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Fluid Phase Equilibria 317 (2012) 3642

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Fluid Phase Equilibria


journal homepage: www.elsevier.com/locate/fluid

The effect of the end group, molecular weight and size on the solubility of
compounds in supercritical carbon dioxide
Fei Chang a , Jing Jin b , Ning Zhang b , Gang Wang a , Hai-Jian Yang b,
a
School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093, PR China
b
Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, Hubei Province, Key Laboratory of Analytical Chemistry of the
State Ethnic Affairs Commission, College of Chemistry and Materials Science, South-Central University for Nationalities, Wuhan 430074, PR China

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

Article history: End groups of bis(2-hydroxyethyl)ether (compound 1) and tetraethylene glycol (compound 2)
Received 2 September 2011 were modied with methyl malonyl chloride to produce two new compounds: malonic acid 2-
Received in revised form 9 December 2011 [2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester (compound 3) and Malonic acid
Accepted 18 December 2011
2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl ester methyl ester (compound
Available online 2 January 2012
4). And then the solubility of compounds 14 were investigated and compared in supercritical carbon
dioxide (scCO2 ) at a temperature range of 313363 K and in the pressure range of 9.225.7 MPa. The
Keywords:
effect of the end group, molecular weight and size for the solubility of the compounds were discussed. In
End group
Molecular weight and size addition, the tested solubility data were calculated and correlated with a semiempirical model at differ-
Carbonyl ent pressures and temperatures, which showed satisfactory agreement with each other and the average
Solubility absolute relative deviation was in the range of 2.61% and 33.25%. The Chrastil model also showed satis-
Supercritical CO2 factory agreement with each other and the average absolute relative deviation was in the range of 1.69%
and 11.53%.
2011 Elsevier B.V. All rights reserved.

1. Introduction scCO2 . According to the literature and based on our research results
[1416], substituted hydrocarbons with ether and alkyl group car-
The use of supercritical uid for industrial applications has been bonyl groups, especially carbonyl group with suitable length, are
widely investigated including chemical reactions, natural prod- easily available, comparably economical, and well dispersive in
uct extraction, cleaning, drying, and dyeing [1]. Carbon dioxide scCO2 , and thus used as desirable alternatives to uorinated com-
is undoubtedly the most researched and employed supercritical pounds. So in the present study, we have designed and synthesized
uid, mainly due to its relatively low critical temperature and an array of diglycolic acid ester derivatives with the alkyl, the car-
critical pressure (Tc = 304.15 K, Pc = 7.38 MPa) as well as to other bonyl, and the ether groups as CO2 -philic moieties, which were
favorable properties such as its high mass and heat transfer rates, subsequently exposed to solubility test in scCO2 over the pres-
nontoxicity, nonammability, and low cost [26]. Solubility data in sure range of 9.225.7 MPa and at the temperature of 313363 K.
supercritical uids are among the most important thermophysical The tested results were correlated by semiempirical model
properties that are essential to the efcient design of supercriti- and Chrastil model and satisfactory agreement were observed
cal processes, so an accurate solubility data test is necessary [7,8]. between experimental results and theoretical data, as expected.
Many research groups have extensively investigated the design of Potentially, these data will support a guideline to practical appli-
so-called CO2 -philic groups that are soluble in scCO2 at moder- cations of these compounds in relevant supercritical processes in
ate pressure [912]. Compounds bearing a peruoroalkyl polyether industries.
(PFPE) tail are highly soluble in CO2 , but this type of compound is
quite expensive and toxic [13]. Silicones are also generally consid-
2. Materials and methods
ered to be CO2 -philic. However, silicone-functioned amphiphiles
require higher pressure to generate a single-phase solution in
2.1. Chemicals and experimental apparatus

Carbon dioxide was purchased from Wuhan Steel Co. (99.99%,


Corresponding author. Tel.: +86 27 67842752; fax: +86 27 67842752. mass fraction). Diethylene glycol (99%), tetraethylene glycol
E-mail address: yanghaijian@vip.sina.com (H.-J. Yang). (99.5%), and methyl malonyl chloride (97%) were bought from Alfa

0378-3812/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2011.12.018
F. Chang et al. / Fluid Phase Equilibria 317 (2012) 3642 37

Table 1
Solubility at temperature T, density , and molar fraction y for compounds 14.

T (K) Compound 1 Compound 2

P (MPa)  (kg m3 ) 103 y 103 ycal AARDy% P (MPa)  (kg m3 ) 103 y 103 ycal AARDy%

11.8 713.51 4.57 5.31 16.24 11.1 689.56 2.59 2.88 11.46
12.8 739.88 6.17 6.80 10.16 12.1 722.18 3.46 4.10 18.47
313 13.7 758.85 7.73 8.04 3.94 12.7 737.53 4.35 4.80 10.16
15.0 781.32 9.18 9.71 5.74 13.3 750.85 5.23 5.48 4.76
15.8 793.14 10.69 10.67 0.13 14.2 768.06 6.04 6.46 6.98
13.8 667.36 4.88 4.64 5.05 13.2 646.02 2.76 2.51 9.12
14.7 693.52 6.58 6.03 8.41 14.0 673.70 3.71 3.43 7.47
323 15.8 719.15 8.16 7.71 5.49 14.7 693.52 4.63 4.26 7.96
16.6 734.83 9.76 8.92 8.61 15.3 708.19 5.54 4.99 10.05
17.7 753.49 11.25 10.55 6.22 16.2 727.25 6.38 6.08 4.68
15.7 629.64 5.18 4.46 13.83 15.2 612.88 2.91 2.50 14.15
16.6 655.62 6.96 5.83 16.28 15.9 635.84 3.93 3.25 17.25
333 17.7 681.96 8.60 7.58 11.87 16.7 658.24 4.88 4.18 14.33
18.7 702.17 10.21 9.23 9.66 17.5 677.53 5.79 5.17 10.82
19.6 718.11 11.80 10.73 9.07 18.4 696.42 6.66 6.33 4.96
17.5 599.31 5.44 4.65 14.56 17.2 590.29 3.02 2.82 6.71
18.3 621.28 7.35 5.84 20.50 17.8 607.88 4.11 3.45 16.04
343 19.3 645.20 9.09 7.45 18.04 18.6 628.83 5.11 4.37 14.38
20.3 665.99 10.77 9.18 14.78 19.5 649.58 6.04 5.51 8.82
21.2 682.59 12.42 10.80 13.01 20.3 665.99 6.97 6.60 5.31
19.6 585.00 5.57 5.71 2.41 19.1 571.96 3.12 3.33 6.69
20.5 606.50 7.52 7.13 5.28 19.8 589.98 4.23 4.09 3.44
353 21.8 633.76 9.26 9.41 1.59 20.7 610.96 5.26 5.18 1.43
22.8 652.23 11.00 11.31 2.90 21.4 625.80 6.27 6.12 2.50
23.6 665.70 12.73 12.92 1.50 22.4 645.07 7.19 7.57 5.21
21.3 565.75 5.76 6.61 14.70 21.1 561.14 3.18 4.24 33.49
22.4 589.55 7.74 8.45 9.14 22.0 581.20 4.30 5.33 23.96
363 23.5 610.95 9.60 10.51 9.39 22.9 599.55 5.36 6.55 22.22
24.6 630.28 11.38 12.76 12.16 23.7 614.61 6.39 7.74 21.22
25.7 647.85 13.08 15.20 16.16 24.5 628.60 7.38 9.03 22.42

T (K) Compound 3 Compound 4


3
P (MPa)  (kg m ) 3
10 y 3
10 ycal AARDy% P (MPa)  (kg m3 ) 103 y 103 ycal AARDy%

9.2 538.22 2.40 1.91 20.21 9.90 624.05 1.52 1.76 15.20
9.5 584.52 3.09 2.87 7.25 10.1 638.82 2.08 2.16 3.61
313 9.7 606.40 3.83 3.45 9.90 10.4 657.22 2.60 2.78 6.83
10.0 631.74 4.50 4.26 5.40 10.7 672.50 3.12 3.42 9.95
10.3 651.49 5.15 4.98 3.45 11.0 685.58 3.61 4.07 12.80
11.1 515.81 2.50 2.12 15.17 12.1 593.19 1.60 1.63 1.77
11.5 551.56 3.28 2.87 12.40 12.5 615.10 2.16 2.21 2.18
323 11.9 580.66 4.00 3.65 8.79 12.8 629.33 2.72 2.69 1.18
12.2 599.03 4.74 4.23 10.70 13.2 646.02 3.24 3.37 4.02
12.6 620.03 5.41 5.00 7.69 13.5 657.17 3.76 3.91 3.92
12.8 494.19 2.61 2.41 7.79 14.0 563.09 1.69 1.56 7.45
13.4 531.44 3.40 3.27 3.87 14.4 581.45 2.29 2.02 12.00
333 13.9 558.17 4.16 4.06 2.60 14.8 597.96 2.86 2.53 11.72
14.3 577.05 4.92 4.71 4.31 15.1 609.28 3.43 2.95 14.16
14.8 597.96 5.61 5.54 1.26 15.6 626.44 3.95 3.71 5.89
14.5 483.50 2.67 3.00 12.36 15.7 537.29 1.77 1.60 9.77
15.0 507.24 3.56 3.63 1.81 16.1 552.85 2.41 1.98 17.86
343 15.6 533.22 4.36 4.46 2.26 16.6 570.78 3.00 2.53 15.73
16.1 552.85 5.14 5.20 1.15 17.0 584.01 3.58 3.02 15.57
16.6 570.78 5.88 5.97 1.49 17.5 599.31 4.13 3.72 9.90
15.9 465.52 2.77 3.51 26.17 17.5 524.06 1.81 1.93 6.49
16.5 488.75 3.70 4.22 14.00 18.0 540.11 2.46 2.40 2.46
353 17.1 510.45 4.55 4.99 9.64 18.5 555.16 3.08 2.95 4.38
17.8 533.82 5.32 5.98 12.34 19.0 569.25 3.68 3.56 3.00
18.4 552.23 6.08 6.88 13.17 19.5 582.45 4.24 4.25 0.23
17.2 450.51 2.87 4.19 46.31 19.1 509.51 1.87 2.28 21.94
17.9 473.36 3.82 5.00 30.88 19.8 528.77 2.52 2.95 17.24
363 18.6 494.93 4.70 5.90 25.54 20.5 546.73 3.13 3.76 20.02
19.4 517.92 5.48 7.02 28.00 21.1 561.14 3.73 4.56 22.20
20.3 541.72 6.20 8.40 35.50 21.6 572.50 4.32 5.30 22.71

Aesar Chem. Co. and used without further purication. NMR exper- Plus intelligent HPLC Pump, and BP-1580-81 Back Pressure
iments were performed on a JEOL Al-400 MHz instrument using Regulator.
TMS as an internal standard. IR spectra were recorded on a Perkin-
Elmer 2000 FT-IR spectrometer. Elemental analysis was conducted 2.2. Modication
on a PE 2400 series II CHNS/O elemental analyzer. The appara-
tuses of supercritical carbon dioxide were bought from JASCO Methyl malonyl acid esters were synthesized according to a gen-
Corporation (Japan): PU-1580-CO2 CO2 Delivery Pump, PU-2080 erally synthetic procedure shown in Scheme 1. To the best of our
38 F. Chang et al. / Fluid Phase Equilibria 317 (2012) 3642

Scheme 1. Synthetic procedure for compounds 3 and 4.

knowledge, the two compounds were new, and their structures was loaded into the high-pressure view cell, and the stainless steel
were fully determined by IR, 1 H NMR, 13 C NMR, and elemental cell was then sealed. The compounds in the cell were stirred by a
analysis. magnetic stirrer, and the temperature was controlled using a tem-
Diethylene glycol (9.271 mmol, 0.88 mL) was dissolved in perature controller jacket with a circulator. A BP-1580-81 back
a CH2 Cl2 solution (30 mL) containing methyl malonyl chloride pressure regulator was used to keep a stable and accurate pressure.
(18.6 mmol, 2 mL), and triethylamine (30 mmol) was added drop- The system was heated to the desired temperature and pressur-
wise to the reaction system under an N2 atmosphere. The mixture ized with CO2 from a syringe pump. The pressure was increased
was stirred at room temperature for a whole night. Then, the reac- gradually by adding CO2 with a ow rate of 0.2 mL min1 until the
tion mixture was washed with 1% HCl aq, saturated NaHCO3 aq, and compound disappeared and the uid in the cell became transparent
then twice with water. The organic phase was collected, dried over single phase: this pressure was dened as dissolution pressure. At
anhydrous Na2 SO4 , and evaporated to a residue, which was puried each condition, the experiment was repeated at least three times.
by a silica gel column chromatography (ethyl acetate:petroleum The uncertainty of the dissolution pressure and temperature was
ether = 1:32:1) to obtain the target compound 3. 0.5 MPa and 0.1 C. The dissolution pressure and temperature
Similarly, tetraethylene glycol (9.267 mmol, 1.6 mL) was added were recorded to obtain the density of CO2 on the Web site page
into a CH2 Cl2 solution (30 mL) of methyl malonyl chloride [17].
(18.6 mmol, 2 mL) to create a clear solution. Triethylamine
(30 mmol) was dropped slowly to the solution under an N2 atmo- 3. Results and discussion
sphere. The mixture was stirred at room temperature for a whole
night. Then, the reaction mixture was washed in sequence with The solubility of the CO2 -philic compounds in scCO2 was deter-
1% HCl aq, saturated NaHCO3 aq, and twice with water, and the mined at 313 K, 323 K, 333 K, 343 K, 353 K, and 363 K and the
organic phase was collected and dried over anhydrous Na2 SO4 . The pressure range of 9.225.7 MPa. The experimental results were
residue was puried by a silica gel column chromatography (ethyl shown in Table 1, and the molar fraction of the solutes was repro-
acetate:petroleum ether = 2:1) and then (ethyl acetate:petroleum ducible within 3%. As expected, at the same temperature, the
ether = 1:2) to supply the compound 4. solubility of all compounds increased with the increase of pressure,
and at the same pressure, the solubility of all compounds decreased
2.2.1. Compounds 3: malonic acid with the increase of temperature [15,16]. All compounds possessed
2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl high solubility. Fig. 1 depicts the temperature increased from 313 K
ester to 363 K, the solubility of compound 1 is higher than compound
A light yellow oil with 89% yield (GC purity > 98.5%). FT-IR (KBr, 2 and the solubility of compound 3 is higher than compound 4.
cm1 ) 1738.5 (C O), 1277.0, 1146.2, 1041.4 (C O C); 1 H NMR We proposed the reason to the stronger intermolecular forces and
(CDCl3 ) H = 3.3473.357 (s, 4H, 2 O CCH2 C O), 4.212 (s, 4H, 2 hydrogen bonding, and the lager molecular size and weight of the
CH2 ), 3.652 (s, 4H, 2 CH2 ), 3.669 (s, 6H, 2 CH3 ); 13 C NMR (CDCl3 ) compound (2, 4) than compound (1, 3), respectively. The solubil-
C = 40.99 (2C, s), 52.32 (2C, s), 64.2968.63 (2C, d), 76.9377.57 ity of compound 3 is somewhat higher than compound 1 and the
(2C, t), 166.35166.75 (4C, d), 22.04 (2C, s), 13.68 (2C, s). Elemental solubility of compound 4 is higher than compound 2. It seems that
Anal.: C12 H18 O9 . Found: C, 47.01; H, 5.90; O, 47.09%. Required: C, the alkyl, the carbonyl, and the ether groups are CO2 -philic parts.
47.06; H, 5.92; O, 47.02%. Methyl malonyl group is more CO2 -philic than hydroxyl group. The
intermolecular attraction of solutesolute, so called solutesolute
2.2.2. Compounds 4: malonic acid 2-(2-{2-[2-(2- self-interaction is hereby reduced and the interaction between the
methoxycarbonyl-acetoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl ester solute and the CO2 molecule (solutesolvent) is enhanced, which
methyl ester favors improving the dispersive ability of compounds [18,19]. It
A light yellow oil with 83% yield (GC purity > 99%). FT-IR (KBr, also could be found that the bond strength between CO2 and the
cm1 ) 1744.9 (C O), 1096.5 (C O C); 1 H NMR (CDCl3 ): H = 3.676 carbonyl group decreased with the increase of temperature faster
(s, 6H, 2 CH3 ), 3.357 (s, 4H, 2 O CCH2 C O), 4.2284.233 (s, than hydroxyl group.
4H, 2 CH2 ), 3.6433.650 (s, 4H, 2 CH2 ), 3.582 (m, 8H, 4 CH2 ); The experimental solubility data for the four CO2 -philic com-
13 C NMR (CDCl ): = 41.09 (2C, s), 52.39 (2C, s), 64.49 (2C, s),
3 C pounds were correlated using the following equation [20,21]
68.5470.51 (2C, s), 76.87 (2C, s), 77.4977.51 (2C, t), 166.41 (2C,    
s), 166.80 (2C, s). Elemental Anal.: C16 H26 O11 . Found: C, 48.70; H, yP 
ln =A+C (1)
6.70; O, 44.60%. Required: C, 48.73; H, 6.65; O, 44.63%. Pref ref

where
2.3. Solubility test
a+b
A= (2)
Solubility measurement was carried out in a stainless steel view T
cell (7.11 mL) with two sapphire windows, which permitted visual where y was the molar fraction of the solutes; P was the pressure;
observation of the phase behavior. A suitable amount of solute Pref was 0.1 MPa;  was the density of pure CO2 at the experimental
F. Chang et al. / Fluid Phase Equilibria 317 (2012) 3642 39

12
10
10

8
8

103y
103y

6
6

4
4

2
a 2 b
9 10 11 12 13 14 15 16 13 14 15 16 17 18 19 20
P/MPa P/MPa
12

12
10

10
8
8
103y

103y
6
6

4
4

2
c 2 d
11 12 13 14 15 16 17 18 15 16 17 18 19 20 21
P/MPa P/MPa

14
12
12

10
10

8
8
103y
103y

6
6

4 4

2
e 2
f
16 17 18 19 20 21 22 23 24 17 18 19 20 21 22 23 24 25 26
P/MPa P/MPa

Fig. 1. Solubility comparison of compounds 14 in scCO2 at 313363 K; , compound 1 (bis(2-hydroxyethyl) ether); , compound 2 (tetraethylene glycol); , compound
3 (malonic acid 2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester); , compound 4 (malonic acid 2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-
ethoxy}-ethoxy)-ethyl ester methyl ester); y, the molar fraction of the solutes; P, pressure.

temperature and pressure; ref was 700 kg m3 ; and A, C, a, and b Table 2


Solubility constants a, b, and C from the data correlation procedure.
were constants.
The rst step was plots of ln(yP/Pref ) values versus ( ref ) Compounds a b/K C (m3 /kg)
(Fig. 2), and the values were tted with a straight line by least- 1 18.86886 6108.44029 0.012521667
squares regression to estimate the C and A parameters. The values 2 18.97549 6252.01508 0.013413333
of C, obtained from the slopes of the corresponding plots, were then 3 16.02985 5083.42241 0.00943
averaged for each compound (Table 2). When the C was held at its 4 18.85614 6084.28689 0.015371667
40 F. Chang et al. / Fluid Phase Equilibria 317 (2012) 3642

1.2
0.4

0.8
0.0
ln(yP/Pref )

0.4

ln(yP/Pref )
-0.4
0.0

-0.8
-0.4

a -1.2
-0.8
b
-120 -80 -40 0 40 80
( - ref
)Kg/m3 -120 -80 -40 0 40 80
( - ref ) Kg/m3
0.4
0.0

0.0
-0.4

-0.4
ln(yP/Pref )

-0.8
ln(yP/Pref )

-0.8 -1.2

-1.2 -1.6

c d
-1.6 -2.0
-240 -200 -160 -120 -80 -40 -180 -150 -120 -90 -60 -30
( - )Kg/m3 ( - ref
)Kg/m3
ref

Fig. 2. Plots of ln(yP/Pref ) vs ( ref ) for compounds 14 at various temperatures. (a) Compound 1 (bis(2-hydroxyethyl)ether); (b) compound 2 (tetraethylene glycol); (c)
compound 3 (malonic acid 2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester); (d) compound 4 (malonic acid 2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)-
ethoxy]-ethoxy}-ethoxy)-ethyl ester methyl ester). , 313 K; , 323 K; , 333 K; , 343 K; , 353 K; , 363 K.

average value, the experimental solubility data was then used to obtained. The resulting a and b values for compounds were also
evaluate the A values at various temperatures for each compound. shown in Table 2. Then, the values of a, b, and C were used to pre-
The plots of A versus 1/T for each compound were tted to a straight dict solubility using Eqs. (1) and (2). Finally, the average absolute
line (Fig. 3), from which the intercept and the slope (a and b) were relative deviation from experimental date (AARDy%) was used to
test the correlation results and calculated with the following Eq.
(3):

  yi,cal yi,exp 
2.0
1   100%
1.5 AARDy (%) =  yi,exp  (3)
n

1.0
where n was the number of experimental points and yi,cal and yi,exp
were the calculated and experimental data, respectively. The values
0.5
of AARDy were in the range of 0.4446.34%.
A

0.0 The solubilities were also correlated using the density-based


equation proposed by Chrastil [22]:
-0.5
m
ln S = k ln  + +n (4)
-1.0 T

where the density of CO2 (, g L1 ) was recommended also by NIST


-1.5
0.0027 0.0028 0.0029 0.0030 0.0031 0.0032 (http://webbook.nist.gov/chemistry/uid/). T was the system tem-
103K/T perature (K), k was the association number of CO2 , m and n were
the parameters of Eq. (4), S was the solubility of the solute (g L1 ),
Fig. 3. Plots of A vs 1/T for compounds; , compound 1 (bis(2-hydroxyethyl)ether); which could be calculated by:
, compound 2 (tetraethylene glycol); , compound 3 (malonic acid 2-[2-(2-
methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester); , compound 4 M2 y
(malonic acid 2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethoxy}-ethoxy)- S= (5)
M1 (1 y)
ethyl ester methyl ester).
F. Chang et al. / Fluid Phase Equilibria 317 (2012) 3642 41

3.0 3.0

2.8 2.8

2.6 2.6

Ln S
Ln S

2.4 2.4

2.2 2.2

2.0 2.0
a b
6.36 6.42 6.48 6.54 6.60 6.66 6.36 6.42 6.48 6.54 6.60 6.66
Ln Ln

3.2
3.2
3.0
3.0

2.8
2.8
Ln S

2.6
Ln S

2.6

2.4
2.4

2.2
2.2
c d
2.0
6.08 6.16 6.24 6.32 6.40 6.48 6.25 6.30 6.35 6.40 6.45 6.50
Ln Ln

Fig. 4. Logarithmic relationship between the solubility S (kg m3 ) of compounds 14 in scCO2 and the density  (kgm3 ) of pure CO2 . (a) Compound 1 (bis(2-
hydroxyethyl)ether); (b) compound 2 (tetraethylene glycol); (c) compound 3 (malonic acid 2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester); (d)
compound 4 (malonic acid 2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl ester methyl ester). Experimental results: , 313 K; , 323 K; , 333 K;
, 343 K; , 353 K; , 363 K calculated by Eq. (4), Chrastils model.

 
1   yi,cal yi,exp  4. Conclusion
AARDy (%) =   100% (6)
n  yi,exp 
In summary, the solubility of the compounds 14 was mea-
where y was the molar fraction of the solute, M1 and M2 were sured at the temperatures from 313 K to 363 K and the pressure
the molecular weights of CO2 and the solute, respectively. The range of 9.225.7 MPa. The solubility of compounds was inu-
constants m, n and k could be estimated from the experimental enced by the end groups, molecular weight and molecular size. The
solubility data in scCO2 . As a result, parameters for the Chrastil modied compounds showed better solubility than the unmodi-
equation are listed in Table 3. The absolute value of average rela- ed counterparts in supercritical CO2 . The solubility of compounds
tive deviation (AARDy%) between experimental data and correlated increased with increasing pressure (at constant T) and decreased
results show that good agreement was achieved by using the with increasing temperature (at constant P). In addition, the sol-
Chrastil equation. ubility of compound was mainly affected by the solutesolute
The consistency of the model with measured data can be seen self-interaction and solutesolvent intermolecular interaction. The
from Fig. 4 and the values of AARDy at different temperatures, which measured data were correlated with the semiempirical model and
are less than 7%. Chrastil model and showed good agreement between the corre-
lated results and the experimental data.

Table 3 Acknowledgements
Parameters of the Chrastil equation.

Parameters Compound 1 Compound 2 Compound 3 Compound 4 We are grateful to National Natural Science Foundation of China
k 7.15 7.65 5.26 8.50 (No. 51073175), The Innovation Program of Shanghai Municipal
m/K 3565.37 3622.83 2336.63 3771.76 Education Commission (11YZ113), the Special Research Fund in
n 33.36 36.20 23.44 40.36 Shanghai Colleges and Universities to Select and Train Outstand-
AARDy% 6.12 7.35 2.71 6.95
ing Young Teachers (slg10014) for nancial support. Hai-Jian Yang
42 F. Chang et al. / Fluid Phase Equilibria 317 (2012) 3642

also wants to appreciate the nancial support of Beijing National [9] R. Fink, D. Hancu, R. Valentine, E.J. Beckman, J. Phys. Chem. B 103 (1999)
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[12] J.F. Liu, H.J. Yang, W. Wang, Z.X. Li, J. Chem. Eng. Data 53 (2008) 21892192.
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