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Thermodynamic study of the NaCl Na2SO4 Na2Cr2O7 H2O system at

the temperature 298.15 K

Article  in  Calphad · March 2001

DOI: 10.1016/S0364-5916(01)00025-6

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Christomir Christov
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 Calphad, Vol. 25, No. 1, pp. 11-17, 2001
Pergamon 0 2001 Elsevier Science Ltd
All rights reserved
0364-5916/01/$ - see front matter
PII: SO364-5916(01)00025-6

THERMODYNAMIC STUDY OF THE NaCl - NasSOd- Nad&O, - Hz0 SYSTEM AT THE

TEMPERATURE 298.15 K

Christomir Christov
Department of Chemistry, University of California, San Diego, La Jolla,
CA 92093-0340, USA

ABSTRACT
The Pitzer ion-interaction model has been used for thermodynamic simulation of the ternary NaCl-
Na2Cr207-HZ0 and NazS04-NazCrz07-Hz0, and the quatemary NaCl-Na#04-Na&07-Hz0
systems at T=298.15 K. The necessary thermodynamic functions (binary and ternary parameters of
inter-ionic interaction and thermodynamic solubility products) have been calculated and the
theoretical solubility isotherms have been plotted. Good agreement between experimentally
determined and calculated solubilities has been found.

1. Introduction
The study of the quatemary NaCl-Na#04-Na&rz07-Hz0 system and the corresponding ternary
subsystems is of great practical importance above all in association with the choice of optimum
preparation conditions of sodium bichromate. For that reason, systems with the participation of
Na&O7 have been the subject of many experimental investigations over a wide temperature
range (l-6). Robertson (l), Gerassimow (2) and Jukow and Shutova (3) have studied the system
NaCl-Na$Zrz07-Hz0 at temperatures T=298.15 K and 293.15 K and established a solubility
isotherm consisting of a very narrow crystallization field of sodium bichromate dihydrate and a
broad field of sodium chloride. According to data available in the literature (3-5), the solubility
isotherm of the NazS04-Na&07-Hz0 system contains crystallization fields of NazCr207.2Hz0,
Na#Od. 10HZOand Na2S04 within the range from T=293.15 K to T=298.15 K. Jukov and Shutova
(3) have established the composition of the invariant point (NaCl+Na,SO,+Na&O,.2HzO) in the
quatemary system NaCl-Na$Oa-Na&YrzO,-Hz0 at T=293.15 K. In the literature we have found no
data on the thermodynamic simulation of ternary and multicomponent solutions with the
participation of sodium bichromate. In a previous study (7) the Pitzer ion-interaction model was
used for simulation of the ternary KCl-KzCrz07-HzO,KBr-K2Cr207-H20 and KzS04-K2Crz07-HzO,
and the quatemary KC1-KzS04-K&Z0,-HZ0 systems at T=298.15 K. It was shown that the Pitzer
equations can be used to obtain a sufficiently exact description of the properties of solutions with
the participation of bichromate salts.

The purpose of the present paper is a thermodynamic simulation, on the basis of Pitzer model, of
the ternary systems NaCl-NazCrz07-Hz0 and Na#04-Na&07-HzO, and the quatemary system
NaC1-Na2S04-NazCrz07-H20at T=298.15 K.

2. Solubility calculations
In agreement with the aim formulated above, the Pitzer ion-interaction model (8-l 1) was used,
which allows the determination of the activity coefficients in saturated and unsaturated electrolyte

Received on 27 August 1999

11
12 C. CHRISTOV

solutions with an accuracy of 2 to 6 per cent (12). The theoretical basis of an ion-interaction model
has been presented in previous papers (7, 13). The basic Pitzer model has been successfully used
for the solution of many theoretical and practical problems. It has been proved that the model can
be used for sufficiently exact descriptions of the properties of saturated and unsaturated binary (6-
8), ternary (7, 12-15) and multicomponent (7, 16-18) electrolyte solutions.

In this paper the systems were investigated using an approach which had already been applied to
other systems from which phases with a constant stoichiometric composition (simple and double
salts) crystallize (7, 13-17). This approach consists of: determination of Pitzer binary parameters
(p(O), p(l), p(2), C$; determination of the Pitzer ternary parameters (@MN and MM);
calculation of the solubility isotherms of the three-component systems; calculation of the solubility
isotherm of the quatemary system.

2.1. Binary Systems

The values of the binary parameters of the systems NaCl-Hz0 and NazS04-HzO at T=298.15 K
have been determined by many authors (8, 16, 18). Since the calculation of the compositions of
saturated ternary solutions is the main purpose of the simulation, the applicability of the binary
parameters to high concentrations of the binary solutions up to saturation at the lowest value of the
standard deviation (6) is a very important criterion for the choice of the binary parameters. The
p(O), p(l), p(2), and C$ values used here are given in Table 1. They are valid up to saturation or
almost to saturation of the binary solutions. Their applicability has been proved by simulation of
the multicomponent seawater system (18).

TABLE 1
Pitzer Binary Parameters at T=298.15 K where CFis the Standard Deviation of the Osmotic
Coefficients
m_
System p’0’ $1) p(2) cs
moL kg-’

NaCl-H20” 0.07650 0.26640 - 0.00127 6.0000 0.00100

Na#04-H20” 0.01958 1.11300 - 0.00497 4.0000 0.00300
NazCr207-HzOb 0.13513 -8.94435 2.03150 -0.00495 3.8792 0.00268

aReference 18.

bReference 6. Calculated with al=2 and (XQ

=l.

In a previous study the isopiestic method has been used to determine the osmotic coefficients of
binary Na&O,-Hz0 solutions at T=298.15 K (6). Optimum values of the binary parameters have
been calculated (Table 1). On the basis of the data concerning p(O), B(l) p(2) and CQ and the
concentration (m’) of the saturated binary solutions, the logarithm of the thermodynamic solubility
product InK”,, for the solid phases (Table 2) was calculated. The small differences between the lnK”sp
 THE NaCI-Na+O~-Na2Cr207-H20 SYSTEM 13

Jalues for NaCl and Na2S04. 10HzO obtained in this paper and those presented in refs. (16, 18) are
nainly due to the different ms values used for the calculation. On the basis of lnK'&values and
Ising initial thermodynamic data of aqueous species (19) the standard molar Gibbs energy of
formation AC”,,, of simple salts crystallizing from saturated binary solutions (Table 2) was
:alculated. The A@,,, values obtained are compared with those proposed by Wagman et al. (19).
The differences ‘are within error limits of an ion-interaction model.

TABLE 2

Calculated Values of the Logarithm of the Thermodynamic Solubility Product Kospand of the
Gibbs Energy of Formation AIG”, of Solid Phases Crystallizing from Saturated Binary
Solutions

“Calculated using thermodynamic data of Wagman et al. (19).

TABLE 3
Pitzer Ternary Parameters at T = 298.15 K

System 0MN Y’MNX

NaCl-Na2S04-HzOa 0.02 0.0014

NaCl-NazCrz07-HzO 0.10 -0.0100
NazS04-NazCrz07-H20 0.09 -0.0100
aReference 18.
14 C. CHRISTOV

2.2. Ternary Systems

The ternary parameters were obtained from the experimental data on the solubilities in the ternary
systems (7, 13-16). The thermodynamic model was built on the basis of Robertson’s results (1)
for the system NaCl-NazCrz07-HzO, and of Rakovskii and Nikitina’s (4) and Borovskih and
Vilnjanskii’s (5) for the system Na#04-Na&07-H20. The choice of the parameters is based on
the minimum deviation of the logarithm of the solubility product lnK& for the whole
crystallization curve of the component, from its value for the saturated binary solution. In
addition, the InKi+, value for Na#Od crystallizing in the Na#04-Na2Crz07-Hz0 system had to be
constant along the whole crystallization branch of sodium sulphate. In our calculations of @IN

and ~Nx the unsymmetrical mixing terms Et3 and E8’, were included according to reference
(9). The lnK:p value found in this study for Na2S04 is equal to that of Harvie and Weare (18).
Simulating the systems KCl-K$&O,-Hz0 and K$04-K&rZ07-H20 (7) the following parameter
values: 8ci,cr207=0.10 and 8 so4,,crzo7=0.09 are proposed. Since the parameters 8c1,,crZo7and
8S04,CrZ07 take into account only the ionic interactions of the type Cl-Crz07 and S04-Cr207,
respectively in ternary solutions, their values have to be constant for the potassium and sodium
solutions. The WM( values only have been varied. The calculated ternary parameters are
presented in Table 3.

The solubility isotherms of the ternary systems at T=298.15 K are calculated on the basis of the
thermodynamic properties obtained. A method described in previous works (7, 13- 16) has been
used. The calculated solubility isotherms are presented in Figs. 1 and 2. Table 4 summarizes the
predicted and experimentally found compositions of eutonic solutions. The calculated results
agree very well with the experimental data.

2.3. Quaternary System

The calculated thermodynamic functions (binary and ternary parameters of interionic interaction
and thermodynamic solubility products) are used for the simulation of the system NaCl-Na$Od-
NazCrz07-H20 in the range of higher CrZ07’- concentrations. The values of Pitzer ternary
parameters for the N&l-Na#04-H,0 system were taken from the literature (18) (Table 3). The
composition of the invariant point (NaC1+NazS04+Na2Crz07) was calculated as a point where the
chemical potential of all three components is constant. Table 4 shows the composition of the
calculated and the experimentally determined [Jukow and Shutova (3)] eutonics. The composition
calculated at T=298.15 K has been compared with those obtained experimentally at T=293.15 K.
The type of the solubility diagrams of the ternary subsystems at T=293.15 K and T=298.15 K is the
same, i.e. the same solid phases crystallize in them (l-5). This fact has permitted the above
comparison. The calculated results agree very well with the experimental data.

3. Conclusion

The theoretical solubility isotherms of the systems NaCl-NazCrz07-Hz0, Na2S04-NazCrz07-Hz0

and NaCl-Na2S04-NazCr207-Hz0 at T=298.15 K have been plotted. The agreement with the
experiment is very good. This permits conclusions concerning (i) the applicability of the
thermodynamic approach used to obtain a sufficiently precise description of the properties of
 THE NaCI-Na2S04-Na2Cr207-H20 SYSTEM 15

-- 7---- / ‘-, / I

WJ - NalCrz0,.2H,0

%rJhoLkg”)

FIG. 1
Molality m’ solubilities in NaCl-Na&O,-H,O system at T = 298.15 K: - , calculated values;
experimental data: l, from reference 1.

1 \_ j
o.ooL__-__L___L _L-~‘-_L -L_ _..\”
0.00 0.50 1 .oo 1.so 2.00

FIG. 2
Molality m’ solubilities in Na,SO.,-Na,Cr,O,-Hz0 system at T = 298.15 K:--, calculated values;
experimental data: o, from reference 4, l, from reference 5.
16 C. CHRISTOV

binary, ternary and multicomponent solutions with the participation of sodium bichromate, (ii) the
correctness of the thermodynamic functions calculated in this paper, and (iii) the correctness of the
experimental data on the solubilities available in the literature.

TABLE 4
Experimental and Predicted Compositions of Invariant Points for the Quaternary System
NaCl - Na$304 - NazCrzO, - Hz0 and for the Ternary Subsystems.

Solid Phases

NaC1+Na2S04
0.69 6.87 NazCrz07.2Hz0+
0.57 7.19 NaCl

0.80 6.66
0.83 6.67
0.11 7.07 NazCrz07.2Hz0+
0.12 7.12 Na2S04

0.05 6.92
0.06 7.06
0.82 2.63 Na2S04. lOH*O+
0.83 2.70 Na$SO,+

0.90 2.68
Calculated 0.84 0.09 6.57 NaC1+Na2S04+
Experimentalb 0.79 0.05 6.62 Na$Zrz07.2H20
I
aExperimental data of Robertson (1) at T=298.15 K; bExperimental data of Jukow and Shutova
(3) at T=293.15 K; “Experimental data of Gerassimow (2) at T=293.15 K; dExperimental data
of Rakovskii and Nikitina (4) at T=298.15 K; eExperimental data of Borovskih and Vilnjanskii
(5) at T=298.15 K.

Acknowledgements

This investigation was supported in part by the German Ministry of Education, Research and
Technology.
 THE NaCI-Na2S04-Na$r207-H20 SYSTEM 17

References
1. J. Robertson, J. Sot. Chem. Zmf. 43,334 (1924).

2. J. Gerassimow, Z. Anorg. Chem. 187,321 (1930).

3. A. Jukow and V. Shutova, Trudy Uralskogo Nauchno-Technicheskogo Znstituta,

Goshimizdat, 1, 1959, pp. 29-35.

4. A. Rakovskii and E. Nikitina, Trudy Instituta Chistqh. Himich. Reaktivov, Gosud. Nauchno-

Technich. Izdattelstvo, 11, 193 1, pp. 5- 14.

5. L. Borovskih, J. Vilnjanskii, Trudy Konferenzii po Usovershenstvovaniy Tehnologii
Proizvodstva hromovqh Iftoristqh solei, Goshimizdat, 1959, pp. 46-54.

6. C. Christov, S. Velikova, K. Ivanova and STanev, Coil. Czech. Chem. Commun. 64, 595
(1999).
7. C. Christov, CALPHAD 22,449 (1998).
8. K. Pitzer, J. Phys. Chem. 77,268 (1973).
9. K. Pitzer, J. Solution Chem. 4, 249 (1975).
10. K. Pitzer and G. Mayorga, J. Phys. Chem. 77,230O (1973).

11. K. Pitzer and G. Mayorga, J. Solution Chem. 3,539 (1974).

12. K. Pitzer and J. Kim, J. Am. Chem. Sot. 96,570l (1974).
13. C. Christov, CALPHAD 20,501 (1996).
14. C. Christov, J. Chem. Thermodynamics 26, 1071 (1994).
15. C. Christov, J. Chem. Thermodynamics 3 I,71 (1999).
16. C. Christov, J. Chem. Thermodynamics 32,285 (2000).
17. C. Christov, S. Petrenko, C. Balarew and V. Valyashko, Monatsh. Chem. 125,137l (1994).

18. C. Harvie and J. Weare, Geochim. Cosmochim. Acta 44,981 (1980).

19. D. Wagman, W. Evans, V. Parker, R. Schumm, I. Halow, S. Bayler, K. Chumey and R.
Nutall, J. Phys. Chem. Re$ Data 11 (1982) (Suppl.2).

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