Thermodynamic study of zinc antimonides by the electromotive force measurements

Aytekin R. Aghayeva; Sakina H. Mammadova; Dunya M. Babanly; Yasin I. Jafarov; Dilgam B. Tagiyev

doi:10.17308/kcmf.2025.27/12485

Aytekin R. Aghayeva French-Azerbaijani University, Azerbaijan State Oil and Industry University, Nizami 183, Baku, Azerbaijan https://orcid.org/0000-0001-8184-0762
Sakina H. Mammadova Institute of Charles Sadron of CNRS, Strasbourg 67200, France https://orcid.org/0009-0000-5731-9993
Dunya M. Babanly French-Azerbaijani University, Azerbaijan State Oil and Industry University, Nizami 183, Baku, Azerbaijan; Institute of Catalysis and Inorganic Chemistry, 113 H. Javid ave., Baku, AZ-1143, Azerbaijan https://orcid.org/0000-0002-8330-7854
Yasin I. Jafarov Baku State University, 23 Z.Khalilov, Baku Az-1048, Azerbaijan https://orcid.org/0000-0002-3968-8725
Dilgam B. Tagiyev Institute of Catalysis and Inorganic Chemistry, 113 H. Javid ave., Baku, AZ-1143, Azerbaijan https://orcid.org/0000-0002-8312-2980

DOI: https://doi.org/10.17308/kcmf.2025.27/12485

Keywords: ZnSb, Zn4Sb3, emf method, Electrochemical cells, Glycerol electrolyte, Thermodynamic functions

Abstract

Zinc antimonides and phases based on them are of great interest as earth-abundant, low-cost, and environmentally friendly thermoelectric materials. The present work demonstrates the results of a thermodynamic study of the ZnSb and Zn₄Sb₃ compounds by a low-temperature electromotive force (emf) method with a glycerol electrolyte in the 300-430 K temperaturesrange.

Measurements were performed using equilibrium samples from the ZnSb+Sb and ZnSb+Zn₄Sb₃ two-phase regions of the Zn-Sb binary system. The phase compositions of prepared samples were controlled by means of the powder X-ray diffraction (PXRD) method. Using the least square method, the linear equations of temperature dependences of the emf data wereobtained.

Based on these equations and relevant thermodynamic expressions, the partial molar Gibbs free energy, enthalpy, and entropy of zinc in alloys were calculated. Utilizing the phase diagram of the Zn-Sb system, the virtual-cell reactions for both binary compounds were determined, based on which their standard hermodynamic functions of formation and standard entropies were calculated. A comparative analysis of the obtained results with available literature data was carried out.

The results of the current work are highly accurate and can be considered a new contribution to the thermodynamics of zinc antimonides

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Author Biographies

Aytekin R. Aghayeva, French-Azerbaijani University, Azerbaijan State Oil and Industry University, Nizami 183, Baku, Azerbaijan

PhD student in physical chemistry, Laboratory assistant, Physics Department, French-Azerbaijani University, (Baku, Azerbaijan)

Sakina H. Mammadova, Institute of Charles Sadron of CNRS, Strasbourg 67200, France

PhD student in polymer chemistry, Institute of Charles Sadron of CNRS (Strasbourg,
France)

Dunya M. Babanly, French-Azerbaijani University, Azerbaijan State Oil and Industry University, Nizami 183, Baku, Azerbaijan; Institute of Catalysis and Inorganic Chemistry, 113 H. Javid ave., Baku, AZ-1143, Azerbaijan

Dr. Sci. (Chem.), Assoc. Professor, Head of the Chemistry Department, researcher-teacher,
French-Azerbaijani University (Baku, Azerbaijan)

Yasin I. Jafarov, Baku State University, 23 Z.Khalilov, Baku Az-1048, Azerbaijan

Dr. Sci. (Chem.), Professor, Head of the General and Inorganic Chemistry Department, Baku State
University (Baku, Azerbaijan)

Dilgam B. Tagiyev, Institute of Catalysis and Inorganic Chemistry, 113 H. Javid ave., Baku, AZ-1143, Azerbaijan

Professor (Chem.), Academician, Vice-President of the National Academy of Sciences of Azerbaijan,
General Director of the “Institute of Catalysis and Inorganic Chemistry” (Baku, Azerbaijan)

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