Osipov A.A., Niyazov S.-A.S.
A.I. Leypunsky Institute for Physics and Power Engineering, Obninsk, Russia
This paper deals with the problem of modeling the thermodynamic activity (TDA) of oxygen (a measured parameter) in metal melts, in particular, heavy liquid metal melts based on lead and lead-bismuth. With regard to promising nuclear power plants with a heavy liquid metal coolant (HLMC), the issue of the interaction of oxide films with a liquid metal is relevant, since oxide films on the surfaces of structural steels act as a protective barrier that prevents the steels from dissolving in HLMC. The thermodynamic stability of oxide films and their diffusion properties depend on the TDA of oxygen in HLMC. At the same time, oxygen TDA in HLMC substantially depends on impurities (mainly iron, as the main component of structural steels). Currently, thermodynamic models of multicomponent metallic solutions based on lead and lead-bismuth are still in their infancy, while the thermodynamic model of Me–O solutions is a fundamental component of more complex systems. Therefore, the success of more complex models describing the thermodynamic properties of real multicomponent solutions based on metal melts depends on the adequacy of the thermodynamic concepts of Me–O solutions. Analysis of the experimental data shows that the solubility of oxygen near the melting point of the metal is much less than unity, therefore, the solutions of Me–O are highly diluted (metal activity equals a unit). In the present work, a thermodynamic model of dilute solutions of Me–O is considered. Within the framework of this model, Me–O solution is considered as a “multicomponent” system, where by components are meant various forms of the existence of oxygen in a metal solution (for example, O, MeO, O2–, Me2O, etc.). As a result of this consideration, it becomes possible to generalize Henry's law to metallic dilute solutions, in which oxygen exists in various forms. The considered approach is of a general nature and can be applied to other diluted multicomponent systems in which the solute can interact with the solvent and with each other.
1. Ulyanov V.V., Alexeyev V.V., Gulevsky V.A., Storozhenko A.N. Prospects of using liquid metal coolants in fast reactors. Research Journal of Pharmaceutical, Biological and Chemical Sciences, 2016, no. 7 (1), pp. 1130–1139.
2. Ivanov I.I., Shelemetyev V.M., Ulyanov V.V., Storozhenko A.N., Skobeyev D.A. Studies on nickel effect on kinetics of lead reduction from its oxide by hydrogen. Research Journal of Pharmaceutical, Biological and Chemical Sciences, 2016, no. 7(1), pp. 1700–1709.
3. Ivanov I.I., Shelemetyev V.M., Ulyanov V.V., Teplyakov Yu.A. Kinetics of the reduction of orthorhombic and tetragonal lead oxides to lead with hydrogen. Kinetics and Catalysis, 2015, no. 56(3), pp. 304–307.
4. Ulyanov V.V., Gulevsky V.A., Storozhenko A.N., Teplyakov Y.A. Control of oxidizing potential of Pb and Pb-Bi coolants. Oriental Journal of Chemistry, 2015, no. 31(4), pp. 2059–2069.
5. Gulevich A.V., Martynov P.N., Gulevsky V.A., Ulyanov V.V. Technologies for hydrogen production based on direct contact of gaseous hydrocarbons and evaporated water with molten Pb or Pb-Bi. Energy Conversion and Management, 2008, no. 49(7), pp. 1946–1950.
6. Martynov P.N., Rachkov V.I., Askhadullin A.N., Storozhenko A.N., Ulyanov V.V. Analiz sovremennogo sostoyaniya tekhnologii svintsovogo i svintsovo-vismutovogo teplonositeley [Analysis of the current state of technology of lead and lead-bismuth heat carriers]. Atomnaya energiya - Atomic Energy, 2014, vol. 116, no. 4, pp. 234–240.
7. Martynov P.N., Lavrova O.V., Ulyanov V.V., Posazhennikov A.M. Tyazhelye teplonositelya v novykh tekhnologiyakh polucheniya vodoroda [Heavy heat carrier in new technologies of production of hydrogen]. Novye promyshlennye tekhnologii - New industrial technologies, 2004, no. 3, pp. 35.
8. Martynov P.N. et al. Sovremennye podkhody k tekhnologii tyazhelykh teplonositeley [Modern approaches to technology of heavy heat carriers]. Novye promyshlennye tekhnologii - New industrial technologies, 2011, no. 1, pp. 3–5.
9. Lepinskikh B.M. et al. Okislenie zhidkikh metallov i splavov [The Oxidation of liquid metals and alloys]. Moscow, Science Publ., 1979. 116 p.
10. Gurvich L., Karachevtsev G., Kondrat'ev V. et al. Energii razryva khimicheskikh svyazey. Potentsial ionizatsii i srodstvo k elektronu [Energy of rupture of chemical bonds. Ionization potential and electron affinity]. Moscow, Science Publ., 1974. 214 p.
11. Mott N., Davis E. Elektronnye protsessy v nekristallicheskikh veshchestvakh. Chast' 1 [Electronic processes in non-crystalline substances. Part 1]. Moscow, Mir Publ., 1982. 368 p.
12. Thompson R. Solvation in liquid alkali metals. Proc. Int. Conf. “Liquid alkali metals”. Nottingham, 1973, pp. 47—50.
13. Kulikov I.S. Raskislenie metallov [Deoxidation of metals]. Moscow, Metallurgy Publ., 1975. 490 p.
14. Girifalco L. Statisticheskaya fizika tverdogo tela [Statistical physics of solids]. Moscow, Mir Publ., 1975. 382 p.
15. Sigworth G.K., Elliot J.F. The thermodynamics of liquid dilute iron alloys. Metal science Journal, 1974, vol. 8, no. 9, pp. 298—310.
16. Taskinen A. Oxygen activities in lead and dilute lead-based alloys. Acta Polytechnica Scand, 1981, no. 146, pp. 3–44.
17. Sobolev V. Database of thermophysical properties of liquid metal coolants for GEN-IV. Mol, Belgium, SCK•CEN Publ., 2011. 173 p.
18. Osipov A.A., Ivanov K.D., Niyazov S.-A.S. O svyazyakh strukturnykh i termodinamicheskikh svoystv zhidkikh metallov [About the connection of structural and thermodynamic properties of liquid metals]. Voprosy Atomnoy Nauki i Tekhniki. Seriya: Yaderno-reaktornye konstanty – Problems of Atomic Science and Technology. Series: Nuclear and Reactor Constans, 2014, no. 2, pp. 69—74.
19. Ganesan R., Gnanasekaran T., Raman S. Electrochemical study on determination of diffusivity, activity and solubility of oxygen in liquid bismuth. Journal of Chemical Thermodynamics, 2006, no. 38, pp. 739–747.
20. Trofimov E.A. Mikhailov G.G. Termodinamika vzaimodeystviya kobal'ta s kislorodom v zhidkoy medi [Thermodynamics of the interaction of cobalt with oxygen in liquid copper]. Izvestiya Chelyabinskogo nauchnogo tsentra – Proceedings of the Chelyabinsk scientific center, 2001, vol. 4 (13).
21. Ganesan R., Gnanasekaran T., Raman S. Diffusivity, activity and solubility of oxygen in liquid lead and lead-bismuth eutectic alloy by electrochemical methods. Journal of Nuclear Materials, 2006, vol. 349, pp. 133–149.
22. Ramanarayanan T.A., Rapp R.A. The Diffusivity and Solubility of Oxygen in Liquid Tin and Solid Silver and the Diffusivity of Oxygen in Solid Nickel. Metallurgical Transactions, 1972, vol. 3, pp. 3246.
23. Shinya Otsuka, Toyokazu Sano, Zensaku Kozuka. Acrivities of Oxygen in Liquid Bi, Sn, and Ge from Electrochemical Measurements. Metallurgical Transactions, 1981, vol. 128, pp. 428.
24. Justyna Nyk, Boguslaw Onderka Thermodynamics of oxygen in dilute liquid silver-tellurium alloys. Monatsh Chem, 2012, vol. 143, pp. 1219–1224.
25. Heshmatpour B., Stevenson D.A. An Electrochemical Study of the Solubility and Diffusivity of Oxygen in the Respective Liquid Metals Indium, Gallium, Antimony and Bismuth. Journal of Electroanalytical Chemistry, 1981, vol. 130, pp. 47–55.
26. Zefirov A.P. Termodinamicheskie svoystva neorganicheskikh veshchestv [Thermodynamic properties of inorganic substances]. Moscow, Atomizdat Publ., 1965. 233 p.
