J. Chem.

Thermodynamics 85 (2015) 120128

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Measurements and modeling of LLE and HE for (methanol + 2,4,4trimethyl-1-pentene), and LLE for (water + methanol + 2,4,4-trimethyl1-pentene)
Saeed Mardani , Helena Laavi, Emeline Bouget 1, Juha-Pekka Pokki, Petri Uusi-Kyyny, Ville Alopaeus
Aalto University, School of Chemical Technology, Department of Biotechnology and Chemical Technology, Research Group of Chemical Engineering, P.O. Box 16100,
FI-00076 Aalto, Finland

a r t i c l e

i n f o

Article history:
Received 5 November 2014
Received in revised form 16 January 2015
Accepted 26 January 2015
Available online 4 February 2015
Keywords:
Water
Methanol
2,4,4-trimethyl-1-pentene
(Liquid + liquid) equilibrium
Excess enthalpy
NRTL model

a b s t r a c t
Excess enthalpy (HE) for the binary system of (methanol + 2,4,4-trimethyl-1-pentene) (TMP-1) is reported at T = 298.15 K and 101 kPa. (Liquid + liquid) equilibrium (LLE) for the same system is measured at
atmospheric pressure (101 kPa). LLE for ternary system of (water + methanol + 2,4,4-trimethyl-1-pentene) is measured at T = (283 and 298) K.
The parameters of Non-Random Two-Liquid (NRTL) model were regressed for the system of (methanol + TMP-1) using HE and LLE from this work combined with isobaric (101 kPa) and isothermal
(T = 331 K) VLE data from literature. The NRTL parameters for the binary system of (water + TMP-1) were
tted to a binary LLE data set from literature. NRTL parameters for the binary system of (water + methanol) were taken from ASPEN PLUS. The LLE for the ternary system was modeled by the three binary NRTL
interaction parameters systems. The binary and ternary models were compared against the measured
data.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Tertiary ethers are used as gasoline additives. Methyl Tertiary
Butyl Ether (MTBE), Ethyl Tertiary Butyl Ether (ETBE), and
Tertiary-Amyl Methyl Ether (TAME) are the main commercially
used compounds. The tertiary ethers can partially be produced
from bio-methanol or bio-ethanol. Recently, the European Union
(EU) directives are promoting the use of biofuels instead of fossil
fuels. Scientists are making efforts to develop new processes for
increasing productivity of new tertiary ethers from bio based raw
materials. [1]
Diisobutylene is mainly made of 2,4,4-trimethyl-1-pentene
(TMP-1) and 2,4,4-trimethyl-2-pentene (TMP-2). Etherication of
diisobutylene with methanol produces 2-methoxy-2,4,4trimethylpentane (TOME). TOME can be applied in the gasoline
to increase the octane number. During the etherication reaction,
Corresponding author. Tel.: +358 50 434 7365; fax: +358 94 702 2694.
E-mail addresses: saeed.mardani@aalto. (S. Mardani), helena.laavi@aalto.
(H. Laavi), emeline.bouget@insa-rouen.fr (E. Bouget), juha-pekka.pokki@aalto.
(J.-P. Pokki), petri.uusi-kyyny@aalto. (P. Uusi-Kyyny), ville.alopaeus@aalto.
(V. Alopaeus).
1
Present address: National institute of applied sciences (INSA), Chemical Engineering and Fine chemistry Department, INSA de Rouen, B.P. 08, Avenue de
luniversit 76801 Saint Etienne du Rouvray CEDEX.
http://dx.doi.org/10.1016/j.jct.2015.01.013
0021-9614/ 2015 Elsevier Ltd. All rights reserved.

dehydration of excess methanol produces dimethyl ether and

water. The water induces a phase split in the system.
The phase equilibria related to TOME production process is rare.
Uusi-Kyyny et al. [2] reported only two sets of (vapor + liquid)
equilibrium (VLE) data for the binary system of (methanol + TMP-1) (isothermal at T = 331 K, and isobaric at 101 kPa)
and one set of VLE data for the (methanol + TOME) (isothermal at
T = 333 K). Halttunen [3] reported the LLE for the binary mixture
of (water + TMP-1). This research aims at presenting measurements and a model to deepen our knowledge on the phase equilibria in a possible process for production of TOME from TMP-1 and
methanol.
The LLE for the binary system of (methanol + TMP-1) and LLE for
the ternary mixture of (water + methanol + TMP-1) were measured
to describe the complex phase equilibrium behavior appearing in
the TOME production process; in addition the excess enthalpy
(HE) was measured to enhance the temperature dependence of
the model (equation (1)).

@ ln ci
@1=T

P;x

E
h
i
R

where ci is the activity coefcient of component i; T is temperature,

 E is partial excess enthalpy of component i in the solution,
K; h
i
J  mol1; and R is universal gas constant, J(mol  K)-1.

S. Mardani et al. / J. Chem. Thermodynamics 85 (2015) 120128

121

Nomenclature

Abbreviations
CAS
chemical abstracts service registry number
ETBE
Ethyl Tertiary Butyl Ether
EU
European Union
FID
ame ionization detector
GC
gas chromatograph
KF
Karl-Fisher Titrator
LLE
(liquid + liquid) equilibrium
MTBE
Methyl Tertiary Butyl Ether
NRTL
Non-Random Two-Liquid model
OF
objective function
TCD
thermal conductivity detector
TAME
Tertiary-Amyl Methyl Ether
TBA
tert-butyl alcohol
TMP-1 2,4,4-trimethyl-1-pentene
TMP-2 2,4,4-trimethyl-2-pentene
TOME
2-methoxy-2,4,4-trimethylpentane
VLE
(vapor + liquid) equilibria/(vapor + liquid) equilibrium
Symbols
aij, aji, bij, bji, cij, dij, eij, eji, fij, fji parameters of NRTL model
Ant. AE extended Antoine equation parameters
HE
excess enthalpy, J  mol1
E
h
partial molar excess enthalpy, J  mol1
i
M
molar mass, gmol1
Pc
critical pressure, kPa
R2
coefcient of determination (R squared)

Measured HE and LLE with two VLE datasets from literature

were combined to regress Non-Random Two-Liquid (NRTL) [4]
activity coefcient model parameters. LLE data for the binary system of (water + TMP-1) from the literature were regressed to
obtain NRTL parameters for the system of (water + TMP-1), was
improved by adding the measured ternary data in this regression.
Finally the binary parameters were used to describe the ternary
system.
This work is novel in reporting LLE and HE for the binary system
of (methanol + TMP-1), and LLE for the ternary system of (water + methanol + TMP-1), in addition to simultaneous modeling of four
binary system datasets including isothermal VLE, isobaric VLE,
LLE and HE. This experience can show the abilities of NRTL model
in describing the properties of a system in a temperature range
of over 120 K.
2. Experimental materials and apparatus
2.1. Materials
Methanol and TMP-1 were dried by adding molecular sieve
(0.3 nm Merck) into the chemical. Table 1 provides the CAS number, water content, purity, measured and literature densities, and
suppliers of the compounds. The molar mass and extended Antoine
equation parameters are available in table 2.
2.2. (Liquid + liquid) equilibrium by turbidimetry [5]
A jacketed cell was applied for LLE measurements by turbidimetry. Figure 1 demonstrates a schematic of the apparatus. ASL F 200
Series Precision Thermometer with accuracy of T = 0.02 K was
applied for measuring the temperature of the mixing cell. The
volume of the cell was 160 cm3. A magnetic stirrer was used for

S
T
Tmax
Tmin
Vc
wt%
xi
ZC

q
qmeas
qlit
ci
rx
x

standard deviation, cm3  mol1

temperature, K
maximum temperature in which the model was examined, K
minimum temperature in which the model was examined, K
critical volume, m3  kmol1
mass fraction, %
mole fraction
critical compressibility
density, kg  m3
measured density, kg  m3
density from literature, kg  m3
activity coefcient of component i
root mean square deviation between the measured data
and the model
acentric factor

Subscripts
1
water
2
methanol
3
2,4,4-trimethyl-1-pentene (TMP-1)
Superscripts
I
phase 1
II
phase 2

mixing the liquids. The temperature of the cell was controlled by

Lauda E 200 cooling thermostat. The cooling agent was a solution
of ethylene glycol and water.
2.3. (Liquid + liquid) equilibrium with analytical method
The direct analytical method was applied using three jacketed
cells. The approximate volume for each cell was 120 cm3. The jackets of the cells were connected in a parallel form. The temperatures
inside the cells were controlled by sufcient amount of cooling
water and three valves to control the ow in each jacket. ASL F
200 Series precision thermometer was applied to obtain the temperature of the cells. Lauda E 200 cooling thermostat was adjusting
the temperature of the cells. Fig. 2 is showing a schematic of the
equipment applied.
2.4. Excess molar enthalpy
Excess molar enthalpy (HE) was measured with a Setaram C80
calvet calorimeter at T = 298.15 K equipped with ow mixing cells.
The accuracy of the calorimeter temperature indicators was 0.1 K
[6]. The chemicals were pumped into the mixing cell by two syringe pumps. The syringe pumps were ISCO 260D and ISCO 500D
with an accuracy of 0.5% of the set point. The calorimeter was
calibrated using the (cyclohexane + hexane) reference system
according to IUPAC recommendation [7]. The relative uncertainty
for calorimeter was 0.024. The experimental setup was further
tested with the binary system of (2-propanol + cyclohexane). The
(2-propanol + cyclohexane) system showed similar behavior in
terms of excess enthalpy in comparison with the system of (methanol + TMP-1), both are (alcohol + hydrocarbon) systems. Result of
the measured (2-propanol + cyclohexane) binary system and comparison with the literature is available in Appendix A.

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S. Mardani et al. / J. Chem. Thermodynamics 85 (2015) 120128

TABLE 1
Water content, purity, measured model densities and suppliers of the compounds.a

qlit/
kg  m3

Supplier

kg  m3

99.99
99.98

786.2

786.58

0.012

99.04

710.7

710.89

Sigma
Aldrich
Fluka

2-propanol

0.164

99.80

780.8

780.93

Cyclohexane

0.008

99.95

773.5

773.9

Water content/
mass%

Purity/
mass%

Water
Methanol

0.013

TMP-1

qmeas/

Description
Water was puried in laboratory by Millipore Elix 20 water purication system.

The main impurity in TMP-1 was 0.84 mass percent of TMP-2 and 0.11 mass
percent of other C8 alkenes.

Sigma
Aldrich
Sigma
Aldrich

ur(water content) = 0.01; for the densimeter u(T) = 0.01 K u(qmeas) = 103 kg  m3; u(P) = 10 kPa.
a
Water content is the mass fraction of water measured by Karl-Fisher Titrator (KF),%; Purity is the mass percent purity of compounds measured by gas chromatography (GC)
and KF,%; qmeas is density measured at T = 298.15 K and atmospheric pressure (101 kPa), with Anton Paar DMA 5000M, kg  m3; and qlit is the density from literature obtained
from Valtz et al. [15] for methanol, Camin and Rossini [16] for TMP-1, Zarei et al. [17] for 2-propanol, Beg et al. [18] for cyclohexane at T = 298.15 K.

TABLE 2
Molar mass, extended Antoine equation parameters from DIPPR.a

M/g  mol1
Ant. A
Ant. B
Ant. C
Ant. D
Ant. E
Tmin/K
Tmax/K

Water

Methanol

TMP-1

18.01528
73.649
7258.2
7.3037
4.17E06
2
273.16
647.09

32.04186
82.718
6904.5
8.8622
7.47E06
2
175.47
512.5

112.2126
66.689
6251
6.5017
1.81E17
6
179.7
550

DIPPR is Design Institute for Physical Properties [19], M is molar mass, g  mol1;
Ant. AE are the extended Antoine equation parameters where vapor pressure can
be calculated by: P expAnt  A Ant  B=T Ant  C  ln T Ant  D  TAnt  E, Tmin
and Tmax are the minimum and maximum temperatures at which extended Antoine
equations are valid, K.

(4)

(2)

temperature at constant composition shows the miscibility gap

boundary by variation of transparency of the mixing liquid. The
temperature reading was veried by approaching the turbidity
limit for 5 times at each composition. The next points were
obtained by increasing the temperature and adding more TMP-1.
10 data points were recorded with this procedure. The cell was
washed, drained and dried and the same experiment was repeated
by injecting TMP-1 in the cell and adding methanol successively
for 6 times to obtain data points for the full composition range of
0 to 1.
The analytical method was performed to check the accuracy of
turbidimetric method. One of the analytical mixing cells shown in
Fig. 2 was lled with 100 cm3 of a binary mixture of (methanol + TMP-1) with mole fractions of 0.6 and 0.4 respectively.
20 cm3 of molecular sieves (0.3 nm Merck) were added to the cell
to decrease the water content in the mixing cell. The cell was insulated to reduce heat transfer. The system was mixed vigorously for
5 h, then the cell was allowed to settle at the same temperature for
1 h and samples were taken from each phase to check the
composition and water content. In this case the largest mole fraction for detected water was 0.0017 which was considered to be
negligible.
3.2. (Liquid + liquid) equilibrium for ternary mixture

8 cm
(1)

5 cm
(3)
0

1000 rmp

FIGURE 1. Equilibrium cell for turbidimetry: (1) Precision Thermometer, (2)

equilibrium cell, (3) mixer, (4) cooling thermostat.

3. Experimental procedure
3.1. (Liquid + liquid) equilibrium for binary mixture
Mixtures of compounds with known mole fractions were placed
in the turbidimetric apparatus, which is a so called synthetic
method [5]. In turbidimetry, the formation of two liquid phases
can be observed by variation in transparency of the studied
mixture. A known amount of methanol was injected into the cell
and the temperature was reduced to 253.15 K. TMP-1 was added
until a phase split was observed. Increasing and decreasing the

Ternary LLE system of (water + methanol + 2,4,4 trimethyl-1pentene) was measured by using the analytical method. Mixtures
of the three compounds with a composition in the miscibility
gap region were injected in the cells and mixed for over 24 h to
reach the equilibrium. The cells with mixed system were turned
to the settling mode to separate completely within 5 h. It was
possible to control the temperature of the cells by 0.10 K for LLE
measurements at T = 298.15 K, and 0.90 K for T = 283.15 K
measurements.
The accuracy of ternary LLE measurement was tested by turbidimetry. The measurement was done at constant temperatures
of (T = 298 and 283) K. Equimolar mixture of TMP-1 and methanol
with total volume of 30 cm3 was added into the cell. Addition of
water initiated the turbidity. The turbidity disappeared by increasing the mole fraction of methanol. Repetition of this process
showed the boundaries of the miscibility gap region. The same procedure was applied to the mixture of water and methanol while
the TMP-1 and methanol was added to nd the miscibility gap
boundaries.
3.3. Excess molar enthalpy
Pumps were lled with pure compounds and degassed under
vacuum. The feed temperatures were set to T = 298 K by control-

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S. Mardani et al. / J. Chem. Thermodynamics 85 (2015) 120128

(a)

(4)
(1)

(2)
13 cm
(3)

3.5cm
0

(b)

(5)

FIGURE 2. Analytical LLE measurement apparatus. (a) Mixing mode, (b) settling mode. (1) Thermometer, (2) equilibrium cell, (3) mixer, (4) cooling thermostat, (5) sampling
syringe.

ling the syringe pumps cylinder temperatures for 60 min before

starting the experiment. The ow rates of the two pumps were
adjusted proportionally to obtain HE for different mole fractions
[8,9]. The total ow rate was kept at 0.5 cm3  min1. The
calorimeter signal was let to stabilize for 30 min before recording
the rst experimental point.

where:

Gij expaij sij

sij aij

bij
eij lnT f ij T
T

aij cij dij T  273:15 K

4. Analysis methods and equipment

sii 0

Agilent 6850 gas chromatograph GC equipped with ame ionization detector (FID) and Agilent 6890N GC equipped with both
thermal conductivity detector (TCD) and FID detectors were
applied to obtain compositions. For all the GC measurements, Agilent GC 2 cm3 glass vials with aluminum crimp caps and PTFE/red
rubber septas were utilized. The GC settings are provided in
Appendix B. Mettler Toledo DL38 volumetric Karl-Fisher Titrator
(KF) was used to analyze the water content. The relative
uncertainty of KF was 0.01. Water contents were measured by
adding relevant amount of organic samples to KF. The samples
were weighed by Precisa 410AM-FR balance with an accuracy of
0.0001 g.
5. Modeling
The Non-Random Two-Liquid model (NRTL) can describe the
activity coefcients and the measured points for the binary mixture discussed in this work. The NRTL model is embedded in ASPEN
PLUS [10] in the following form (equation (2)):

X
xj sji Gji
j

ln ci X

xk Gki
k

0
X
j

xG B
Xj ij B
sij 
xk Gkj @
k

1
xm smj Gmj
C
m
C
X
xk Gkj A

Gii 1

aij is non-randomness parameter. aij, bij, cij, dij, eij, fij are binary interaction parameters. In NRTL equation cij = cji and dij = dji.
The objective function was maximum likelihood [11]. The
BrittLuecke algorithm [12] with Deming initialization method
was applied to regress the parameters. OthmerTobias equation
TABLE 3
Excess molar enthalpy HE at T = 298.15 K and atmospheric pressure (101 kPa) for
binary systems of (methanol + TMP-1).a
x1

HE (J  mol1)

0.023
0.100
0.198
0.301
0.398
0.498
0.598
0.698
0.798
0.899

239
449
524
577
584
584
563
511
428
282

u(x1) = 0.0007; ur(HE) = u(HE)/|HE| = 0.024; for the calorimeter u(T) = 0.1 K;
u(P) = 10 kPa.
a
x1 is the mole fraction of methanol; HE is the excess molar enthalpy at
T = 298.15 K.

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S. Mardani et al. / J. Chem. Thermodynamics 85 (2015) 120128

[13] was applied to verify the reliability of the ternary LLE measured data (equation (3)).

ln





1  x1aq
1  x3org
a b  ln
x1aq
x3org

The ternary model and experimental data were compared using

root-mean-square-deviation (rx ) values of the composition (equation (4)):

rx

where x1aq is the mole fraction of water in aqueous phase and x3org
is mole fraction of TMP-1 in organic phase, a and b are parameters
of Othmer-Tobias correlation.

TABLE 4
Analytical (liquid + liquid) equilibrium (LLE) for the binary system of (methanol
(1) + TMP-1 (2)) at atmospheric pressure (101 kPa).a
T/K

xI1

H2O con.

xII1

H2O con.

257.75
263.05
264.55
266.15
268.05
270.45

0.2443
0.2861
0.3048
0.3352
0.3740
0.4281

0.0003
0.0003
0.0002
0.0001
0.0003
0.0001

0.8257
0.8046
0.7902
0.7700
0.7484
0.7106

0.0010
0.0017
0.0002
0.0002
0.0004
0.0005

s

Pn P P  meas
calc 2
i1
P
M xiPM  xiPM

6Z

TABLE 6
Upper critical solution temperatures for the binary mixture of (methanol + TMP-1)
obtained by polynomial regression of turbidimetry method and NRTL model
(101 kPa).a
Method

x1

T/K

Polynomial regression of turbidimetry results

NRTL model

0.592
0.563

272.0
272.3

a
x1 is the mole fraction of methanol, and T is the corresponding temperature at
which the (liquid + liquid) split occur, K.

u(T) = 0.02 K; u(xI1 ) = u(xII1 ) = 0.0001; ur(H2O con.) = u(H2O con.)/|H2O con.| = 0.01;
u(P) = 10 kPa.
a
T is temperature, K, xI1 , xII1 are mole fractions of methanol on the borders of
miscibility gap, H2O con. is water content absorbed from surrounding environment,
mole fraction.

TABLE 5
Turbidimetric (liquid + liquid) equilibrium (LLE) for the binary system of (methanol
(1) + TMP-1 (2)) at atmospheric pressure (101 kPa).a
T/K

x1

T/K

x1

254.46
264.59
269.83
271.14
271.80
271.92
254.75
263.03

0.2411
0.3150
0.4083
0.4608
0.5258
0.5623
0.8439
0.8018

265.46
268.94
270.70
271.49
271.84
272.05
272.05
271.90

0.7841
0.7450
0.7082
0.6686
0.6305
0.5960
0.5664
0.5378

u(T) = 0.02 K; u(P) = 10 kPa.

x1 is the mole fraction of methanol, u(x1) = 0.0001; T is the temperature at which
the turbidity was visually detected K.

FIGURE 3. Excess enthalpy (HE) at T = 298.15 K and atmospheric pressure (101 kPa)
for the binary system of (methanol (1) + TMP-1 (2)): j measured excess enthalpy
(HE); comparison with the NRTL model for the same binary system presented in
this work.

FIGURE 4. Pressure-composition diagram for the system of (methanol (1) + 2,4,4trimethyl-1-pentene (2)) at T = 331 K: d x1 liquid-phase mole fraction from Uusikyyny et al. [2]; N y1 vapor-phase mole fraction from Uusi-kyyny et al. [2]; x1
liquid-phase mole fraction calculated with the NRTL model; y1 vapor-phase mole
fraction calculated with the NRTL model.

FIGURE 5. Temperature-composition diagram for the system of (methanol

(1) + 2,4,4-trimethyl-1-pentene (2)) at 101 kPa: j x1 liquid-phase mole fraction
from Uusi-kyyny et al. [2]; N y1 vapor-phase mole fraction from Uusi-kyyny et al.
[2]; x1 liquid-phase mole fraction calculated with the NRTL model; y1 vaporphase mole fraction calculated with the NRTL model.

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S. Mardani et al. / J. Chem. Thermodynamics 85 (2015) 120128

where i is the compound, P is the phase, M is the tie line, Z is number of the tie lines.

constant temperature was jDxmethanol j 0:006. The upper critical

solution temperature obtained by the polynomial and by NRTL
model is available in table 6.

6. Results and discussion

Results of HE is given in table 3. The analytical and turbidimetric
measurement data points for the system of methanol + TMP-1 are
provided in tables 4 and 5 respectively. A polynomial was tted to
the turbidimetric measured data only to nd 10 isothermal tie
lines and the upper critical solution temperature, the R-squared
value for the polynomial was 0.9999. These generated tie lines in
addition to analytical LLE were applied in the regression of the
NRTL model parameters. The average deviation between analytical
isothermal tie lines and the tie lines made by the polynomial at

TABLE 7
NRTL parameters for the binary mixtures.a

FIGURE 6. LLE for the binary system of (methanol (1) + TMP-1 (2)) at atmospheric
pressure (101 kPa): 4 x1 LLE measured by turbidimetry; d LLE measured by
analytical method; NRTL model; j Upper critical solution by polynomial
regression of turbidimetry results;  Upper critical solution temperature by NRTL
model.

i and j are providing the order of compounds in NRTL model; af are the NRTL
model parameters; Tmin and Tmax are the lowest and highest temperatures at which
the models are examined respectively, K; jDPj is average absolute pressure error for
isothermal VLE dataset, kPa; jDyit j is average absolute composition error for
isothermal VLE datasets; jDTj is average absolute temperature error for isobaric
datasets, K; jDylb j is average absolute composition error for isobaric datasets; DHE is
average absolute excess enthalpy error for the excess enthalpy dataset, J  mol1.
jDxj is the average absolute deviation for LLE. The it subscript is for isothermal
and subscript ib is for isobaric.
b
APV73 VLE-IG binary mixture parameters were applied for the (water + methanol)
system.

TABLE 8
Analytical (liquid + liquid) equilibrium (LLE) data for the system of (water (1) + methanol (2) + TMP-1 (3)) at 101 kPa (atmospheric pressure).a
T/K

298.28
298.27
298.14
298.15
298.16
298.27
298.23
298.16
298.16
298.16
298.13
298.25
298.11
298.15
298.14
298.05
298.18
298.17
298.24
298.21
298.23
283.63
283.63

Aqueous phase

Organic phase

T/K

xI1

xI2

xII1

xII2

0.020
0.030
0.038
0.063
0.095
0.108
0.159
0.166
0.224
0.232
0.321
0.325
0.351
0.441
0.513
0.519
0.641
0.710
0.748
0.753
0.757
0.027
0.065

0.691
0.783
0.818
0.829
0.843
0.843
0.799
0.804
0.758
0.751
0.647
0.666
0.640
0.555
0.486
0.480
0.357
0.290
0.252
0.247
0.243
0.789
0.852

0.001
0.010
0.008
0.009
0.005
0.004
0.004
0.004
0.003
0.003
0.002
0.002
0.002
0.002
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.005
0.005

0.254
0.161
0.129
0.106
0.057
0.048
0.032
0.029
0.023
0.020
0.013
0.014
0.011
0.007
0.006
0.006
0.000b
0.000b
0.000b
0.000b
0.000b
0.154
0.072

283.98
283.80
283.91
283.80
284.09
283.74
283.86
283.87
283.41
283.89
283.92
283.45
283.41
283.51
283.32
283.41
283.46
283.69
283.35
284.05
283.75
283.35
283.97

u(T) = 0.02 K; u(x) = 0.006, for organic phase u(x) = 0.001; u(P) = 10 kPa.
a
xI1 , xII1 is mole fraction of water, xI2 , xII2 is mole fraction of methanol, for aqueous phase T is temperature, K.
b
Under detection limit of gas chromatograph.

Aqueous phase

Organic phase

xI1

xI2

xII1

xII2

0.072
0.080
0.108
0.115
0.153
0.182
0.207
0.246
0.329
0.349
0.349
0.366
0.379
0.434
0.477
0.500
0.502
0.521
0.578
0.709
0.717
0.790
0.792

0.864
0.861
0.853
0.847
0.820
0.799
0.778
0.743
0.661
0.647
0.644
0.631
0.618
0.565
0.523
0.493
0.497
0.471
0.421
0.291
0.283
0.210
0.208

0.003
0.002
0.003
0.003
0.002
0.002
0.002
0.002
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.003
0.001
0.001
0.001
0.001

0.053
0.047
0.035
0.035
0.027
0.020
0.017
0.014
0.009
0.008
0.007
0.007
0.007
0.004
0.004
0.000b
0.000b
0.010
0.000b
0.000b
0.000b
0.000b
0.000b

126

S. Mardani et al. / J. Chem. Thermodynamics 85 (2015) 120128

TABLE 9
Phase boundary with turbidimetry method for the system of (water (1) + methanol (2) + TMP-1 (3)) at 101 kPa (atmospheric pressure).a
x1

x2

x1

x2

x1

x2

x1

x2

x1

x2

298 0.10 K
0.009
0.009
0.009
0.009
0.010
0.009
0.010
0.010
0.010
0.010
0.011
0.010
0.011
0.011
0.011
0.011
0.011
0.011
0.012
0.012
0.012
0.012
0.012
0.012
0.013
0.012
0.013
0.013
0.014
0.014
0.014

0.496
0.518
0.518
0.529
0.529
0.540
0.539
0.551
0.551
0.560
0.560
0.571
0.571
0.581
0.581
0.590
0.590
0.601
0.601
0.609
0.608
0.615
0.614
0.622
0.622
0.629
0.629
0.637
0.637
0.646
0.645

0.014
0.014
0.014
0.015
0.015
0.015
0.015
0.015
0.015
0.016
0.015
0.016
0.016
0.017
0.016
0.017
0.017
0.018
0.017
0.019
0.018
0.019
0.019
0.021
0.019
0.021
0.020
0.023
0.021
0.025
0.024
0.028

0.650
0.649
0.655
0.654
0.661
0.661
0.665
0.665
0.673
0.672
0.683
0.683
0.691
0.690
0.699
0.698
0.708
0.707
0.717
0.716
0.724
0.723
0.735
0.734
0.749
0.748
0.759
0.758
0.772
0.769
0.782
0.779

0.026
0.030
0.028
0.035
0.033
0.038
0.036
0.041
0.039
0.045
0.042
0.048
0.045
0.047
0.050
0.048
0.052
0.050
0.055
0.053
0.058
0.056
0.060
0.059
0.063
0.061
0.065
0.063
0.068
0.066
0.070
0.068

0.794
0.790
0.809
0.803
0.812
0.808
0.815
0.811
0.821
0.816
0.829
0.824
0.834
0.833
0.830
0.836
0.832
0.839
0.835
0.841
0.837
0.841
0.837
0.843
0.839
0.843
0.840
0.845
0.840
0.844
0.841
0.846

0.072
0.070
0.076
0.073
0.078
0.076
0.080
0.078
0.084
0.081
0.087
0.086
0.089
0.087
0.092
0.090
0.095
0.092
0.098
0.096
0.100
0.098
0.102
0.098
0.106
0.103
0.110
0.107
0.112
0.109
0.116
0.111

0.842
0.847
0.842
0.847
0.842
0.846
0.842
0.848
0.842
0.847
0.841
0.844
0.841
0.846
0.841
0.845
0.840
0.844
0.839
0.842
0.839
0.842
0.838
0.843
0.836
0.841
0.835
0.839
0.835
0.839
0.832
0.840

0.121
0.116
0.126
283.15 0.50 K
0.006
0.006
0.007
0.006
0.007
0.006
0.007
0.007
0.009
0.008
0.011
0.010
0.013
0.011
0.016
0.015
0.021
0.019
0.025
0.023
0.031
0.028
0.038
0.036
0.045
0.040
0.051
0.048

0.830
0.837
0.828
0.555
0.582
0.581
0.611
0.611
0.658
0.657
0.691
0.689
0.732
0.730
0.755
0.752
0.787
0.783
0.806
0.800
0.823
0.817
0.832
0.825
0.842
0.834
0.844
0.837
0.853
0.844
0.853

u(x1,2) = 0.01; u(T) = 0.02 K; u(P) = 10 kPa.

x1 is mole fraction of water, x2 is mole fraction of methanol; T is temperature, K.

The HE, and LLE measured data in addition to isobaric VLE and
isothermal VLE data from Uusi-Kyyny et al. [2] were regressed to
obtain NRTL parameters for the binary system of (methanol + TMP-1). The ideal gas law was used for the vapor phase model. Simultaneous modeling of the four different measured and
literature datasets was challenging. All the parameters of NRTL
equation including a were regressed to improve the accordance
of the data and the model. The dataset weights were changed to
improve the correspondence of the data with the model. The
weight for isobaric VLE, isothermal VLE, LLE, HE were assigned to
be 15, 15, 9, 8 respectively. Figures 36 are demonstrating the
comparison of the data and the model. Table 7 provides regressed
parameters and average absolute composition deviation between
the NRTL model and the measured data for the binary systems of
(methanol + TMP-1). The nal NRTL model was successful in representing VLE and HE but have slightly larger deviation for LLE which
can be due to the lower weight assigned on LLE during data
regression.
The analytical method tie lines and the turbidimetry results for
LLE of (water + methanol + TMP-1) are provided in tables 8 and 9.
OthmerTobias plots for different temperatures are shown in
gure 7; and the parameters of OthmerTobias correlation with
R-squared values are provided in table 10.
The LLE for binary system of (water + TMP-1) has been measured by Halttunen [3]. This data was scattered due to minor solubility of water and TMP-1 in each other. The measured tie lines of
ternary LLE data were regressed to obtain the parameters for binary mixture of (water + TMP-1), the ternary system was also added
during this regression to enhance the accuracy of the model. The
regressed parameters for binary mixture of (water + TMP-1) are
available in Table 7.
Finally, the binary interaction parameters were applied to calculate the tie lines for the ternary system and the miscibility gap

FIGURE 7. OthmerTobias correlation for the ternary mixture of (water

(1) + methanol (2) + TMP-1 (3)): d T = 298.15 K; j T = 283 K; OthmerTobias
plot for T = 298.15 K; - - - OthmerTobias plot for T = 283 K.

TABLE 10
OthmerTobias correlation parameters, R squared, and root mean square deviation at
different temperatures.a
T/K

R2

rx

298
283

0.0892
0.2719

147.56
187.47

0.9929
0.9924

0.060
0.049

a
T is the measurement temperature, K; a and b are parameters of OthmerTobias
correlations; R2 is the coefcient of determination (R squared) for OthmerTobias
correlation; rx is the root mean square deviation between the measured data and
the model (equation (5)).

boundary. The root mean square deviations (rx) are presented in

table 10. The work was reasonably successful in modeling the ternary LLE, the rx was less than small value of 0.06 for the LLE at the

127

S. Mardani et al. / J. Chem. Thermodynamics 85 (2015) 120128

for this system. The maximum value for this correlation is

221 J  mol1. The calibrated calorimeter was checked with the
binary system of (2-propanol + cyclohexane) to check the ability
of the calorimeter for measuring the HE of a binary system of
(hydrocarbon + alcohol). This system was used to understand the
accuracy of calorimeter at higher HE values.
The HE values for the system of (2-propanol + cyclohexane)
were comparable with the HE of binary mixture of methanol + TMP-1. A polynomial (equation (A-1)) was tted to the measured results to compare measured data with the literature.

HE x1  xa0 a1 1  2x a2 1  2x2 a3 1  2x3

A-1

In this polynomial a0a3 are the parameters and x is mole fraction of cyclohexane. Table A-1 demonstrates the results of HE
measurements for the binary mixture of (2-propanol + cyclohexTABLE A-1
Excess enthalpies at T = 298.15 K and atmospheric pressure (101 kPa) for the binary
mixture of (2-propanol (1) + cyclohexane (2)).a
x1

HE (J  mol1)

0.9005
0.8005
0.7010
0.6011
0.5016
0.4014
0.3009
0.2009
0.0995

239
438
600
723
801
831
801
702
519

ur(HE) = u(HE)/|HE| = 0.024; for the calorimeter u(T) = 0.1 K; u(P) = 10 kPa.
u(x1) = 0.0007.
a
x1 is the mole fraction of 2-propanol, HE is the excess molar enthalpy at
T = 298.15 K.

TABLE A-2
Comparison of the regressed polynomial (equation (A-1)) with measured data and the
literature for the binary mixture of (2-propanol + cyclohexane).
Deviation (%)
Measured
Letcher, Mercer-Chalmers et al. [20]
Battler, Clark et al. [21]
Nagata, Fujiwara et al. [22]
Singh, Kalra et al. [23]

2.2
1.8
3.4
5.6
12.1

FIGURE 8. LLE for the ternary mixture of (water (1) + methanol (2) + TMP-1 (3)) at
atmospheric pressure (101 kPa) and (a) T = 298 K, (b) T = 283 K: d Turbidimetry; j
Measured tie lines; - - - tie lines made by NRTL model; miscibility gap boundaries
by NRTL model.

two different temperatures, and the model was showing correspondence with the measured data. Figure 8 is demonstrating
the LLE for the ternary mixture.
Notes
The authors declare no competing nancial interest.
Funding statement
Saeed Mardani, Petri Uusi-Kyyny and Juha-Pekka Pokki
acknowledge Academy of Finland for nancial support.
Appendix A
The calorimeter was calibrated using the binary system of (cyclohexane + hexane). Sabbah et al. [24] recommended a correlation

FIGURE A-1. Excess enthalpy (HE) at T = 298.15 K and atmospheric pressure

(101 kPa) for the binary system of (2-propanol (1) + cyclohexane (2)):  measured
data; regressed polynomial (equation (A-1)); N Letcher et al. [20];  Battler, Clark
and Rowley [21];  Nagata, Fujiwara and Ogasawara [22]; d Singh et al. [23].

128

S. Mardani et al. / J. Chem. Thermodynamics 85 (2015) 120128

TABLE B-1
Settings for Agilent 6850 and Agilent 6890 GCs.
GC name

Agilent 6850

Agilent 6890

Mode
Initial temp/K
Pressure/kPa
Split ratio
Gas type

Inlet
Split
443.15
148.4
30:01
Helium

Split
443.15
226.84
3.4:1
Argon

Initial temp/K
Initial temperature time/min

Oven
323.15
0

338.15
3

Ramp rate/K  min1

Final temp/K
Isothermal time after the ramp/
min

- First ramp:
10
373.15
5

- Second ramp:
Ramp rate/K  min1
20
Final temp/K
453.15
Isothermal time after the ramp/
5
min
Run time/min
20
Type
Model number
Column coating material
Nominal length/m
Nominal diameter/lm
Nominal lm thickness/lm
Type
Temp/K
Type
Temp/K

Columns
Capillary
Agilent 19091Z236E
HP-1 Methyl
Siloxane
60
250
1
Detector
FID
573.15

12
368.15
10

12
433.15
5
25.92
Capillary
Agilent 1227033
DB-WAX
30
320
50
FID
563.15
TCD
523.15

ane), and table A-2 is comparing the deviation between measured

and the literature. Figure A-1 compares the measured and the
literature.
Appendix B
Gas chromatograph (GC) settings for Agilent 6850 and Agilent
6890 equipped with deans switch [14] is provided in table B-1.

[2] P. Uusi-Kyyny, J. Pokki, J. Aittamaa, S. Liukkonen, Vapor liquid equilibrium for

the binary systems of methanol + 2,4,4-trimethyl-1-pentene at 331 K and 101
kPa and methanol + 2-methoxy-2,4,4-trimethylpentane at 333 K, J. Chem. Eng.
Data 46 (2001) 12441248.
[3] Halttunen, S. Measurement of solubilities of liquid mixtures, Lappeenranta
University of technology, 2000.
[4] H. Renon, J.M. Prausnitz, Local compositions in thermodynamic excess
functions for liquid mixtures, AIChE J. 14 (1968) 135144.
[5] J.D. Raal, A.L. Mhlbauer, Phase Equilibria: Measurement and Computation,
Taylor & Francis, Washington, 1998.
[6] SETARAM C80 Calorimeter, SETARAM Instrumentation, Caluire France, 2010.
[7] I. Wads, R.N. Goldberg, Standards in isothermal microcalorimetry, IUPAC
Technical Report, 73, 2001, pp. 16251639.
[8] SETARAM Technical note 12 C80 Flow mixing cell, SETARAM
Instrumentation, Caluire France, 2010.
[9] M. Polednicek, Dev eloppement dappareillages pour lacquisition des donne s
` es dinter e^t environnemental et en erget
thermodynamiques dans les system
ique, Blaise Pascal University, Clermont- Ferrand, France, 2000.
[10] Aspen Technology Inc. ASPEN PLUS. 2011.
[11] D.S. Bunch, D.M. Gay, R.E. Welsch, Algorithm 717: subroutines for maximum
likelihood and quasi-likelihood estimation of parameters in nonlinear
regression models, ACM Trans. Math. Softw. 19 (1993) 109130.
[12] H.I. Britt, R.H. Luecke, The estimation of parameters in nonlinear, implicit
models, Technometrics 15 (1973) 233247.
[13] D. Othmer, P. Tobias, Liquidliquid extraction data the line correlation, Ind.
Eng. Chem. 34 (1942) 693696.
[14] Agilent Technologies, Inc., Capillary Flow Technology: Deans Switch, Increase
the resolving power of your GC, 2013.
[15] A. Valtz, C. Coquelet, D. Richon, Volumetric properties of the
monoethanolaminemethanol mixture at atmospheric pressure from 283.15
to 353.15 K, Thermochim. Acta 428 (2005) 185191.
[16] D.L. Camin, F.D. Rossini, Physical properties of 16 selected C7 and C8 alkene
hydrocarbons, J. Chem. Eng. Data 5 (1960) 368372.
[17] H.A. Zarei, S. Asadi, H. Iloukhani, Temperature dependence of the volumetric
properties of binary mixtures of (1-propanol, 2-propanol and 1,2-propanediol)
at ambient pressure (81.5 kPa), J. Mol. Liq. 141 (2008) 2530.
[18] S.A. Beg, N.M. Tukur, D. Al-Harbi, Densities and excess volumes of
cyclohexane + hexane between 298.15 K and 473.15 K, Fluid Phase Equilib.
113 (1995) 173184.
[19] Design Institute for Physical Properties, Sponsored, by AIChE DIPPR Project 801
Full Version.
[20] T.M. Letcher, J. Mercer-Chalmers, A.K. Prasad, Excess molar enthalpies of
mixtures of a cycloalkane and an alkanol, Thermochim. Acta 188 (1991) 157
162.
[21] J.R. Battler, W.M. Clark, R.L. Rowley, Excess enthalpy and liquidliquid
equilibrium surfaces for the cyclohexane-2-propanol-water system from
293.15 to 323.15 K, J. Chem. Eng. Data 30 (1985) 254259.
[22] I. Nagata, K. Fujiwara, Y. Ogasawara, Excess enthalpies of 2-propanol +
cyclohexane and 2-propanol + benzene + cyclohexane at 298.15 K, J. Chem.
Thermodyn. 10 (1978) 12011203.
[23] K.C. Singh, K.C. Kalra, S. Maken, V. Gupta, Excess enthalpies and volumes of
mixing of 1-propanol or 2-propanol + cyclohexane at 298.15 and 308.15 K,
Fluid Phase Equilib. 123 (1996) 271281.
[24] R. Sabbah, A. Xu-wu, J.S. Chickos, M.L.P. Leito, M.V. Roux, L.A. Torres,
Reference materials for calorimetry and differential thermal analysis,
Thermochim. Acta 331 (1999) 93204.

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JCT 14-613