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Ind. Eng. Chem. Res.

2008, 47, 56515659 5651

Evaluation of the Nonrandom Hydrogen Bonding (NRHB) Theory and the Simplified
Perturbed-Chain-Statistical Associating Fluid Theory (sPC-SAFT). 2. Liquid-Liquid
Equilibria and Prediction of Monomer Fraction in Hydrogen Bonding Systems
Ioannis Tsivintzelis, Andreas Grenner, Ioannis G. Economou,*,, and Georgios M. Kontogeorgis
Center for Phase Equilibria and Separation Processes (IVC-SEP), Department of Chemical and Biochemical
Engineering, Technical UniVersity of Denmark, DK-2800 Lyngby, Denmark, and Molecular Thermodynamics
and Modeling of Materials Laboratory, Institute of Physical Chemistry, National Center for Scientific Research
Demokritos, GR-15310 Aghia ParaskeVi Attikis, Greece

Two statistical thermodynamic models, the nonrandom hydrogen bonding (NRHB) theory, which is a compressible
lattice model, and the simplified perturbed-chain-statistical associating fluid theory (sPC-SAFT), which is based
on Wertheims perturbation theory, were used to model liquid-liquid equilibria and predict the fraction of non-
hydrogen bonded molecules in various hydrogen bonding mixtures. Carefully selected binary mixtures, which
include water-hydrocarbon, 1-alkanol-hydrocarbon, water-1-alkanol, and glycol-hydrocarbon, were used to
benchmark the accuracy of the models. Both models yielded satisfactory and often very similar results for the
phase behavior of the investigated mixtures. sPC-SAFT yielded more accurate predictions, while NRHB yielded
more accurate correlations, in mixtures of water with normal alkanes and cycloalkanes. In water-aromatic
hydrocarbon mixtures, satisfactory correlations were obtained only when solvation was accounted for. Both models
resulted in satisfactory correlations for all other mixtures, while for specific mixtures, one model may perform
better than the other. Finally, both models, despite that they are based on totally different approaches for the treatment
of hydrogen bonding, yielded similar predictions for the fraction of non-hydrogen bonded molecules (monomer
fraction) in pure 1-alkanols and in 1-alkanol-n-hexane mixtures.

1. Introduction thorough discussion of the two approaches for the treatment of

hydrogen bonding is made through a detailed comparison of
Advances in applied statistical mechanics in recent years have model predictions for the fraction of non-hydrogen bonded
resulted in a number of equations of state (EoSs) for real molecules in alcohol solutions.
complex fluids with strong theoretical basis. Two of the most
successful and widely used families of such models are based 2. Theory
on Wertheims first-order thermodynamic perturbation theory14
and lattice theory.5 PC-SAFT6 is one of the most successful 2.1. Nonrandom Hydrogen Bonding (NRHB). The NRHB
models of the first family, while a simplified version of the theory is a compressible lattice model, where holes are used to
model, sPC-SAFT,7 reduces the computing time without account for density variation as a result of temperature and
compromising its performance. On the other hand, lattice models pressure changes. NRHB accounts explicitly for the nonrandom
have been used in industry and academia since the 1970s. A distribution of molecular sites, while Veytsmans statistics is
recent development in this respect is the nonrandom hydrogen used to calculate the contribution of hydrogen bonding to the
bonding theory (NRHB), which accounts explicitly for hydrogen thermodynamics of the system.8,9 Thus, the model is suitable
bonding as well as for the nonrandom distribution of molecular for property calculations of highly nonideal fluids. According
segments and free volume.8,9 to NRHB theory, the molecules are assumed to be arranged on
In this series of papers, we attempt to evaluate the perfor- a quasi-lattice of Nr sites, N0 of which are empty, with a lattice
mance of the sPC-SAFT and the NRHB model using complex coordination number, z. Each molecule of type i in the system
fluid mixtures as benchmarks. In the first paper,10 we have tried occupies ri sites of the quasi-lattice. It is characterized by three
to address capabilities and limitations of the models in the scaling parameters and one geometric, or surface-to-volume-
description of vapor-liquid equilibria (VLE) of several mixtures ratio, factor, s. The first two scaling parameters, h* and s*, are
that consisted of nonpolar and also weakly, strongly, and very used for the calculation of the mean interaction energy per
strongly polar fluids. A standard database of Danner and molecular segment, *, according to the following expression:
Guess,11 which is a collection of VLE experimental data for
104 mixtures, was used, and different approaches were adopted * ) /h + (T - 298.15)s/ (1)
for the description of phase equilibrium. *
while the third scaling parameter, sp,0, is used for the calculation
In this work, the models are applied to predict and correlate of the close-packed density, F* ) 1/sp *
, as described by the
liquid-liquid equilibria (LLE) of carefully selected hydrogen following expression:
bonding mixtures, such as water-hydrocarbon, 1-alkanol-
/ / /
hydrocarbon, water-1-alkanol, and glycol-hydrocarbon. A sp ) sp,0 + (T - 298.15)sp,1 (2)
Parameter sp,1 in eq 2 is treated to as a constant for a given
* Corresponding author. Tel.: +302106503963. Fax: +302106511766.
E-mail: homologous series.9,12 Furthermore, the hard-core volume per

Technical University of Denmark. segment, *, is constant and equal to 9.75 cm3 mol-1 for all

National Center for Scientific Research Demokritos. fluids. The following relation holds: r ) MW sp *
/*. Finally,
10.1021/ie071382l CCC: $40.75 2008 American Chemical Society
Published on Web 06/25/2008
5652 Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008

the shape factor is defined as the ratio of molecular surface to gas and the dispersion are identical to the PC-SAFT expressions.
molecular volume, s ) q/r, and is calculated from the UNIFAC The modifications of von Solms et al.7 affect only the hard-
group contribution method.13 sphere chain and the association terms. First, it is assumed that
As described in detail elsewhere,9 the equation of state for a all segments in the mixture have the same diameter. This
fluid mixture assumes the following form, diameter is calculated as follows:

[ ( li
) ( iximidi3
P + T ln(1 - F ) - F r - i
2 ( q
- ln 1 - F + F +
r ) dav )


z Using eq 7, n is calculated as follows:

ln 00 ) 0 (3)

n ) dnav Fiximi (8)
while the chemical potential for the component i is given by 6
i i jlj By now setting the volume fraction 3, a simpler expression
) ln - rij + ln F + ri( - 1) ln(1 - F ) - for ghs (radial distribution function) compared to the original
RT iri rj

[ ] [
PC-SAFT is obtained,
z qi q zqi
r - 1 +
2 i ri r[
ln 1 - F + F +
2 ]
ln ii +
ghs() )

(1 - )3
ri P qi Hi
( - 1) ln 00 + ri - + (4) and ahs (hard-sphere term of the Helmholtz energy) reduces to
qi T T RT
i the Carnahan-Starling equation:14
where i is the site fraction of component i, while li and i are
4 - 32
characteristic quantities for each fluid. Parameters oo and ii hs
acs ) (10)
(1 - )2
are nonrandom factors for the distribution of empty sites around
an empty site and of molecular segments of component i around In addition, sPC-SAFT7 employs a slightly different expression
a molecular segment of component i, respectively. For associat- for the association strength AiBj than in PC-SAFT,6 given by
ing fluids, H denotes the number of hydrogen bonds per the following expression:

[ ( ) ]
molecular segment, while the term Hi/RT is the hydrogen
bonding contribution to the chemical potential of component i. AiBj
AiBj ) NAV 3ijghs()AiBj exp -1 (11)
Finally, parameters T ) T/T*, P ) P/P*, and v ()1/F ) F*/F) 6 kT
are the reduced temperature, pressure, and specific volume, Consistent with earlier simplifications, the radial distribution
respectively. The characteristic temperature, T*, and pressure, function with the simpler expression is used. Finally, the
P*, are related to the mean intersegmental energy by diameter cubed is replaced by the sphere volume. The replace-
ment of gijhs by ghs () makes the composition dependence of
* ) RT * ) P * * (5)
AiBj (required for evaluation of the fugacity coefficient) much
Detailed expressions for the calculation of all these parameters simpler, since this dependence is contained only in .
can be found elsewhere.9 For associating fluids, NRHB has three
more pure-component parameters that are the energy, EijH, the 3. Pure-Fluid Parameters
volume, VijH, and the entropy change, SijH, for the formation of a
hydrogen bond between proton donors of type i and proton Pure-fluid parameters for the two models are summarized in
acceptors of type j in different molecules. However, usually Tables 1 and 2. Parameters for the majority of the fluids were
the volume change for the formation of the hydrogen bond, VH ij , adopted from literature. However, in some cases, new param-
is set equal to zero, so the number of hydrogen bonding eters were estimated by fitting the predictions of the theories to
parameters are reduced to two without compromising the vapor-pressure and saturated liquid-density data of the Design
performance of the model.9,12 Institute for Physical Property Data (DIPPR) correlation.15 In
2.2. Simplified Perturbed-Chain-Statistical Associating the NRHB model, the parameter sp,1 , which is used in eq 2,
Fluid Theory (sPC-SAFT). The sPC-SAFT7 EoS was devel- was treated as a characteristic parameter of a given homologous
oped with the goal to reduce the computational and program- series. As before,9,12 it was set equal to -0.412 10-3 cm3
ming effort with respect to the original PC-SAFT without g-1 K-1 for non-aromatic hydrocarbons, -0.310 10-3 cm3
essentially changing the performance of the model. Thus, sPC- g-1 K-1 for alcohols, -0.300 10-3 cm3 g-1 K-1 for water,
SAFT7 is identical to PC-SAFT6 in the case of pure nonasso- and 0.150 10-3 cm3 g-1 K-1 for all the other fluids.
ciating compounds, but not for associating compounds and for
multicomponent mixtures, in general. The sPC-SAFT7 EoS uses 4. Mixture Phase Equilibria
simpler mixing rules by taking into account that the segment
The two models were applied in order to describe the LLE
diameters are usually similar for segments belonging to different
of various hydrogen bonding mixtures. A number of representa-
tive binary mixtures were examined. The mixture scaling
The Helmholtz energy for a mixture of associating molecules
parameters were calculated using appropriate mixing and
combining rules.10 In both models, one binary interaction
A parameter, kij, was used in the combining rule for the dispersion
a ) aid + ahc + adisp + aassoc (6) energy between unlike molecules:
where aid is the ideal gas contribution, ahc is the contribution ij ) (1 - kij)iijj (12)
of the hard-sphere chain reference mixture, and adisp and aassoc
are the contributions of dispersion forces and association, In mixtures of two self-associating fluids, the following com-
respectively. The expressions for the contribution from the ideal bining rules were used for the NRHB model,10
Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008 5653
Table 1. NRHB Pure-Component Parameters and Deviation in the Correlation of Vapor-Pressure and Saturated Liquid-Density Data
h* s* *
sp,0 EH SH % AADb %AADb
fluid (J mol-1) (J mol-1 K-1) (cm3 g-1) s (J mol-1) (J mol-1 K-1) Nsitesassoca Psat Fliq Tr ref.
n-hexane 3957.1 1.6580 1.27753 0.857 1.1 0.5 0.51-0.97 12
n-heptane 4042.0 1.7596 1.25328 0.850 0.5 0.5 0.52-0.97 12
n-octane 4105.3 1.8889 1.23687 0.844 0.7 0.4 0.53-0.97 12
n-tetradecane 4306.8 2.2030 1.18931 0.826 1.3 0.3 0.58-0.97 12
n-hexadecane 4339.0 2.2657 1.18135 0.823 1.6 0.3 0.54-0.97 12
cyclohexane 4469.2 1.8391 1.19596 0.801 0.6 1.9 0.53-0.97 12
ethylcyclohexane 4402.3 2.3146 1.17802 0.800 0.8 1.6 0.50-0.98 this work
benzene 5148.5 -0.2889 1.06697 0.753 0d-2a 1.7 0.5 0.52-0.97 12
ethylbenzene 5024.8 0.3985 1.05355 0.763 0d-2a 1.3 1.3 0.50-0.87 10
methanol 4202.3 1.5269 1.15899 0.941 -25100 -26.5 1d-1a 2.2 2.6 0.52-0.97 12
ethanol 4378.5 0.7510 1.15867 0.903 -24000 -27.5 1d-1a 1.8 1.1 0.54-0.97 10
1-butanol 4463.1 1.1911 1.13403 0.867 -24000 -27.5 1d-1a 0.2 0.5 0.55-0.97 10
1-pentanol 4471.7 1.55212 1.12869 0.857 -24000 -27.5 1d-1a 1.4 0.4 0.55-0.97 10
water 5336.5 -6.5057 0.97034 0.861 -16100 -14.7 2d-2a 1.3 2.0 0.45-0.99 10
ethylene glycol (MEG) 5800.9 0.8653 0.84239 0.933 -22500 -27.5 2d-2a 2.8 1.8 0.52-0.92 this work
1,2-propylene glycol (1,2-PG) 5088.8 1.0526 0.84239 0.903 -22500 -27.5 2d-2a 5.0 0.7 0.52-0.92 this work
diethylene glycol (DEG) 5518.4 1.8177 0.84161 0.892 -22500 -27.5 2d-2a 0.4 0.3 0.52-0.92 this work
triethylene glycol (TEG) 5371.5 2.0918 0.81214 0.872 -22500 -27.5 2d-2a 1.6 0.9 0.52-0.92 this work
d ) donor and a ) acceptor. b
%AAD ) (100/n) (Xical - Xiexp) Xiexp where n is the number of data points and X represents vapor pressure, Psat,
or saturated liquid density, Fliq.

Table 2. sPC-SAFT Pure-Component Parameters and Deviation in the Correlation of Vapor-Pressure and Saturated Liquid-Density Data
fluid m () /k (K) AB/k (K) AB c Nsitesassoc %AADa Psat %AADa VL,sat Tr ref.
n-hexane 3.0576 3.7983 236.77 0.3 0.8 0.35-0.99 6
n-heptane 3.4831 3.8049 238.40 0.3 2.1 0.34-1.15 6
n-octane 3.8176 3.8373 242.78 0.8 1.6 0.38-1.00 6
n-tetradecane 5.9002 3.9396 254.21 4.8 1.3 0.40-1.00 6
n-hexadecane 6.6485 3.9552 254.70 4.9 0.7 0.40-1.00 6
cyclohexane 2.5303 3.8499 278.11 0.5 3.1 0.50-1.00 6
ethylcyclohexane 2.8256 4.1039 294.04 2.4 1.0 0.35-1.00 6
benzene 2.4653 3.6478 287.35 1b 0.6 1.4 0.49-1.00 6
ethylbenzene 3.0799 3.7974 287.35 1b 0.4 1.1 0.29-1.00 6
methanol 1.5255 3.2300 188.90 2899.5 0.06718 2 2.4 2.0 0.39-0.99 39
ethanol 1.2309 4.1057 316.91 2811.02 0.00633 2 1.1 2.2 0.50-0.90 40
1-butanol 2.3983 3.7852 276.90 2811.02 0.00633 2 2.2 0.5 0.50-0.90 40
1-pentanol 2.6048 3.9001 282.31 2811.02 0.00633 2 2.9 0.3 0.50-0.90 40
water 1.5000 2.6273 180.30 1804.22 0.18000 4 0.9 2.6 0.50-0.90 40
ethylene glycol (MEG) 1.9088 3.5914 325.23 2080.03 0.04491 4 0.6 1.6 0.50-0.89 this work
1,2-propylene glycol (1,2-PG) 0.04491 3.6351 284.62 2080.03 0.04491 4 2.1 1.4 0.45-0.80 this work
diethylene glycol (DEG) 3.0582 3.6143 310.29 2080.03 0.04491 4 0.7 0.2 0.49-0.63 this work
triethylene glycol (TEG) 3.1809 4.0186 333.17 2080.03 0.04491 4 1.5 0.4 0.48-0.70 this work
a b c
For the % AAD definition, see the footnote of Table 1. Only solvation with water or glycols. Note that AB values in ref 40 are in fact AB/6.

( ) mixtures. Mixtures of water with linear alkanes, cycloalkanes,

13 13 3
EHi + EHj SHi + SHj
EHij ) , SHij ) (13) and aromatic hydrocarbons were studied. Experimental data
2 2
were taken from the literature.16,17 Results are summarized
and for sPC-SAFT,10 in Tables 3 and 4 for NRHB and sPC-SAFT, respectively.
AiBi + AjBj Two correlations were performed for each mixture. In the
AiBj ) , AiBj ) AiBiAjBj (14) first, the binary interaction parameter was fitted to the
4.1. Water-Hydrocarbon Mixtures. Initially, the two experimental data for both phases. However, the solubility
theories were applied to describe the LLE of water-hydrocarbon of hydrocarbons in water is very low, while in many industrial
Table 3. NRHB Calculations for LLE of Water-Hydrocarbon (HC) Mixtures
prediction (kij ) 0) kij fitted to HC rich phase kij fitted to both phases
HC in water water in HC HC in water water in HC HC in water water in HC
mixture T (K) ref. % AADa % AADa kij % AADa % AADa kij % AADa % AADa
n-hexane-water 280-480 16 >100 97.5 0.1879 53.4 4.2 0.1683 32.6 6.6
n-octane-water 280-520 17 >100 86.7 0.1769 47.9 5.9 0.1641 32.4 7.2
cyclohexane-water 280-510 16 >100 >100 0.2096 75.2 9.8 0.1468 24.3 23.8
ethylcyclohexane-water 280-540 17 >100 93.4 0.1717 70.2 6.7 0.1359 34.2 13.1
benzene-water 280-540 16 83 56.0 -0.1512 >100 10.7 0.0342 25.1 62.1
0.0812b 17.9 5.0 0.0812b 17.9 5.0
ethylbenzene-water 280-540 17 >100 33.3 -0.0717 >100 13.0 0.0576 17.7 47.7
0.1013b 17.5 3.6 0.1013b 17.5 3.6
total >100 82.4 47.0b 5.9b 26.5b 9.9b
For the % AAD definition, see the footnote of Table 1. b
Solvation was accounted for water-aromatic hydrocarbon mixtures, E12HB ) -6900 J
mol-1, fitted to experimental data.
5654 Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008

Table 4. sPC-SAFT Calculations for LLE of Water-Hydrocarbon (HC) Mixtures

prediction (kij ) 0) kij fitted to HC rich phase kij fitted to both phases
HC in water water in HC HC in water water in HC HC in water water in HC
mixture T (K) ref. % AADa % AADa kij % AADa % AADa kij % AADa % AADa
n-hexane-water 280-480 16 >100 12.3 0.025 >100 5.0 0.0571 32.1 15.3
n-octane-water 280-520 17 >100 22.8 0.037 >100 3.9 0.0609 31.5 11.6
cyclohexane-water 280-510 16 >100 25.8 0.044 >100 4.4 0.0692 19.0 15.9
ethylcyclohexane-water 280-540 17 >100 10.7 -0.018 >100 6.0 0.0533 36.3 32.3
benzene-water 280-540 16 >100 67.8 -0.15 >100 30.8 0.0273 26.6 72.7
0.048b,1 37.5 17.5 0.059b,2 22.6 19.2
ethylbenzene-water 280-540 17 >100 56.1 -0.04 >100 45.0 0.025 19.1 62.6
0.039b,3 45.3 10.2 0.046b,4 17.8 18.3
total >100 32.6 >100b 7.8b 26.6b 18.7b
For the % AAD definition, see the footnote of Table 1. b Solvation was accounted for water-aromatic hydrocarbon mixtures: (1) ) 0.1780, (2)
) 0.1728, (3) ) 0.1833, and (4) ) 0.1466, fitted to experimental data.

SAFT, the association volume, , was calculated by fitting the

experimental data while the association energy, AiBj, was set equal
to one-half of waters self-association energy. The results for the
benzene-water mixture are illustrated in Figure 2. It is obvious
that predictions and correlations fail if solvation is not accounted
for. On the other hand, both models yield satisfactory correlations
when solvation is taken into account.
An alternative approach is the explicit introduction of polar
interactions in the model to account for aromatic hydrocarbon
-electron-water interactions. Recently, Economou and co-
workers proposed PC-Polar SAFT (PC-PSAFT) where
dipole-dipole, quadrupole-quadrupole, and dipole-quadrupole
interactions were calculated using appropriate terms.20,21 PC-
PSAFT was shown to be superior over SAFT and over PC-
SAFT (without solvation interactions) for the correlation of
Figure 1. n-Hexane-water LLE, experimental data16 (points) and model water-hydrocarbon mixtures.22 It remains to be seen whether
calculations (lines).

applications, the accurate correlation of the water solubility

in hydrocarbons is needed.18 Subsequently, in the second
correlation, the binary interaction parameter was fitted only
to experimental data for the hydrocarbon rich phase (water
Both models perform satisfactorily for n-alkane-water
mixtures considering the complexity of such mixtures, using a
binary interaction parameter. sPC-SAFT yields more accurate
predictions (kij ) 0) in the LLE of water with linear alkanes
and cycloalkanes, while NRHB yields more accurate correla-
tions. Typical results for the n-hexane-water mixture are
presented in Figure 1.
The largest deviations between experimental data and cor-
mixtures. The solubility of aromatic hydrocarbons in water is at
least 1 order of magnitude higher compared to the solubility of
normal alkanes. This should be attributed to the weak interaction
of water molecules due to the -electrons of the aromatic ring. In
order to account for this effect, solvation was considered in both
models and the aromatic ring was assumed to act as a proton-
acceptor site that could associate with the proton donors of water
molecules. This assumption is based on experimental measurements
and theoretical calculations showing that, for pure benzene at low
temperatures, one of the most energetically favorable conformations
consists of molecules lining up perpendicular to one another rather
than parallel.19 A proton of a given molecule points directly to the
center of another ring, indicating a weak hydrogen bonding
interaction. For the application of the NRHB model, the association
energy for the water-benzene cross-interaction, EijH, was calculated
by fitting the theory to the experimental data. The corresponding
association entropy, SijH, was set equal to one-half of waters self- Figure 2. Benzene-water LLE, experimental data16 (points) and models
association entropy. In a similar way, for the application of sPC- calculations (lines): (a) NRHB and (b) sPC-SAFT.
Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008 5655
Table 5. Calculations for LLE of 1-Alkanol-Hydrocarbon Mixtures
alkanol in HC HC in alkanol alkanol in HC HC in alkanol
mixture T (K) ref. kij % AADa in x1 % AADa in x1 kij % AADa in x1 % AADa in x1
ethanol (1)-n-tetradecane (2) 279.96-307.81 41 0.0180 8.3 5.4 -0.0065 11.9 11.0
ethanol (1)-n-hexadecane (2) 298.66-326.98 41 0.0207 8.2 6.5 -0.0040 11.3 10. 9
methanol (1)-n-hexane (2) 245.15-306.51 23 0.0304 13.3 6.0 0.0254 23.4 4.6
methanol (1)-n-heptane (2) 291.15-323.15 23 0.0320 42.0 1.4 0.0255 10.5 2.7
methanol (1)-cyclohexane (2) 280.05-318.93 23, 24 0.0250 23.7 11.4 0.0365 14.9 7.6
total 19.1 6.2 14.4 7.4
For the % AAD definition, see the footnote of Table 1.

Figure 4. Methanol-n-hexane LLE and VLE, experimental data23,25 (points)

Figure 3. Ethanol-n-tetradecane LLE, experimental data41 (points) and and model correlations (lines).
model correlations (lines).
presented in Figures 5 and 6 for water-1-butanol and water-1-
the explicit polar terms or a solvation term result in more pentanol, respectively. Both models exhibit similar behavior in
accurate representation of these highly complex phase equilibria. the water-1-butanol mixture: if the 1-butanol rich phase is
4.2. 1-Alkanol-Hydrocarbon Mixtures. Alkanols are among correlated with low deviations, then the deviations increase for
the most important self-associating fluids for industry. Subse- the water rich phase and vice versa. In this mixture, NRHB
quently, the accurate description of phase equilibria in such performs better in LLE, while sPC-SAFT yields more accurate
mixtures is of great importance. In this work, the models were predictions for VLE. Lower deviations from experimental data
applied to describe the LLE of 1-alkanol-hydrocarbon mixtures. were obtained for both models in the correlation of water-1-
Results are summarized in Table 5. pentanol phase equilibria. sPC-SAFT yields more accurate
Initially, the LLE of ethanol with higher n-alkanes, such as correlations for LLE, while NRHB yields more accurate
n-tetradecane and n-hexadecane, was investigated. In these predictions for VLE.
mixtures, NRHB yields more accurate correlations, while both 4.4. Glycol-Hydrocarbon Mixtures. Modeling of glycols
models overestimate the critical solution temperature. Charac- is a challenging task because of the complexity of their molecules.
teristic results for the ethanol-n-tetradecane are illustrated in Recently, sPC-SAFT was successfully used for the correlation of
Figure 3. VLE and LLE of glycol-hydrocarbon mixtures.28 In that work,
Furthermore, the models were used to correlate the phase glycol molecules were modeled assuming that they have four
equilibria of methanol-n-alkane mixtures. Experimental data association sites (two proton donors and two proton acceptors
were obtained from the literature.2326 Such mixtures exhibit known as 4C scheme according to Huang and Radosz29). This
LLE at lower temperatures and VLE at higher temperatures. approach does not account for the complex hydrogen bonding
For both models, a binary interaction parameter was optimized behavior that often is observed in such mixtures (i.e., intramolecular
to LLE data23,24 and then was used to predict the VLE data.2527 hydrogen bonding), but it could be very useful in the modeling of
For the LLE correlation, NRHB is more accurate for the phase equilibria for the rational design of many chemical and
methanol-n-hexane mixture, while sPC-SAFT is superior for petrochemical applications.
methanol mixtures with n-heptane and cyclohexane. Further- Using a similar approach, in this work, the phase equilibria
more, both models yield accurate predictions for the VLE. of n-heptane mixtures with monoethylene glycol (MEG), dieth-
Results for the VLE calculations are presented in Table 6, while ylene glycol (DEG), triethylene glycol (TEG), and 1,2-propylene
calculations for a characteristic mixture, namely, methanol-n- glycol (1,2-PG) was investigated. Experimental data were obtained
hexane, are illustrated in Figure 4. from Derawi et al.30 As is presented in Table 7, both models yield
4.3. Water-1-Alkanol Mixtures. Cross-association occurs satisfactory correlations considering the complexity of these
in water-alkanol mixtures, rendering the description of their mixtures. However, NRHB yields better correlations than PC-SAFT
phase behavior as a challenging task for thermodynamic models. in most cases. Using a small value for the binary interaction
In this work, the models were used to describe the phase parameter, AAD lower than 20% can be obtained for both glycol
equilibria of water-1-butanol and water-1-pentanol mixtures. and heptane rich phase for MEG, DEG, and 1,2-PG. However,
Again, one binary interaction parameter was optimized to LLE relatively higher deviations occur for TEG. sPC-SAFT performs
data, and then it was used to predict the VLE data. Results are better in the DEG-n-heptane system, while NRHB yields more
5656 Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008

Figure 5. Water-1-butanol LLE and VLE, experimental data23 (points) Figure 7. MEG-n-heptane LLE, experimental data30 (points) and model
and model correlations (lines). correlations (lines).

5. Monomer Fractions of Associating Fluids

The sPC-SAFT model is based on Wertheims theory14 and
explicitly accounts for hydrogen bonding. In the basic equations
of the model, the fraction of molecules nonbonded at a given site
A, XA, is incorporated. In general, this quantity is not identical to
the monomer fraction. However, the latter can be easily calcu-
lated;31 e.g., for the 2B scheme (one proton-donor and one proton-
acceptor site following the terminology of Huang and Radosz29),
it is equal to XA2, and for 4C, it is equal to XA4, if all sites are
assumed to be identical.
On the other hand, the NRHB model uses a hydrogen bonding
term, which was proposed by Panayiotou and Sanchez32 and
was used in the LFHB model.32,33 According to this approach,
the number of ways of distributing the hydrogen bonds among
the different proton donors and proton acceptors of the mixture
Figure 6. Water-1-pentanol LLE and VLE, experimental data23 (points) is calculated. Nevertheless, even if the number of hydrogen
and model correlations (lines).
bonds in the mixture is known, calculation of the number of
bonded molecules is not a straightforward issue. In other words,
accurate correlations in all other investigated mixtures. Character- for a certain number of hydrogen bonds, the number of bonded
istic results for MEG-n-heptane are presented in Figure 7. (or unbonded) molecules may vary. In order to obtain the

Table 6. Calculations for VLE of 1-Alkanol-Hydrocarbon Mixtures

mixture ref. T (K) kij y a T a (K) kij y a T a (K)
methanol (1)-n-hexane (2) 25 245.15-306.51 0 0.1199 5.25 0.0304 0.0512 2.18
methanol (1)-n-heptane (2) 26 291.15-323.15 0 0.0601 5.53 0.0320 0.0303 1.84
methanol (1)-cyclohexane (2) 27 280.05-318.93 0 0.0477 3.59 0.0250 0.0137 0.82
total 0.0759 4.79 0.0317 1.61
methanol (1)-n-hexane (2) 25 245.15-306.51 0 0.9500 4.66 0.0254 0.0336 1.93
methanol (1)-n-heptane (2) 26 291.15-323.15 0 0.0366 4.25 0.0255 0.0112 1.43
methanol (1)-cyclohexane (2) 27 280.05-318.93 0 0.0607 4.80 0.0365 0.0120 1.50
total 0.3491 4.57 0.0189 1.62
z ) 1/n |zicalc - ziexp| where n is the number of data points and z represents T or y.

Table 7. NRHB and sPC-SAFT Calculations for Glycol-Hydrocarbon LLE

HC in glycol glycol in HC HC in glycol glycol in HC
mixture ref T (K) kij % AADa in x2 % AADa in x1 kij % AADa in x2 % AADa in x1
MEG (1)-n-heptane (2) 30 315.95-351.85 0.0566 7.7 16.1 0.0400 16.9 20.3
1,2-PG (1)-n-heptane (2) 30 308.05-342.05 0.0166 6.5 8.5 0.0100 11.2 10.3
DEG (1)-n-heptane (2) 30 312.75-353.05 0.0514 7.2 10.6 0.0320 5.6 8.3
TEG (1)-n-heptane (2) 30 309.35-350.95 0.0573 3.7 45.9 0.0450 29.1 50.0
total 6.3 20.3 15.7 22.2
For the % AAD definition, see the footnote of Table 1.
Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008 5657

Figure 9. Fraction of non-hydrogen bonded molecules in n-hexane-1-

alkanol mixtures; experimental data34,38 (points), NRHB (solid lines), and
sPC-SAFT predictions (dashed lines) for mixtures of n-hexane with (a)
methanol and (b) ethanol.

number of bonded (or unbonded) molecules, the type of

oligomers that are present in the mixture must be known. In
that direction, Economou and Donohue31 assumed the formation
of linear oligomers for alkanols and obtained an equation for
the number of unbonded molecules. They showed that the quasi-
chemical approach followed by Panayiotou and Sanchez,32
which is incorporated in the NRHB model, and Wertheims
theory, which is used in the sPC-SAFT model, lead to
expressions that are of the same functional form for pure
components and for mixtures.31
In the modeling of alkanols, usually two hydrogen bonding
sites are assumed (i.e., one proton donor and one proton
acceptor). According to the aforementioned approach, the
fraction of unbonded molecules is obtained from the following
X1 ) (15)
1 + 2FK + 1 + 4FK
where F is the density and

K ) AiBj (16)
for sPC-SAFT, while

( )
K ) exp (17)
r RT
for NRHB.
The fact that both models, despite that they are based on
different approaches, result in similar equations for the extent
Figure 8. Fraction of non-hydrogen bonded molecules in pure 1-alkanols; of hydrogen bonding makes the comparison of their predictions
experimental data3537 (points), NRHB (solid lines), and sPC-SAFT an interesting task. In this work, we present the predictions of
predictions (dashed lines) for (a) methanol, (b) ethanol, (c) 1-propanol, and
(d) 1-octanol. the models for the monomer (unboded molecules) fraction in
5658 Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008

pure alkanols and alkanol-n-alkane mixtures. Experimental data than sPC-SAFT, and this should be related to the better
based on spectroscopic studies were taken from the literature.3438 performance of this model for the LLE of the same system.
For the application of sPC-SAFT, we assumed for all alkanols The results presented here (and also in the first paper of this
the 2B association scheme (terminology that refers to the work series10) show clearly that the two advanced models can be used
of Huang and Radosz29). In a similar manner, for the application successfully for a wide range of fluid-phase equilibria calcula-
of the NRHB theory, we assumed one proton-donor and one tions. Despite their different initial points (i.e., lattice fluid theory
proton-acceptor site per alkanol molecule. for NRHB and Wertheims first-order thermodynamic perturba-
As presented in Figure 8a, both models underestimate the tion theory for sPC-SAFT), they yield satisfactory and often
monomer fraction for pure methanol, while NRHB performs very similar results for various hydrogen bonding mixtures.
better than sPC-SAFT. On the other hand, both models perform However, for specific mixtures, one model may perform better
satisfactorily in predicting the monomer fraction for ethanol, than the other. Work is underway in, among others, evaluating
1-propanol, and 1-octanol (Figure 8 parts b-d, respectively). the models in the description of the phase behavior in polymer
However, a trend to underestimate the fraction of monomers is systems.
The models were also applied to predict the monomer
fractions in 1-alkanol-n-hexane mixtures. Predictions were Acknowledgment
compared with the experimental data of Asprion et al.,34 who The authors are grateful to the Danish Research Council for
published a systematic study for this kind of mixtures. In Technology and Production Sciences for financial support of
methanol-n-hexane (Figure 9a), both models underestimate the this work as part of the project Advanced Thermodynamic
monomer fraction, in a similar way as observed in pure Tools for Computer-Aided Product Design.
methanol. However, NRHB clearly yields better predictions than
sPC-SAFT, a result that is in line with the superiority of the
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