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4 vizualizări19 paginiCalculations and predictions of excess enthalpy (HE) and vapor-liquid equilibrium
(VLE) were performed using the Gibbs energy mixing rules MHV2 and a modification of it by Soave. The Soave-Redlich-Kwong equation of state was combined with
the UNIQUAC equation. Four sets of parameters estimated in the UNIQUAC model
were used for each of seven binary systems: the first estimated from VLE data, the
second and the third estimated from HE data for two versions of the UNIQUAC
equation, and the fourth estimated from both HE and VLE data simultaneously.
It was found that HE calculations can be performed with the mixing rules; the average
relative errors fell from around 200% for the conventional mixing rule to around 60%
for MHV2 combined with DECHEMA UNIQUAC parameters and was as little as
20% when the UNIQUAC parameters had been estimated from HE and VLE data
simultaneously. However, the approach suffers from the same shortcomings as far
as cross-prediction between HE and VLE data is concerned, as does the UNIQUAC
equation used alone. There is a discrepancy between values obtained with the mixing
rule and those obtained with the UNIQUAC equation directly. This discrepancy is
smaller for the Soave modification of the mixing rule.

Nov 09, 2018

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Calculations and predictions of excess enthalpy (HE) and vapor-liquid equilibrium
(VLE) were performed using the Gibbs energy mixing rules MHV2 and a modification of it by Soave. The Soave-Redlich-Kwong equation of state was combined with
the UNIQUAC equation. Four sets of parameters estimated in the UNIQUAC model
were used for each of seven binary systems: the first estimated from VLE data, the
second and the third estimated from HE data for two versions of the UNIQUAC
equation, and the fourth estimated from both HE and VLE data simultaneously.
It was found that HE calculations can be performed with the mixing rules; the average
relative errors fell from around 200% for the conventional mixing rule to around 60%
for MHV2 combined with DECHEMA UNIQUAC parameters and was as little as
20% when the UNIQUAC parameters had been estimated from HE and VLE data
simultaneously. However, the approach suffers from the same shortcomings as far
as cross-prediction between HE and VLE data is concerned, as does the UNIQUAC
equation used alone. There is a discrepancy between values obtained with the mixing
rule and those obtained with the UNIQUAC equation directly. This discrepancy is
smaller for the Soave modification of the mixing rule.

© All Rights Reserved

4 vizualizări

00 voturi pozitive00 voturi negative

Calculations and predictions of excess enthalpy (HE) and vapor-liquid equilibrium
(VLE) were performed using the Gibbs energy mixing rules MHV2 and a modification of it by Soave. The Soave-Redlich-Kwong equation of state was combined with
the UNIQUAC equation. Four sets of parameters estimated in the UNIQUAC model
were used for each of seven binary systems: the first estimated from VLE data, the
second and the third estimated from HE data for two versions of the UNIQUAC
equation, and the fourth estimated from both HE and VLE data simultaneously.
It was found that HE calculations can be performed with the mixing rules; the average
relative errors fell from around 200% for the conventional mixing rule to around 60%
for MHV2 combined with DECHEMA UNIQUAC parameters and was as little as
20% when the UNIQUAC parameters had been estimated from HE and VLE data
simultaneously. However, the approach suffers from the same shortcomings as far
as cross-prediction between HE and VLE data is concerned, as does the UNIQUAC
equation used alone. There is a discrepancy between values obtained with the mixing
rule and those obtained with the UNIQUAC equation directly. This discrepancy is
smaller for the Soave modification of the mixing rule.

© All Rights Reserved

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EQUILIBRIA WITH THE MHV2 AND SOAVE

MIXING RULES

a a

Åsa U. Burman & Krister H. U. Ström

a

Department of Chemistry and Biological Engineering , Chalmers

University of Technology , Göteborg, Sweden

Published online: 21 Jun 2011.

To cite this article: Åsa U. Burman & Krister H. U. Ström (2011) EXCESS ENTHALPY AND VAPOR-

LIQUID EQUILIBRIA WITH THE MHV2 AND SOAVE MIXING RULES, Chemical Engineering Communications,

198:11, 1435-1452, DOI: 10.1080/00986440903287874

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Chem. Eng. Comm., 198:1435–1452, 2011

Copyright # Taylor & Francis Group, LLC

ISSN: 0098-6445 print=1563-5201 online

DOI: 10.1080/00986440903287874

with the MHV2 and Soave Mixing Rules

Department of Chemistry and Biological Engineering, Chalmers

Downloaded by [Memorial University of Newfoundland] at 20:44 11 November 2013

(VLE) were performed using the Gibbs energy mixing rules MHV2 and a modifi-

cation of it by Soave. The Soave-Redlich-Kwong equation of state was combined with

the UNIQUAC equation. Four sets of parameters estimated in the UNIQUAC model

were used for each of seven binary systems: the first estimated from VLE data, the

second and the third estimated from HE data for two versions of the UNIQUAC

equation, and the fourth estimated from both HE and VLE data simultaneously.

It was found that HE calculations can be performed with the mixing rules; the average

relative errors fell from around 200% for the conventional mixing rule to around 60%

for MHV2 combined with DECHEMA UNIQUAC parameters and was as little as

20% when the UNIQUAC parameters had been estimated from HE and VLE data

simultaneously. However, the approach suffers from the same shortcomings as far

as cross-prediction between HE and VLE data is concerned, as does the UNIQUAC

equation used alone. There is a discrepancy between values obtained with the mixing

rule and those obtained with the UNIQUAC equation directly. This discrepancy is

smaller for the Soave modification of the mixing rule.

equilibria

Introduction

The last decade, new Gibbs energy mixing rules for cubic equations of state (GE-eos

models) have been developed (Huron and Vidal, 1979; Dahl and Michelsen, 1990;

Holderbaum and Gmehling, 1991; Wong and Sandler, 1992). With these, a mixture

parameter is obtained through a formal match between the expression for Gibbs

excess energy (GE) from the equation of state and that from a GE model (or activity

model). The mixing rules have proven to work excellently in calculations of

vapor-liquid equilibrium (VLE), even for mixtures containing polar compounds.

The aim of this study is to investigate if they can be used successfully in excess

enthalpy calculations. The issue is of both practical and theoretical interest. As HE

is related to the temperature dependency of phase equilibria, simultaneous compu-

tation of VLE and HE may be seen as a test of the thermodynamic consistency of

the model. The influence of the approximating equation, the GE model parameters,

Biological Engineering, Chalmers University of Technology, SE-412 96 Göteborg, Sweden.

E-mail: krister@chalmers.se

1435

1436 Å. U. Burman and K. H. U. Ström

and the parameters that describe the temperature dependence for the pure

component will be addressed. The investigation includes a comparison with the

conventional van der Waals one-fluid mixing rule, as a reference to a typical

engineering situation.

Two GE mixing rules with reference pressure zero are used in this study:

. MHV2 (Dahl and Michelsen, 1990), which is simple and much discussed.

. A modification by Soave (1992) of MHV2 that was designed to give a mixing rule

that was asymptotically correct as the temperature approaches infinity.

The equation of state chosen for this study is the Soave-Redlich-Kwong (SRK,

Downloaded by [Memorial University of Newfoundland] at 20:44 11 November 2013

Soave (1972)) with an expression for the temperature dependency of the energy para-

meter (a) from Mathias and Copeman (1983). This has been the most frequently used

equation in other MVH2 studies. The UNIQUAC equation (universal quasi chemi-

cal, Abrams and Prausnitz (1975)) is used as the GE model. Calculations were carried

out for seven binary systems with four parameter sets regressed in the UNIQUAC

model: one from the DECHEMA data series (Gmehling et al., 1977–1996) estimated

from VLE data, two estimated from HE data in two versions of the UNIQUAC

equation, and one estimated from HE and VLE data simultaneously. The binary

systems were chosen so that different kinds of HE behavior would be represented.

Systems for which there were both VLE and HE data available at two (or more)

temperatures in the DECHEMA data collection series (Christensen et al., 1984–

1991; Gmehling et al., 1977–1996) were preferred.

Theory

Vapor-liquid equilibrium can be modeled by two different approaches. With an

equation of state, the same model is used for both the liquid and the vapor phase.

The other approach uses a GE model for the liquid phase and an equation of state

(such as the ideal gas law) for the gas phase.

When an equation of state is used for calculations of properties for mixtures, the

model parameters are computed using a mixing rule. The most common one is the

van der Waals one-fluid mixing rule (also called the conventional or the classical):

XX pﬃﬃﬃﬃﬃﬃﬃﬃ

a¼ xi xj aij aij ¼ ai aj ð1 kij Þ

i j

XX bi þ b j ð1Þ

b¼ xi xj bij bij ¼ ð1 lij Þ

i j

2

These mixing rules have a sound theoretical background and they have proven to

work well for mixtures that can be described by regular solution theory. When used

with a cubic equation of state, they cannot handle mixtures with polar compounds

nor mixtures for which there is a large difference in molecular size or critical tem-

perature (Sandler et al., 1994). With the Peng-Gasem-Robinson (PGR) segment-

segment interaction equation of state, asymmetric mixtures can be modeled applying

one-fluid mixing rules (Row et al., 2008). For HE calculations, the classical mixing

rules tend to be unreliable, and the results are extremely sensitive to the value of

the binary interaction parameter kij (Christensen and Rowley, 1988). In this study,

one interaction parameter kij ¼ kji will be estimated and used. The lij ¼ lji parameter

HE and VLE with MHV2 and Soave 1437

will be set to zero. A more elaborate version could have been applied. However, the

intention was not to investigate the possibilities of the van der Waals mixing rules,

but rather to use them as a reference to an ordinary engineering situation.

For polar systems at low pressure, GE models give a good representation of VLE.

Cross-prediction, that is prediction of VLE data from a GE model fitted to HE data or

vice versa, is typically not reliable or quantitative (Christensen and Rowley, 1988).

However, satisfactory results have been obtained for some systems (Pando et al.,

1983). With simultaneous regression of VLE and HE data, both properties can be

modeled (Burman and Ström, 2007; Kundu and Bandyopadhyay, 2007). This

approach has been applied even to solid liquid equilibrium and enthalpy in ice slurries

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(Cézac et al., 2009). As one model is used for the liquid phase and another for the gas

phase, problems arise when the GE models are to be used near the critical point. The

GE mixing rules were developed as an attempt to incorporate the information

contained in the GE model into a cubic equation of state. The basic idea behind rules

like MHV2 is to match the GE expression from the equation of state, at zero pressure,

with GE from a GE model. In order to obtain an explicit expression for the a

parameter, an approximating equation q(a) is applied. The dimensionless parameter

a is equal to a=bRT. For MHV2 it is a second-order polynomial expression

q(a) ¼ q0 þ q1a þ q2a2, where q1 ¼ 0.478 and q2 ¼ 0.0047. That is:

! !

X X GE X b

2

q1 a zi aii þ q2 a zi a2ii ¼ þ zi ln ð2Þ

i i

RT i

b ii

Dahl and Michelsen (1990) found that MHV2 was successful in VLE calculations for

polar compounds using the UNIQUAC equation with parameters from DECHEMA

or the UNIFAC method. The model performed well in liquid-liquid (LLE) and

vapor-liquid-liquid equilibria (VLLE) calculations, provided that the GE model

gave a correct representation of the system (Dahl et al., 1991; Abdel-Ghani and

Heidemann, 1996). MHV2 has been applied to VLE and LLE predictions for solu-

tions containing a salt. Again, the results depend heavily on the GE model (Dahl and

Macedo, 1992). It could also successfully correlate VLE and VLLE of near-critical

and supercritical carbon dioxide-methanol-water (Yoon et al., 1993). The mixing

rule has been used for predictions of gas solubilities, Henry’s law coefficients, and

c1 (Dahl et al., 1991).

However, some serious criticism has been raised against the zero-pressure mixing

rules. Orbey and Sandler (1995) criticize them because they do not produce second

virial coefficients that are quadratic in compositional dependency; a known bound-

ary condition should be regarded and this violation will affect the fugacity coeffi-

cients computed for the vapor phase. One problem with MHV2 is that the fitting

of GEs for the liquid phase influences the vapor phase calculations too much, pro-

ducing too high GEs for that phase (Michelsen and Heidemann, 1996).

Several studies on extrapolation of VLE from low-pressure data to high pres-

sures have been presented. The MHV1 mixing rule (with a first-order linear approxi-

mation as approximating equation) was found to handle extrapolations better than

MHV2 (Fischer and Gmehling, 1996). It was puzzling that the first-order approxi-

mation, MHV1, produces better extrapolations than the second-order approxi-

mation, MHV2. Michelsen (1996) found that a very common inadequacy in the

temperature dependence of the GE models happens to be canceled out partially by

1438 Å. U. Burman and K. H. U. Ström

the lack of fit between the true q(a) and that computed with MHV1 at high tempera-

tures. This discrepancy in match is smaller for MHV2. According to Heidemann

(1996) reliable extrapolations are possible only when the GE model is accurate in

the temperature and pressure ranges of the extrapolation. Deviations between the

GE computed with the mixing rule and with the GE model are found to be caused

mainly by the approximating equation q(a) (Kalospiros et al., 1995). Plotting (@q=

@a) versus a, Kalospiros and coworkers visualized the problem. The MHV1 rule fits

only at a ¼ 13, the point it was fitted to, and the difference between the approximat-

ing equation and the real q(a) approaches infinity as the temperature approaches

infinity. Michelsen (1996) showed that if the difference in ai for the compounds in

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the mixture is large, i.e., for asymmetric systems, these errors quickly increase even

at ordinary temperatures.

According to the analysis of Kalospiros et al. (1995), an approximating equation

proposed by Soave (1992) resulted in an improved fit to the GE model. The Soave

q(a) expression is derived to be asymptotically correct when the temperature

approaches infinity:

qﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ

a lnð2Þ þ ða lnð2ÞÞ2 þ 69

qðaÞ ¼ 3:365 ð3Þ

2

Soave (1992) found that his expression performed as well in low-pressure VLE

calculations as did MHV2. For both MHV2 and Soave, a linear mixing rule is used

for the b parameter of the mixture.

The equation of state most frequently used in MHV2 studies is the SRK equation of

state:

RT a

P¼ ð4Þ

v b vðv þ bÞ

2 3 2

ðRTci Þ2 1=2 1=2 1=2

aii ¼ 0:4286 1 þ c1 1 Tri þ c2 1 Tri þc3 1 Tri ð5Þ

Pci

RTci

bii ¼ 0:08664 ð6Þ

Pci

The expression chosen for the temperature dependency of the a parameter was

proposed by Mathias and Copeman (1983). It is applied in order to ensure a good

representation of pure component vapor pressure data. Dahl and Michelsen

(1990) obtained the so called Mathias-Copeman parameters in Equation (5), c1,

c2, and c3, by fitting the equation of state to the vapor pressure correlations of

Daubert and Danner (1986). In the work presented here, the Mathias-Copeman

parameters were estimated from experimental vapor pressure data published by

Boublı́k et al. (1984). The ratio of the difference in experimental and calculated

pressure to the experimental pressure was minimized. The resulting parameters are

presented in Table I. The correlations between the parameters are very high.

HE and VLE with MHV2 and Soave 1439

Compound c1 c2 c3

Cyclohexane 0.788 0.021 0.251

1-Propanol 1.198 1.616 3.156

2-Methyl-1-propanol 1.083 2.033 2.926

Ethanol 1.374 0.591 2.188

Methanol 1.402 0.553 0.285

Water 1.057 0.465 0.345

Benzene 0.811 0.244 0.750

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Tetrachloromethane 0.785 0.215 0.588

Trichloromethane 0.841 0.390 0.827

The incorporated GE model was the UNIQUAC equation. For the original

UNIQUAC equation, the molecular structure constants r and q are obtained from

the DECHEMA data series (Gmehling et al., 1977–1996). Anderson and Prausnitz

(1978) modified the equation by introducing a new external area parameter, q0 , in

the residual part of the equation for water and lower alcohols. In calculations with

the Anderson modification of the UNIQUAC equation, the same r and q values as

for the original equation were used, and the q0 values were taken from Anderson and

Prausnitz (1978).

The VLE calculations were performed as bubble point calculations following the

algorithm given in van Ness and Abbott (1982). Expressions for the compositional

derivative of the a parameter are given in the appendix. The HE calculations are also

described in the appendix.

In order to compare the MHV2 mixing rule and the one proposed by Soave,

predictions of HE were made with UNIQUAC parameters obtained from the

DECHEMA series (called DECHEMA in the tables) for both mixing rules. With

the MHV2 mixing rule, calculations were also performed with UNIQUAC para-

meters estimated from HE data, both for the original UNIQUAC equation (called

HE in the tables) and for the Anderson modification (called Anderson in the tables).

The mixing rule proposed by Soave was also combined with UNIQUAC parameters

estimated from HE and VLE data simultaneously (called HEGE in the tables). The

UNIQUAC parameters are found in Table II, and the procedure for their estimation

is described elsewhere (Burman and Ström, 2007).

For calculations with the van der Waals mixing rule, kij parameters for the

binary mixtures were estimated from the experimental VLE data listed in

Table III. The difference in the square of the fugacity between the liquid and the

vapor phase was minimized. The modified Marquardt algorithm (Bard, 1974) was

used for the minimization. The initial estimate of kij was 0.01, but the parameter esti-

mation generally converged to the same kij value for initial kij values ranging from

0.1 to 0.1. The resulting values for the kij parameter are found in Table III. The lar-

gest root mean square deviation (RMSD) of the fugacity differences between the

phases was observed for acetone-water. This was expected for a system with a large

difference in pure component covolume (bii) parameters (see, for example, Knudsen

et al. (1993)). For the other systems, the fit is closer but there are definite trends in

the residuals. In the tables for the results, results from the van der Waals mixing rule

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Model= Cyclohexane-1- Acetone- tetrachloro- trichloro- methyl-1- Methanol- Ethanol-

system Parameter propanol water methane methane propanol water water

DECHEMA n 12 [J=mol] 3894 1747 713.2 2974 2691 1375 547.8

n 21 [J=mol] 835.0 177.6 2010 4668 367.3 2119 381.7

Original W12 [J=mol] 5349 1907 2156 1350 14975 3315 5058

UNIQUAC W21 [J=mol] 5718 782.8 3027 1142 5035 3527 4822

HE l12 [J=mol K] 10.48 13.55 3.296 1.994 122.5 1.491 9.399

l21 [J=mol K] 17.16 21.43 3.371 5.869 3.584 7.301 18.33

1440

Anderson W12 [J=mol] 1.436 104 3150 1.499 104 3437 6625

modification W21 [J=mol] 3505 160.2 1937 3638 6715

l12 [J=mol K] 57.89 15.46 128.8 0.6222 15.12

l21 [J=mol K] 13.40 17.73 13.71 10.22 29.98

HEGE W12 [J=mol] 4085 2902 779.3 997.3 1723 1653 822.4

W21 [J=mol] 977.9 563.8 2146 22.18 98.44 2436 2190

l12 [J=mol K] 3.504 16.07 1.260 9.302 15.92 8.280 13.09

l21 [J=mol K] 2.914 12.20 1.776 4.486 7.868 28.91 35.06

For temperature-dependent parameters: n ij ¼ Wij þ lij(T T Ref). The reference temperature (T Ref) used was 300 K for all systems.

HE and VLE with MHV2 and Soave 1441

Table III. Binary interaction parameters for the van der Waals one-fluid mixing rule

and observed root-mean-square deviation of the objective function

Cyclohexane-1-propanol 0.072 0.09 Smirnova and Kurtynina, 1969

Acetone-water 0.251 0.21 Lieberwirth and Schubert, 1979

Acetone-tetrachloromethane 0.0566 0.03 Brown and Smith, 1957

Acetone-trichloromethane 0.061 0.01 Kudryavtseva and Susarev, 1963

Benzene-2-methyl-1-propanol 0.081 0.04 Brown et al., 1969

Methanol-water 0.082 0.02 Ratcliff and Chao, 1969

Downloaded by [Memorial University of Newfoundland] at 20:44 11 November 2013

were also performed in which kij was set to zero, referred to as kij ¼ 0 in the tables.

VLE and HE calculations were performed for seven binary mixtures and compared

to experimental data from the DECHEMA series (Christensen et al., 1984–1991;

Gmehling et al., 1977–1996). The systems chosen represent different HE behavior.

E

The endothermal systems are acetone-tetrachloromethane (HMax 300 J=mol), cyclo-

E E

hexane-1-propanol (HMax 700 J=mol), and benzene-2-methyl 1-propanol (HMax

E

1600 J=mol). For these, the H versus composition curve is moderately skewed. One

E

of the exothermal systems, acetone-trichloromethane (HMin 2000 J=mol), is fairly

E

symmetric, whereas the other, methanol-water (HMin 900 J=mol) is strongly

skewed (minimum at xmethanol 0.2). Acetone-water is exothermal at high water

contents and endothermal at low. The HE behavior of ethanol-water changes from

exothermal at low temperatures to endothermal at high temperatures.

It was possible to use the equation of state-GE mixing rule approach to calculate HE

data and to predict it from VLE data. The results of the calculations are presented in

Table IV as root mean square deviation (RMSD), which is defined as the square root

of the arithmetical average of the squared deviation between the experimental and

the calculated values. The HE curves predicted by MHV2 combined with

DECHEMA parameters are qualitatively correct; they typically reproduce the shape

of the curve, but the values are generally too low. Astonishingly, the shape of the

curve computed with MHV2 was often correct even when the UNIQUAC model

itself with the same parameters did not catch the HE behavior (Figure 1). MHV2

with DECHEMA parameters often gave HE values closer to the experimental values

than did the UNIQUAC model upon which MHV2-DECHEMA was based. The

phenomenon is most likely a fortunate cancellation of errors. Fischer and Gmehling

(1996) report a similar behavior for VLE calculations with the MHV1 and predictive

Soave-Redlich-Kwong (PSRK) mixing rules. Michelsen (1996) concludes that a com-

mon error in the temperature dependence of the GE mixing rule appears to be can-

celed out by errors in the mixing rule. The RMSD between HE calculated with the

equation of state-GE model and the GE model alone are given in Table V. Dahl

and Michelsen (1990) fitted the approximating equation q(a) in MHV2 to a values

ranging from 8 to 18. The a value for water at 25 C is above 18. As may be seen from

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Mixing rules

MixturenParameters kij ¼ 0 kij-VLE DECHEMA HE Anderson DECHEMA H EG E T [ C] Source

Ccyclohexane-1-propanol 0.28 1.4 0.38 0.48 0.08 0.24 0.05 25 III 1 570

0.21 1.2 0.44 0.34 0.06 0.40 0.19 50 III 1 572

Acetone-water 4.9 1.5 0.28 0.38 0.37 0.51 0.14 35 III 1 518

3.5 0.80 0.16 0.13 0.13 0.17 0.05 90 III 1 520

Acetone-tetrachloromethane 0.22 0.61 0.07 0.02 x 0.05 0.02 45 III 1 19

0.15 0.56 0.07 0.01 x 0.08 0.02 25 Fuchs et al., 1984

Acetone-trichloromethane 1.3 0.53 0.16 0.04 x 0.15 0.05 50 III 1 150

1.7 0.71 0.12 0.02 x 0.09 0.03 70 III 1 149

1442

Benzene-2-methyl-1-propanol 1.3 0.28 1.0 0.12 0.20 0.96 0.09 45 III 1 749

0.99 0.61 0.84 0.72 0.63 0.68 0.15 25 III 1 750

Methanol-water 2.0 0.89 0.40 0.05 0.06 0.51 0.04 25 III 1 304

2.0 0.75 0.28 0.08 0.10 0.38 0.06 53.5 III 1 305

Ethanol-water 2.2 0.65 0.19 0.09 0.10 0.26 0.06 70 III 1 458

2.9 1.2 0.59 0.19 0.25 0.74 0.09 25 III 1 457

1.8 0.33 0.09 0.19 0.18 0.10 0.15 110 III 1 459

Average 1.8 0.88 0.33 0.21 x 0.34 0.08

The Source column refers to the volume, part, and page number in the DECHEMA data series where the experimental data may be found. The

UNIQUAC parameters are found in Table II.

x ¼ the Anderson modification was not applicable for these systems.

HE and VLE with MHV2 and Soave 1443

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Figure 1. Excess enthalpy for acetone (1)-water (2) at 35 C. Experimental data (^) from

Belosouv and Sokolova (1966). With DECHEMA parameters the MHV2 mixing rule (solid

line) produces a better prediction than does the UNIQUAC equation (dashed line) used in

the mixing rule.

and the incorporated GE model are large for systems containing water.

When the MHV2 and the Soave mixing rules are compared, MHV2 appears to

be the better one. The arithmetical average of the RMSD from the experimental

values for all the data points in the study is 325 J=mol instead of 339 J=mol

(Table IV). However, the difference can be explained by the discrepancy described

above. The Soave mixing rule produced HE values closer to the GE model incorpor-

ated. For all the systems studied, the total arithmetical average of the RMSD from

the UNIQUAC equation decreased from 144 J=mol for the MHV2 mixing rule to

50 J=mol for the Soave mixing rule (Table V). For VLE calculations (Table VI),

the MHV2 and the Soave mixing rules with DECHEMA parameters were similar,

as reported by Soave (1992).

The MHV2 mixing rule combined with the original UNIQUAC equation with

parameters estimated from HE data (MHV2-HE) generally yielded HE values closer

to the experimental ones than the MHV2-DECHEMA model did (Table IV).

However, the improvement in the fit of the GE model to the experimental data

was not always reflected in the combined model because of the discrepancy between

the combined model and the GE model (see Figure 2).

Exchanging the original UNIQUAC equation for the Anderson modification,

still with parameters estimated from HE data, in the MHV2 mixing rule produced

similar results. The Anderson modification was much better for the cyclohexane-1-

propanol system.

The MHV2 mixing rule based on GE models that had parameters regressed from

H data alone (MHV2-HE and MHV2-Anderson) did not give reliable VLE predic-

E

tions (Table VI). The direct use of these GE models also failed to cross-predict VLE

accurately (Burman and Ström, 2007). Thus, it seems that the GE mixing rule

approach suffers from the same shortcoming on this point as the GE models do.

The UNIQUAC equation with parameters estimated simultaneously from HE

and VLE data (HEGE) combined with the Soave mixing rule produced the lowest

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Table V. Root-mean-square deviation between HE [kJ=mol] calculated with the GE mixing rules and with the UNIQUAC equation used

in the mixing rule

Mixing rule

MixturenParameters DECHEMA HE Anderson DECHEMA HEGE T [ C] Source

Cyclohexane-1-propanol 0.19 0.65 0.06 0.05 0.06 25 III 1 570

0.08 0.70 0.03 0.03 0.05 50 III 1 572

Acetone-water 0.35 0.38 0.37 0.09 0.09 35 III 1 518

0.12 0.11 0.11 0.08 0.08 90 III 1 520

Acetone-tetrachloromethane 0.012 0.014 x 0.004 0.005 45 III 1 19

0.02 0.005 x 0.013 0.013 25 Fuchs et al. (1984)

Acetone-trichloromethane 0.16 0.019 x 0.011 0.011 50 III 1 150

1444

0.07 0.018 x 0.032 0.033 70 III 1 149

Benzene-2-methyl-1-propanol 0.14 0.17 0.26 0.05 0.05 45 III 1 749

0.29 0.69 0.59 0.19 0.07 25 III 1 750

Methanol-water 0.13 0.037 0.054 0.019 0.016 25 III 1 304

0.14 0.085 0.099 0.037 0.038 53.5 III 1 305

Ethanol-water 0.20 0.19 0.20 0.04 0.04 25 III 1 457

0.13 0.07 0.07 0.05 0.06 70 III 1 458

0.05 0.19 0.20 0.05 0.05 110 III 1 459

Average 0.14 0.26 x 0.050 0.048

The Source column refers to the volume, part, and page number in the DECHEMA data series where the experimental data may be found. The

UNIQUAC parameters are found in Table II.

x ¼ the Anderson modification was not applicable for these systems.

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Table VI. Average absolute deviation between the calculated vapor phase composition and the experimental (%)

Mixing rule

MixturenParameters kij ¼ 0 kij-VLE DECHEMA HE Anderson DECHEMA HEGE T [ C] Source

Cyclohexane-1-propanol 7.7 2.6 1.1 – 13 1.1 1.3 25 I 2c 544

13 4.2 1.7 – 20 1.7 1.6 55 I 2a 582

12 3.9 1.5 – 19 1.5 1.9 65 I 2a 583

Acetone-water – 4.1 0.9 2.8 2.3 0.9 0.9 35 I 1a 195

– 6.2 0.7 8.7 7.2 0.6 0.9 100 I 1a 194

Acetone-tetrachloromethane 5.6 1.5 0.6 8.3 x 0.6 0.8 45 I 3 84

Acetone-trichloromethane 6.6 1.1 0.6 2.8 x 0.6 0.3 15 I 3 108

6.3 0.9 0.6 2.8 x 0.6 0.3 20 I 3 109

1445

Benzene-2-methyl-1-propanol 3.8 1.0 1.2 3.2 5.4 1.2 1.7 25 I 2b 282

6.1 0.8 0.3 5.7 7.7 0.3 1.3 45 I 2b 283

Methanol-water 27 4.9 1.6 12 9.8 2.1 1.0 25 I 1 42

10 1.2 0.4 6.6 5.2 0.4 0.5 25 I 1a 49

21 2.2 0.7 14 11 0.8 1.4 60 I 1 41

Ethanol-water 22 3.5 0.8 19 19 0.8 1.8 25 I 1a 126

21 4.2 0.9 21 21 0.8 1.9 25 I 1a 125

19 2.6 0.9 21 21 0.8 1.4 55 I 1 173

Average – 3.2 0.9 – – 0.9 1.2

The Source column refers to the volume, part, and page number in the DECHEMA data series (Gmehling et al., 1977–1996) where the experimental

data may be found.

x ¼ the Anderson modification was not applicable for these systems.

– ¼ VLE calculations did not converge.

1446 Å. U. Burman and K. H. U. Ström

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Figure 2. Excess enthalpy for acetone (1)-water (2) at 35 C. Experimental data (^) from

Belosouv and Sokolova (1966). When UNIQUAC parameters fitted to HE data are used,

the discrepancy between HE computed with the GE model alone (dashed line) and with the

MHV2 mixing rule (solid line) is still large and deteriorates the results for the mixing rule.

average RMSD (81 J=mol) for HE calculations. It could also model the more com-

plicated HE behavior shown by some of the systems (Figure 3). The discrepancy

between the UNIQUAC equation and the mixing rule was similar for the

Soave-DECHEMA and Soave-HEGE models (Table V). The errors in calculated

VLE were somewhat larger than those computed with the DECHEMA parameters

(Table VI). The average absolute deviation in the vapor phase composition increased

from 0.9 to 1.2 molar%.

Theoretically, the pure component a(T) expression (the Mathias-Copeman para-

meters) would also be important to the calculation of HE. Following Michelsen and

Heidemann (1996), excess enthalpies for the system pentane-methanol were

Figure 3. Excess enthalpy for ethanol-water at 70 C. The solid line is computed with Soave’s

mixing rule and HEGE parameters and the dashed line with UNIQUAC and HEGE para-

meters. Experimental data (^) from Larkin (1975).

HE and VLE with MHV2 and Soave 1447

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Figure 4. Excess enthalpy for pentane (1) methanol (2) at 25 C computed with the MHV2

mixing rule, the Wilson equation, and binary interaction parameter from the DECHEMA

series. Three sets of Mathias-Copeman parameters were used: estimated in this study from

experimental data (dashed line), from Dahl and Michelsen (1990) (solid line), and from Huang

and Sandler (1993) (dotted line). Experimental data (^) from Collins et al. (1980).

computed using MHV2 in combination with the Wilson equation. Three different

sets of Mathias-Copeman parameters were used: first, parameters for pentane found

in this study from experimental data in Boublı́k et al. (1984) (giving c1 ¼ 0.8880,

c2 ¼ 0.2954, c3 ¼ 0.5850, the parameters for methanol are found in Table I); second,

parameters of Dahl and Michelsen (1990) estimated from the vapor pressure corre-

lation of Daubert and Danner (1986); and a third set from Huang and Sandler

(1993). It is not clear how the parameters used by Huang and Sandler were obtained.

As shown in Figure 4, the choice of parameters does influence the results signifi-

cantly. The difference was smaller for other binaries, most likely because the para-

meters were more similar for them.

Figure 5. Excess enthalpy for cyclohexane (1)-1-propanol (2) at 25 C. Experimental data (^)

from Vesely et al. (1979). The prediction of HE with the van der Waals mixing rule is not

improved when kij is estimated from VLE data (solid line) rather than set to zero (dashed line).

1448 Å. U. Burman and K. H. U. Ström

HE curves computed with the van der Waals mixing rules were symmetrical

and, thus, could not reproduce skewed HE versus composition curves. The

introduction of a binary interaction parameter estimated from VLE data did

improve the HE predictions for most of the systems. The average RMSD

from the experimental data decreased from 1767 to 877 J=mol. For some systems,

however, the results deteriorated (compare columns van der Waal kij ¼ 0 and kij-

VLE in Table IV and see Figure 5). According to Christensen and Rowley (1988),

HE calculations with the van der Waals mixing rule are very sensitive to the kij-

value.

As might be expected for mixtures with polar compounds, the bubble point

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calculations with the van der Waals mixing rule and no interaction parameter were

not successful: the calculations would sometimes even fail to converge (see Table VI

column van der Waals, kij ¼ 0). Introducing one interaction parameter improved the

results significantly (Table VI, column van der Waals, kij-VLE).

Conclusion

VLE and HE calculations were performed using the SRK equation of state with

MHV2 and Soave mixing rules combined with four different sets of UNIQUAC

parameters regressed in the UNIQUAC model. The MHV2 mixing rule with

UNIQUAC parameters from DECHEMA produces qualitatively correct HE

curves, sometimes closer to the experimental values than those predicted by the

UNIQUAC equation alone. The Soave q(a) function produces HE values closer

to those of the incorporated GE model. There is still a discrepancy between HE

values computed with the equation of state model and the GE model for both

mixing rules. The GE-eos approach seems to inherit the problems of the GE mod-

els as far as cross-prediction between HE and VLE is concerned. Simultaneous

estimation of parameters from VLE and HE data enables calculations of both

properties using one and the same model, but reduces the precision of the GE

model to some extent.

Improved GE models would be necessary if VLE and HE data are to be calcu-

lated successfully from the same model. More experimental measurements of HE

would be needed.

Nomenclature

a equation of state parameter, Nm4=mol2

b equation of state parameter, m3=mol

c Mathias-Copeman parameters

G molar Gibbs free energy, J=mol

H molar enthalpy, J=mol

k binary interaction parameter

l binary interaction parameter

n amount of substance, mol

P pressure, Pa

q external area parameter (UNIQUAC)

q auxiliary function (Equation (2))

R gas constant, J=mol K

HE and VLE with MHV2 and Soave 1449

T temperature, K

v molar volume, m3=mol

x molar fraction, liquid phase

Z compressibility factor

Greek Letters

a parameter (equation of state)

c activity coefficient

W binary interaction parameter (UNIQUAC), J=mol

H contact area fraction (UNIQUAC),

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n binary interaction parameter (UNIQUAC), J=mol

s parameter (UNIQUAC)

Superscripts

E excess property

O ideal state

Subscripts

c critical

i component

j component

k component

r reduced

Appendix

When VLE calculations are performed with an equation of state, the compositional

derivative of the a parameter can be obtained as:

@na @n @a @a @q

¼a þn ¼aþn ðA:1Þ

@ni @ni @ni @q @ni

where:

@q 1 b bi

¼ qðaÞ þ qðai Þ þ lnðcÞ þ ln þ 1 ðA:2Þ

@ni n bi b

@a 1

¼ ðA:3Þ

@q q1 þ 2q2 a

@a 1 17:25

¼ ðA:4Þ

@q lnð2Þ lnð2Þð3:365 qÞ2

1450 Å. U. Burman and K. H. U. Ström

When excess enthalpy is computed from the UNIQUAC model alone, the Gibbs-

Helmholtz relation is applied to the UNIQUAC equation. For a binary mixture, this

results in the following expression:

0

E 2 q1 x1 H02 @s21 q02 x2 H01 @s12

H ¼ RT þ 0 ðA:5Þ

H01 þ H02 s21 @T H2 þ H01 s12 @T

q0 xi n ij

H0i ¼ P i 0 sij ¼ eRT

qk xk

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@a

H Ho T @T a b

¼Z1þ ln 1 þ ðA:6Þ

RT RTb v

The compressibility, Z, and the volume, v, are the liquid roots from the equation of

state. The pressure used for the calculations was 1 atm.

With the van der Waals mixing rule, the derivative of a is:

@a 2 @a1 2 @a2 1 kij @a2 @a1

¼ x1 þ x2 þ x1 x2 pﬃﬃﬃﬃﬃﬃﬃﬃﬃ a1 þ a2 ðA:7Þ

@T @T @T a1 a2 @T @T

When the GE-mixing rules are used, the derivative is computed from the derivative

for a:

@a a @a a @a @q

¼ þ RTb ¼ þ RTb ðA:8Þ

@T T @T T @q @T

The derivative of a with respect to q are Equations (A.3) and (A.4) for the MHV2

and Soave expressions, respectively. The temperature derivative of q for the

MHV2 mixing rule is:

0 E 1

G

@ RT X 2

@q @ A @ai @ai

¼ þ q1 x i þ q2 xi ðA:9Þ

@T @T i

@T @T

2 3

@ GE

X xi ln 2 @ai 6

@q RT ai ln 2 7

¼ þ 41 þ qﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ5 ðA:10Þ

@T @T 2 @T 2

i ðai ln 2Þ þ69

The derivative of the pure component a parameter with respect to temperature is:

2

@ai ðRTci Þ2 1=2 1=2

¼ 0:4286 1 þ c1 1 Tri þ c2 1 Tri

@T Pci

3 2 ðA:11Þ

1=2 1=2 1=2 1=2

þ c3 1 Tri c1 þ c2 1 Tri þ c3 1 Tri Tri

HE and VLE with MHV2 and Soave 1451

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