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Thermal decomposition of tris(piperidyldithiocarbamates) of As(III), Sb(III) and Bi(III)

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Abstract

Thermal studies by TG, DTG and DTA of tris(piperidyldithiocarbamates) of arsenic(III), antimony(III) and bismuth(III) of the general type M[S2CN(CH2)5]3 (M=As, Sb and Bi) have been carried out in nitrogen and air, as well as under vacuum, to determine their modes of decomposition. The apparent activation energies were determined by graphical methods and the TIN temperatures were calculated from the TG profiles.

A possible mechanism of the decomposition reaction is suggested on the basis of the results of their pyrolysis and their mass spectral data.

The intermediates obtained at the end of various decomposition steps were identified via their elemental analysis, i.r. spectral data and X-ray diffraction studies. A dimeric structure of type M2[S2CN(CH2)5]4 (M=As, Sb) is proposed.

Zusammenfassung

TG-, DTG- und DTA-Untersuchungen von Tris(piperidyldithiocarbamaten) von Arsen(III), Antimon(III) and Wismut(III) des allgemeinen Typs M[S2CN(CH2)5]3 (M=As, Sb und Bi) wurden sowohl in Stickstoffatmosphäre und Luft als auch unter Vakuum ausgeführt, um die Art der Zersetzung zu ermitteln. Die scheinbaren Aktivierungsenergien wurden nach der graphischen Methode bestimmt und die TTN-Temperaturen aus den TG-Profilen berechnet. Es wird ein auf den Ergebnissen der Pyrolyse der Verbindungen und der dabei erhaltenen massenspektrometrischen Daten beruhender Mechanismus für die Zersetzungsreaktion vorgeschlagen. Die am Ende der verschiedenen Zersetzungsschritte erhaltenen Zwischenprodukte wurden durch Elementaranalyse, IR-Spektrophotometrie und Röntgendiffraktometrie identifiziert. Eine dimere Struktur des Typs M2[S2CN(CH2)5]4 (M=As, Sb) wird vorgeschlagen.

Резюме

Трис-пиперидилдитиокарбаматы трехвалентных мышьяка, сурьмы и висмута общей формули M[S2CN(CH2)5]3, гдеM=As, Sb, Bi, были изучены методом ТГ, ДТГ и ДТА в вакууме, в атмосфере воздуха и азота с целыо определения типа их разложения. Кажущиеся знергии активации были вычислены графическими методами, а ТИН температуры были вычислены на основе профиля кривых ТГ. Исходя из результатов анализа продуктов пиролиза и масс-спектроскопических данных, предлозен возможный механизм разложения этих соединений. Промежуточные продукты, получаемые на различных стадиях разложения, идентифицированы посредством элементарного анализа. ИК спектроскопии и рентгенографии. Предложена димерная структура типа M2[S2CN(CH2)5]4, гдеM=As, Sb.

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References

  1. G. P. Afanasova, I. V. Shkhiyants, N. A. Nechitailo, V. V. Sher and P. I. Sanim, Neftekhimiya, 11 (1971) 911.

    CAS  Google Scholar 

  2. Shyam Kumar and Narendra Kumar Kaushik, Thermochim. Acta, 41 (1980) 19.

    Article  CAS  Google Scholar 

  3. H. B. Singh, Suman Maheshwari and Harion Tomer, Thermochim. Acta, 64 (1983) 47.

    Article  CAS  Google Scholar 

  4. G. E. Manoussakis and C. A. Tsipis, J. Inorg. Nucl. Chem., 35 (1973) 743.

    Article  CAS  Google Scholar 

  5. M. A. Bernard and M. Borel, Bull. Soc. Chim. France, 7 (1970) 2478.

    Google Scholar 

  6. G. D'Ascenzo and T. Bica, Thermochim. Acta, 18 (1977) 301.

    Article  Google Scholar 

  7. G. K. Bratspies, J. F. Smith, J. O. Hill and P. J. Derrick, J. Thermal Anal., 16 (1979) 369.

    Article  CAS  Google Scholar 

  8. C. Duval Inorganic Thermogravimetric Analysis, Elsevier Publ. Co., London, 1963, p. 424–426.

    Google Scholar 

  9. L. Reich and D. W. Levi, Makromol. Chem., 66 (1963) 102.

    Article  CAS  Google Scholar 

  10. E. S. Freeman and B. Carroll, J. Phys. Chem., 62 (1958) 394.

    Article  CAS  Google Scholar 

  11. G. O. Piloyan, I. D. Ryabchnikov and O. S. Novikova, Nature, 212 (1966) 1229.

    Article  CAS  Google Scholar 

  12. G. O. Piloyan and O. S. Novikova, Russ. J. Inorg. Chem., 12 (1967) 313.

    Google Scholar 

  13. C. G. Sceney, J. O. Hill and R. J. Magee, Thermochim. Acta, 11 (1975) 301.

    Article  CAS  Google Scholar 

  14. F. Bonati and R. Ugo, J. Organom. Chem., 10 (1967) 257.

    Article  CAS  Google Scholar 

  15. G. O. Doak and L. D. Freeman, Organometallic Compounds of Arsenic, Antimony and Bismuth, John Wiley, 1970, p. 441.

  16. R. E. Dessy, P. M. Weissman and R. L. Pohl, J. Am. Chem. Soc., 88 (1966) 5117.

    Article  CAS  Google Scholar 

  17. S. Gomiscek, L. Golic and Z. Lengar, Anal. Chim. Acta, 79 (1975) 296.

    Article  CAS  Google Scholar 

  18. C. G. Sceney, J. F. Smith, J. O. Hill and R. J. Magee, J. Thermal Anal., 9 (1976) 415.

    Article  CAS  Google Scholar 

  19. C. L. Raston and A. H. White, J. C. S. Dalton, 3 (1975) 2425.

    Article  Google Scholar 

  20. C. L. Raston and A. H. White, J. C. S. Dalton, 9 (1976) 791.

    Article  Google Scholar 

  21. G. K. Bratspies, J. F. Smith, J. O. Hill and R. J. Magee, Thermochim. Acta, 19 (1977) 361.

    Article  CAS  Google Scholar 

  22. A. V. Dubrovin, K. M. Dunaeva and V. I. Spitsyn, Russ. J. Inorg. Chem., 23 (1978) 1701.

    Google Scholar 

  23. J. V. Braun and K. Wissbach, Ber., 63 (1930) 2836.

    Google Scholar 

  24. G. E. Manoussakis, E. D. Mikromastoras and C. A. Tsipis, Z. Anorg. Allgem. Chem., 403 (1974) 87.

    Article  Google Scholar 

Download references

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Authors and Affiliations

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

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

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  1. M. Lalia-Kantouri
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  2. A. G. Christofides
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  3. G. E. Manoussakis
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Lalia-Kantouri, M., Christofides, A.G. & Manoussakis, G.E. Thermal decomposition of tris(piperidyldithiocarbamates) of As(III), Sb(III) and Bi(III). J. Thermal Anal. 29, 279–295 (1984). https://doi.org/10.1007/BF02720063

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  • DOI: https://doi.org/10.1007/BF02720063

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