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Thermal decomposition of halo-bis(piperidyldithio-carbamates) of As(III), Sb(III) and Bi(III)

Estimation of kinetic parameters (k, n) of some dithiocarbamates by QIA techniques

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Abstract

Simultaneous TG/DTG/DTA studies under non-isothermal conditions have been carried out in air and nitrogen on some halo-dithiocarbamates of the general formula XM[S2CN(CH2)5]2 (X=Cl, Br and I; andM=As, Sb and Bi).E* values for the 1st stage of decomposition were determined by graphical methods and the TTN temperatures were calculated from the TG profiles. A possible mechanism of the decomposition reaction is suggested, based on the thermoanalytical and pyrolysis results and the mass spectral data. The kinetic analysis data on five of the above dithiocarbamates and nine complexes of the general formula M[S2CN<]3 (M=As, Sb and Bi; and N<=NEt2, N(CH2)5 and N(CH2)4O) were studied by the QIA (quasi-isothermal analysis) technique in air atmosphere. An example of kinetic parameter (k andn) estimation for the first decomposition stage is given for Bi[S2CN(CH2)5]3, with the assumption of different kinetic equations.

Zusammenfassung

Einige helo-Dithiocarbamate der allgemeinen Formal XM[S2CN(CH2)5]2 (X=Cl, Br und I;M=As, Sb und Bi) wurden mittels simultaner TG/DTG/DTA unter nichtisothermen Bedingungen in Luft und Stickstoff untersucht. Für den ersten Zersetzungsschritt wurden E*-Werte durch graphische Methoden bestimmt und die TIN-Temperaturen aus den TG-Profilen berechnet. Ein auf den Ergebnissen der Thermogravimetrie und Pyrolyse sowie auf massenspektroskopischen Daten beruhender möglicher Mechanismus wird vorgeschlagen. Fünf der angeführten Dithiocarbamate und 9 Komplexe der allgemeinen Formel M[S2CN<]3] (M=As, Sb und Bi;N=NEt2, N(CH2)5 und N(CH2)4O) wurden mittels QIA (quasi-isotherme Analyse) in Luft untersucht. Als Beispiel ist die Bestimmung der kinetischen Parameter (k undn) für den ersten Schritt der Zersetzung von Bi[S2CN(CH2)5]3 unter Annahme verschiedener kinetischer Gleichungen angegeben.

Резюме

Совмещенным методом ТГ, ДТГ и ДТА в неизотермических ус ловиях в атмосфере воздуха и азота изуче ны комплексы галоген-дитиокарбам атов с общей формулой XM[S2CN(CH2)5]2, гдеХ=Cl, Вr и l, a M=As, Sb и Bi. Зна ченииЕ a для первой стадии разложения были вычи слены графическими м етодами, а ТИН температуы были о пределены из профилей ТГ-кривых. На основе полученных результатов и данных масс-спектров предложен возможный механизм реакции раз ложения. Методом квазиизотер мического анализа в атмосфере в оздуха проведен анал из кинетики реакции разложения п яти вышеупомянутых дити окарбаматных компле ксов и девяти комплексов с общей фо рмулой M[S2CN<]3, где M=As, Sb и Bi, a N<=NEt2, N(CH2)5 и N(CH2)4O. На основе различных кинетических уравне ний определены парам етрыk ип первой стадии разлож ения комплекса В3[S2СN(СН2)5]3.

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Authors and Affiliations

  1. Department of General and Inorganic Chemistry, Thessaloniki, Greece

    M. Lalia-Kantouri, A. Christofides & G. E. Manoussakis

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  1. M. Lalia-Kantouri
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  2. A. Christofides
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  3. G. E. Manoussakis
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Lalia-Kantouri, M., Christofides, A. & Manoussakis, G.E. Thermal decomposition of halo-bis(piperidyldithio-carbamates) of As(III), Sb(III) and Bi(III). Journal of Thermal Analysis 30, 399–427 (1985). https://doi.org/10.1007/BF02156506

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