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Possibilities of applying the Piloyan method of determination of decomposition activation energies in the differential thermal analysis of polynitroaromatic compounds and of their derivatives

Part I. Polymethyl and polychloro derivatives of 1,3,5-trinitro-benzene

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Abstract

Conditions are presented for application of the Piloyan method to the DTA of poly-nitro aromatic compounds. Activation energies (E) of the thermal decomposition and the initial valuesT D of the exotherms are determined for trinitrotoluene, trinitro-m-xylene, trinitromesitylene, picryl chloride and dichlorotrinitrobenzene. Linear relationships are derived between the termsE · T −D and published kinetic data on these compounds, obtained by an isothermal manometric method. The mechanisms of the primary steps in the thermolyses of these polynitro compounds are discussed. A negative influence on their thermal stability has been confirmed, arising from the contact of the measured compounds with the glass surface.

Résumé

On présente les conditions de l'application de la méthode Piloyan à l'ATD des composés polynitroaromatiques. On a déterminé les énergies d'activation (E) et les valeurs initialesT D des réactions exothermiques pour le trinitrotoluène, le trinitro-m-xylène, le trinitromé sitylène, le chlorure picrylique et le dichloro-trinitrobenzène. On a trouvé des corrélations linéaires entre les valeursE.T −D et les données cinétiques publiées des composés mentionnés obtenues par une méthode isotherme manométrique. On discute le mécanisme de l'étape primaire de la thermolyse des composés polynitrés étudiés. On a confirmé l'influence négative, sur la stabilité thermique, provenant du contact de ces composés avec le verre.

Zusammenfassung

Die Bedingungen der Anwendung der Methode von Piloyan bei der DTA polynitroaromatischer Verbindungen werden beschrieben. Die Aktivierungsenergien (E) der thermischen Zersetzung und die AnfangswerteT D der exothermen VorgÄnge werden für Trinitrotoluol, Trinitro-m-xylol, Trinitromesitylol, Picrylchlorid und Dichlortrinitro-benzol bestimmt. Lineare ZusammenhÄnge werden zwischen den WertenE.T −D und den unter Anwendung der isothermen manometrischen Methode erhaltenen veröffentlichten kinetischen Angaben der besagten Verbindungen, abgeleitet. Der Mechanismus der primÄren Stufe in der Thermolyse der untersuchten Polynitroverbindungen wird diskutiert. Der sich aus dem Kontakt der gemessenen Verbindungen mit dem Glas ergebende negative Einflu\ auf ihre StabilitÄt wird bestÄtigt.

РЕжУМЕ

пРЕДстАВлЕНы УслОВИ ь пРИМЕНЕНИь МЕтОДА пИлОьНА Дль ДтА пОлИН ИтРОАРОМА-тИЧЕскИх сОЕДИНЕНИИ. ОпРЕДЕлЕ Ны ЁНЕРгИИ АктИВАцИИ (E) тЕРМИЧЕскОгО РАжлОж ЕНИь И НАЧАлАT D ЁкжОтЕРМ Дль тРИНИтРОтОлУОлА, тРИНИтРО-М-ксИлОлА, тР ИНИтРОМЕжИтИлА, пИк-Р ИлхлОРИДА И тРИхлОРтРИНИтРОБЕ НжОлА. УстАНОВлЕНА лИНЕИНАь ВжАИМОсВьж ь МЕжДУ ВЕлИ-ЧИНАМИ E · т −1D И кИНЕтИЧЕскИМИ ДАННыМИ, ОпУБлИкОВАННыМИ И кО тОРыЕ БылИ пОлУЧЕНы ИжОтЕРМИЧЕскИМ МАНО МЕтРИЧЕскИМ МЕтОДОМ. ОБсУжДЕН МЕхАНИжМ пЕРВОНАЧАл ьНОИ стАцИИ тЕРМОлИжА ИсслЕДОВА ННых пОлИНИтРОАРОМА тИЧЕскИх сОЕДИНЕНИИ. ВОжНИкАУ ЩИИ ВслЕДстВИИ кОНтАктА ИжУЧЕННых с ОЕДИНЕНИИ с пОВЕРхНО стьУ стЕклА ЁФФЕкт ОкАжыВАЕт ОтР ИцАтЕльНОЕ ВлИьНИЕ НА тЕРМИЧЕск УУ стАБИльНОсть сОЕД ИНЕНИИ.

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  1. Department of Research, Chemko, 072 22, StráŽske, Czechoslovakia

    S. Zeman

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The author is obliged to Mrs Klara Kováčová M. S. for her most generous help in processing the results of measurements on the Wang 2200 computer.

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Zeman, S. Possibilities of applying the Piloyan method of determination of decomposition activation energies in the differential thermal analysis of polynitroaromatic compounds and of their derivatives. Journal of Thermal Analysis 17, 19–29 (1979). https://doi.org/10.1007/BF02156593

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  • DOI: https://doi.org/10.1007/BF02156593

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