Journal of Thermal Analysis and Calorimetry

, Volume 106, Issue 1, pp 267–275 | Cite as

Thermal behaviour of nickel(II) sulphate, nitrate and halide complexes containing ammine and ethylenediamine as ligands

Kinetics and evolved gas analysis
  • K. S. Rejitha
  • Suresh MathewEmail author


Thermal behaviour of nickel amine complexes containing SO4 2−, NO3 , Cl and Br as counter ions and ammonia and ethylenediamine as ligands have been investigated using simultaneous TG/DTA coupled with mass spectroscopy (TG/DTA–MS). Evolved gas analyses detected various transient intermediates during thermal decomposition. The nickel ammonium sulphate complex produces NH, N, S, O and N2 species. The nickel ammonium nitrate complex generated fragments like N, N2, NO, O2, N2O, NH2 and NH. The halide complexes produce NH2, NH, N2 and H2 species during decomposition. The ligand ethylenediamine is fragmented as N2/C2H4, NH3 and H2. The residue hexaamminenickel(II) sulphate produces NiO with crystallite size 50 nm. Hexaammine and tris(ethylenediamine)nickel(II) nitrate produce NiO in the range 25.5 nm and 23 nm, respectively. The halide complexes produce nano sized metallic nickel (20 nm) as the residue. Among the complexes studied, the nitrate containing complexes undergo simultaneous oxidation and reduction.


Kinetic parameters Nickel amine complexes Non-mechanistic equations Thermal behaviour 



The authors are grateful to Prof. T. Ichikawa, the Institute for Advanced Materials Research, Hiroshima University, Japan, for the TG–MS analyses.


  1. 1.
    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.CrossRefGoogle Scholar
  2. 2.
    Kapoor IPS, Kapoor M, Singh G, Singh UP, Goel N. Preparation, characterization and thermolysis of nitrate and perchlorate salts of 2,4,6-trimethylaniline. J Hazard Mater. 2010;173:173–80.CrossRefGoogle Scholar
  3. 3.
    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;181:253–8.CrossRefGoogle Scholar
  4. 4.
    Alcolea A, Ibarra I, Caparrós A, Rodríguez R. Study of the MS response by TG–MS in an acid mine drainage efflorescence. J Therm Anal Calorim. 2010;101:1161–5.CrossRefGoogle Scholar
  5. 5.
    Yu Z, Sun Y, Wei W, Lu L, Wang X. Preparation of NdCrO3 nanoparticles and their catalytic activity in the thermal decomposition of ammonium perchlorate by DSC/TG-MS. J Therm Anal Calorim. 2009;97:903–9.CrossRefGoogle Scholar
  6. 6.
    Coats AW, Redfern JP. Kinetic parameters from thermogravimetric data. Nature. 1964;201:68–9.CrossRefGoogle Scholar
  7. 7.
    Madhusudanan PM, Krishnan K, Ninan KN. A new approximation for the p(x) function in the evaluation of non-isothermal kinetic data. Thermochim Acta. 1986;97:189–201.CrossRefGoogle Scholar
  8. 8.
    Horowitz HH, Metzger G. A new analysis of thermogravimetric traces. Anal Chem. 1963;35:1464–8.CrossRefGoogle Scholar
  9. 9.
    MacCallum JR, Tanner J. The kinetics of thermogravimetry. Eur Polym J. 1970;6:1033–9.CrossRefGoogle Scholar
  10. 10.
    Rochow EG, editor. Inorganic synthesis, vol. 6. New York: McGraw-Hill; 1960.Google Scholar
  11. 11.
    Vogel AI. A text book of quantitative inorganic analysis. 4th ed. New York: Longmann; 1978.Google Scholar
  12. 12.
    Mockenhaupt C, Eßmann R, Lutz HD. [Ni(NH3)6]SO4: crystal structure and infra red spectra. Z Naturforsch. 1999;54b:843–8.Google Scholar
  13. 13.
    Cotton FA, Wilkinson G. Advanced inorganic chemistry. 5th ed. New York: Wiley; 1988.Google Scholar
  14. 14.
    Skoczylas ML, Mikuli E, Szklarzewicz J, Hetmańczyk J. Thermal behaviour, phase transition and molecular motions in [Co(NH3)6](NO3)2. Thermochim Acta. 2009;496:38–44.CrossRefGoogle Scholar
  15. 15.
    Madarász J, Bombicz P, Mátyás C, Réti 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.CrossRefGoogle Scholar
  16. 16.
    Norris AC, Pope MI, Selwood M. The determination of kinetic parameters for reactions involving solids. Thermochim Acta. 1980;41:357–60.CrossRefGoogle Scholar
  17. 17.
    Frost AA, Pearson RG. Kinetics and mechanism. New York: Wiley; 1961.Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2011

Authors and Affiliations

  1. 1.School of Chemical SciencesMahatma Gandhi UniversityKottayamIndia

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