Chemical Engineering Science 55 (2000) 2673}2686

Extended UNIQUAC model for correlation and prediction

of vapour}liquid}solid equilibria in aqueous salt systems containing
non-electrolytes. Part A. Methanol}water}salt systems
Maria C. Iliuta, Kaj Thomsen, Peter Rasmussen*
Department of Chemical Engineering, Institut for Kemiteknik IVC-SEP, Technical University of Denmark, Building 229, DK-2800 Lyngby, Denmark
Received 16 June 1999; received in revised form 19 October 1999

Abstract

The Extended UNIQUAC model has previously been used to describe the excess Gibbs energy for aqueous electrolyte mixtures. It
is an electrolyte model formed by combining the original UNIQUAC model, the Debye}HuK ckel law and the Soave}Redlich}Kwong
equation of state. In this work the model is extended to aqueous salt systems containing non-electrolytes in order to demonstrate its
ability in representing solid}liquid}vapour (SLV) equilibrium and thermal property data for these strongly non-ideal systems. The
model requires only pure component and binary temperature-dependent interaction parameters. The calculations are based on an
extensive database consisting of salt solubility data in pure and mixed solvents, VLE data for solvent mixtures and mixed
solvent}electrolyte systems and thermal properties for mixed solvent solutions. Application of the model to the methanol}water
system in the presence of several ions (Na>, K>, NH>, Cl\, NO\, SO\, CO\ and HCO\) shows that the Extended UNIQUAC
    
model is able to give an accurate description of VLE and SLE in ternary and quaternary mixtures, using the same set of binary
interaction parameters. The capability of the model to predict accurately the phase behaviour of methanol}water}three salts systems
is illustrated.  2000 Elsevier Science Ltd. All rights reserved.

Keywords: Extended UNIQUAC; Vapour}liquid}solid equilibria; Electrolytes; Nonelectrolytes

1. Introduction mussen, 1986; Mock, Evans & Chen, 1986; Macedo,

Phase equilibria for electrolyte systems and more spe-
ci"cally, for mixed solvent}electrolyte mixtures are of
considerable importance in a variety of "elds such as
extractive distillation of salt-containing liquids, extrac-
tive crystallisation and liquid}liquid extraction for mix-
tures including salts. Hence, accurate models describing
such equilibria are necessary for analysing, designing
and optimising processes and equipment in chemical
industry.
Several thermodynamic models have been developed
to represent the vapour}liquid equilibria (VLE) in mixed
solvent}electrolyte systems (Sander, Fredenslund & Ras-
* Corresponding author. Tel.: 00-45-45252877; fax: 00-45-4588-2258.
E-mail address: pr@kt.dtu.dk (P. Rasmussen).
 On leave from the University `Politehnicaa of Bucharest, Faculty of
Industrial Chemistry, Department of Applied Physical Chemistry,
Polizu 1, RO-78126 Bucharest, Romania.
Skovborg & Rasmussen, 1990; Kikic, Fermeglia &
Rasmussen, 1991; Achard, Dussap & Gros, 1994; Zerres
& Prausnitz, 1994; Li, Polka & Gmehling, 1994; Polka,
Li & Gmehling, 1994). Only a few studies have been
carried out concerning solid}liquid equilibria (SLE)
(Lorimer, 1993; Chiavone-Filho, 1993; Kolker & de
Pablo, 1996). Some attempts have also been made on
liquid}liquid equilibria (LLE) calculations (Mock et al.,
1986; Zerres & Prausnitz, 1994). The above models are
not applied to mixed-electrolyte systems and as far as we
know, no previous work in the open literature concerns
the simultaneous representation of vapour}liquid,
liquid}liquid and solid}liquid equilibria.
In this work we present a general model that should
allow the description of vapour}liquid}liquid}solid equi-
libria of aqueous single and mixed electrolyte systems
containing non-electrolytes. The model is the Extended
UNIQUAC model described by Thomsen, Rasmussen
and Gani (1996) and Thomsen and Rasmussen (1999)
and applied for describing SLE, VLE and thermal

0009-2509/00/$ - see front matter  2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 5 3 4 - 5
2674 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686

Nomenclature u, u, uR UNIQUAC interaction parameters

x liquid composition, mole fraction
a activity of component i x liquid composition (mole fraction) expressed
G
A Debye}HuK ckel parameter, kg mol\ on a salt-free basis
b Debye}HuK ckel parameter, kg mol\ y vapour phase mole fraction
C heat capacity for component i, J mol\ K\ z charge of solute i, C
NG G
d density, kg m\
F Faraday's constant, C mol\ Greek letters
g mass of component n, grams
L
G# excess Gibbs energy, J mol\ c symmetrical water activity coe$cient
U
H# excess enthalpy, J mol\ c symmetrical methanol activity coe$cient

 
D H enthalpy of formation for component i,
D G
J mol\
I ionic strength based on molality
m molality of species i, mol kg\
G
M molar mass of water, kg mol\
U H
N Avogadro's number, mol\
P pressure, bar
q surface area parameter
r volume parameter
R gas constant, J mol\ K\
S objective function
¹ temperature, K
properties of aqueous electrolyte systems. The model
consists of the original UNIQUAC model, a
Debye}HuK ckel long-range term, and the Soave}Red-
lich}Kwong (SRK) cubic equation of state for calculating
vapour phase fugacities.
This work represents the "rst part of a study concern-
ing the application of the Extended UNIQUAC model to
represent the solid}liquid}vapour equilibria in aqueous
salt systems containing non-electrolytes, and includes
mixtures consisting of methanol, water, and various salts.
Unfortunately, insu$cient experimental LLE data were
found in the literature. Therefore no LLE calculations
for this system are presented. LLE calculations will
be presented for higher alcohol systems in a following
publication.
Hence, the aim of this work is to demonstrate the
ability of the model to represent with good accuracy the
solid}liquid and vapour}liquid equilibria in meth-
anol}water}single/mixed electrolyte systems using the
same set of parameters.
We calculate excess properties relative to the ideal
dilute solution. Water is considered as the solvent, while
methanol and ions are considered as solutes. This does
not limit the model to dilute solutions but also allows us
to perform calculation for solutions with a mole fraction
of water close or equal to zero. The Debye}HuK ckel con-
tribution to the activity coe$cients of the solutes is
proportional to the charge of the solutes. This term for
cHV asymmetrical rational activity coe$cient
G
for solute i
c symmetrical activity coe$cient for
G
component i at in"nite dilution
*G the increment in standard state Gibbs
energy of formation by equilibrium j
e vacuum permittivity, C J\ m\

e relative permittivity (dielectric constant,
P
dimensionless)
k chemical potential of species i
G
l stoichiometric coe$cient of component i
G
u fugacity coe$cient of component i
G
methanol therefore is zero. For salt-free mixtures the
model reduces to the original UNIQUAC equation. As
water is considered the solvent, the Debye}HuK ckel limit-
ing slope is calculated on the basis of the properties of
water, even in systems containing little or no water. As
a result, the calculated activity coe$cients of ions in pure
methanol solution are expected to show some deviations
from experimental values.
The same standard state is used for all solutes. Hence
we avoid the particular problems concerning the stan-
dard state in connection with LLE and SLE calculations
in complex electrolyte systems containing two or more
solvents, as encountered for example by Sander et al.
(1986).
Only pure component and binary parameters are used
in the model. The evaluation of model parameters is
based on binary, ternary and quaternary experimental
data. The interaction parameters are temperature depen-
dent.
2. Equilibria in aqueous salt systems containing
non-electrolytes
The criterion for VLE and SLE is that the chemical
potential of each component is identical in all phases.
The chemical potential of a component is the sum of
a standard state chemical potential and a term that
 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686 2675

describes the concentration dependence, the latter being
calculated using the Extended UNIQUAC model.
We adopt the symmetrical convention for water and
the asymmetrical convention based on mole fraction for
all other species.
The chemical potential for water can be written as
k "k #R¹ ln a "k #R¹ ln (c x ) (1)
U U U U U U
where k is the standard state chemical potential for pure
U G
liquid water at system temperature and pressure, a is the
U
water activity and c is the symmetrical water activity
U
coe$cient. According to the symmetrical convention, the
activity coe$cient of water is unity in the pure compon-
ent state at all temperatures, c "1 for x "1.
U U
The chemical potential for solutes can be written as
SLE calculation reduces therefore to solution of Eq. (5)
in order to obtain the composition of the liquid phase in
equilibrium with a solid phase.
2.2. VLE calculations
The condition for phase equilibrium between liquid
and vapour can be written as
k* " k4.
G
(7)
For the liquid phase, the chemical potential of water
and methanol are given by the Eqs. (1) and (2), respec-
tively.
The chemical potential of the volatile components
i (water, methanol) in the vapour phase is given by

k "kHV#R¹ ln (cHVx ) (2) k4"kE#R¹ ln (y u P) (8)

G G G G G G G G
where cHV is the asymmetrical rational activity coe$cient where kE is the standard state chemical potential of
G G
for solute i. kHV is the standard state chemical potential component i in the vapour phase de"ned as the pure
G ideal gas at one bar and at the temperature ¹, y is
for solute i based on the asymmetrical convention and G
mole fraction scale. This is the hypothetical ideal state of the vapour phase mole fraction of component i, u is the
G
pure solute i de"ned by the constraint that the activity fugacity coe$cient of component i calculated from the
coe$cient of solute i is 1 at in"nite dilution at all temper- SRK equation of state and P is the total pressure.
atures. Based on the expressions for the chemical potential (1),
(2) and (8) the equilibrium condition (7) for component
2.1. SLE calculations i (water, methanol) can be expressed by the relation:
*G yuP
The equilibrium between an aqueous methanol phase ! "ln G G (9)
R¹ xc
and the solid salt K A ) nH O (s) consisting of i cations G G
G ? 
K, a anions A and n water molecules, can be described by where
the equation
*G " kE!kJ (10)
G G
K A ) nH O (s) 0 iK (aq)#aA (aq)#nH O (l). (3)
G ?   is the increment in standard state chemical potential by
The criterion for SLE is that the chemical potential of evaporating one mole of component i. kJ represents
G
the crystalline salt is equal to the sum of the chemical k for water or kHV for methanol and c represents c for
U G G U
potentials of the constituent parts of the salt in the water or cHV for methanol.
G
aqueous solution
2.3. Speciation equilibria
k G ?  "ik #ak #nk (4)
)  & -  )        
Based on the expressions for the chemical potential (1) Dissociation equilibria can be treated in the same
and (2), the equilibrium condition (4) can be expressed as manner as described for SLE and VLE above. The
hydrogen carbonate ion dissociates according to the
*G equilibrium reaction:
! "i ln (cHVx )#a ln (cHVx )#n ln (c x ) (5)
R¹ ) )   U U
HCO\ (aq) 0 CO\ (aq)#H> (aq). (11)
 
where If the hydrogen carbonate ion is given the stoichiometric
*G"ikHV#akHV#nk !k G ?  (6) coe$cient !1, the equilibrium reaction can be described
)  U )  & - by the equation
represents the increment in standard state chemical po-
*G x \ ) cHV\ ) x > ) cH>V
tential by equilibrium (3) at the temperature ¹. The ! " ln !- !- & & (12)
R¹ x \ ) cHV \
chemical potential of the salt is equal to its standard state &!- &!-
chemical potential because the solid salt is in its standard where
state de"ned as the pure crystalline component at system
temperature and pressure. *G"kHV\ #kHV !kHV \ (13)
!- &> &!-
2676 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686

represents the increment in standard state chemical po- and by using the Gibbs}Helmholtz equation
tential by the equilibrium reaction (11) at the temper-


*((kHV!k)/R¹) D HH!D H
ature ¹. G G "! D G D G (18)
Generally, all types of equilibrium (SLE, VLE, speci- *¹ R¹
.V
ation equilibria) can be expressed as
The standard state heat capacity was obtained by
*G di!erentiating the above expression with respect to tem-
! H " l ln a (14) perature
R¹ GH G
G

 
*(D HH!D H)
where *G is the increment in standard state chemical CH !C " D G D G
H NG NG *¹
potential by equilibrium j at temperature ¹, a is the
G .V
activity of component i, and l is the stoichiometric



GH * ln c * ln c
coe$cient of component i involved in equilibrium j. "!R 2¹ G #¹ G .
*¹ *¹
. .
(19)
2.4. Standard chemical potentials
In these relations k is the standard state chemical poten-
G
The standard state chemical potentials of water (k )
U tial for pure liquid methanol, D HH is the standard state
D G
and most solutes (kHV) at 298.15 K were taken from enthalpy of formation for methanol based on the asym-
G
thermodynamic tables (NIST, 1990) where the standard metrical convention, D H is the standard state enthalpy
D G
state for solutes is given as the hypothetical ideal unit of formation for pure liquid methanol, CH is the
NG
mean molal solution, kHK. Tabulated values can be con- standard state heat capacity for methanol based on the
G
verted from the molality scale to the mole fraction scale asymmetrical convention, C is the standard state heat
NG
by using the relation: capacity for pure liquid methanol.

kHV"kHK!R¹ ln M (15)

G G U 2.5. Excess enthalpy calculation
where M is the molar mass of water (kg mol\).
U Experimental excess enthalpy data for water}meth-
The corresponding values for some complex salts
(double salts and hydrates) were "tted to experimental anol systems are given relative to the ideal solution.
solubility data in aqueous systems (Thomsen & Rasmus- Hence, symmetrical excess enthalpy for water}methanol
sen, 1999). At temperatures di!erent from 298.15 K, the solutions is derived from the model by proper di!erenti-
standard state chemical potentials were calculated from ation with respect to temperature
the Gibbs-Helmholtz equation. The standard state heat


*(G#/R¹) H#
capacity of pure crystalline salts is considered constant in "!
*¹ R¹
the temperature range from 273.15 to 383.15 K while .V

   
a three parameter correlation was used for the ions * ln c * ln c
(Thomsen et al., 1996). "x U #x
 
(20)
U *¹
  *¹
Calculation of the standard state thermodynamic .V .V
properties at 298.15 K (Gibbs energy, enthalpy and heat where c is the symmetrical methanol activity

 
capacity) of methanol was based on the UNIQUAC
model parameters and the standard state thermodyn-
amic properties of pure liquid methanol.
The standard state Gibbs energy (chemical potential)
was calculated from the expression relating the standard
state chemical potentials based on the asymmetrical and
the symmetrical convention
kHV!k"R¹ ln c (16)
G G G
where c is the value of the symmetrical activity coe$c-
G
ient of methanol at in"nite dilution.
The standard state enthalpy of formation was cal-
culated by di!erentiating Eq. (16) with respect to temper-
ature
coe$cient. The symmetrical activity coe$cient for meth-
anol can be obtained from the asymmetrical by using the
equation
ln c "ln cHV#ln c. (21)
G G G
The activity coe$cients are determined by the Ex-
tended UNIQUAC model.
3. Extended UNIQUAC model
The thermodynamic model used in this work is the
Extended UNIQUAC model described earlier by Nic-
olaisen, Rasmussen and S+rensen (1993) for aqueous elec-
trolyte systems. The model is applied here to aqueous salt



*((kHV!k)/R¹) * ln c systems containing non-electrolytes using the method of
G G " G (17)
*¹ *¹ Thomsen et al. (1996) for aqueous systems.
.V .
 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686
It is a local composition model derived from the orig-
inal model (Abrams & Prausnitz, 1975; Maurer & Praus-
nitz, 1978) by adding a Debye}HuK ckel term (Sander,
1984; Sander et al., 1986) to take into account the pres-
ence of the ionic species in the mixture. Because
UNIQUAC theory is in the Lewis}Randell thermodyn-
amic framework while Debye}HuK ckel theory is in the
McMillan}Mayer framework, there is an inherent in-
consistency in simply adding G# (UNIQUAC) to G#
(Debye}HuK ckel). The nature of this inconsistency is ob-
scure; while it is possible to include corrections, they are
usually not important (except for large solute molecules)
(Haynes & Newman, 1998).
Hence, the excess Gibbs energy expression is repre-
sented by the sum of three terms: a combinatorial or
entropic term and a residual or enthalpic term, as for
nonelectrolyte systems (short-range contribution), and
an electrostatic term (long-range contribution)
G#"G# #G#
10 *0
"G# #G# #G# } ( (22)
!
2677
strength based on molality
I" m z (26)
 G G
G
where m is the molality of solute i and z is the charge of
G G
solute i.
For aqueous electrolyte systems, the calculation of the
Debye}HuK ckel A parameter is based on the density
d (kg m\) and the dielectric constant e (dimensionless)
P
of pure water rather than that of the solution. The dielec-
tric constant of an aqueous NaCl solution changes from
79.7 in pure water to 48.4 in a 5 molal solution at
294.15 K (Hasted, Ritson & Collie, 1948). The dielectric
constant of water}methanol mixtures has a similar con-
centration dependency. The dielectric constant of such
mixtures changes from 80.37 in pure water to 32.35 in
pure methanol at 293.15 K (As kerloK f, 1932). There is no
reason why the e!ect of methanol on the mixture dielec-
tric constant should be included, when the e!ect of other
solutes is ignored. Good results have been obtained with
the Extended UNIQUAC model in its present form, but

   0   "
 & an improved expression for the electrostatic contribution
The combinatorial and the residual terms are identical to
those used in the traditional UNIQUAC equation. The
interaction parameters are considered temperature de-
pendent
u "u #uR (¹!298.15)
IJ IJ IJ
which is also used in the case k"l. The combinatorial
and the residual terms of the UNIQUAC excess Gibbs
energy function are based on the rational, symmetrical
activity coe$cient convention.
The Debye}HuK ckel electrostatic term is expressed in
terms of the rational, symmetrical convention for water
and the rational, asymmetrical convention for the sol-
utes. The following expression for the Debye}HuK ckel
contribution to the excess Gibbs energy was used
G# } (
to the excess Gibbs energy function might bene"t the
model.
Based on table values of the density and the dielectric
constant of pure water, the Debye}HuK ckel parameter
A can be approximated in the temperature range
(23) 273.15 K(T(383.15 K by
A"[1.131#1.335;10\(¹!273.15)
#1.164;10\(¹!273.15)] (kg mol\). (27)
The parameter b is dependent on the size of the involved
ions but is usually considered constant. The value used in
this work is 1.50 (kg mol\).
The SRK cubic equation of state is used to calculate
the vapour phase fugacities.
The only parameters for the Extended UNIQUAC
model are the UNIQUAC interaction parameters and
"
 &
R¹ the volume and surface area parameters. No parameters
are required in the Debye}HuK ckel or the SRK terms.

 
4A bI
"!x M ln (1#bI)!bI# . (24)
U U b 2

This expression is a simpli"cation of the excess Gibbs 4. Model parameter estimation

energy term given by Debye and HuK ckel (1923), as sug-
gested by Fowler and Guggenheim (1949). The expres- The existing databank (IVC-SEP, 1999) for aqueous
sion for the Debye}HuK ckel A parameter is given by electrolyte systems was extended by the addition of
a considerable amount of SLE, VLE and thermal prop-

 
F d  erty data for mixed solvents. The experimental data were
A" . (25) mainly taken directly from the original papers. This
4pN 2(e e R¹)
  P allows us to avoid misprints noticed in data compilations
In this expression F is Faradays constant (C mol\), of Linke and Seidell (1965) and Stephen and Stephen
N is Avogadros number (mol\), e is the vacuum (1979) and gives more information concerning the data.
 
permittivity (C J\ m\), R is the gas constant 1309 binary, ternary and quaternary VLE, SLE and
(J mol\ K\), ¹ is the temperature (K). I is the ionic excess enthalpy experimental data points in aqueous
2678 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686

methanol systems were included in the databank. Unfor-

tunately, a relatively large amount of experimental data
existing in the literature is incomplete, e.g. VLE data at
saturation without reporting the salt solubility in the
mixture, SLE data with the liquid composition expressed
as molarity or gram/liter without reporting the mixture
density. Such data have not been used.
The estimation of model parameters was performed
as a least-squares minimization. The weighted sum of
squared residuals

 
P !P 
S"
0.05(P#0.01)
4*#  

 
H# !H# 
#
12Rx
# 

 
g !g 
#     ) 100
1g
1*#   
Fig. 1. y}x phase diagram for the system methanol}water saturated



*G#R¹ l ln a  with NaCl (salt molality range: 0.06}5.97 mol kg\) at 1.013 bar
# Max G G G ,0 (28)
0.25R¹ (Johnson & Furter, 1960).
1*#  
was minimized. `calca and `expa signify values calculated
by the model and experimental values. g is the mass of
 
salt and g is the mass of the mixture, both expressed in

grams. The factors 0.05, 12, 1 and 0.25 (for the four terms
of the S function, respectively) are weighting factors.
The weighting factor for VLE data was chosen so that
for relatively high pressures, a 5% di!erence between
calculated and experimental pressures would give
a squared residual of 1. In order not to give too much
weight to data at very low pressures, 0.01 bar is added to
experimental pressures in the denominator of the VLE
data term in Eq. (28). An experimental pressure of 0.01
bar would give a squared residual of 1 if the calculated
pressure deviates from it by 10%.
The calculated pressures that were compared with
experimental pressures in the sum of squared residuals
(Eq. (28)) were bubble point pressures.
The excess enthalpy data were weighted so that an
absolute di!erence of 100 J between the calculated and
the experimental data would give a squared residual of 1. Fig. 2. y}x phase diagram for the system methanol}water saturated
x"1 K is included in Eq. (28) in order to make the with NH Cl (salt molality range: 1.08}12.46 mol kg\) at 1.007 bar

expression dimensionless. (Furter (1958) quoted from Ohe (1991).

Table 1
UNIQUAC interaction parameters, u "u and uR "uR (u "u #uR (¹!298.15)) valid in the temperature range 273.15 } 383.15 K
GH HG GH HG GH GH GH
H O CH OH Na> K> NH> Cl\ NO\ SO\ CO\ HCO\ OH\
      
u (K)
GH
CH OH 259.64 373.43 1723.57 667.88 235.55 1637.99 1115.75 1112.81 849.03 637.78 633.52

uR
GH
CH OH !0.070 !0.728 21.729 0.458 0.610 14.480 8.797 8.021 !24.034 1.793 0.00

Note: The Extended UNIQUAC parameters for ions and for ion}ion and ion}water interactions are given in Thomsen and Rasmussen (1999).
 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686 2679

Table 2
VLE calculation results in the methanol}water system with and without dissolved salt: mean absolute deviations between experimental and calculated
vapour phase mole fraction (*y) and pressure (*P/bar)

Salt Salt molality range ¹ (K) or P (bar) Data *y (!) *P (bar) Reference
(mol kg\) points

Without 0 1.013 bar 29 0.010 0.056 Uchida and Kato (1934)

4.274 bar 12 0.019 0.148 Swami, Rao and Rao (1956)
1.013 bar 12 0.008 0.025 Swami et al. (1956)
1.013 bar 16 0.008 0.022 Costa Novella and Moragues Tarraso
(1952)
1.013 bar 9 0.008 0.025 Lesteva, Ogorodnikov and Kazakova
(1970)
1.013 bar 21 0.010 0.025 Kojima, Tochigi, Seki and Watase
(1968)
5.066 bar 11 0.007 0.147 Hirata and Suda (1967)
3.040 bar 10 0.009 0.100 Hirata and Suda (1967)
298.15 K 10 0.011 0.002 Hall, Mash and Pemberton (1979)
333.15 K 18 0.011 0.002 Kurihara, Minoura, Takeda and
Kojima (1995)
1.013 bar 22 0.012 0.027 Kurihara, Nakamichi and Kojima
(1993)

NaCl 0}3.00 298.15 K 9 0.008 0.002 Yang and Lee (1998)

KCl 0}1.50 298.15 K 8 0.010 0.002 Yang and Lee (1998)

NaCl#KCl 0.50}2.50/NaCl 298.15 K 5 0.005 0.004 Yang and Lee (1998)

1.00/KCl

NaCl 0.06}5.97 1.013 bar 13 0.012 0.024 Johnson and Furter (1960) (Fig. 1)

KCl 0.13}6.4 1.013 bar 12 0.019 0.044 Johnson and Furter (1960)

KCl 0.50}2.00 1.013 bar 32 0.028 0.048 Boone, Rousseau and Schoenborn
(1976)

NaNO 1.64}4.83 1.013 bar 18 0.025 0.051 Natarajan (1981)


NH Cl 1.08}12.46 1.007 bar 12 0.011 0.042 Ohe (1991) (Fig. 2)

Total number of data points and average deviation 279 0.014 0.043

The second term for SLE data is zero for the pertinent
salt(s) at equilibrium, according to Eq. (14). For all other
salts potentially formed in the solution the "rst term
in the inner bracket should be negative and is then
neglected. If the "rst term in the inner bracket for such
salts is positive, then the second term for SLE data is
added to the sum of squared residuals. The SLE data
were weighted so that 1% di!erence between calculated
and experimental salt solubility would give a squared
residual of 1.
The Extended UNIQUAC parameters for the aqueous
5. Results and discussions
UNIQUAC interaction parameters are reported in
Table 1. UNIQUAC volume and surface area parameters
for methanol were obtained by "tting to all experimental
data (VLE, SLE, H# ), as in the case of the other solute
species. The values obtained are respectively r  "
!& -&
3.3496 and q  "3.7386. The following values for the
!& -&
standard state thermodynamic properties for pure meth-
anol at 298.15 K were obtained by "tting to experimental
data: kHV "!165.72 kJ mol\, D HH "
  D
 
systems including Na>, K>, NH>, Cl\, NO\, SO\, !245.32 kJ mol\, CH "94.84 J mol\ K\.
   
 
CO\ and HCO\ were given in Thomsen and Rasmus-
 
sen (1999). In this work r and q parameters for methanol
and parameters for the interaction between water and
methanol and between methanol and the ions were
evaluated using both VLE, SLE and excess enthalpy
(H# ) experimental data.
The results of the VLE data correlation are illustrated
in Figs. 1 and 2, and Table 2. Experimental data are
plotted along with the calculated curves for the
water}methanol system in the presence of NaCl and
NH Cl at saturation where the salt solubility is very

large for the last system. The liquid concentration is
2680 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686

Table 3
SLE calculation results: mean absolute deviation between experimental and calculated salt solubility (wt%)

Salt Solubility range (wt%) Temperature range Data points Mean absolute Reference
(K) deviation (wt%)

NaCl 1.36}26.48 298.15 11 0.207 As kerloK f and Turck (1935)

23.49}26.63 273.15}298.15 9 0.118 Armstrong and Eyre (1910)
1.23}26.87 298.15}323.15 18 0.177 Pinho and Macedo (1996) (Fig. 3)

NaNO 3.96}47.92 298.15 8 0.267 As kerloK f and Turck (1935)


2.81}53.89 298.15}328.15 63 0.597 Winkler, Emons and Klauer (1972) (Fig. 6)

Na SO 0.012}32.62 283.15}328.15 51 0.176 Emons and RoK ser (1966) (Figs. 10 and 11)
 
0.02}32.52 313.15 21 0.090 Fleischmann and Mersmann (1984)

Na CO 0.27}21.96 295.15 10 1.350 Ellingboe and Runnels (1966)

 
NaHCO 0.92}13.17 295.15}323.15 20 0.297 Ellingboe and Runnels (1966) (Fig. 7)

KCl 0.52}26.46 298.15 12 0.299 As kerloK f and Turck (1935)
17.84}26.69 273.15}298.15 10 0.208 Armstrong and Eyre (1910)
0.52}26.46 298.15 13 0.281 Malahias and Popovych (1982)
0.54}30.02 298.15}323.15 18 0.527 Pinho and Macedo (1996)
3.91}20.93 293.15 6 0.332 Barkan (1955)

KNO 0.61}27.62 298.15 9 0.564 As kerloK f and Turck (1935)


0.34}49.10 298.15}328.15 63 1.417 Winkler et al. (1972)
0.43}31.30 303.15 7 0.866 Schreinemakers (1909)

K SO 0.06}10.72 298.15 7 0.145 As kerloK f and Turck (1935)

 
1.57}11.76 333.15 12 0.210 Chmarzynski (1977)
0.001}10.31 298.15}333.15 72 0.213 Chmarzynski (1989) (Fig. 5)
0.29}5.46 293.15 5 0.463 Barkan (1955)

K CO 0.015}44.79 298.15 5 0.670 Frankforter and Frary (1913)

 
NH Cl 3.42}28.31 298.15 9 1.132 As kerloK f and Turck (1935)

7.60}26.50 290.15 6 0.688 Mochalov (1939)
20.53}28.32 273.15}298.15 10 0.488 Armstrong and Eyre (1910)
3.48}29.29 297.95}303.15 16 1.889 Remy}Gennete and Bourhis (1950)

NH NO 29.09}70.09 303.15 6 1.112 Schreinemakers (1909)

 
16.80}69.85 303.15 15 1.210 Aravamudan (1956)

(NH ) SO 0.16}43.89 303.15 19 0.775 Aravamudan (1956) (Fig. 4)

 
NaCl#Na SO 1.03}27.02/NaCl 283.15}328.15 155 0.177/NaCl Emons and RoK ser (1967) (Fig. 8)
 
0.30}31.56/Na SO 0.272/Na SO
   
KCl#K SO 3.13}30.92/KCl 283.15}328.15 113 0.255/KCl Emons and RoK ser (1967)
 
0.08}14.78/K SO 0.297/K SO
   
Na SO #K SO 0.47}31.74/Na SO 298.15}328.15 64 0.227/Na SO Emons, RoK ser and Roschke (1970) ( Fig. 9)
       
0.58}14.78/K SO 0.178/K SO
   
Total number of data 863 0.377
points and average
deviation

expressed as the methanol mole fraction on a salt-free
basis, x . y represents the methanol mole fraction in the
 
vapour phase. It can be seen that the experimental data
are represented with very good accuracy in the whole
range of liquid composition. All experimental values
from 0 to 1 (methanol mole fraction on a salt-free basis)
were used for data reduction, even though the model
considers methanol to be a solute. In Table 2 an overview
 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686
Fig. 3. Solubility of sodium chloride in aqueous methanol solutions at
298.15 and 323.15 K (Pinho & Macedo, 1996).
Fig. 4. Solubility of ammonium sulphate in aqueous methanol solu-
tions at 303.15 K (Aravamudan, 1956).
of the data used for the evaluation of model parameters is
given. Only minor deviations between experimental and
calculated curves are observed. Very good results are
obtained in representing the composition of the vapour
phase in equilibrium with the liquid phase, with and
without dissolved salt.
The results of the SLE data correlation are presented
in Table 3 and depicted in Figs. 3}11. The salt solubility
and the liquid composition are expressed as wt%. The
largest deviations were observed when large discrepan-
cies between the experimental data from di!erent sources
occur. Generally, SLE representation in ternary systems
2681
Fig. 5. Solubility of potassium sulphate in aqueous methanol solutions
at 323.15 K (Chmarzynski, 1989).
Fig. 6. Solubility of sodium nitrate in aqueous methanol solutions at
298.15, 313.15 and 328.15 K (Winkler et al., 1972).
is very accurate. Figs. 3}7 present several phase dia-
grams in order to illustrate the capacity of the model to
represent the ternary SLE data. The experimental solu-
bility data are marked with symbols while the lines are
drawn using the parameters presented in this work. The
small di!erences between NaCl solubility at 298.15 and
323.15 K are well represented in Fig. 3. The solubility of
ammonium and potassium sulphate is also very well
represented (Figs. 4 and 5). It can be shown that the
model is able to represent accurately the temperature
dependency of the salt solubility (Fig. 6).
Fig. 7 shows an accurate description of NaHCO

solubility in aqueous methanol. Speciation equilibria
(Eq. (11)) have to be taken into account in order to
represent the behaviour of this system.
2682 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686

Table 4
Results for the excess enthalpy of methanol}water solutions: mean absolute deviations between experimental and calculated excess enthalpy (*H#) in
J mol\

¹ (K) Data points *H# in J mol\ Reference

298.15 11 48.9 Abello (1973) (Fig. 14)

298.15 9 35.9 Belousov and Panov (1976) (Fig. 13)
298.15 15 52.7 Benjamin and Benson (1963) (Fig. 13)
298.15 9 45.8 Bertrand, Millero, Wu and Hepler (1966) (Fig. 13)
278.15}323.15 52 50.3 Katayama (1962)
298.15 18 53.9 Lama and Lu (1965) (Fig. 13)
308.15}326.65 18 47.7 OcoH n and Taboada (1959a)
289.15 10 53.9 OcoH n and Taboada (1959b)
298.15 13 57.5 Duttachoudhury and Mathur (1974)

Total number of data points and 155 50.3

average deviation

Fig. 7. Solubility of sodium bicarbonate in aqueous methanol solutions

at 323.15 K (Ellingboe & Runnels, 1966). Fig. 9. Solubility diagram for sodium sulphate/potassium sulphate in
methanol}water solutions at 313.15 K (Emons et al., 1970). ab * solu-
bility curve for K SO ; bc * solubility curve for NaK (SO ) ;
   
cd * solubility curve for Na SO ; b * two salts (K SO #
   
NaK (SO ) ) saturation point; c * two salts (NaK (SO ) #
   
Na SO ) saturation point.
 

Potassium carbonate appears to be the only salt that is

Fig. 8. Solubility diagram for sodium chloride/sodium sulphate in
methanol}water solutions at 328.15 K (Emons & RoK ser, 1967). ab
* solubility curve for Na SO ; bc * solubility curve for NaCl;
 
b * two salts (Na SO #NaCl) saturation point.
 
capable of causing aqueous methanol solutions to split
into two liquid phases. Unfortunately, due to the insu$-
cient experimental data involving the LLE in this system
(4 tie-lines at 4 di!erent temperatures), the data correla-
tion was not performed. However, the calculation results
concerning the K CO solubility in methanol}water
 
mixture in the homogeneous range are rather good
(Table 3).
Di$culties in correlating the experimental data of the
methanol}water}Na CO system are mainly due to
 
the fact that Ellingboe and Runnels (1966) did not specify
the solid phase. Hence the number of hydrate water of
sodium carbonate was obtained on the basis of its behav-
iour in aqueous systems. The calculation results show
 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686 2683

Fig. 10. Solubility diagram for sodium sulphate in methanol}water solutions at 283.15 K (Emons & RoK ser, 1966). ab * solubility curve for Na SO
 
(the solubility of Na SO in pure methanol is extremely low); bc * solubility curve for Na SO ) 10H O; b * two salts (Na SO #
      
Na SO ) 10H O) saturation point.
  

Fig. 11. Solubility diagram for sodium sulphate in methanol}water

solutions at 313.15 and 328.15 K (Emons & RoK ser, 1966). ab * solubil-
ity curve for Na SO .
 
that at 295.15 K various salts are precipitating consecut-
ively, with the increase of the methanol concentration:
Na CO ) 10H O, Na CO ) 7H O, Na CO ) H O
        
and Na CO .
 
The model is also able to represent the location of
uni-variant points with very good accuracy both in
ternary and quaternary systems. This is illustrated in
Figs. 8}10. Both quaternary systems (Figs. 8 and 9) are
very well represented, the methanol concentration vary-
ing between 0 and about 30 wt%. The diagram for the
Fig. 12. JaK necke projection (JaK necke, 1906) of the phase behaviour for
the system sodium/potassium}chloride/sulphate in methanol#water
at constant solvent composition (19 wt% methanol) and at 283.15 K
(Emons et al., 1970). a}e * two salts saturation points; f}h * three salts
saturation points.
ternary system containing water, methanol and Na SO
 
at 283.15 shows clearly the two-salts saturation point
(Fig. 10). The same behaviour is observed at 298.15 K. At
313.15 and 328.15 K the solid phase is Na SO in the
 
whole range of liquid composition (Fig. 11). The set of
experimental data reported by Okorafor (1999) for
2684 M.C. Iliuta et al. / Chemical Engineering Science 55 (2000) 2673}2686
Fig. 13. Excess enthalpy for methanol}water solutions at 298.15 K.
Comparison of experimental and calculated values.
water}methanol}Na SO system was excluded from the
 
parameter evaluation due to the strong contradiction
with all other data included in the databank for this
system.
Pure component and binary model parameters, that
are the only ones needed in the Extended UNIQUAC
model, were estimated using binary, ternary and quater-
nary experimental data. The ability of the model to
predict the phase behaviour of methanol}water}three
salts systems is illustrated in Fig. 12. Experimental values
of two-salt and three-salt saturation points are marked
with symbols. Taking into account the very high com-
plexity of this kind of system, we can conclude that the
prediction is very good.
In the entire range of liquid compositions the excess
enthalpy of water}methanol solutions is negative. The
Extended UNIQUAC model is able to reproduce the
shape of the curves, the mean absolute deviation between
experimental and calculated values being 50.3 J mol\
(11% mean deviation from the experimental data). In
Fig. 13 the calculated excess enthalpies at 298.15 K are
compared with experimental values. Table 4 gives an
overview of excess enthalpy data used for the evaluation
of model parameters.
6. Conclusion
The Extended UNIQUAC model has been shown to
be an accurate thermodynamic model for describing the
complex phase behaviour of methanol}water}single/
mixed electrolyte systems. The model only requires pure
component and binary temperature-dependent interac-
tion parameters. The model is able to represent with
a very good accuracy VLE of ternary and quaternary
electrolyte systems. SLE representation in ternary
systems is shown to be very accurate too. The model
is able to represent with a good accuracy uni-variant
points both in ternary and quaternary systems. The
phase behaviour of methanol}water}three salts
systems can be predicted with good accuracy. The
Extended UNIQUAC model is furthermore able to
represent excess enthalpy data for methanol}water
mixtures.
Acknowledgements
The authors appreciate the many valuable comments
provided by Professor John M. Prausnitz (University of
California, Berkeley) during the reviewing process. Maria
Iliuta recognizes with thanks the "nancial support of the
Research Group IVC-SEP at the Institut for Kemiteknik
IVC-SEP, Technical University of Denmark for a post-
doctoral position.
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