Fluid Phase Equilibria 317 (2012) 36–42

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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 modified 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 1–4 were investigated and compared in supercritical carbon
dioxide (scCO2 ) at a temperature range of 313–363 K and in the pressure range of 9.2–25.7 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
[14–16], substituted hydrocarbons with ether and alkyl group car-
The use of supercritical fluid 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 fluorinated com-
is undoubtedly the most researched and employed supercritical pounds. So in the present study, we have designed and synthesized
fluid, 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, nonflammability, and low cost [2–6]. Solubility data in sure range of 9.2–25.7 MPa and at the temperature of 313–363 K.
supercritical fluids are among the most important thermophysical The tested results were correlated by semiempirical model
properties that are essential to the efficient 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 [9–12]. Compounds bearing a perfluoroalkyl 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.fluid.2011.12.018

04 6.30 5. / Fluid Phase Equilibria 317 (2012) 36–42 37 Table 1 Solubility at temperature T.5 488.73 3.06 2.43 7.07 12.78 6.4 696.00 21.33 18.57 5.99 6.6 734.7 693.6 572. T (K) Compound 1 Compound 2 P (MPa)  (kg m−3 ) 103 y 103 ycal AARDy% P (MPa)  (kg m−3 ) 103 y 103 ycal AARDy% 11.90 15.3 645.71 4.17 6.36 4.76 3.55 4.03 4.5 606.64 5.6 533.16 4.74 21.1 509.4 589.44 3.95 10.7 737.52 7.6 570.81 1.71 Aesar Chem.83 15.65 14.50 2.00 333 13.31 5.31 19.25 3.73 4.11 11.85 5.38 17.50 22.45 9.83 16.24 4. “PU-2080 erally synthetic procedure shown in Scheme 1.99 10.40 1.5 555.7 702.41 19.2 612.49 16.88 13.92 12.22 16.36 4.05 17.76 15.00 3.4 531.76 15.53 15.3 665.77 2.45 4. 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.50 21.72 6.96 5.18 4.96 17.92 1. F.8 597.15 4.50 3.97 6.61 5.33 2.17 10.95 3.39 7.41 1.98 4.85 5.69 10.76 2.32 5.16 12.2.90 624.71 18.58 11.88 11.62 6.61 14.87 2.36 6.28 19.51 1.38 9.11 3.35 4.0 569.21 9.45 13.88 6.60 2.09 1.8 533.8 713.20 9.16 7.37 4.3 708.19 46.32 9.72 2.7 672.70 12.53 5.33 4.46 2.86 2.94 12.64 5.42 6.55 5.5 649.25 333 17.42 10.58 3.28 21.6 665.29 2.4 552.00 2. Modification on a PE 2400 series II CHNS/O elemental analyzer.99 9.06 6.32 5.31 16.23 11.4 581.5 551.8 629.70 13.3 541.90 10.8 528.95 17.06 1.90 21.19 1.40 3.17 17.17 4.47 323 15.80 11.78 5.76 9.3 577.36 3.23 17.2 768.19 2.92 8.25 0.7 629.67 0.11 4.55 7.39 22.73 16.50 14.50 4.9 635.02 15.28 15.05 13.77 9.58 6.08 4.45 4.45 16.28 7.20 20.80 10.87 12.42 T (K) Compound 3 Compound 4 −3 P (MPa)  (kg m ) 3 10 y 3 10 ycal AARDy% P (MPa)  (kg m−3 ) 103 y 103 ycal AARDy% 9.85 13.5 599.8 793.20 1.01 3.19 5.40 35.53 11.41 7.2 538.03 8.3 665.75 5.53 4.02 19.14 10.1 593.71 5.21 2.25 10.08 2.22 4.0 581.22 2.03 22.78 3.08 6.70 21.96 363 23.25 17.16 14. Chang et al.24 363 18.24 33.31 19.08 2.01 20.26 9.54 1.45 9.71 5.55 22.60 9.24 4.18 14.20 4.3 750.78 19.98 13.77 3.00 5.50 17.80 10.79 5.2 727.31 4.58 6.68 3.02 3.70 3.83 9.77 15.56 22.1 561.87 4.14 3.00 7.03 5.8 652.69 1.18 4.38 12.60 7.0 781.5 582.52 2.56 2. Plus” intelligent HPLC Pump.46 13.2 450.40 3.7 610.83 10.74 4.5 657.96 2.10 18. and used without further purification.33 23. NMR exper.61 313 9.28 3.83 3.24 3.93 3.48 4.91 2.29 1.18 9.14 3.1 552.15 16.18 3.82 5.7 758.5 610.59 12.0 631.7 693.7 753.16 15.50 4.9 473.07 18.77 11.12 3.09 3.7 658.51 26.6 585.95 14.2 590.61 15.52 2.40 2.87 16.25 6.34 19.16 24.88 4.76 8.17 10.94 17.6 628.80 10.14 22.16 3.46 2.17 19.79 12.88 2.82 19.67 3.93 4.8 597.64 18.69 20.82 5.87 7.1 515.60 14.20 16.69 13.52 1.63 1.56 7.15 8.5 584.0 507.49 22.5 615.1 510.44 4.26 5.66 4.41 14.51 4.51 2.31 15.73 12.26 16.28 2.12 2.3 621.66 6.02 28.00 18.96 5.50 7.18 12.13 3.72 9.17 12.2 599.73 8.4 625.80 13.2 646.82 2. Co.81 16.7 537.95 9.35 5.22 14.21 21.44 3.51 9.2 682.1 638.8 719.89 14.04 3.5 628.5 524.57 5.17 3.65 8.86 343 15.5 677.18 323 11.88 5.60 5.26 15.33 6.79 14.82 6.3 565.8 739.50 2.16 2.56 3.08 15.77 1.75 3.8 494.51 9.36 15.00 11.0 673.40 10.52 6.73 9.54 20.5 546.99 10.96 16.22 25.18 1.3 651.38 6.71 5.05 1.42 9.88 4.46 4.96 3.4 517.85 2.22 24. Elemental analysis was conducted 2.50 23.47 313 13.1 609.71 2.98 17.98 12.29 3.97 1.56 3.9 580.23 6.1 552.5 599.16 3.24 3.6 718.84 3.12 3.61 4.70 4.23 10.6 620.43 22.00 18.74 8.13 5.11 2.20 9.0 685.23 9.48 7.07 7.74 4.1 722.61 6.52 3.05 4.49 17.92 4.9 599.23 5.59 2.56 3.69 1.54 4.81 2.02 2.0 563. density .7 647.60 1.13 14.76 12.7 606.21 9.49 11.84 20.96 8.55 6.7 614.8 633.59 20.6 570.00 12.9 465.09 2.68 15.76 20.14 5.26 7.12 14.31 2.46 6.00 30.41 5.41 1.09 7.20 8. IR spectra were recorded on a Perkin- Elmer 2000 FT-IR spectrometer.19 7.8 589.91 3.95 4.4 657.8 667.63 1.96 5.30 22.26 5.4 645.76 6.70 5.52 4.58 3.61 2.22 2.45 11.98 3.74 13. and “BP-1580-81” Back Pressure iments were performed on a JEOL Al-400 MHz instrument using Regulator.1 561.1 571.12 15.87 14.83 5.02 12.80 6.88 4.9 558.63 4. and molar fraction y for compounds 1–4.40 12.44 353 21.8 607.15 17. TMS as an internal standard.90 25.5 483.27 3. To the best of our .04 18.66 17.6 626.60 10.28 11.18 14.60 7.85 7.92 5.46 12.49 14.37 14.0 540.02 12.6 630.72 14.45 18.91 20.38 20.10 2.1 689.25 10.24 11.16 23.57 5.57 16.88 19.45 2.82 21.23 4.71 3.43 2.13 3.49 5.7 681.0 584.27 6.2 646.02 2.56 17.04 343 19.6 655.51 8.93 6.6 494.46 353 17.04 5.

the solubility of compound 1 is higher than compound A light yellow oil with 89% yield (GC purity > 98. O.87 (2C. 22.51 (2C.2–25. The compounds in the cell were stirred by a analysis.9 (C O).16].68 (2C. 48. 77. 6H.99 (2C.35–166. 1 H NMR. self-interaction” is hereby reduced and the interaction between the methoxycarbonyl-acetoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl ester solute and the CO2 molecule (solute–solvent) is enhanced.02%. 0.06.2. 1 depicts the temperature increased from 313 K ester to 363 K. 1 H NMR We proposed the reason to the stronger intermolecular forces and (CDCl3 ) ıH = 3.09 (2C.228–4. tetraethylene glycol (9. 166.93–77.70. Compounds 3: malonic acid with the increase of temperature [15.80 (2C.32 (2C.41 (2C.347–3.  was the density of pure CO2 at the experimental .1 ◦ C. s). d). 4× CH2 ).7 MPa. the reac.1 MPa. 47. 4. Methyl malonyl group is more CO2 -philic than hydroxyl group. t).357 (s. d).6 mmol. 4H.73. the ether = 1:2) to supply the compound 4. Results and discussion sphere.63 (2C. 3 C pounds were correlated using the following equation [20.21] 68. so called “solute–solute 2. s). O. 3. The organic phase was collected. also could be found that the bond strength between CO2 and the cm−1 ) 1744. 1 H NMR (CDCl3 ): ıH = 3.650 (s.65. (18. 52. 13.652 (s. magnetic stirrer. saturated NaHCO3 aq. and triethylamine (30 mmol) was added drop. 2× O CCH2 C O). The solubil- ıC = 40. 4H. s). 47. 166. and the mined at 313 K.70.60%. All compounds possessed 2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl high solubility. 333 K. 47.49 (2C. 5. The pressure was increased was stirred at room temperature for a whole night.90.19]. FT-IR (KBr.643–3. at the same temperature. The experimental results were residue was purified by a silica gel column chromatography (ethyl shown in Table 1. s). 5. the carbonyl.2 mL min−1 until the tion mixture was washed with 1% HCl aq. gradually by adding CO2 with a flow rate of 0.     s).6 mmol. 2× CH2 ).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].92. respectively. 1146.54–70. 76. Triethylamine (30 mmol) was dropped slowly to the solution under an N2 atmo. 3. dried over single phase: this pressure was defined as dissolution pressure. t). 52. Elemental solubility of compound 4 is higher than compound 2. H.233 (s. 2× CH2 ). the experiment was repeated at least three times. Compounds 4: malonic acid 2-(2-{2-[2-(2. 4H. and twice with water. The experimental solubility data for the four CO2 -philic com- 13 C NMR (CDCl ): ı = 41. Chang et al.4 (C O C). Then. the alkyl. solubility of all compounds increased with the increase of pressure. observation of the phase behavior. s).01.5 (C O C).5 (C O). yP  ln =A+C (1) 6. As expected. 76. A suitable amount of solute Pref was 0.04 (2C.39 (2C. 44. O.2. The mixture ized with CO2 from a syringe pump.09%. 44.2. s). and the molar fraction of the solutes was repro- acetate:petroleum ether = 2:1) and then (ethyl acetate:petroleum ducible within ±3%. 48.57 ity of compound 3 is somewhat higher than compound 1 and the (2C. ±0. the reaction mixture was washed in sequence with The solubility of the CO2 -philic compounds in scCO2 was deter- 1% HCl aq. Synthetic procedure for compounds 3 and 4. 1041. 2× CH3 ). 2× CH2 ). and the lager molecular size and weight of the CH2 ). 4.267 mmol. which permitted visual where y was the molar fraction of the solutes. 4) than compound (1. 166. 2× CH3 ). and their structures was loaded into the high-pressure view cell. 3. and 363 K and the organic phase was collected and dried over anhydrous Na2 SO4 .271 mmol. H. Required: C.3.11 mL) with two sapphire windows. saturated NaHCO3 aq. (18. It A light yellow oil with 83% yield (GC purity > 99%). 3. 2 mL) to create a clear solution. s). The pressure range of 9. and the stainless steel were fully determined by IR.669 (s. and compound disappeared and the fluid in the cell became transparent then twice with water. At anhydrous Na2 SO4 . H. Required: C. knowledge. s). 353 K. FT-IR (KBr.88 mL) was dissolved in perature controller jacket with a circulator. 343 K.1.51 (2C. Pref ref where 2.: C16 H26 O11 . and the ether groups are CO2 -philic parts. The intermolecular attraction of solute–solute. The mixture was stirred at room temperature for a whole night. s). H. 1096. cm−1 ) 1738.676 carbonyl group decreased with the increase of temperature faster (s. s).357 (s. 4H. the solubility of all compounds decreased 2. 3. 8H. than hydroxyl group.5 MPa and ±0.582 (m. and evaporated to a residue.5%). / Fluid Phase Equilibria 317 (2012) 36–42 Scheme 1. and the temperature was controlled using a tem- Diethylene glycol (9. 4H. Then. 323 K.38 F. 6. 2× O CCH2 C O).29–68. 2 mL). P was the pressure. 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. The system was heated to the desired temperature and pressur- wise to the reaction system under an N2 atmosphere. 13 C NMR (CDCl3 ) compound (2. 1277. and at the same pressure.2. Fig. 64.49–77. Found: C. 64. and elemental cell was then sealed.212 (s. by a silica gel column chromatography (ethyl acetate:petroleum The uncertainty of the dissolution pressure and temperature was ether = 1:3–2:1) to obtain the target compound 3.0. 3).75 (4C.: C12 H18 O9 . 47. 2× hydrogen bonding. The dissolution pressure and temperature Similarly. O. Elemental Anal. Found: C. 1. 13 C NMR. It seems that Anal. which methyl ester favors improving the dispersive ability of compounds [18. 6H. Solubility test a+b A= (2) Solubility measurement was carried out in a stainless steel view T cell (7. 4H. the two compounds were new. which was purified each condition. 2 and the solubility of compound 3 is higher than compound 4. 3.63%.

The values 2 18. P. .00943 averaged for each compound (Table 2). and the values were fitted with a straight line by least. were constants.85614 −6084. . were then 3 16. and C from the data correlation procedure. compound 2 (tetraethylene glycol).44029 0. F. When the C was held at its 4 18. . 1 18. the molar fraction of the solutes. y. compound 3 (malonic acid 2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester). / Fluid Phase Equilibria 317 (2012) 36–42 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. compound 1 (bis(2-hydroxyethyl) ether).97549 −6252. temperature and pressure. a.86886 −6108. 1. ref was 700 kg m−3 . pressure. Chang et al. obtained from the slopes of the corresponding plots. The first step was plots of ln(yP/Pref ) values versus ( − ref ) Compounds a b/K C (m3 /kg) (Fig. Solubility comparison of compounds 1–4 in scCO2 at 313–363 K. 2).012521667 squares regression to estimate the C and A parameters. C.015371667 . and b Table 2 Solubility constants a. 䊉. b.42241 0. compound 4 (malonic acid 2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]- ethoxy}-ethoxy)-ethyl ester methyl ester).01508 0. and A.013413333 of C.28689 0.02985 −5083.

compound 3 (malonic acid 2-[2-(2- methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester). Chang et al.4 -0.0031 0. . .0 1   × 100% 1.8 b -120 -80 -40 0 40 80 (ρ . and C were used to pre- The plots of A versus 1/T for each compound were fitted to a straight dict solubility using Eqs.0 0. average value.nist.exp  2. 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.0032 (http://webbook. . compound 2 (tetraethylene glycol).exp were the calculated and experimental data. the average absolute line (Fig.cal and yi. 3. T was the system tem- 103K/T perature (K). S= (5) M1 (1 − y) ethyl ester methyl ester). compound 4 M2 y (malonic acid 2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethoxy}-ethoxy).2 -0. The values 0. 363 K. . A 0. .ρ ref )Kg/m3 -120 -80 -40 0 40 80 (ρ .8 -1.2 0. shown in Table 2. The resulting a and b values for compounds were also evaluate the A values at various temperatures for each compound.6 c d -1.ρ )Kg/m3 (ρ . (b) compound 2 (tetraethylene glycol). Then.5 of AARDy were in the range of 0.8 0. / Fluid Phase Equilibria 317 (2012) 36–42 1.4 0. (c) compound 3 (malonic acid 2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester).0029 0.2 -1. 333 K. (d) compound 4 (malonic acid 2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)- ethoxy]-ethoxy}-ethoxy)-ethyl ester methyl ester).4 a -1. 2.4 0. the experimental solubility data was then used to obtained.8 -0. (3):   yi.cal − yi.0 -0. S was the solubility of the solute (g L−1 ).5 AARDy (%) =  yi.5 0.4 ln(yP/Pref ) -0.ρ ref ) Kg/m3 0.5 m ln S = k ln  + +n (4) -1.0 T where the density of CO2 (.0027 0.exp  (3) n 1. (1) and (2).34%.8 ln(yP/Pref ) -0. g L−1 ) was recommended also by NIST -1. k was the association number of CO2 .44–46. respectively. Plots of A vs 1/T for compounds. 343 K. . 䊉. Finally. m and n were the parameters of Eq.2 -1. (4). compound 1 (bis(2-hydroxyethyl)ether). Fig.0 ln(yP/Pref ) 0.4 0. .0030 0.0 The solubilities were also correlated using the density-based equation proposed by Chrastil [22]: -0. (a) Compound 1 (bis(2-hydroxyethyl)ether). . Plots of ln(yP/Pref ) vs ( − ref ) for compounds 1–4 at various temperatures.0 -0.0 -240 -200 -160 -120 -80 -40 -180 -150 -120 -90 -60 -30 (ρ .ρ ref )Kg/m3 ref Fig.0 where n was the number of experimental points and yi. the values of a. 313 K.0028 0.gov/chemistry/fluid/). 3). which could be calculated by: 䊉. .40 F. 323 K.6 -2. b.4 ln(yP/Pref ) -0. 353 K.

. .0 3. 4 and the values of AARDy at different temperatures. 51073175).8 2.63 −3771. 363 K calculated by Eq.08 6.50 Lnρ Lnρ Fig.48 6.0 2.83 −2336. 䊉.exp  4. parameters for the Chrastil modified compounds showed better solubility than the unmodi- equation are listed in Table 3.35 6. (c) compound 3 (malonic acid 2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethyl ester methyl ester).6 Ln S Ln S 2. Chrastil model and showed good agreement between the corre- lated results and the experimental data.8 2. molecular weight and molecular size. Parameters Compound 1 Compound 2 Compound 3 Compound 4 We are grateful to National Natural Science Foundation of China k 7.2 3.8 Ln S 2.0 a b 6.20 −23.7 MPa.66 Lnρ Lnρ 3. The solubility data in scCO2 .66 6. the solubility of the compounds 1–4 was mea- where y was the molar fraction of the solute. .40 6.95 ing Young Teachers (slg10014) for financial support. (b) compound 2 (tetraethylene glycol). Table 3 Acknowledgements Parameters of the Chrastil equation.2 3.0 2.6 Ln S 2.45 6. 323 K.36 6. / Fluid Phase Equilibria 317 (2012) 36–42 41 3.12 7.42 6.6 2.2 2.48 6.0 6. n and k could be estimated from the experimental enced by the end groups. Chrastil’s model. 4. The range of 9. (d) compound 4 (malonic acid 2-(2-{2-[2-(2-methoxycarbonyl-acetoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl ester methyl ester). As a result.24 6.48 6. (4).40 6.54 6. 343 K.36 −36.60 6. The solubility of compounds was influ- constants m.0 2.cal − yi. F. .30 6.35 2. In addition.26 8.exp  In summary.2 c d 2. ubility of compound was mainly affected by the solute–solute The consistency of the model with measured data can be seen self-interaction and solute–solvent intermolecular interaction.60 6.25 6. respectively. Chang et al. the sol- Chrastil equation.2–25. Logarithmic relationship between the solubility S (kg m−3 ) of compounds 1–4 in scCO2 and the density  (kgm−3 ) of pure CO2 .37 −3622. which measured data were correlated with the semiempirical model and are less than 7%.6 2.71 6.65 5. 353 K.36 Shanghai Colleges and Universities to Select and Train Outstand- AARDy% 6. The Innovation Program of Shanghai Municipal m/K −3565.4 2. Conclusion AARDy (%) =   × 100% (6) n  yi. fied counterparts in supercritical CO2 . The from Fig.50 (No.44 −40.4 2.0 3.2 2.   1   yi.15 7. 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). Experimental results: . 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. 333 K.2 2.42 6.54 6. (a) Compound 1 (bis(2- hydroxyethyl)ether). Hai-Jian Yang .4 2.32 6.16 6.76 Education Commission (11YZ113).8 2. 313 K.4 2.36 6. The absolute value of average rela. the Special Research Fund in n −33.

Y. J.H. C. Chem. 1–12. Miao. Valentine. Miller. Teng. J. C. J. R. Chem. 7 (2005) 518–523.J. [12] J. W. Eng. K. J. J. Kim. H. M. Liu. References [13] C.Y. J. Zhang. Chem. Drohmann. J.C. Wallen.M. Chang et al. Data 53 (2008) 2189–2192. S.F. Li.J. Am. J. Chang. B 103 (1999) Laboratory for Molecular Sciences (BNLMS) and Prof. Z. Guo. Eng. Joo. Wright. Phys. Chem. G. Data 55 (2010) 4130–4139. 272 (2008) 8–17. [16] H. Data 56 (2011) [1] J.A. Guo.F. H. Styranec. K. South-Central Univ. E. Y. Zhang. Sun. J. Kim.J. Supercrit. Equilib. Chem. D. J.M. Phys. Shen. Huang. Wang. Green Chem. Chrastil. Xiang. Chem. H. Clifford. J. 779–786. Li. Chem. Quan. Liu. 86 (1982) 3016–3021. Data 41 (1996) [22] J. L. S. Kim.M. An. F. H. Cai. [3] C. T.J. Liu.L.42 F. Sarbu.L. 111 (2008) 104–109. Xie. E. Fluids 28 (2004) 121–191. Y. Jin. Ding. Park. S. Fink. Eng. Buxing Han 6441–6444. Chen.J. Fluids 22 (2002) 103–110.H. H.N. J. Fluids 17 (2000) 259–287. J. Sci. N.J. Han.F. C. Beckman.X. Tian.M. [18] Z. Zhu. 124 (2002) 7274–7275. [17] http://www. Tian. Wang. Nation- [7] Z. Bai. J. L. [4] E. Raveendran. L. Soc. from ICCAS for his valuable help. Su. T. J.P. H. B. Fluid Phase alities (Nat. D.B. Yang. W. [14] Y. H. Hawthrone. S. Fluid Phase Equilib. Erkey.htm. Yang. Kim.Y.L.J.J. Eng. Chem. Supercrit. Supercrit. Ed.B. Yang. Lott. Eng. Nature 405 (2000) 165–168. Li. J. C. K. [11] Y. Chem.D.gov/srd/fluids. Beckman. Miao. Beckman. H.Y. Chem. Science 297 (2002) 799–803. Beckman.X. [19] F. G. Yang. Fluids 45 (2008) 43–50. J. 216 (2004) [5] Y. He. R. [2] T. Feng. DeSimone. A. E.J.A. Eng. Quan.J. J. Data 54 (2009) 102–107. [6] Z. / Fluid Phase Equilibria 317 (2012) 36–42 also wants to appreciate the financial support of Beijing National [9] R. H. McHugh. Yang. . S. [21] Y. J. Data 50 (2005) 1125–1128. Kong.J. Y. Eng.nist.E. Supercrit. Du. [10] P. Yang.J. [8] D.Y. [20] H. Yang. B. Microporous Mesoporous Mater. [15] Z. Z. Guo. T. M. 1191–1196. Hancu. Data 52 (2007) 2074–2076. M.) 3 (2011) 1–6. Wu. Chiew. Yang.