UNIVERSITY OF NI FACULTY OF OCCUPATIONAL SAFETY IN NI

PROCEEDINGS
The 16th Conference of the series Man and Working Environment INTERNATIONAL CONFERENCE SAFETY OF TECHNICAL SYSTEMS IN LIVING AND WORKING ENVIRONMENT

Endorsed by: Government of the Republic of Serbia MINISTRY OF EDUCATION AND SCIENCE

Ni, 27-28 October 2011

UNIVERSITY OF NIS FACULTY OF OCCUPATIONAL SAFETY IN NI

PROCEEDINGS
The 16th Conference of the series Man and Working Environment INTERNATIONAL CONFERENCE SAFETY OF TECHNICAL SYSTEMS IN LIVING AND WORKING ENVIRONMENT PUBLISHED BY: FACULTY OF OCCUPATIONAL SAFETY IN NIS arnojevi a 10a, 18000 Ni FOR THE PUBLISHER: Prof. dr Ljiljana ivkovi , dean EDITORS OF PROCEEDINGS: Prof. Dejan Petkovi , PhD Prof. Ivan Krsti , PhD GRAPHIC DESIGN AND PREPRESS: Rodoljub Avramovi PRINTED BY: M COPS CENTER , Ni CIRCULATION: 300 copies
CIP , 331.45/.46(082) 502/504(082) 614.8.084(082) INTERNATIONAL Conference of the Series Man and Working Environment Safety of Technical Systems in Living and Working Environment (16 ; 2011 ; Ni ) Proceedings / The 16th International Conference of the Series Man and Working Environment Safety of Technical Systems in Living and Working Environment - [STS-11], Ni , 27-28 October 2011. ; [organizer Faculty of Occupational Safety in Ni ; editors Dejan Petkovi , Ivan Krsti ]. - Ni : Faculty of Occupational Safety, 2011 (Ni : M Kops Centar). - 493 str. : ilustr. ; 30 cm Slike autora i bele ke o njima. - Tira 300. - Bibliografija uz svaki rad. ISBN 978-86-6093-035-6 1. Fakultet za tite na radu (Ni ) a) b) c) COBISS.SR-ID 187155980

NICOLAY BARBIN1 DMYTRI TERENTEV2 SERGEI ALEXEEV3

Ural Institute of State Fire Service of Emercom of Russia
1

THERMODYNAMIC SIMULATING OF LIQUID AlCu ALLOY EVAPARATION

Abstract: In this work the pressure of the gaseous phase vapor above melts of Al-Cu and Pb-Bi systems has been studied. The study has been performed using the method of thermodynamic simulation (TS), a TERRA program package. Key words: evaporation, AlCu, alloy, modeling.

NMBarbin@yandex.ru 2 svireppey@mail.ru 3 3608113@mail.ru

INTRODUCTION
Systematic investigations into high-temperature evaporation of liquid alloys in a wide range of temperatures and concentrations of alloying elements have been unavailable so far. Experimental studies on evaporation of liquid alloys at high temperatures and pressures are laborious, complicated, and erroneous. Studies of this kind can be reasonably performed using methods of thermodynamic simulation; that is, mathematical modeling of equilibrium states in heterogeneous multi-component systems. Correctness of thermodynamic calculations depends on the choice of a mathematical model, which is close to the real model as much as possible, and the accuracy of the thermodynamic parameters of all the constituent components. In this work the pressure of the gaseous phase vapor above melts of the Al-Cu system has been studied. The study has been performed using the method of thermodynamic simulation (TS), a TERRA program package.

METHOD
The thermodynamic analysis of the equilibrium state of systems as a whole (a full thermodynamic analysis) has been performed. The calculations of the thermodynamic equilibrium of arbitrary systems (determination of all the parameters, the thermodynamic properties, chemical and phase compositions) are performed by minimizing the entropy of the system taking into account all individual substances, which are potentially possible in the equilibrium state. The calculation methods haven been developed on the basis of the variation principles of thermodynamics: 1. Among all permissible moles of individual substances in a thermodynamic system, only those that minimize the thermodynamic potential of the system correspond to equilibrium values. 2. Among all permissible values of energy provided by each independent component (atom), only those that

maximize the total contribution of energy from individual atoms to the system correspond to equilibrium values. The extensive thermodynamic parameters of the system, i.e., those proportional to the number or the mass of the substance in the system are the volume V, the entropy S, the internal energy U, the enthalpy H, the Helmholtz energy F (F = U - TS), and the Gibbs energy G (G = H - TS). The intensive thermodynamic parameters, i.e., those independent of the quantity or the mass of the system are the pressure P, the thermodynamic temperature T, the concentration, mole and specific thermodynamic values. For any thermodynamic system to be presented explicitly, one has to assign two independent parameters out of V, S, U, H, P, T, F, and G and the full initial chemical composition of the system. In this case, each pair of the independent parameters will determine a characteristic function, namely, "a function of state of a thermodynamic system of the corresponding thermodynamic parameters, with a characteristic that this function and its derivatives with respect to those parameters can be used to express explicitly all the thermodynamic properties of the system." A criterion that a system reaches its equilibrium state is an extreme of its characteristic function. With the independent parameters P and T, the characteristic function is the Gibbs free energy G, and a minimum of this energy of the system (Gmin) is a criterion for reaching the equilibrium state. With the parameters U and V, the characteristic function for an isolated system is the entropy S, and a maximum of the entropy of the system, Smax is a criterion for reaching the equilibrium state. The calculation algorithm in the TERRA program package [1] was developed with the following assumptions of the mathematical model: - a consideration is given to closed and isolated thermodynamic systems, in which the boundaries are impermeable to exchange of matter, heat, and work with the environment; - systems in a state of external and internal thermodynamic (full or local) equilibrium are analyzed;

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Safety of Technical Systems in Living and Working Environment - STS 2011, October 27-28, 2011, Ni, Serbia

- the system under study is assumed to be heterogeneous; it consists of several homogeneous parts (phases) separated by visible boundaries; - the presence of a gas phase in the system is mandatory; - all the gaseous individual substances (atoms, molecules, atomic and molecular ions, and electron gas) are part of one gas phase; - the gas phase is described by the equation of ideal gas state; - surface effects at the interface are disregarded; gases do not dissolve in condensed (liquid and solid) phases; condensed matter may be absent; - condensed matter forms single immiscible phases or enters into the composition of ideal condensed solutions; - individual substances, which have the same chemical formula, but are part of different phases, are assumed to be different components; - substances, which have the same chemical formula, but are in different polymorphous modifications, the crystalline or liquid state, are assumed to be one component whose properties change stepwise at transformation temperatures; - the volume of condensed components is negligibly small. In accordance with the second law of thermodynamics, the equilibrium of such systems is characterized by a maximum of the entropy relative to thermodynamic degrees of freedom, which include the concentration of components in an equilibrium system (Mq, mole/kg), the temperature T, and the pressure P.

pressure of Al and Cu changes insignificantly, while the vapor pressure of Al2 and Cu2 decreases due to dissociation of molecules.

Figure 1. Composition of the gas phase in the Cu-Al

system (1:1)

REFERENCES
[1] G.K. Moiseyev, G.P. Vyatkin, N.M. Barbin: Application of thermodynamic modelling for studying of interaction with participation of ionic melts, SUSU, 2002, Chelyabinsk.

RESULTS AND DISCUSSION

The simulation was performed in argon at a total pressure of 105 Pa. The study was carried out in the temperature range of 1350 to 2500 K at the Cu-Al concentration being 0.1 to 0.9. The simulation was performed taking into account the thermodynamic properties of pure substances and compounds: gaseous Al, Al2, Cu, Cu2, Al+, Cu+, e-, and Ar; condensed Al, Cu, CuAl2, Cu2Al3, Cu3Al, Cu4Al, and Cu9Al4. Concentration dependences of the vapor pressure of the components in the gas phase (Al, Al2, Cu, Cu2, Al+, Cu+, e-, Ar) above Cu-Al melts were obtained. It was found that, as the Cu concentration of the Cu-Al system rises, the pressure of Cu, Cu2, and Cu+ vapor increases, and the pressure of Al, Al2, and Al+ decreases. As the temperature elevates from 1350 to 2700 K, the vapor pressure of all the components grows in the whole concentration range. The dependences lg(Pi, mPa) = f(1/T) are linear for all the components and are described by the equation lg Pi = A + B/T. Figure 1 has presented the temperature dependence of the logarithm of the partial pressures of the gas phase components, which are formed upon heating of the CuAl system (1:1). The partial pressures of all the vapor components increase in the temperature range of 1400 to 2700 K. At temperatures above 2700 K the vapor 68 | P a g e