Advertisement

Journal of Thermal Analysis and Calorimetry

, Volume 134, Issue 3, pp 1575–1587 | Cite as

Determination of thermokinetic parameters and thermodynamic functions from thermoforming of LiMnPO4

  • Chuchai SronsriEmail author
  • Banjong BoonchomEmail author
Article
  • 150 Downloads

Abstract

This article presents the determination of thermokinetic parameters and thermodynamic functions from the thermoforming of LiMnPO4. In our previous paper, a couple of thermoreaction processes, e.g., co-elimination and polycondensation of thermokinetics and thermodynamics, were incompletely determined. The co-elimination process is considered as dehydration and a deammoniation process in this paper. Evidently, an alternative technique was applied for calculating the extent of conversion values using the ratio of the peak area of the deconvoluted DTG peak after applying the Fraser–Suzuki deconvolution. An iterative equation of the integral isoconversional technique was used to estimate the reliable activation energy Eα. Each separated peak, including dehydration, deammoniation, and polycondensation, was obviously evaluated as a single kinetic process with its own kinetic parameters. In order to choose reliable mechanisms, the y(α) master plots or the plots between the experiment and the model were compared. The plots thus obtained showed that the dehydration, deammoniation, and polycondensation processes were found to be 3/2-order chemical reaction (F3/2), 2-order chemical reaction (F2), and nucleation (P3/2) mechanisms, respectively. The pre-exponential factor values were obtained from Eα, and the reaction mechanisms were found to be 3.78 × 1012, 7.05 × 1012, and 1.96 × 1013 s−1, respectively. The evaluated thermodynamic data of the activated complexes showed that the thermal reaction required thermal energy to complete the reaction.

Keywords

Thermokinetic and thermodynamic data Alternative technique Fraser–Suzuki deconvolution Integral isoconversional technique Master plot 

Notes

Acknowledgements

This work is supported by King Mongkut’s Institute of Technology Ladkrabang (KREF146001). I would like to thank the Advanced Phosphate Materials and Alternative Fuel Energy Research Unit, Department of Chemistry, Faculty of Science, King Mongkut’s Institute of Technology Ladkrabang, Thailand. I also thank Assoc. Prof. Dr. Chanaiporn Danvirutai for carefully reading the manuscript.

References

  1. 1.
    Boonchom B, Maensiri S, Danvirutai C. Soft solution synthesis, non-isothermal decomposition kinetics and characterization of manganese dihydrogen phosphate dihydrate Mn(H2PO4)2 2H2O and its thermal transformation products. Mater Chem Phys. 2008;109:404–10.CrossRefGoogle Scholar
  2. 2.
    Sronsri C, Noisong P, Danvirutai C. Synthesis, non-isothermal kinetic and thermodynamic studies of the formation of LiMnPO4 from NH4MnPO4 H2O precursor. Solid State Sci. 2014;32:67–75.CrossRefGoogle Scholar
  3. 3.
    Vyazovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA, Popescu C, Sbirrazzuoli N. ICTAC kinetics committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. 2011;520:1–19.CrossRefGoogle Scholar
  4. 4.
    Kissinger HE. Reaction kinetics in differential thermal analysis. J Anal Chem. 1957;29:1702–6.CrossRefGoogle Scholar
  5. 5.
    Akahira T, Sunose T. Method of determining activation deterioration constant of electrical insulating materials. Res Rep Chiba Inst Technol (Sci Technol). 1971;16:22–31.Google Scholar
  6. 6.
    Ozawa TA. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.CrossRefGoogle Scholar
  7. 7.
    Flynn JH, Wall LA. A quick, direct method for the determination of activation energy from thermogravimetric data. Polym Lett. 1966;4:323–8.CrossRefGoogle Scholar
  8. 8.
    Coats AW, Redfern JP. Kinetic parameters from thermogravimetric data. Nature. 1964;20:68–9.CrossRefGoogle Scholar
  9. 9.
    Perejón A, Sánchez-Jiménez PE, Criado JM, Pérez-Maqueda LA. Kinetic analysis of complex solid-state reactions. A new deconvolution procedure. J Phys Chem B. 2011;115:1780–91.CrossRefGoogle Scholar
  10. 10.
    Vlaev LT, Nikolova MM, Gospodinov GG. Non-isothermal kinetics of dehydration of some selenite hexahydrates. J Solid State Chem. 2004;177:2663–9.CrossRefGoogle Scholar
  11. 11.
    Sronsri C, Noisong P, Danvirutai C. Synthesis and properties of LiMIIPO4 (MII = Mg, Mn0.5Mg0.5, Co0.5Mg0.5) affected by isodivalent doping and Li-sources. Solid State Sci. 2014;36:80–8.CrossRefGoogle Scholar
  12. 12.
    Sronsri C, Noisong P, Danvirutai C. Synthesis, characterization and vibrational spectroscopic study of Co, Mg co-doped LiMnPO4. Spectrochim Acta A Mol Biomol Spectrosc. 2016;153:436–44.CrossRefGoogle Scholar
  13. 13.
    Sronsri C, Noisong P, Danvirutai C. Solid state reaction mechanisms of the LiMnPO4 formation using special function and thermodynamic studies. Ind Eng Chem Res. 2015;54:7083–93.CrossRefGoogle Scholar
  14. 14.
    Sronsri C, Noisong P, Danvirutai C. Double function method for the confirmation of the reaction mechanism of LiCoPO4 nanoparticle formation, reliable activation energy, and related thermodynamic functions. React Kinet Mech Catal. 2017;121:555–77.CrossRefGoogle Scholar
  15. 15.
    Chai Q, Chen ZP, Liao S, He Y, Li Y, Wu WW, Li B. Preparation of LiZn0.9PO4:Mn0.1·H2O via a simple and novel method and its non-isothermal kinetics using iso-conversional calculation procedure. Thermochim Acta. 2012;533:74–80.CrossRefGoogle Scholar
  16. 16.
    Genieva SD, Vlaev LT, Atanassov AN. Study of the thermooxidative degradation kinetics of poly(tetrafluoroethene) using iso-conversional calculation procedure. J Therm Anal Calorim. 2010;99:551–61.CrossRefGoogle Scholar
  17. 17.
    Seo DK, Park SS, Kim YT, Hwang J, Yu TU. Study of coal pyrolysis by thermo-gravimetric analysis (TGA) and concentration measurements of the evolved species. J Anal Appl Pyrolysis. 2011;92:209–16.CrossRefGoogle Scholar
  18. 18.
    Chrissafis K, Paraskevopoulos KM, Papageorgiou GZ, Bikiaris DN. Thermal decomposition of poly(propylene sebacate) and poly(propylene azelate) biodegradable polyesters: Evaluation of mechanisms using TGA, FTIR and GC/MS. J Anal Appl Pyrolysis. 2011;92:123–30.CrossRefGoogle Scholar
  19. 19.
    Senum GI, Yang RT. Rational approximations of the integral of the Arrhenius function. J Therm Anal Calorim. 1977;11:445–7.CrossRefGoogle Scholar
  20. 20.
    Vlaev L, Nedelchev N, Gyurova K, Zagorcheva M. A comparative study of non-isothermal kinetics of decomposition of calcium oxalate monohydrate. J Anal Appl Pyrolysis. 2008;81:253–62.CrossRefGoogle Scholar
  21. 21.
    Cai J, Chen S. A new iterative linear integral isoconversional method for the determination of the activation energy varying with the conversion degree. J Comput Chem. 2009;30:1986–91.CrossRefGoogle Scholar
  22. 22.
    Vyazovkin S, Dollimore D. Linear and nonlinear procedures in isoconversional computations of the activation energy of nonisothermal reactions in solids. J Chem Inf Comput Sci. 1996;36:42–5.CrossRefGoogle Scholar
  23. 23.
    Budrugeac P. An iterative model-free method to determine the activation energy of non-isothermal heterogeneous processes. Thermochim Acta. 2010;511:8–16.CrossRefGoogle Scholar
  24. 24.
    Sronsri C, Noisong P, Danvirutai C. Thermal decomposition kinetics of Mn0.9Co0.1HPO4·3H2O using experimental-model comparative and thermodynamic studies. J Therm Anal Calorim. 2017;127:1983–94.CrossRefGoogle Scholar
  25. 25.
    Málek J. A computer program for kinetic analysis of non-isothermal thermoanalytical data. Thermochim Acta. 1989;138:337–46.CrossRefGoogle Scholar
  26. 26.
    Sronsri C, Noisong P, Danvirutai C. Isoconversional kinetic, mechanism and thermodynamic studies of the thermal decomposition of NH4Co0.8Zn0.1Mn0.1PO4·H2O. J Therm Anal Calorim. 2015;120:1689–701.CrossRefGoogle Scholar
  27. 27.
    Liu SH, Shu CM. Advanced technology of thermal decomposition for AMBN and ABVN by DSC and VSP2. J Therm Anal Calorim. 2015;121:533–40.CrossRefGoogle Scholar
  28. 28.
    Rooney JJ. Eyring transition-state theory and kinetics in catalysis. J Mol Catal A: Chem. 1995;96:L1–3.CrossRefGoogle Scholar
  29. 29.
    Sronsri C, Noisong P, Danvirutai C. Synthesis, characterization, non-isothermal kinetic and thermodynamic studies of the formation of LiCoPO4 from NH4CoPO4·H2O precursor. In: Pure and applied chemistry international conference, Khon Kaen. 2014. p. 413–6.Google Scholar
  30. 30.
    Sronsri C. Thermal dehydration kinetic mechanism of Mn1.8Co0.1Mg0.1P2O7·2H2O using Málek’s equations and thermodynamic functions determination. Trans Nonferrous Met Soc China. 2018;28:1016–26.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Advanced Phosphate Materials and Alternative Fuel Energy Research Unit, Department of Chemistry, Faculty of ScienceKing Mongkut’s Institute of Technology LadkrabangBangkokThailand

Personalised recommendations