Skip to main content
SpringerLink
Log in

Thermal decomposition studies of [Ni(NH3)6]X2 (X = Cl, Br) in the solid state using TG-MS and TR-XRD

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

Detailed investigation on the thermal behaviour of hexaamminenickel(II) chloride and hexaamminenickel(II) bromide has been carried out by means of simultaneous TG/DTA coupled online with mass spectroscopy (TG-MS) and temperature-resolved X-ray diffraction (TR-XRD). Evolved gas analyses by TG-MS revealed the presence of NH2, NH, N2 and H2 fragments in addition to ammonia during the deamination process. These transient species resulted due to the fragmentation of the evolved ammonia during pyrolysis. The intermediates formed during the thermal deamination stages were monitored by in situ TR-XRD. The final product of the decomposition was found to be nano size metallic nickel in both cases. Morphology of the complexes, intermediates and the residue formed at various decomposition stages was analysed by scanning electron microscope (SEM). Kinetic analyses using isoconversional method for deamination and dehalogenation reaction show that the activation energies vary with the extent of conversion, indicating the multi-step nature of these solid state decomposition reactions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Wendlandt WW, Smith JP. Thermal properties of transition metal amine complexes. Amsterdam: Elsevier; 1967.

    Google Scholar 

  2. Mathew S, Nair CGR, Ninan KN. Thermal decomposition kinetics: kinetics and mechanism of thermal decomposition of bis(ethylenediamine)copper(II) halide monohydrate. Thermochim Acta. 1991;181:253–68.

    Article  CAS  Google Scholar 

  3. Singh G, Pandey DK. Studies on energetic compounds: kinetics of thermal decomposition of nitrate complexes of some transition metals with propylenediamine. Combust Flame. 2003;135:135–43.

    Article  CAS  Google Scholar 

  4. Mathew S, Nair CGR, Ninan KN. Thermal decomposition kinetics: kinetics and mechanism of thermal decomposition of tetraamminecopper(II) sulphate monohydrate. Thermochim Acta. 1989;144:33–43.

    Article  CAS  Google Scholar 

  5. Madara’sz J. Evolved gas analyses on a mixed valence copper(I, II) complex salt with thiosulfate and ammonia by in situ TG-EGA-FTIR and TG/DTA-EGA-MS. J Therm Anal Calorim. 2009;97:111–6.

    Article  Google Scholar 

  6. Sanders JP, Gallagher PK. Kinetic analysis of complex decomposition reactions using evolved gas analysis. J Therm Anal Calorim. 2009;96:805–11.

    Article  CAS  Google Scholar 

  7. Mathew S, Eisenreich N, Engel W. Thermal analysis using X-ray diffractometry for the investigations of the solid state reaction of ammonium nitrate and copper oxide. Thermochim Acta. 1995;269/270:475–89.

    Article  CAS  Google Scholar 

  8. Nair PS, Scholes GD. Thermal decomposition of single source precursors and the shape evolution of CdS and CdSe nanocrystals. J Mater Chem. 2006;16:467–73.

    Article  CAS  Google Scholar 

  9. Navaladian S, Viswanathan B, Viswanath RP, Varadarajan TK. Thermal decomposition as a route for silver nanoparticles. Nanoscale Res Lett. 2007;2:44–8.

    Article  CAS  Google Scholar 

  10. Li X, Zhang X, Li Z, Qian Y. Synthesis and characteristics of NiO nanoparticles by thermal decomposition of nickel dimethylglyoximate rods. Solid State Commun. 2006;137:581–4.

    Article  CAS  Google Scholar 

  11. Chen Y, Peng D, Lin D, Luo X. Preparation and magnetic properties of nickel nano particles via thermal decomposition of nickel organometallic precursors in alkylamine. Nanotechnology. 2007;18:505703–8.

    Article  Google Scholar 

  12. Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.

    Article  CAS  Google Scholar 

  13. Flynn JH, Wall LA. A quick, direct method for the determination of activation energy from thermogravimetric data. J Polym Sci B. 1996;4:323–8.

    Article  Google Scholar 

  14. Friedman HL. New methods for evaluating kinetic parameters from thermal analysis data. J Polym Sci B. 1969;7:41–6.

    Article  CAS  Google Scholar 

  15. Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 1957;29:1702–6.

    Article  CAS  Google Scholar 

  16. Akahira T, Sunose T. Research report of Chiba Institute Technology. 1971;16:22–31.

    Google Scholar 

  17. Brauer G. Hand book of preparative inorganic chemistry. 2nd ed. New York: Academic Press; 1965.

    Google Scholar 

  18. Vogel AG. Text book of quantitative inorganic analysis. 4th ed. London, UK: Longmann; 1978.

    Google Scholar 

  19. Badrinarayanan P, Zheng W, Simon SL. Isoconversional analysis of the glass transition. Thermochim Acta. 2008;468:87–93.

    Article  CAS  Google Scholar 

  20. Curtis SD, Kubiak M, Kurdziel K, Materazzi S, Vecchio S. Crystal structure and thermoanalytical study of a cadmium(II) complex with 1-allylimidazole. J Anal Appl Pyrolysis. 2010;87:175–9.

    Article  Google Scholar 

  21. Cai JM, Bi LS. Kinetic analysis of wheat straw pyrolysis using isoconversional methods. J Therm Anal Calorim. 2009;98:325–30.

    Article  CAS  Google Scholar 

  22. Su TT, Zhai YC, Jiang H, Gong H. Studies on the thermal decomposition kinetics and mechanism of ammonium niobium oxalate. J Therm Anal Calorim. 2009;98:449–55.

    Article  CAS  Google Scholar 

  23. Tanaka N, Kagawa M, Kamada M. The thermal decomposition of hexaamminenickel(II) complexes. Bull Chem Soc Jpn. 1968;41:2908–13.

    Article  CAS  Google Scholar 

  24. Madarasz J, Bombicz P, Matyas C, Reti F, Kiss G, Pokol G. Comparative evolved gas analytical and structural study on trans-diammine-bis(nitrito)-palladium(II) and platinum(II) by TG/DTA-MS, TG-FTIR and single crystal X-ray diffraction. Thermochim Acta. 2009;490:51–9.

    Article  CAS  Google Scholar 

  25. Mikuli AM, Hetmanczyk J, Mikuli E, Hetmanczyk L. Thermal behaviour of polycrystalline [Ba(H2O)3](ClO4)2 and [Ba(NH3)4](ClO4)2. Thermochim Acta. 2009;487:43–8.

    Article  Google Scholar 

  26. Leineweber A, Jacobs H. Preparation and crystal structure of Ni(NH3)2Cl2 and of two modifications of Ni(NH3)2Br2 and Ni(NH3)2I2. J Solid State Chem. 2000;152:381–7.

    Article  CAS  Google Scholar 

  27. Li C, Shuford KL, Chen M, Lee EJ, Cho SO. A facile polyol route to uniform gold octahedra with tailarable size and their optical properties. ACS Nano. 2008;9:1760–9.

    Article  Google Scholar 

  28. Padhi SK. Solid state kinetics of thermal release of pyridine and morphological study of [Ni(ampy)2(NO3)2]; ampy = 2-picolylamine. Thermochim Acta. 2006;448:1–6.

    Article  CAS  Google Scholar 

  29. Green M, O’Brien P. The preparation of organically functionalized chromium and nickel nanoparticles. Chem Commun. 2001;1912–3.

  30. Vyazovkin S. Kinetic concepts of thermally stimulated reactions in solids: a view from a historical perspective. Int Rev Phys Chem. 2000;19:45–60.

    Article  CAS  Google Scholar 

  31. Vyazovkin S. A unified approach to kinetic processing of nonisothermal data. Int J Chem Kinet. 1996;28:95–101.

    Article  CAS  Google Scholar 

  32. Millan A, Clemente RR, Veintemillas S, Spinner B. Decomposition and synthesis of NiCl2 ammoniate salts: an optical microscopy study. J Chem Soc Faraday Trans. 1997;93(18):3363–9.

    Article  CAS  Google Scholar 

  33. Vyazovkin S. Modification of the integral isoconversional method to account for variation in the activation energy. J Comput Chem. 2001;22:178–83.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are grateful to the Sophisticated Test and Instrumentation Centre (STIC), Cochin, for recording TR-XRD patterns.

Author information

Authors and Affiliations

  1. School of Chemical Sciences, Mahatma Gandhi University, P.D. Hills P.O., Kottayam, Kerala, 686 560, India

    K. S. Rejitha & S. Mathew

  2. Institute for Advanced Materials Research, Hiroshima University, Higashi-Hiroshima, 739-8530, Japan

    T. Ichikawa

Authors
  1. K. S. Rejitha
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. T. Ichikawa
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. S. Mathew
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to S. Mathew.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rejitha, K.S., Ichikawa, T. & Mathew, S. Thermal decomposition studies of [Ni(NH3)6]X2 (X = Cl, Br) in the solid state using TG-MS and TR-XRD. J Therm Anal Calorim 103, 515–523 (2011). https://doi.org/10.1007/s10973-010-1054-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-010-1054-8

Keywords

Search

Navigation