Abstract
The molten CuCl–CuCl2 system was studied by means of the maximum bubble pressure method, thermodynamics and molecular dynamics simulations at temperatures of 835, 866, 905 and 943 K. The equilibrium constant of CuCl2 decomposition has been determined with thermodynamic simulation. The density and molar volume of the CuCl–CuCl2 system were established as a function of composition. Some evidence of ideality of CuCl–CuCl2 solutions was observed. The molar volumes of pure liquid CuCl2 are equal to 44.64, 46.23, 46.55 and 46.81 cm3·mol−1 at 835, 866, 905 and 943 K, correspondingly. Radial distribution functions, coordination numbers, self-diffusion coefficients and trajectories of motion were obtained by molecular dynamics simulation. For this reason a new pair potential for Cu2+–Cl− pair has been designed. The coordination number of Cu2+ by Cl− is about 4. This value corresponds to literature data with regards to this coordination. The self-diffusion coefficients are close to diffusion coefficients measured in molten salts solutions.
Similar content being viewed by others
References
Anfinogenov, A.I., Martem’yanova, Z.S.: Spontaneous mass transfer and deposition of carbon and silicon on titanium in LiCl–Li ionic–electronic melts. J. Min. Metall. 39, 295–301 (2003)
Anfinogenov, A.I., Chebykin, V.V., Chernov, Y.B.: Spontaneous electrochemical transport reactions in ionic and ionic–electronic salt melts: the production of diffusion coatings. Russ. J. Electrochem. 43, 968–976 (2007)
Daněk, V., Ličko, T., Pánek, Z.: Conductivity of melts in the system CaO–FeO–Fe2O3–SiO2. Chem. Pap. 40, 215–223 (1986)
Bredig, M.A.: Molten Salt Chemistry. Interscience, New York (1964)
Heus, R.J., Egan, J.J.: Electronic conductivity in molten lithium chloride–potassium chloride eutectic. J. Phys. Chem. 77, 1989–1993 (1973)
Egan, J.J., Freyland, W.: Thermodynamic properties of liquid non metallic Na–NaBr solutions. Ber. Bunsenges. Phys. Chem. 89, 381–384 (1985)
Nattland, D., Heyer, H., Freyland, W.: Metal–nonmetal transition in liquid alkali metal–alkalihalide melts: electrical conductivity and optical reflectivity study. Z. Phys. Chem. N. F. 149, 1–15 (1986)
Liu, J., Poignet, J.-C.: Electronic conductivity of salt-rich Li–LiCl melts. J. Appl. Electrochem. 22, 1110–1112 (1992)
Nattland, D., Von Blanckenhagen, B., Juchem, R., Schellkes, E., Freyland, W.: Localized and mobile electrons in metal–molten-salt solutions. J. Phys. 8, 9309–9314 (1996)
Warren, W.W., Sotier, S., Brennert, G.F.: Resolution of the conductivity dilemma in liquid solutions of alkali metals in alkali halides. Phys. Rev. Lett. 50, 1505–1508 (1983)
Budimirov, M.A., Red’kin, A.A., Hohlov, V.A., Batalov, N.N.: Fiziko-himicheskie issledovaniya rasplavlennich smesey (LiCl–KCl)evt–CuCl–CuCl2 (in Russian). Rasplavy. 3, 47–53 (1993)
Shevelin, P.Yu., Molchanova, N.G., Yolshin, A.N., Batalov, N.N.: Electron transfer in an electron-ion molten mixture of CuCl–CuCl2–MeCl (Me = Li, Na, K, Cs). Electrochim. Acta 48, 1385–1394 (2003)
Saluev, A.B., Redkin, A.A., Hohlov, V.A.: Electroprovodnost rasplavov sistemy CsCl–CeCl3–Cl2 pri razlichnich davleniyah hlora (in Russian). Rasplavy. 4, 66–72 (1999)
Zinchenko, V.F., Shapovalov, A.V., Sadovskaya, L.V.: Ionno-elektronnaya provodimost rasplavov slozhnih halkogenidov evropiya (II) (in Russian). Rasplavy. 2, 78–80 (1997)
Elshin, A.N., Shevelin, P.Yu., Molchanova, N.G., Batalov, N.N., Red’kin, A.A.: Electron transfer in the CuCl–CuCl2–LiCl melt. Russ. J. Electrochem. 33, 1299–1305 (1997)
Shevelin, P.Yu., Raskovalov, A.A., Molchanova, N.G.: An electron transfer in CuCl–CuCl2 melt at different Cl2 partial pressures. Ionics 23, 3163–3168 (2017)
Smirnov, M.V., Stepanov, V.P.: Density and surface tension of molten alkali halides and their binary mixtures. Electrochim. Acta 27, 1551–1563 (1982)
Janz, G.J., Tomkins, R.P.T., Allen, C.B., Downey Jr., J.R., Garner, G.L., Krebs, U., Singer, S.K.: Molten salts: volume 4, part 2, chlorides and mixtures, electrical conductance, density, viscosity, and surface tension data. J. Phys. Chem. Ref. Data 4, 871–1178 (1975)
Sinyarev, G.B., Trusov, B.G., Slynko, L.E.: A universal program for determination of the composition of multicomponent working bodies and calculation of some thermal processes, in: Proceedings of the MVTU, No. 159, MVTU, Moscow (1973)
Glushko, V.P., Gurvich, L.V., Bergman, G.A., Veits, I.V., Medvedev, V.A., Khachkuruzov, G.A., Yungman, V.S.: Thermodinamicheskie Svoitsva Individual’nykh. Veshchestv, vol. I–IV. Science, Moscow (1978–1982)
Smith, W., Forester, T.: The DL_POLY Project. TCS Division, Daresbury Laboratory, Daresbury, Warrington WA4 4AD
Stafford, A.J., Silbert, M., Trullas, J., Giro, A.: Potentials and correlation functions for the copper halide and silver iodide melts: I. Static correlations. J. Phys. 2, 6631–6641 (1990)
Shannon, R.D.: Revised effective ionic radii and systematic studies of interatomic distances in halides and chaleogenides. Acta Crystallogr. A 32, 751–767 (1976)
Andreev, O.L., Raskovalov, A.A., Larin, A.V.: A molecular dynamics simulation of lithium fluoride: volume phase and nanosized particle. Russ. J. Phys. Chem. 84, 48–52 (2010)
Ezhov,Y.S., Gusarov, A.V.: Copper dichloride. Chemical Department of Moscow State University. http://www.chem.msu.su/Zn/Cu/CuCl2.html (2006); accessed 19 January 2006
Ruthven, J.D.M., Kenney, C.N.: Equilibrium chlorine pressures over cupric chloride melts. J. Inorg. Nucl. Chem. 30, 931–944 (1968)
Lurie, YuYu.: Spravochnik po analiticheskoy himii. Chemistry, Moscow (1971)
Giazitzoglou, Z.: Redox electromotive force measurments in the molten CuCl–CuCl2 system and thermodynamics properties of liquid CuCl2. J. Chem. Eng. Data 29, 3–5 (1984)
Eisenberg, S., Jal, J.-F., Dupuy, J., Chieux, P., Knoll, W.: Neutron diffraction determination of the partial structure factors of molten CuCl. Phil. Mag. A 46, 195–209 (1982)
Alcaraz, O., Trullàs, J., Tahara, S., Kawakita, Y., Takeda, S.: The structure of molten CuCl: reverse Monte Carlo modeling with high-energy X-ray diffraction data and molecular dynamics of a polarizable ion model. J. Chem. Phys. 145, 094503 (2016). https://doi.org/10.1063/1.4962181
Kolmel, Ch., Ahlrichs, R.: An ab initio investigation of copper complexes with supershort copper-copper distances. J. Phys. Chem. 94, 5536–5542 (1990)
Zhao, H., Chang, J., Boika, A., Bard, A.J.: Electrochemistry of high concentration copper chloride complexes. Anal. Chem. 85, 7696–7703 (2013)
Liu, W., Brugger, J., McPhail, D.C., Spiccia, L.: A spectrophotometric study of aqueous copper(I)–chloride complexes in LiCl solutions between 100 °C and 250 °C. Geochim. Cosmochim. Acta 66, 3615–3633 (2002)
Elshin, A.N., Budimirov, M.A., Zakharov, V.V., Batalov, N.N.: Koefficienty diffuzii Cu+ i Cu2+ v legkoplavkikh smesyakh galogenidov shelochnykh metallov (in Russian). Rasplavy. 3, 120–123 (1989)
Acknowledgements
The reported study was funded by Russian Foundation for Basic Research (RFBR), according to the research Project No. 16-33-60095 mol_a_dk. The calculations were performed using “Uran” supercomputer of IMM UB RAS.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Raskovalov, A.A., Shevelin, P.Y. Physico-chemical Properties of the Molten CuCl–CuCl2 System: Experiment, Thermodynamics and Molecular Dynamics Simulations. J Solution Chem 47, 1779–1793 (2018). https://doi.org/10.1007/s10953-018-0817-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-018-0817-x