Fluid Phase Equilibria 420 (2016) 68e73

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Determination and correlation of heat of mixing of the carbon

dioxide þ tert-butyl methyl ether system at 298.15 and 303.15 K and
5.0e7.0 MPa
Kiyofumi Kurihara*, Tomohiro Kobayashi, Tomoaki Kasai, Hiroyuki Matsuda,
Katsumi Tochigi
Department of Materials and Applied Chemistry, Nihon University, 1-8-14 Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan

a r t i c l e i n f o a b s t r a c t

Article history: The heat of mixing (DHM) of the carbon dioxide þ tert-butyl methyl ether system was measured near the
Received 29 September 2015 critical point of carbon dioxide using a flow-type isothermal microcalorimeter at 298.15 and 303.15 K and
Received in revised form 5.0e7.0 MPa. The mixtures showed strong exothermic behavior in these regions. The maximum absolute
18 January 2016
value of DHM (maximum exothermic value) was about 7.9 kJ mol1 at 298.15 K and 5.0 MPa. A two-phase
Accepted 18 January 2016
Available online 21 January 2016
region, where DHM varied linearly with composition, was found in the CO2 rich region at all temperatures
and pressures except at 298.15 K and 7.0 MPa.
© 2016 Elsevier B.V. All rights reserved.
Keywords:
Heat of mixing
Carbon dioxide
Equation of state

1. Introduction 5.0e7.0 MPa using a flow-type isothermal microcalorimeter. The

Many researchers have measured the heat of mixing (DHM) of
mixtures containing carbon dioxide (CO2) and an organic solvent
near the critical point of CO2 (Tc ¼ 304.2 K, Pc ¼ 7.376 MPa [1])
[2e17]. Our research group has also measured DHM for binary
systems of CO2 þ alcohol (methanol [18,19], 2-propanol [20], 2-
butanol [20], and 2-methyl-1-propanol [21]), þ ester (dimethyl
carbonate (DMC) [22], diethyl carbonate (DEC) [23], ethyl acetate
[24]), þ ether (diisopropyl ether (DIPE) [25]), and the ternary sys-
tem CO2 þ ethanol þ water [21]. The CO2 þ ester and þ ether
systems showed extremely large exothermic behavior in their DHM
data. This large heat effect is expected to be applicable to the
development of a new energy supply system [26].
The objective of the present work was to identify a solvent that
can be combined with CO2 to produce a large heat effect for the
development of an efficient energy supply system. In this work, we
selected the tert-butyl methyl ether (MTBE) as the organic solvent
to be mixed with CO2. The DHM data for this mixture have not been
reported previously in the literature. Thus, measurement of DHM
for the CO2 þ MTBE system was carried out at 298.15, 303.15 K and
* Corresponding author.
E-mail address: kurihara.kiyofumi@nihon-u.ac.jp (K. Kurihara).
mixtures showed exothermic behavior in these regions. A two-
phase region in which DHM varies linearly with composition was
found in the CO2-rich region except under the condition 298.15 K
and 7.0 MPa. The experimental DHM data within the one-phase
region were correlated with the modeified RedlicheKister (mRK)
equation proposed by Myers and Scott [27], and the Pen-
geRobinson (PR) equation of state [28] coupled with the van der
Waals one fluid mixing rule. DHM data reduction was also carried
out using the linear expression for the mole fraction of CO2 in the
two-phase region.
2. Experimental
2.1. Materials
The chemicals used in this work are summarized in Table 1.
First-grade pure reagent MTBE (Wako Pure Chemical Industry Ltd.,
Japan) was used after the removal of trace water with a 3 A mo-
lecular sieve. The mole purity of the MTBE was confirmed to be
>99.9% by gas chromatography. The volume fraction purity of the
CO2 was 99.99% (Showa Carbonic Acid Company Ltd., Japan). The
CO2 was filtered through a 0.5-mm inline filter (Nupro Company,
Japan) before use.
Flow rates measured in cm3 min1 at a constant temperature of

http://dx.doi.org/10.1016/j.fluid.2016.01.033
0378-3812/© 2016 Elsevier B.V. All rights reserved.
 K. Kurihara et al. / Fluid Phase Equilibria 420 (2016) 68e73 69

Table 1
Chemicals used in this work.

Chemical name Source Purification method Final purity Analysis method

Carbon dioxide Showa Carbonic Acid Company Limited, Japan none 0.9999a e
tert-Butyl methyl ether Wako Pure Chemical Industry Limited, Japan 3 A molecular sieves 0.999b Gas chromatography
a
Volume fraction.
b
Mass fraction.

283.15 K were converted to mole min1 and then to mole fractions Table 3
using the densities of the pure materials, which were estimated as Experimental heats of mixing DHM at temperature T of 298.15 and 303.15 K, pressure
P from 5.0 to 7.0 MPa, and mole fraction x1 for the system CO2 (1) þ tert-butyl methyl
follows. The density of CO2 at 283.15 K and the pressures studied ether (2).a
was calculated using the equation of state (EOS) for CO2 proposed
by Span and Wagner [29,30]. The density of MTBE at 283.15 K and x1 DHM (J mol1) x1 DHM (J mol1) x1 DHM (J mol1)
the pressures studied was obtained by interpolating the literature 298.15 K, 5.00 MPa
values of Ihmels et al. [31]. The estimated densities of the pure 0.100 1150 0.600 6280 0.870b 6273
0.200 2164 0.700 7102 0.900b 4405
components are given in Table 2. The uncertainty of the calculated
0.299 3311 0.770 7648 0.950b 1503
mole fraction was ±0.001. 0.400 4362 0.799 7812
0.500 5332 0.850b 7302
2.2. Apparatus and procedure 298.15 K, 5.50 MPa
0.100 1030 0.600 5881 0.900 7825
0.200 2067 0.700 6649 0.920b 6377
A high-pressure, flow-type isothermal microcalorimeter (Calo- 0.300 3155 0.799 7353 0.930b 5121
rimetry Sciences Corporation, UT, USA) was used to measure DHM. 0.400 4109 0.850 7635 0.950b 2948
The apparatus consisted of a mixing unit, constant temperature 0.500 5012 0.880 7769
water bath, two high-pressure ISCO syringe pumps for sample 298.15 K, 6.00 MPa
0.100 1011 0.600 5443 0.930b 7107
supply, cooling circulation system for the syringe, pressure-
0.200 2029 0.700 6132 0.950b 4838
adjustment device, degassing unit, and a personal computer for 0.300 2926 0.799 6735 0.960b 3251
signal collection and data processing. Measurements could be 0.399 3813 0.850 7023
made from 233 K to 353 K and from 0.1 MPa to 20 MPa. The details 0.500 4673 0.900 7153
298.15 K, 7.00 MPa
of the experimental apparatus and procedure have been described
0.100 279 0.500 1009 0.850 867
elsewhere [18e20,32]. The temperature stability of the water bath 0.200 527 0.600 1069 0.900 681
was within ±0.0005 K. The pressure was also kept within 0.01 MPa 0.299 737 0.700 1045 0.929 532
during the DHM measurements. The uncertainty of our experi- 0.400 900 0.800 960 0.950 389
mental DHM data could be estimated to within ±1.0% (maximum 303.15 K, 5.00 MPa
0.100 1149 0.500 5351 0.750 7357
absolute error of 8 J mol1). This uncertainty was caused primarily
0.200 2253 0.600 6234 0.850b 5022
by the high sensitivity of DHM to small changes in temperature and 0.300 3332 0.700 7049 0.900b 3356
pressure. The total flow rate was varied from 0.05 cm3 min1 to 0.400 4384 0.720 7240 0.950b 1295
0.20 cm3 min1, and the effect of the total flow rate on the mea- 303.15 K, 5.50 MPa
surement of DHM was taken into consideration. The optimal total 0.200 2151 0.700 6784 0.900b 5274
0.300 3210 0.750 7126 0.920b 3948
flow rate was 0.08 cm3 min1 for all cases. 0.400 4170 0.799 7470 0.950b 2304
Each pure component was charged into an ISCO syringe after 0.500 5111 0.819 7532 0.979b 499
degassing. The temperatures of the syringes and their contents 0.600 6027 0.849 7719
were kept constant with a water thermostat. The supply of the pure 303.15 K, 6.00 MPa
0.100 1042 0.600 5675 0.930b 5099
components to the mixing unit was carried out at a constant
0.200 2118 0.700 6377 0.950b 3478
temperature of 283.15 K (about 20 K lower than the critical 0.300 3056 0.800 6966 0.980b 506
temperature of CO2) to prevent variations in the density caused by 0.400 3990 0.850 7268
slight changes in temperature and pressure. 0.500 4863 0.900 7345
303.15 K, 7.00 MPa
0.100 827 0.600 4474 0.960b 5199
3. Results and discussion 0.200 1665 0.700 5049 0.970b 2788
0.299 2402 0.800 5396 0.979b 447
DHM was measured for the CO2 þ MTBE system over the entire 0.400 3196 0.850 5545
composition range of 298.15, 303.15 K under pressures of 0.500 3828 0.950 5385
5.0e7.0 MPa. The experimental results of DHM are summarized in a
Standard uncertainties u are u(T) ¼ 0.01 K, u(p) ¼ 0.01 MPa, u(x) ¼ 0.001, and the
combined expanded uncertainty Uc is Uc(DHM) ¼ 1.0%.
b
Two-phase region.
Table 2
Densities r of the pure components at 283.15 K.
Table 3. Figs. 1 and 2 show the DHM vs. x1 (mole fraction of CO2)
3
P (MPa) r (kg m ) isobars obtained at 298.15, and 303.15 K, respectively. The mixtures
CO2a tert-Butyl methyl etherb showed large exothermic mixing throughout the region studied.
The maximum absolute value (i.e., maximum exothermic value
5.00 868.63 755.82
5.50 875.48 756.32 jDHMjmax) at each temperature and pressure was about
6.00 881.78 756.82 5.4e7.9 kJ mol1, except at the
condition

298.15 K and 7.0 MPa. The
7.00 893.11 757.82 mole fraction of CO2 at which
DHM
max appeared was also shifted
a
Span and Wagner [29,30]. to the CO2-rich side with increasing pressure. These tendencies are
b
Ihmels et al. [31].
70 K. Kurihara et al. / Fluid Phase Equilibria 420 (2016) 68e73

same way as discussed in our earlier paper [24,25] as follows. CO2 is

liquid at 298.15 K and 7.0 MPa and vapor at other temperatures and
pressures. In contrast, MTBE (Tc ¼ 497.1 K and Pc ¼ 3.435 MPa [1]) is
liquid at all temperatures and pressures. When CO2 vapor is mixed
with liquid MTBE, the CO2 is dissolved in the MTBE and its state
changes from vapor to that of a liquid mixture component. As a
consequence, the enthalpy of condensation of CO2 is thought to be
the main contribution to the large exothermic effects observed in
this work. However, when the pure components are mixed at
298.15 K and 7.0 MPa, the enthalpy of condensation of CO2 is not
generated because the CO2 is in
a liquid

state at this temperature
and pressure. Therefore, the
DHM
max (about 1069 J mol1)
measured at 298.15 K and 7.0 MPa is smaller than those observed at
other temperatures and pressures, and the vapor and liquid sepa-
ration region does not form in this condition.

4. Correlation models

The experimental results of DHM in the homogeneous phase

were correlated using the following mRK equation proposed by
Myers and Scott [27]:
Fig. 1. Heat of mixing for the CO2 (1) þ tert-butyl methyl ether (2) system at 298.15 K
C, experiment data at 5.0 MPa; -, 5.5 MPa; :, 6.0 MPa; ;, 7.0 MPa; B, solubility
X
N1
ci ð2x1  1Þi
limits of CO2 in MTBE; d, eq. (1); ∙∙∙∙, eq. (13); , PengeRobinson equation of state. DHM ¼ x1 ð1  x1 Þ (1)
1  [ð2x1  1Þ
i¼0

where ci and [ are adjustable parameters, x1 is the liquid mole

fraction of CO2, and N is the number of adjustable parameters ci.
These DHM data were also correlated using the PR EOS [28]:

RT a
P¼  (2)
v  b vðv þ bÞ þ bðv  bÞ

where P is the pressure, R is the gas constant, T is the temperature,

and v is the molar volume of mixture. a and b are the energy and
size parameters of the mixture, respectively. For pure component i,
these parameters are calculated from Tc,i and Pc,i using the following
equations:

aii ¼ aci ai (3)

0:45724R2 Tci2
aci ¼ (4)
Pci

  
pffiffiffiffiffiffi 2
ai ¼ 1 þ mi 1  Tri (5)

Fig. 2. Heat of mixing for the CO2 (1) þ tert-butyl methyl ether (2) system at 303.15 K mi ¼ 0:37464 þ 1:5422ui  0:26992u2i (6)
C, experiment data at 5.0 MPa; -, 5.5 MPa; :, 6.0 MPa; ;, 7.0 MPa; B, solubility
limits of CO2 in MTBE; d, eq. (1); ∙∙∙∙, eq. (13); , PengeRobinson equation of state.
0:07780RTc;i
bi ¼ (7)
Pc;i
similar to those observed for systems of CO2 þ DMC [22], þ DEC
[23], þ ethyl acetate


[24], and þ DIPE [25] by our research group. where ui is the acentric factor of pure component i. Tc,i, Pc,i, and ui,
The largest
DHM
max found in the region studied was about
which are necessary to calculate the aii and bi values of the pure
7.9 kJ mol1 at 298.15 K and 5.5 MPa. The DHM data were shifted
components investigated in this work, are shown in Table 4 [1].
towards smaller exothermic energy with increasing pressure. This
was somewhat lower than those observed for the CO2 þ DMC
Table 4
[22], þ DEC [23], and þ ethyl acetate [24] systems, but higher than
Critical temperature Tc, critical pressure Pc, and acentric factor u of the pure
that for the CO2 þ DIPE [25] system. components.a
At all temperatures and pressures except 298.15 K and 7.0 MPa,
Component Tc (K) Pc (MPa) u
DHM varied linearly with composition in the CO2-rich region, which
corresponded to the two-phase (vapor and liquid) region. This CO2 304.2 7.376 0.225
behavior of DHM for the CO2 þ MTBE system is explained in the tert-Butyl methyl ether 497.1 3.435 0.267
a
DDB2015 [1].
 K. Kurihara et al. / Fluid Phase Equilibria 420 (2016) 68e73 71

Table 5
Determined parameters and deviations between the experimental and calculated DHM using Eqs. (1) and (13) for the CO2 (1) þ tert-butyl methyl ether (2) system.

Parameter and deviation 5.00 MPa 5.50 MPa 6.00 MPa 7.00 MPa

298.15 K, one-phase region

[ 9.5984  101 9.8373  101 9.8600  101 7.1807  101
c0 (J mol1) 2.1334  104 1.9999  104 1.8628  104 4.0485  103
c1 (J mol1) 2.0785  103 3.7664  103 4.5880  103 2.1846  103
D1a (J mol1) 21 22 14 9
D2b (%) 0.8 1.0 0.5 1.4
298.15 K, two-phase region
A (J mol1) 5.6970  104 1.1047  105 1.2313  105 e
B (J mol1) 5.8386  104 1.1322  105 1.2474  105 e
D1a (J mol1) 56 36 130 e
D2b (%) 0.9 0.8 2.9 e
298.15 K, overall
D1a (J mol1) 39 29 72 9
D2b (%) 0.8 0.9 1.7 1.4
303.15 K, one-phase region
[ 9.4366  101 9.7475  101 9.8226  101 9.8058  101
c0 (J mol1) 2.1400  104 2.0452  104 1.9413  104 1.5344  104
c1 (J mol1) 2.4030  103 3.6316  103 4.8013  103 4.5863  103
D1a (J mol1) 14 17 18 31
D2b (%) 0.9 0.3 0.6 1.2
303.15 K, two-phase region
A (J mol1) 3.6754  104 5.8900  104 9.1151  104 2.4041  105
B (J mol1) 3.7262  104 5.9640  104 9.2437  104 2.4504  105
D1a (J mol1) 60 47 95 18
D2b (%) 3.1 1.7 5.7 1.4
303.15 K, overall
D1a (J mol1) 37 32 52 25
D2b (%) 2.0 1.0 3.2 1.3
PNDP
a jDHexptl
M
DHcalcd
M
jn
D1 ¼ n

NDP



PNDP
DHexptl

b 100
M
DHcalcd
M


D2 ¼ NDP

.
n
DHexptl M


n

In this work, the van der Waals one fluid mixing rule was used to
calculate the mixture energy parameter a and the size parameter b: 2 !0:5


va 1XNC X
NC 
4
acj aii
¼ xi xj 1  kij mj
vT v;xi 2 i j
Tcj T
3 (11)
X
NC X
NC
pffiffiffiffiffiffiffiffiffiffi 
0:5
a¼ xi xj aii ajj 1  kij kij ¼ kji ; kii ¼ kjj ¼ 0 (8) aci ajj
þ mi 5
i j Tci T


vaii aci mi
X
NC ¼ pffiffiffiffiffiffiffiffiffiffiffiffi
ffi (12)
b¼ x i bi (9) vT vi Tci Tai
i
where NC is the number of components and kij is a binary inter- At the region where the two phases form, the linear section of
action parameter. DHM values was expressed using the following equation:
The DHM is thermodynamically expressed by the following
equations derived from Eq. (2)(9).
Table 6
Determined parameters and deviations between the experimental and calculated
DHM using the Peng-Robinson EOS combined with the van der Waals one fluid


 mixing rule for the CO2 (1) þ tert-butyl methyl ether (2) system.
T va a 2 pffiffiffi 3
vT vþ 1 2 b Parameter and deviation 5.00 MPa 5.50 MPa 6.00 MPa 7.00 MPa
v;xi
DH M
¼ pffiffiffi ln4  pffiffiffi 5 2
2b 2 vþ 1þ 2 b 298.15 K, one-phase region, k12 ¼ 7.977  10

 D1a (J mol1) 70 85 95 e
  3
T vaii
 aii 2v þ 1  pffiffiffi (10)
D2b (%) 1.6 1.6 1.9 e
X
NC vT
vi i 2 bi 303.15 K, one-phase region, k12 ¼ 8.154  102
þ xi p ffiffiffi ln4  pffiffiffi 5 D1a (J mol1) 78 114 80 56
2bi 2 vi þ 1 þ 2 bi
i D2b (%) 1.9 1.8 1.7 1.8
!
XNC
a
PNDP
jDHexptl
M
DHcalcd
M
jn
þP v xi vi D1 ¼ n

NDP

i P
DHM DHM

b 100 NDP
exptl

D2 ¼ NDP
DHM calcd

n
exptl

n
72 K. Kurihara et al. / Fluid Phase Equilibria 420 (2016) 68e73

Table 7 equation and the PR EOS gave reasonable correlated results at all
1 from DH for the CO2 (1) þ tert-butyl methyl ether (2) system.
M
Solubility Limits xVL temperatures and pressures in the one-phase region. However the
P (MPa) xVL
1 DHM (J mol1) (Calculated) results from the mRK equation are better than those from the PR
298.15 K
EOS. The correlated results by the mRK equation and PR EOS are
5.00 0.841 7985 shown graphically in Figs. 1 and 2, respectively.
5.50 0.907 7780 Finally, we determined the liquid composition xVL 1 of CO2 at the
6.00 0.930 7066 vaporeliquid equilibrium (VLE) of the mixture at each tempera-
303.15 K
tures and pressures where a two-phase region was formed. In other
5.00 0.784 7559
5.50 0.856 7696 words, xVL1 was the solubility limit of CO2 in MTBE, and was ob-
6.00 0.905 7321 tained by combining Eqs. (1) and (13) as simultaneous equations of
7.00 0.962 5092 xVL VL
1 . The determined x1 of CO2, are listed in Table 7 and illustrated in
Figs. 1 and 2.
VLE data for the present system was available in Ref. [34]. Un-
fortunately, the temperatures (310.15, 329.15, and 338.15 K) of this
VLE data disagreed with those studied in this work. However, we
dared to compare the obtained xVL1 with the high-pressure VLE data
1 determined from our DH data are
at 310.15 K. In Fig. 3, the xVL M

shown along with the liquid composition of the experimental VLE

at 310.15e338.15 K reported in Ref. [34]. As can been seen in Fig. 3,
1 obtained from the DH data is in relatively good
the behavior of xVL M

agreement with that of the liquid compositions of VLE.

5. Conclusions

1 from the experimental DH
Fig. 3. Comparison between the solubility limit points xVL
data and the liquid compositions of the experimental vaporeliquid equilibrium data
reported by Wu et al. [34] for CO2 (1) þ tert-butyl methyl ether (2) system. circle, xVL
obtained from DHM data (C, 298.15 K; , 303.15 K); triangle, liquid compositions of
VLE data (:, 310.15 K; , 329.15 K; , 338.15 K).
The heat of mixing (DHM) was measured for the CO2 þ tert-butyl
methyl ether system over the entire composition range at 298.15,
303.15 K and 5.0e7.0 MPa. These experimental DHM data indicated
exothermic behavior for all compositions at all studied tempera-
tures and pressures studied. The maximum absolute value of DHM
for each temperature and pressure was about 5.6e7.9 kJ mol1. At
all studied temperatures and pressures except 7.0 MPa, 298.15 K, a
two-phase region, where DHM varies linearly with composition,
was found in the CO2-rich region. Experimental DHM data within
the one-phase region were correlated with the mRK equation, and
with the PR EOS combined with the van der Waals one fluid mixing
M
rule. The correlated results from the mRK equation were found to
be better than those from the PR EOS.
1
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