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Thermodynamics and kinetics of the thermal decomposition of cupric chloride in its hydrolysis reaction

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Abstract

The hydrolysis of copper(II) chloride is the water splitting process in the copper–chlorine thermochemical hydrogen production cycle. In this paper, a simultaneous differential scanning calorimetry and thermogravimetric analysis (DSC/TG) technique is used to determine the transitional temperature and kinetics of the thermal decomposition of CuCl2. Thermodynamic analysis is performed on the decomposition reaction for a comparison with the thermogravimetric analysis results. The CuCl2 decomposition temperature obtained from thermogravimetric experiments is found to be higher than that predicted from the thermodynamic analysis. This broadens the available operating temperature range of the CuCl2 hydrolysis step for the Cu–Cl cycle. It is also found that the decomposition product CuCl may completely evaporate if the temperature is higher than its melting point, so the CuCl2 hydrolysis reaction should be operated below the melting point of CuCl (430 °C) to avoid the undesirable CuCl and Cl2 byproducts. A preliminary correlation is proposed in this paper for the decomposition kinetics in terms of the extent of converting CuCl2 to CuCl and Cl2.

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Abbreviations

Cp :

Specific heat/kJ mol−1K−1

G :

Gibbs free energy/kJ mol−1

J r :

Reaction quotient

H :

Enthalpy/kJ mol−1

K :

Reaction equilibrium constant

N Cl2,f :

Final amount of Cl2/mol

N S,i :

Initial sample amount/mol

R TG :

Reading of TG/mass%

S :

Entropy/kJ mol−1K−1

T :

Temperature/°C or K

T :

Time/min

λ :

Decomposition extent/%

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Acknowledgements

Support of this research from Atomic Energy of Canada Limited and the Ontario Research Excellence Fund is gratefully acknowledged.

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Authors and Affiliations

  1. Clean Energy Research Laboratory, University of Ontario Institute of Technology, 2000 Simcoe St N, Oshawa, ON, L1H 7K4, Canada

    Z. Wang

  2. Colorado Salt Products, 3910 Joliet St, Denver, CO, 80239, USA

    G. Marin

  3. Faculty of Engineering and Applied Science, Memorial University of Newfoundland, St. John’s, Newfoundland, A1B 3X5, Canada

    G. F. Naterer

  4. Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe St N, Oshawa, ON, L1H 7K4, Canada

    K. S. Gabriel

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  1. Z. Wang
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  4. K. S. Gabriel
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Correspondence to Z. Wang.

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Wang, Z., Marin, G., Naterer, G.F. et al. Thermodynamics and kinetics of the thermal decomposition of cupric chloride in its hydrolysis reaction. J Therm Anal Calorim 119, 815–823 (2015). https://doi.org/10.1007/s10973-014-3929-6

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  • DOI: https://doi.org/10.1007/s10973-014-3929-6

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