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Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 5, 2003, pp. 738!741. Original Russian Text Copyright + 2003 by Patrov.
Abstract The activities of components in the bulk and surface layer of melts of chloride3fluoride ternary mutual systems were calculated in the framework of the regular solution model using surface tension values and considering the surface layer is a separate phase.
Study of the surface tension of chloride3fluoride melts is of theoretical and practical significance, because they can be used in electroslag remelting as flux and for welding of nonferrous metals. Determination of the activity of melt components is of great importance for thermodynamic calculations of salt systems [1]. The most widely used method in studying the metallurgical systems is the model of regular solutions. A calculation of the component activity for mutual melts from experimental surface tension values has been described previously [2]. For the exchange reaction MA + NB = NA + MB, the diagonal MA3NB is stable at DG0 >0. The mole fractions x and (1 3 x) of T substances MA and NB in the initial mixture become (x 3 y) and (1 3 x 3 y) in the equilibrium mixture, i.e., become lower by the value of y equal to the mole fraction of the reaction products. Within the framework of the regular solution model [3, 4], we can write
ln g1 = A(1 3 x 3 y)2/RT, ln g2 = A(x 3 y)2/RT, (1) (2)
(3)
The interaction parameter A was determined from experimental data on the surface tension described by the Burylev equation [5] for regular solutions
s = s1x1 + I2x2 + Cx1x2,
(4)
where x1 and x2 are the mole fractions of components MA and NB (x1 = x, x2 = 1 3 x), and s1 and s2 are the surface tensions of these components comprising a mixture, the calculated surface tension of which s was compared with the experimental value for the mutual system. The constant C includes the mutual exchange energy [5] and is related to the interaction parameter A from Eqs. (1) and (2). To find A, it is sufficient to multiply C by the molar surface area:
A = Cw, (5)
where g1 and g2 are the activity coefficients of components MA and NB belonging to the stable diagonal; A is the interaction parameter determined from comparison of the experimental and calculated phase diagrams [4]. Because the concentration of the components belonging to the unstable diagonal did not exceed 6 mol %, their activities aNA and aMB were assumed equal to the mole fraction y. The latter was derived from the equation for the equilibrium constant of exchange reaction:
where w = V2/3 N1/3, and N is the Avogadro number. m To a first approximation, the molar volume of the mixture is calculated by the additivity equation Vm = xVMA + (1 3 x)VNB, and more exactly it is calculated from the equation
Vm = (x ! y)VMA + (1 3 x ! y)VNB + yVNA + yVMB.
The necessary data on the density of components involved in the exchange were taken from [6]. Comparison of the component activities in LiF3 NaCl and LiF3KCl systems, calculated by the Fellner
[Nauka/Interperiodica]
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procedure [4] and by the method proposed, showed that the maximal difference is 0.008 at the mole fraction x = 0.5 and does not exceed 2%, i.e., both methods yield the similar values. Consequently, the proposed calculation method using surface tension gives reliable data on the component activity in ternary mutual systems. From the condition [7] for equilibrium of a component in solution surface layer and bulk,
mM 3 mi = swi, i
Table 1. Activity of components in the surface layer of the LiF (1)3CsCl (2), NaF (1)3CsCl (2), and KF (1)3CsCl (2) systems
x1 aM aM gM gM xM xM 1 2 1 2 1 2
LiF3CsCl, 1173 K 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
(6)
we obtain the expression for the binary solution at the equal molar surface areas:
RT RT s = s1 + ln (aM/a1) = s2 + ln (aM/a2). (7) 1 2 w w
0.0022 0.8876 0.0755 0.9972 0.0296 0.0082 0.7152 0.1845 0.9936 0.0444 0.0210 0.5511 0.3634 0.9892 0.0577 0.0441 0.3891 0.5997 0.9825 0.0735 0.0839 0.2584 0.7911 0.9640 0.1060 0.1362 0.1464 0.9225 0.9313 0.1477 0.2102 0.0759 0.9749 0.8593 0.2156 0.3347 0.0364 0.9909 0.6892 0.3378 0.4430 0.0106 0.9987 0.5263 0.4436
NaF3CsCl, 1100 K
This equation yields the component activities in the surface layer of mutual melts:
s 3 s1 ln aM = w + ln a1, 1 RT s 3 s2 ln aM = w + ln a2. 2 RT
(8) (9)
0.0027 0.8692 0.184 0.9995 0.0147 0.0094 0.7214 0.3104 0.9979 0.0303 0.0211 0.5739 0.4753 0.9956 0.0444 0.0402 0.4427 0.6398 0.9912 0.0628 0.0674 0.3161 0.7937 0.9840 0.0849 0.1163 0.2323 0.8775 0.9614 0.1325 0.1936 0.1568 0.9355 0.9086 0.2069 0.3275 0.0939 0.9675 0.7738 0.3385 0.5428 0.0371 0.9882 0.5089 0.5493
KF3CsCl, 1073 K
The component activities a1 and a2 of the systems studied have been reported elsewhere [2, 8, 9]. Assumption is made that the melt surface layer, like bulk, is a regular solution. For regular solutions, the activity coefficients of components belonging to the stable diagonal in the surface layer are as follows:
gM = exp {A(aM)2/[RT(gM)2]}, 2 1 1
ln gM = A(aM)2/[RT(gM)2], 1 2 2
(10) (11)
where A is the interaction parameter determined from the experimental data on the surface tension described by the Burylev equation [5]. Substitution in Eq. (10) of the expression for the activity coefficient of the second component in the surface layer gives
A (aM)2 2 ln gM = . 1 M)2] 3 exp [RT(gM)2]}2 RT {exp [A(a1 1 (12)
0.0137 0.9072 0.5127 0.9994 0.0266 0.9077 0.0428 0.7903 0.6001 0.9959 0.0713 0.7936 0.0828 0.6581 0.6983 0.9888 0.1180 0.6656 0.1400 0.5642 0.7614 0.973 0.1839 0.5799 0.2023 0.4358 0.8445 0.9545 0.2395 0.4566 0.2926 0.3368 0.8964 0.9172 0.3264 0.3672 0.3958 0.2300 0.9446 0.8673 0.4190 0.2652 0.5080 0.1278 0.9797 0.8041 0.5185 0.1589 0.7383 0.0516 0.9947 0.6398 0.7422 0.0807
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
First, systems comprising cesium chloride and lithium, sodium, and potassium fluorides are considered. Their characteristics (Gibbs energy of exchange reaction, constant of the Burylev equation, molar surface area, and interaction parameter) are presented below:
System T, K
DG0 , T J 3C, mJ m!2 w, m2 mol!1 3A, J mol!1
Thus, the activity coefficients in the surface layer of the components belonging to the stable diagonal are calculated by Eqs. (10) and (12), and the mole fractions, by the equations
xM = aM/gM, xM = aM/gM. 1 1 1 2 2 2 (13)
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The calculated component activities in the surface layer of the melts are listed in Table 1.
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PATROV
Fig. 1. (1) Activity aM and (2) mole fraction xM of components in the surface layer vs. their mole fraction in the KF3CsCl melt.
Table 2. Activity of components in the surface layer of the LiF (1)3NaCl (2), LiF (1)3KCl (2), and NaF (1)3KCl (2) systems
x1 aM aM gM gM xM xM 1 2 1 2 1 2
LiF3NaCl, 1123 K 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
The data obtained on the component activity should be discussed taking into account the Gibbs energy of the exchange reactions. In the series of the KF3CsCl, NaF3CsCl, and LiF3CsCl systems, with increasing Gibbs energy, a eutectic phase diagram of the stable diagonal changes to a singular phase diagram with separation [8, 9]. In this series of systems comprising different fluorides and the same chloride, the cesium chloride surface activity increased simultaneously. It is noteworthy that the cesium chloride activity in the surface layer of the systems studied appeared to be equal to the mole fraction: aw ~ xw. This is clearly 2 2 illustrated by the aw = f (x2) and xw = f (x2) plots for 2 2 the KF3CsCl system in which the difference between the activities and mole fractions was the largest (Fig. 1). The activity of lithium, sodium, and potassium fluorides was also equal to the mole fraction, but at a high mole fraction of fluorides (higher than 0.5). At a lower content of fluorides, the difference between the activity and mole fraction in the surface layer ranged from 0.02 to 0.04. The second group of chloride3fluoride mutual systems included the LiF3NaCl, LiF3KCl, and NaF3KCl systems characterized by the following values of the Gibbs energy, constant of the Burylev equation, molar surface area, and interaction parameter:
System T, K
DG0 , T J 3C, mJ m!2 w, m2 mol!1 3A, J mol!1
0.0254 0.8864 0.5605 0.9985 0.0452 0.0607 0.7743 0.6400 0.9934 0.0949 0.1069 0.669 0.7119 0.9836 0.1501 0.1660 0.5671 0.7768 0.967 0.2137 0.2407 0.4667 0.8346 0.9407 0.2884 0.3341 0.3677 0.8848 0.9006 0.3776 0.4499 0.2702 0.9270 0.8411 0.4853 0.5943 0.1752 0.9612 0.7552 0.6183 0.7724 0.0831 0.9876 0.6381 0.7821
LiF3KCl, 1123 K
0.8877 0.7795 0.6802 0.5864 0.4961 0.4083 0.3212 0.2320 0.1302 0.9049 0.8064 0.6605 0.5098 0.3723 0.2618 0.1737 0.1000 0.0580
95 212 113
0.0077 0.9023 0.1988 0.9971 0.0385 0.0229 0.7956 0.2773 0.9867 0.0824 0.0474 0.6444 0.4229 0.9755 0.1120 0.0834 0.4906 0.5989 0.9624 0.1393 0.1328 0.3506 0.7608 0.9417 0.1745 0.1992 0.2363 0.8735 0.9025 0.2281 0.2835 0.1453 0.9422 0.8365 0.3009 0.3743 0.0750 0.9805 0.7501 0.3818 0.5432 0.0321 0.9934 0.5544 0.5469
NaF3KCl, 1173 K
With respect to the Gibbs energy, the systems of this group can be presented as a series LiF3NaCl, LiF3KCl, LiF3CsCl, with the same fluoride (LiF) and different chlorides. However, the LiF3CsCl system was considered within the first group. Replacement of this system by the system NaF3KCl should not affect the eutectic phase diagrams of the stable diagonal [10]. The calculated component activities in the surface layer of the melts are presented in Table 2. As seen, the general conclusions made for the systems of the first group are also true for the systems of the second group. For example, the activity of chlorides in the surface layer is virtually equal to the mole fraction. The activity of fluorides is equal to the mole fraction when their content xw is higher 1 than 0.6, with the activity coefficient gw of fluorides 1 exceeding 0.9. Consequently, Eq. (7) for the surface-active comVol. 76 No. 5 2003
0.0103 0.8621 0.4729 0.9995 0.0217 0.8625 0.0301 0.7497 0.5660 0.9972 0.0532 0.7518 0.0600 0.6442 0.6538 0.9916 0.0918 0.6497 0.1029 0.5425 0.7347 0.9804 0.1401 0.5533 0.1621 0.4413 0.8084 0.9603 0.2005 0.4596 0.2433 0.3418 0.8714 0.9245 0.2792 0.3697 0.3534 0.2439 0.9227 0.8627 0.3830 0.2827 0.4985 0.1495 0.9621 0.7631 0.5181 0.1959 0.7061 0.0625 0.9891 0.5986 0.7139 0.1044
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For the surface-inactive components, i.e., fluorides, in the concentration range x1 = 0.531, this equation becomes
RT s = s1 + ln (xM/a1). 1 w (15)
6.
CONCLUSION
7.
The equations were obtained for calculating the surface tension of mutual chloride3fluoride systems as a function of the concentration of fluorides and chlorides in the surface layer. REFERENCES
1. Gorodyskii, A.V., Termodinamicheskie svoistva rasplavov solevykh sistem: Spravochnoe posobie (Ther-
8. 9. 10.
modynamic Properties of Salt Systems: Handbook), Kiev: Naukova Dumka, 1985. Patrov, B.V., Zh. Prikl. Khim., 1998, vol. 71, no. 3, pp. 5073508. Hildebrand, J.H., Solubility of Non-Electrolytes, New York: Reinhold, 1936. Fellner, P., Chem. Zvesti, 1983, vol. 37, pp. 6033 607. Burylev, B.P. and Vasilev, V.V., Fizicheskaya khimiya poverkhnostnykh yavlenii v rasplavakh (Physical Chemistry of Surface Phenomena in Melts), Kiev: Naukova Dumka, 1971, pp. 144 3149. Morachevskii, A.G., Spravochnik po rasplavlennym solyam (Handbook on Molten Salts), Leningrad: Khimiya, 1971. Popel, S.I., Poverkhnostnye yavleniya v rasplavakh (Surface Phenomena in Melts), Moscow: Metallurgiya, 1994. Patrov, B.V., Zh. Prikl. Khim., 1998, vol. 71, no. 3, pp. 5083510. Patrov, B.V., Zh. Prikl. Khim., 1998, vol. 71, no. 7, pp. 1206 31207. Posypaiko, V.I., and Alekseeva, E.A., Diagrammy plavkosti solevykh sistem: Troinye vzaimnye sistemy (Fusibility Curves of Salt Systems: Ternary Mutual Systems), Moscow: Khimiya, 1977.
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No. 5
2003