THE CALCULATION OF SPECIFIC HEATS FOR SOME IMPORTANT SOLID COMPONENTS IN HYDROGEN PRODUCTION PROCESS BASED ON CuCl CYCLE

Abstract

Hydrogen is one of the most promising energy sources of the future enabling direct production of power and heat in fuel cells, hydrogen engines or furnaces with hydrogen burners. One of the last remainder problems in hydrogen technology is how to produce a sufficient amount of cheap hydrogen. One of the best options is large scale thermochemical production of hydrogen in combination with nuclear power plant. copper-chlorine (CuCl) cycle is the most promissible thermochemical cycle to produce cheap hydrogen.This paper focuses on a CuCl cycle, and the describes the models how to calculate thermodynamic properties. Unfortunately, for many components in CuCl cycle the thermochemical functions of state have never been measured. This is the reason that we have tried to calculate some very important thermophysical properties. This paper discusses the mathematical model for computing the thermodynamic properties for pure substances and their mixtures such as CuCl, HCl, Cu2OCl2 important in CuCl hydrogen production in their fluid and solid phase with an aid of statistical thermodynamics. For the solid phase, we have developed the mathematical model for the calculation of thermodynamic properties for polyatomic crystals. In this way, we have used Debye functions and Einstein function for acoustical modes and optical modes of vibrations to take into account vibration of atoms. The influence of intermolecular energy we have solved on the basis of Murnaghan equation of state and statistical thermodynamics.

Keywords

Dates

  • Submission Date2013-12-16
  • Revision Date2014-03-28
  • Acceptance Date2014-04-12
  • Online Date2014-09-06

DOI Reference

10.2298/TSCI1403823A

References

  1. Naterer, G. F., et al., Clean Hydrogen Production with the Cu-Cl Cycle - Progress of International Consortium, Part 2, Simulations, Thermochemical Data and Materials, Int. J. Hydrogen Energy, 36 (2011), 24, pp. 15486-15501
  2. Wang, Z. L., Naterer, G. F., Greenhouse Gas Reduction in Oil Sands Upgrading and Extraction Operations with Thermochemical Hydrogen Production, Int. J. Hydrogen Energy, 36 (2011), 24, pp. 15486- 15501
  3. Okabe, H., et al., New Pyrochlore-like Compound Cu2OCl2 with S=1/2, Journal of Physical Society of Japan, 75 (2006), 123765, pp. 1-4
  4. Nixon A., et al., Thermochemical Production of Hydrogen Synthesis, Characterization, and Decomposition of Copper Oxychloride, J. Therm. Analys. Calorim., 110 (2011), 3, pp. 1095-1105
  5. Krivoichiev, S. V., et al., The Cuprite-Like Framework of OCu4 Tetrahedra in the Crystal Structure of Syntetic Melanothallite Cu2OCl4 and its Negative Thermal Expansion, The Canadian Mineralogist, 40 (2002), pp. 1185-1190
  6. Zamfirescu, C., et al., Thermophysical Properties of Copper Compounds in Copper-Chlorine Thermochemical Water Splitting Cycles, International Journal of Hydrogen Energy, 35 (2010), 10, pp. 4839- 4852
  7. Parry T.,Thermodynamics and Magnetism of Cu2OCl2, M. Sc. thesis, Birgham Young University, Provo, Ut., USA, 2008
  8. Kawashima, K., et al., Antiferromagnetic Ordering in Cu2OCl2 Studied by the Muon Spin Rotation/ relaxation Technique, Journal of Physics (condens. Matter), 19 (2007), pp. 1-5
  9. Lewis, M. A., et al., Evaluation of Alternative Thermochemical Cycles, Part I, The Methodology, International Journal of Hydrogen Energy, 34 (2009), 9, pp. 4115-4124
  10. Avsec, J., Naterer, G. F., Thermodynamic Property Evaluation of Copper-Chlorine Fluid Components at High Temperatures, AIAA 40th Thermophysics conference, Seattle, Wash., USA, 2008
  11. McClelland, B. J., Statistical Thermodynamics, Chapman and Hall, London, 1980
  12. Munster, A., Statistical Thermodynamics, Springer-Verlag, Berlin, Germany, 1974
  13. Avsec, J., Watanabe, K., An Approach to Calculate Thermodynamic Properties of Mixtures Including Propane, n-Butane and Isobutane. Int. J. Thermophys., 26 (2005), 6, pp. 1769-1780
  14. Avsec, J., Oblak, M., Thermal Vibrational Analysis for Simply Supported Beam and Clamped Beam, J. Sound Vib., 308 (2007), 3/5, pp. 514-525
  15. Avsec, J., Marčič, M., Calculation of Elastic Modulus and Other Thermophysical Properties for Molecular Crystals, J. thermophys. heat transf., 16 (2002), 3, pp. 463-468
  16. Rosen, M. A., et al., Nuclear-Based Hydrogen Production with a Thermochemical Copper-Chlorine Cycle and Supercritical Water Reactor, Canadian Hydrogen Association Workshop, Montreal, Quebec, Canada, 2006
  17. Mathias, P. M., Modeling of the Copper Chloride Thermochemical Cycle: Thermodynamic Properties of CuCl, Technical Report, Argonne National Laboratory, DuPage County, Ill., USA, 2006
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