidence: 99%

“…What HCl was found can potentially be ascribed to phosgene hydrolysis, water being formed when peroxides or hydroperoxides react by breaking the O-O bond (43), vide infra, Eqs. (26) and (27).…”

Section: Mechanism 1-photodissociation Of a Chlorine Atommentioning

confidence: 99%

Photocatalysis of Chloroform Decomposition by Tetrachlorocuprate (II) on Dowex 2‐X8

Harvey

Hoggard

2014

Photochem & Photobiology

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“…In addition, a chemical analysis for phosgene was conducted by taking aliquots from the photolysate during and following irradiation and mixing them with 3.00 mL solutions of approximately 0.01 M Bu 4 NI in CHCl 3 from which ethanol had been removed. After 20 min, the absorbance at 365 nm was used to determine the concentration of I 3 − , arising from the reaction

COC {normall}_{2} + 2 {normalI}^{-} \to CO false(normalg false) + {normalI}_{2} + 2 C {normall}^{-}

and the subsequent formation of I 3 − from the excess of iodide ion. Iodide also reduces Cl 2 , peroxides and other oxidizing species; thus, the true concentration of COCl 2 could be overestimated by this measure.…”

Section: Methodsmentioning

confidence: 99%

Photodecomposition of Chloroform Catalyzed by Unmodified MCM‐41 Mesoporous Silica

Peña

Chan

Cohen

et al. 2014

Photochem & Photobiology

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Unactivated MCM-41 mesoporous silica catalyzes the photodecomposition of chloroform to phosgene and hydrogen chloride under near-UV (λ > 360 nm) irradiation. The rate of photodecomposition increases toward an asymptotic limit as the O(2) partial pressure is increased. Deuterochloroform does not decompose under the same experimental conditions. Low concentrations of both cyclohexane and ethanol quench the photodecomposition, whereas water, up to its solubility limit, does not. Dissolved tetraalkylammonium salts suppress photodecomposition. The data are consistent with a mechanism in which light absorption by an SiO(2) defect yields an electron-deficient oxygen atom, which then abstracts hydrogen from chloroform. The resulting CCl(3) radicals react with oxygen to form a peroxy radical that decomposes, eventually yielding phosgene and hydrogen chloride.

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“…A comprehensive investigation on the determination of certain elements such as titanium in aluminium by utilisation of " homologous pairs of lines " is now available, with details of the manner in which this procedure may be utilised practically. 15 Attention is directed to a development in the methods of determining halogens, including fluoride, in organic compounds. There are few convenient and rapid methods for this purpose, especially in compounds containing high proportions of halogens.…”

mentioning

confidence: 99%

“…Carbon monoxide is oxidised to dioxide by a suspension of iodine pentoxide in oleum,ll by copper oxide deposited on quartz,12 and by silver oxide.13 A number of modified methods of determining carbon dioxide are described; l4 the aniline method and the sodium iodide-acetone method have been adapted to give concordant results for carbonyl chloride in presence of other chlorine compounds. 15 Hydrogen is readily absorbed by a silver permanganate reagent ; l6 two manometric methods for the determination of hydrogen peroxide are described.17 Work on helium is continued.18…”

mentioning

confidence: 99%