Professional Documents
Culture Documents
Solubilities of NaCl, KCl, LiCl, and LiBr in Methanol, Ethanol, Acetone, and
Mixed Solvents and Correlation Using the LIQUAC Model
Miyi Li,†,‡ Dana Constantinescu,‡ Lisheng Wang,† André Mohs,‡ and Jürgen Gmehling‡,*
School of Chemical Engineering & EnVironment, Beijing Institute of Technology, 100081 Beijing, China,
Technische Chemie, Institut für Reine und Angewandte Chemie, Carl Von Ossietzky UniVersität Oldenburg,
D-26111, Oldenburg, Germany
The solubilities of NaCl, KCl, LiCl, and LiBr in pure methanol, ethanol, and acetone were measured over a
temperature range from 293.15 to 333.15 K. Furthermore salt solubilities in the mixed solvents (water +
methanol, water + ethanol, water + acetone, methanol + ethanol, methanol + acetone, ethanol + acetone)
were determined at 313.15 K. For a few systems solubility data are reported for the first time. In a few cases
a comparison with published data stored in the Dortmund Data Bank (DDB)1 showed disagreement. The
Downloaded from pubs.acs.org by UNIV OF TEXAS SW MEDICAL CTR on 10/08/18. For personal use only.
LIQUAC model was used to correlate the experimental data. The calculated salt solubilities are in good
agreement with the experimental results for the systems NaCl + water + methanol and KCl + water +
methanol.
solvents (methanol, ethanol, and acetone) or binary mixture with salt from the saturated solution. The solubility of each sample
the desired composition were added. The cell was tightly closed was calculated by eq 1. As solubility the mean value of the
during the measurement and care was taken to ensure that the three samples was chosen. When the relative standard
composition of the mixed solvents was not changed because of deviation of one of the samples was greater than 0.5%, the
evaporation by leaving only 3-5 mL of gas-phase in the cell. measurement was repeated, whereby the relative standard
Cell and bath temperatures were measured by precision Pt 100 deviation (RSD) within a set of different experimental results
thermometers with an accuracy of (0.01 K. was defined as
The binary solvent mixtures (water + methanol, water +
[ ]
n 0.5
ethanol, water + acetone, methanol + ethanol, methanol +
acetone, and ethanol + acetone) were prepared using a balance
1
n-1 ∑ (x i - jx)2
i)1
with an uncertainty of (0.0001 g (Sartorius A200S). The RSD % ) 100 (2)
experimental points for mixed solvents were arranged in 10% jx
steps by varying the salt-free mass fraction. where xi is the experimental solubility of sample i and jx is
To avoid the formation of microcrystals and supersaturation the mean solubility of n measurements. In the case of
during the measurements, the solutions were stirred at a speed solubilities less than 0.1 mol · kg-1, the criterion was extended
of around 600 rpm for approximately 12 h in the case of to 3%.
organic solvents or organic solvent mixtures and 6 h for
water-organic electrolyte systems. This ensured an intensive 3. Solubility Data
contact between the solid and the liquid phase. After
sedimentation for 24 h in the case of the organic or mixed The salt solubilities measured in organic solvents are listed
organic electrolyte systems and 12 h for water-organic in Table 1. To avoid the evaporation of acetone in the system
electrolyte systems, three liquid samples of about 3 mL were LiCl + acetone, a maximum temperature of 328.15 K was used.
taken by using a syringe equipped with a 0.45 µm filter and The systems with NaCl or KCl in ethanol or acetone were not
transferred to capped vials with a volume of 15 mL. Prior to investigated, since the accuracy of the balance was not sufficient
sampling, syringe and filter were thermostatted to a temper- to determine the small solubilities with the required accuracy.
ature 5 K above the temperature of the solution. The mass A comparison of the KCl solubilities in methanol measured in
of the empty vial (W3) and the mass of the sample together this work and those reported by Pinho and Macedo2 show good
with the vial (W1) were determined by using an electric agreement regarding the absolute solubilities and the temperature
balance (Sartorius CP225D) with an uncertainty of (0.00001 dependence, as can be seen from Figure 2. But the solubilities
g. The liquid samples were first dried in an oven at 353 K measured in this work are systematically 1.5% higher than the
for 2 days, and then at 433 K for at least 24 h. The mass of
solid together with the vial (W2) was weighed by the same
balance ((0.00001 g). The drying of the samples was
continued until a constant mass was reached. The solubility
of the salt can then be calculated by the following relation:
(5)
investigated in the whole composition range. For most of the
investigated systems, the well-equipped apparatus together with The LR term is calculated using the Debye-Hückel theory as
an elaborate measurement procedure allowed the reliable
modified by Fowler and Guggenheim (1949). Ms is the molar
measurement of salt solubilities. For some of the systems, for
mass of solvent s (kg · mol-1), ds (kg · m-3) is the density of the
example, LiCl in mixed organic solvents (methanol, ethanol,
and acetone), there was no data available in the literature until pure solvent s, and dm the density of the mixed solvents,
now. calculated using the following equations:
The uncertainty of the measurements is mainly influenced
by the error caused by the balance, but it is also influenced by dm ) ∑φ soldsol (6)
temperature fluctuations and evaporation effects. In summary sol
4984 Ind. Eng. Chem. Res., Vol. 49, No. 10, 2010
xs′Vs the parameters between cations (c) and anions (a). B′(I) is equal
φs ) (7) to dB(I)/dI. Mm is the mean molar mass of the mixed solvents
∑ x′ solVsol (kg · mol-1).
sol
The SR term is calculated by the UNIQUAC model:
∑m
I ) 0.5
[ ( )]
2
ionzion (8) Vs Vs
ln γsSR ) 1 - Vs + ln Vs - 5qs 1 - + ln +
{ ( ) ]}
ion
Fs Fs
∑qxψ
[
A ) 1.327757 × 105dm0.5 /(DT)1.5 (9) i i i,s
qixiψs,i
qs 1 - ln
i
- ∑ (17)
b) 6.35969dm0.5 /(DT)0.5 (10)
∑qx i i i ( ∑q x ψ k k k,i)
i k
where x′s is the salt-free mole fraction of solvent s in the solvent
mixture and Vs (m3 · mol-1) is the molar volume of pure solvent Vs ) rs / ∑rx i i (18)
s. Subscript sol covers all the solvents in the solution. I is the i
D ) D1 + [(D2 - 1)(2D2 + 1)/2D2 - (D1 - 1)]φ2′ (11) ψi,j ) exp(-ai,j /T) (20)
For a multicomponent mixture, D can be estimated by where ri and qi are the van der Waals volumes and surface areas,
and ai,j represents the UNIQUAC interaction parameters,
D) ∑ φ′ solDsol (12) whereby ai,j is different to aj,i. xi is the mole fraction of species
i in the solution. In these equations, the indices i and j cover all
sol
solvents and ions.
The MR term was originally proposed by Li et al3,4 with the For ions j, each part of the activity coefficient is given on
objective to represent the indirect effects between pair species. the basis of the unsymmetrical convention on molality scale.
On the basis of approximate results for the radial distribution
functions, the interactions between equally charged ions are zj2A√I
ignored. It is assumed that due to the interionic repulsion of ln γ*j LR ) - (21)
1 + b√I
ions with the same kind of charge (positive or negative) the
∑B
interactions can be neglected, since they cannot be found in
ln γ*j MR ) (Mm)-1 j,sol(I)x'sol +
the direct neighborhood. The middle range effects between
[ ]∑ ∑
sol
molecular groups are also equal to zero, because in the middle
zj2
range term only polarization effects are considered, and these
are only caused by charged particles. This leads to the following 2Mm
B'sol,ion(I)x'solmion + ∑B j,ion(I)mion +
( )∑ ∑
sol ion ion
expression for the middle range term: zj2 Bj,s(I ) 0)
B'ca(I)mcma - (22)
( )∑ ∑
Ms 2 Ms
∑B
c a
ln γsMR ) s,ion(I)mion - [Bsol,ion(I) +
ion
Mm sol ion
ln γ*j SR ) ln γSR
j - ln γj (B)
SR
(23)
IB'sol,ion(I)]x'solmion - Ms ∑∑ [Bca(I) + IB'ca(I)]mcma (13)
() [ ( )]
c a rj rj rjqs rjqs
j (B) ) 1 -
ln γSR + ln - 5qj 1 - + ln +
rs rs rsqj rsqj
Bsol,ion(I) ) bsol,ion + csol,ion exp(-1.2I1/2 + 2dsaltI) (14)
qj(1 - ψj,s - ln ψs,j) (24)
Bc,a(I) ) bc,a + cc,a exp(-I1/2 + dsaltI) (15) The superscripted asterisk (/) indicates the unsymmetrical
convention for ions based on the mole fraction scale. The
Mm ) ∑ x′ solMsol (16) standard state of ion j is defined as the hypothetical ideal solution
at unit molality. In this hypothetical ideal solution, mj ) m°j )
where dsalt, bsol,ion, and csol,ion are the MR interaction parameters 1mol · kg-1 and γj*′ ) 1. The superscripted prime (′) indicates
between the solvents (sol) and the ions. bc,a,, cc,a, and dsalt are the molality scale. The reference state at infinite dilution for
Table 2. Salt Solubilities (mol · kg-1) in the Mixed Solvents at 313.15 K for Different Salt-Free Mass Fractions (w′1)
methanol(1) + methanol(1) + ethanol(1) +
water(1) + methanol(2) water(1) + ethanol(2) water(1) + acetone(2) ethanol(2) acetone(2) acetone(2)
w′1 mNaCl mKCl mLiCl mNaCl mKCl mLiCl mNaCl mKCl mLiCl mLiCl mLiCl mLiCl
0.1 0.369 0.137 11.83 0.074 0.0295 6.94 0.0164 0.0097 5.75 1.04 0.486
0.2 0.601 0.256 12.76 0.286 0.121 7.91 0.0983 6.14 1.76 0.819
0.3 0.957 0.471 13.56 0.647 0.336 9.77 6.85 2.87 1.182
0.4 1.405 0.790 14.37 1.176 0.672 10.98 7.35 3.91 1.470
0.5 2.000 1.235 15.46 1.786 1.122 12.57 11.21 7.83 4.83 2.052
0.6 2.665 1.789 16.43 2.460 1.685 14.25 13.69 8.39 5.46 2.666
0.7 3.409 2.508 17.59 3.215 2.346 15.89 2.550 15.55 8.87 6.77 3.417
0.8 4.255 3.334 18.64 4.038 3.170 17.05 4.210 3.352 17.75 9.30 8.04 4.229
0.9 5.194 4.283 19.83 5.035 4.150 19.23 5.179 4.309 19.56 9.80 8.93 5.108
Ind. Eng. Chem. Res., Vol. 49, No. 10, 2010 4985
( ) ( )
ion j is normalized, so that γ*′ f 1 when xs f 1 and I f 0. In 1 1 raq+org
eq 24, the term ln γjSR is the same as in eq 18. The terms ln ωM(aq/aq+org) ) rM - + ln +
raq+org raq raq
j (B) and (Bj,s(I ) 0))/Ms in eq 23 represent the reference state
( ) ( )
γSR qaq qaq+org raqqaq+org
for ion j at infinite dilution based on the mole fraction scale. 5rM - - 5qM ln +
raq raq+org raq+orgqaq
[( )
The subscript s in eqs 22 and 24 indicates the reference solvent.
x´aqψaq,M + x´orgψorg,M
The pure solvent is considered as a reference solvent. The qM ln +
variables given in eqs 3 -24 were already defined in detail in ψaq,M
the paper of Li et al.3,4 On the basis of the molality scale, the
complete expression of the activity coefficient of ion j can be
(x´aqψM,aq + x´orgψM,org - ψM,aq) +
BM,aq+org(I ) 0)
]
BM,aq(I ) 0)
Maq
-
obtained from
+ ln(Maq /Maq+org) (29)
Maq+org
j ) (ln γ* + ln γ*j MR + ln γ*j SR) -
LR
) ( )
ln γ*′
(
j
raq+org
∑m
1 1
ln(Ms /Mm + Ms ion) (25) ωX(aq/aq+org) ) rX - + ln +
raq+org raq raq
( ) ( )
ion
qaq qaq+org raqqaq+org
5rX - - 5qX ln +
5. Calculation of Salt Solubilities in Water-Methanol raq raq+org raq+orgqaq
Electrolyte Systems
[(
qX ln
x´aqψaq,X + x´orgψorg,X
ψaq,X
+ )
]
In this work, the LIQUAC model based on Huang et al7 was
BX,aq(I ) 0)
used to correlate the solubility data. For the ions in the (x´aqψX,aq + x´orgψX,org - ψX,aq) + -
electrolyte solutions, the unsymmetrical convention for the Maq
activity coefficients and the molality scale were used. With the BX,aq+org(I ) 0)
+ ln(Maq /Maq+org) (30)
assumption that all salts completely dissociate in the solution, Maq+org
one can obtain
Bi,aq(I ) 0) ) bi,aq + ci,aq (31)
Mν+Xν- · nH2O(solid) a ν+M(liquid) + ν-X(liquid) + Bi,aq+org(I ) 0) ) xaq
′ bi,aq + xorg
′ bi,org + xaq
′ ci,aq + xorg
′ ci,org
nH2O(liquid) (26) (32)
raq+org ) xaq
′ raq + xorg
′ rorg (33)
where Mv+Xv- · nH2O indicates the solid salt consisting of V+
cations M, V- anions X, and n water molecules in the hydrated qaq+org ) xaq
′ qaq + xorg
′ qorg (34)
crystal. On the basis of eq 26, a chemical equilibrium constant
Ksp can be defined: The electrolyte system water + methanol + NaCl and water
+ methanol + KCl were chosen to test the derived expression
ν+ ν- n
aM aX aH2O by Huang et al.7 It has been shown that eqs 28-34 can be
ln Ksp(T) ) ln applied successfully for the prediction of salt solubilities in the
aMX · nH2O system water + methanol.
M + ν- ln(mXγ*′)
) ν+ ln(mMγ*′) X + n ln(xH2OγH2O)
(27) 6. Results and Discussion
All parameters required for the calculations were taken from
where a are activities and γ are the activity coefficients of the Huang et al.7 Additionally new parameters for LiCl and LiBr
different species. Ksp is identical with the solubility product of were fitted using vapor-liquid equilibria (VLE), osmotic
the salt Mv+Xv- · nH2O, since aMX · nH2O is unity. Equation 27 coefficients, solid-liquid equilibria (SLE), and mean ion activity
can be used not only for aqueous solutions but also for organic coefficients stored in the Dortmund Data Bank. The parameters
or mixed solvent electrolyte solutions. The solubility product used for the calculation are listed in Table 3 or were taken from
can be calculated using standard thermodynamic properties of ref 7. The salt solubilities of NaCl and KCl in the mixed solvents
the salt and the ions, such as the standard Gibbs energy of at 313.15 K were predicted with the existing parameters. The
formation, standard enthalpy of formation, and standard heat calculated results are shown in Figures 4-5 together with the
capacity as mentioned by Li et al.6 The solubility product of experimental solubilities of this work and data published by
the salts in aqueous systems can easily be obtained from the other authors stored in the DDB. From the figures it can be
available standard thermodynamic properties, for example, of seen that the measured salt solubilities in the mixed solvents
the ions in aqueous solution. Unfortunately, these data are are in good agreement with the data of Pinho and Macedo8 and
that the LIQUAC model is able to describe the salt solubilities
usually not available for the ions in organic or mixed solvent
electrolyte systems. Huang et al.7 proposed a procedure to solve Table 3. The Correlated MR and SR Parameters of the Model in
this problem. By using the following equations, the solubility This Work
product of the salt in aqueous electrolyte systems can, for i j bij cij aij aji dij
example, be transferred to mixed solvent electrolyte systems +
Li H2O -0.25121 0.01648 -927.39 -4469.29
containing water, whereby Li+ MeOH -0.27605 0.11215 -1075.56 -5151.06
Br- H2O 0.04002 -0.03810 4179.03 1078.11
ln Ksp(aq+org)(T) ) ln Ksp(aq)(T) - [ν+ωM(aq/aq+org) + Br- MeOH -0.02844 -0.05433 27.59 1101.21
Li+ Cl- 0.32999 -0.30497 -887.60 -4297.14 0.15343
ν-ωX(aq/aq+org)] (28) Li+ Br- 0.40366 0.52021 -70.18 -6532.19 0.13686
4986 Ind. Eng. Chem. Res., Vol. 49, No. 10, 2010
Figure 4. NaCl solubility in the system methanol + water at different salt- Figure 6. Molal osmotic coefficients for aqueous electrolyte systems: (0)
free mole fractions: (9) this work at 313.15 K; (s) LIQUAC model at LiCl + water system at 298.15 K from DDB;1 (s) LIQUAC model at
313.15 K; (O) Pinho and Macedo8 at 298.15 K; ( · · · ) LIQUAC model at 298.15 K; (O) LiBr + water system at 298.15 K from DDB;1 ( · · · ) LIQUAC
298.15 K; (4) Pinho and Macedo8 at 323.15 K; (---) LIQUAC model at model at 298.15 K.
323.15 K.
( )
model are shown in Figures 6-9. As can be seen for both salts
Qexp - Qcalc 2
F(aij, aji, bij, cij) ) ∑ ∑w Q
Qexp
100 ) min good agreement of the correlations with the experimental data
is observed. Not only is the osmotic coefficient in the mixed
np nt
(35) solution reliably described up to high molalities (up to about
Ind. Eng. Chem. Res., Vol. 49, No. 10, 2010 4987
The quality of the correlations by using the LIQUAC model
can be judged by calculating the average absolute relative
deviation (AARD):
| |
Ndata
Qcalc - Qexp
AARD )
1
Ndata ∑ i
Qexp
i
100 (36)
i)1 i
7. Conclusion
Salt solubility measurements for four salts (NaCl, KCl, LiCl,
and LiBr) in pure organic and mixed solvents were carried out
by using a static method. Reliable and reproducible experimental
data were obtained for the entire composition and temperature
Figure 9. LiCl solubility in the system water + methanol at different salt- range. For a few systems no data are available in literature.
free mole fractions: (0) this work at 313.15 K; (s) LIQUAC model at The experimental data were correlated with the LIQUAC
313.15 K; (O) data set in DDB1 at 298.15 K; ( · · · ) LIQUAC model at 298.15
K. model. The results show that the LIQUAC model is able to
describe osmotic coefficients, mean activity coefficients of the
Table 4. AARD and Solubility Product Estimated in the Correlation salts, salt solubilities, and the VLE behavior in aqueous, organic,
AARD (%) ln Ksp and water + organic solvent electrolyte systems.
osmotic system The main focus of this work was to measure and correlate
coefficient (φ) solubility pressure 298.15 K 313.15 K the salt solubilities in the system water-methanol.
LiCl + H2O 2.0 2.6
LiBr + H2O 2.3 3.6
LiCl · H2O(aq) -12.06 -11.78 Acknowledgment
LiCl(aq) -15.50 -15.10
LiCl + H2O + 1.5 The authors thank the Deutsche Forschungsgemeinschaft for
methanol financial support of the ongoing research project. We also thank
NaCl + H2O + 2.6 the DDBST GmbH (Oldenburg, Germany) for providing the
methanol
KCl + H2O + 5.1 latest version of the Dortmund Data Bank for the model
methanol comparison.
20 mol/kg) but also the VLE behavior in aqueous and mixed
solvents (Figures 7 and 8) is described correctly. The model is
even capable of predicting the conversion point between LiCl Literature Cited
and the monohydrate in aqueous methanol solutions and the (1) Dortmund Data Bank, version 2008; DDBST Software and Separa-
temperature dependence (Figure 9). tion Technology GmbH: Oldenburg, Germany, 2008; www.ddbst.de.
4988 Ind. Eng. Chem. Res., Vol. 49, No. 10, 2010
(2) Pinho, S. P.; Macedo, E. A. Solubility of NaCl, NaBr, and KCl in (10) Harner, R. E.; Sydnor, J. B.; Gilreath, E. S. Solubilities of
Water, Methanol, Ethanol, and Their Mixed Solvents. J. Chem. Eng. Data Anhydrous Ionic Substances in Absolute Methanol. J. Chem. Eng. Data
2005, 50, 29. 1963, 8, 411.
(3) Li, J.; Polka, H.-M.; Gmehling, J. A. gE Model for Single and Mixed (11) Pavlopoulos, T.; Strehlow, H. The Solubilities of Alkali Halogenides
Solvent Electrolyte Systems. 1. Model and Results for Strong Electrolytes. in Methanol, Acetonitrile and Formic Acid. Z. Phys. Chem. 1954, 202, 474.
Fluid Phase Equilib. 1994, 94, 89. (12) Emons, H.-H.; Dümke, D.; Förtsch, M. Investigation of Systems
(4) Polka, H.-M.; Li, J.; Gmehling, J. A. gE Model for Single and Mixed Consisting of Salts and Mixed Solvents. II The Systems Sodium Chloride
Solvent Electrolyte Systems. 2. Results and Comparison with Other Models. Resp. Potassium Chloride, Methanol-Water and Sodium Chloride-Potassium
Fluid Phase Equilib. 1994, 94, 115. Chloride-Methanol-Water. Wiss. Z. TH Leuna-Merseburg 1966, 8, 195.
(5) Pinho, S. P.; Macedo, E. A. Experimental Measurement and (13) Turner, W. E. S.; Bissett, C. C. The Solubilities of Alkali Haloids
Modeling of KBr Solubility in Water, Methanol, Ethanol and its Binary in Methyl, Ethyl, Propyl, and iso-Amyl Alcohols. J. Chem. Soc. London
Mixed Solvents at Different Temperatures. J. Chem. Thermodyn. 2002, 34, 1913, 103, 1904.
337. (14) Simmons, J. P.; Freimuth, H.; Russel, H. The Systems Lithium
(6) Li, J.; Lin, Y.; Gmehling, J. gE Model for Single- and Mixed-Solvent Chloride-Ethyl Alcohol and Lithium Bromide-Water-Ethyl Alcohol.
Electrolyte Systems. 3. Prediction of Salt Solubilities in Aqueous Electrolyte J. Am. Chem. Soc. 1936, 58, 1692.
Systems. Ind. Eng. Chem. Res. 2005, 44, 1602. (15) Vlasov, Yu. G.; Antonov, P. P.; Anokhin, V. N. The System LiCl-
(7) Huang, J.; Li, J.; Gmehling, J. Prediction of Solubilities of Salts, LiBr-Ethanol at 25 °C. Zh. Prikl. Khim. 1975, 48, 1155.
Osmotic Coefficients, and Vapor-Liquid Equilibria for Single and Mixed (16) Plyushchev, V. E.; Shakhno, I. V.; Komissarova, L. N.; Nadezhdina,
Solvent Electrolyte Systems using the LIQUAC Model. Fluid Phase Equilib. G. V. Study of Solubility of Alkali Metal Chlorides in Some Aliphatic
2009, 275, 8. Alcohols. Tr. Mosk. Inst. Tonkoj Khim. Tekhnol. 1958, 7, 45.
(8) Pinho, S. P.; Macedo, E. A. Representation of Salt Solubility in
Mixed Solvents: A Comparison of Thermodynamic Models. Fluid Phase
Equilib. 1996, 116, 209. ReceiVed for reView January 5, 2010
(9) Kiepe, J.; Noll, O.; Gmehling, J. Modified LIQUAC and Modified ReVised manuscript receiVed March 15, 2010
LIFACsA Further Development of Electrolyte Models for the Reliable Accepted March 24, 2010
Prediction of Phase Equilibria with Strong Electrolytes. Ind. Eng. Chem.
Res. 2006, 45, 2361. IE100027C