Abstract
Thorium–cerium mixed oxides (Th1−xCex)O2 (x = 0.25, 0.5, 0.75) were prepared by the citrate gel combustion technique. X-ray diffraction investigations of these samples revealed the formation of single-phase (fluorite) solid solutions. Heat capacity and enthalpy increments of these samples were measured by using a differential scanning calorimeter and a drop calorimeter (MHTC 96) in the temperature range 298–800 K and 523–1723 K, respectively. The values of heat capacity in the temperature range 523–1800 K were computed from the enthalpy increment data. With the help of these data, analytical expression for the heat capacity of (Th1−xCex)O2 (x = 0.25, 0.5, 0.75) as well as entropy and Gibb’s energy functions were obtained. The heat capacity values at 298 K pertaining to (Th1−xCex)O2 (x = 0.25, 0.5, 0.75) were found to be 64.92, 64.80, and 64.27 J K−1 mol−1, respectively. The thermodynamic functions are being reported for the first time.
Similar content being viewed by others
References
International Atomic Energy Agency, Thorium fuel cycle—Potential benefits and challenges, IAEA-TECDOC-1450, Vienna; 2005.
Sinha RK, Kakodkar A. Design and development of the AHWR—the Indian thorium fuelled innovative nuclear reactor. Nucl Eng Des. 2006;236:683–700.
Naik YP, Ramarao GA, Banthiya A, Chaudhary D, Arora C. Synthesis and characterization of nano structured Th1−xCexO2 mixed oxide. J Therm Anal Calorim. 2012;107(1):105–10.
Raj B, Vijayalakshmi M, Vasudeva Rao PR, Rao KBS. Challenges in materials research for sustainable nuclear energy. Mater Res Bull. 2008;33:327–37.
Shein IR, Shein KL, Ivanovskii AL. Elastic and electronic properties and stability of SrThO3, SrZrO3 and ThO2 from first principles. J Nucl Mater. 2007;361:69–77.
Osaka M, Takano S, Yamane Y. On a fast reactor cycle scheme that incorporates a thoria-based minor actinide-containing cermet fuel. Prog Nucl Energy. 2008;50:212–8.
Lombardi C, Luzzi L, Padovani E, Vettraino F. Thoria and inert matrix fuel for a sustainable nuclear power. Prog Nucl Energy. 2008;50:944–53.
Mathews MD, Ambekar BR, Tyagi AK. Bulk and lattice thermal expansion of Th1−xCexO2. J Nucl Mater. 2000;280:246–9.
Mathews MD, Ambekar BR, Tyagi AK. Bulk thermal expansion studies of Th1−xCexO2 in the complete solid solution range. J Nucl Mater. 2001;288:83–5.
Freshley MD, Mattys HM, General electric report HW-76559; 1962, p. 11.6.
Muta H, Kawano T, Uno M, Ohishi Y, Kurosaki K, Yamanaka S. Lattice parameter and thermal conductivity of Th1−xMxO2−y (M = Y, La, Ce, Nd, Gd and U). J Nucl Mater. 2013;434:124–8.
Shvareva TY, Alexandrov V, Asta M, Navrotsky A. Energetics of mixing in ThO2–CeO2 fluorite solid solutions. J. Nucl Mater. 2011;419:72–5.
Sanjay Kumar D, Ananthasivan K, Venkata Krishnan R, Amirthapandian S, Dasgupta A. Bulk systhesis of nanocrystalline urania powders by citrate gel-combustion method. J Nucl Mater. 2016;468:178–93.
Certificate of Standard Reference Materials 720, Synthetic sapphire (Al2O3) was supplied along with High temperature Calorimeter procured. U.S. Department of Commerce, Washington, DC. https://wwws.nist.gov/srmors/certificates/720.pdf?CFID.
Babu R, Kandan R, Jena HN, Govindan Kutty KV, Nagarajan K. Calorimetric investigations on cubic BaTiO3 and Ba0.9Nd0.1TiO3 systems. J Alloys Compd. 2010;506:565–8.
Cullity BD. Elements of xray diffraction, Chapter 11. 2nd ed. Reading, MA: Addison Wesely Co.; 1978.
Venkata Krishnan R, Nagarajan K, Vasudeva Rao PR. Heat capacity measurements on BaThO3 and BaCeO3. J Nucl Mater. 2001;299:28–31.
Kandan R, Babu R, Manikandan P, Venkata Krishnan R, Nagarajan K. Calorimetric measurements on (U,Th)O2 solid solution. J Nucl Mater. 2009;384:231–5.
Bakker K, Cordfunke EHP, Conings RJM, Schram RPC. Critical evaluation of the thermal properties of ThO2 and Th1−yUyO2 and a survey of literature data on Th1−yPuyO2. J Nucl Mater. 1997;250:1–12.
Kubaschewski O, Alcock CB. Metallurgical thermochemistry. London: Pergamon Press; 1974.
Shannon RD. Revised effective ionic Radii and systematic studies of inter atomic distances in halides and chalcogenides. Acta Cryst. 1976;A32:751–67.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Babu, R., Balakrishnan, S., Venkata Krishnan, R. et al. Thermodynamic functions of thorium–cerium mixed oxides. J Therm Anal Calorim 136, 2421–2427 (2019). https://doi.org/10.1007/s10973-018-7902-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-018-7902-7