CVIII.—Chloropicrin. Part I

Gardner, John A.; Fox, F. W.

doi:10.1039/ct9191501188

Cited by 9 publications

(8 citation statements)

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“…This latter was indeed not detected in the experiments by Battin-Leclerc et al, 11 whereas it was found to be the primary product of chloropicrin decomposition in previous experimental studies. 7,9,10 The very low Cl−NO BDE (37.2 kcal mol −1 ) makes almost impossible the quantification of the species by gasphase chromatography, and we assumed that nitrosyl chloride decomposed completely into NO and Cl during the analytical process. The model slightly overestimates the formation of NOCl at 225 °C.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Few quantitative experimental studies have been devoted to chloropicrin thermal decomposition [7][8][9][10][11] . High toxicity of this compound induces a high level of complexity for any experiments.…”

Section: Introductionmentioning

confidence: 99%

“…Note that chloropicrin, which does not contain any H-atom, is known as non-combustible, but enhances the reactivity of combustible mixtures and broaden the flammability limits of gas mixtures thanks to the oxidant role of the NO2 function 12,13 . The first analytical attempts demonstrated that the decomposition of chloropicrin starts at its boiling temperature (~112°C) and that the main products of decomposition are phosgene (COCl2) and nitrosyl chloride (ClNO) 7 . Radulescu and Zemfirecu 8 later measured the global rate of decomposition in the temperature range 130-160°C and found an activation energy around 40 kcal mol -1 , which is consistent with a reaction occurring mainly by the unimolecular breaking of the C-N bond, which BDE equals 42.1 kcal mol -1 (Fig.…”

Section: Introductionmentioning

confidence: 99%

“…Few quantitative experimental studies have been devoted to chloropicrin thermal decomposition. − High toxicity of this compound induces a high level of complexity for any experiments. Consequently, there is a considerable lack of knowledge on the behavior of this chemical under high-temperature conditions with or without oxygen.…”

Section: Introductionmentioning

confidence: 99%

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Combustion and Pyrolysis Kinetics of Chloropicrin

Lizardo-Huerta

Sirjean

Verdier³

et al. 2018

J. Phys. Chem. A

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Chloropicrin (CClNO) is widely used in agriculture as a pesticide, weed-killer, fungicide or nematicide. It has also been used as a chemical agent during World War I. The precise understanding of its combustion chemistry for destruction processes or in the event of accidental fire of stored reserves is a major safety issue. A detailed chemical kinetic model for the combustion and pyrolysis of chloropicrin is proposed for the first time. A large number of thermo-kinetic parameters were calculated using quantum chemistry and reaction rate theory. The model was validated against experimental pyrolysis data available in the literature. It was shown that the degradation of chloropicrin is ruled by the breaking of the C-N bond followed by the oxidation of the trichloromethyl radical by NO through the formation of the adduct CClONO, which can decompose to NO, chlorine atom, and phosgene. Phosgene is much more stable than chloropicrin and its decomposition starts at much higher temperatures. Combustion and pyrolysis simulations were also compared and demonstrated that the addition of oxygen has very little effect on the reactivity or product distribution due to the absence of hydrogen atoms in chloropicrin.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Combustion and Pyrolysis Kinetics of Chloropicrin

Lizardo-Huerta

Sirjean

Verdier³

et al. 2018

J. Phys. Chem. A

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“…14 However chloropicrin is unstable at temperatures above its boiling point, decomposing to phosgene COCl 2 and nitrosyl chloride NOCl. 15,16 Temperatures routinely employed in thermal desorption analysis, greater than 110 °C, could result in an underestimation of the amount of chloropicrin due to thermal degradation. Previously, we demonstrated the utility of thermal desorption for the analysis of some chemical warfare agents.…”

Section: Introduction and Aim Of Investigationmentioning

confidence: 99%

Application of central composite design in the optimisation of thermal desorption parameters for the trace level determination of the chemical warfare agent chloropicrin

Muir

Carrick

Cooper

2002

Analyst

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A quantitative trace-level thermal desorption gas chromatography mass spectrometry method was developed for chloropicrin CCl3NO2 using central composite design. Factors influencing the thermal decomposition were elucidated and optimum conditions for maximum response deduced. Four factors were investigated: desorption time, desorption temperature, valve temperature and line temperature. Only valve and line temperature influenced the response. The storage stability of chloropicrin on Tenax TA was investigated. Only the storage conditions affected recovery: no significant loss of chloropicrin was observed for spiked tubes stored in a refrigerator for up to 30 days. The application of central composite design to study thermal degradation of chloropicrin has not been described in the literature. The benefits in adopting this approach are reflected in the limit of detection, 22 ng on the sorbent tube (equivalent to 3.2 ppbv), the lowest atmospheric detection limit reported to date.

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Die Darstellung des Chlorpikrins

Frahm¹

1931

Recl. Trav. Chim. Pays‐Bas

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CVIII.—Chloropicrin. Part I

Cited by 9 publications

References 0 publications

Combustion and Pyrolysis Kinetics of Chloropicrin

Combustion and Pyrolysis Kinetics of Chloropicrin

Application of central composite design in the optimisation of thermal desorption parameters for the trace level determination of the chemical warfare agent chloropicrin

Die Darstellung des Chlorpikrins

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