Supporting Information

ldquoSpecific Solvation Interactions of CO2 on Acetate

and Trifluoroacetate Imidazolium Based Ionic

Liquids at High Pressuresrdquo

Pedro J Carvalhodagger Viacutector H Aacutelvarezsect Bernd Schroumlderdagger Ana M Gildagger Isabel M Marruchodagger Martiacuten

AznarsectLuiacutes M N B F Santosyen Joatildeo A P Coutinhodagger

daggerCICECO Departamento de Quiacutemica Universidade de Aveiro 3810-193 Aveiro Portugal

sectFaculdade de Engenharia Quiacutemica Universidade Estadual de Campinas 13083-970 Campinas-SP

Brasil

yenCentro de Investigaccedilatildeo em Quiacutemica Faculdade de Ciecircncias da Universidade do Porto Universidade

do Porto R Campo Alegre 687 4169-007 Porto Portugal

Corresponding author Tel +351 234 401 507 Fax + 351 234 370 084

E-mail address jcoutinhouapt (J A P Coutinho)

Results and Discussion

The results of the application of the thermodynamic consistency test to the binary systems

containing ionic liquid is presented in Table 1 In this Table NP is the number of data points T is the

temperature k12 α12 g12-g22 and g21-g11 are the interaction parameters of the model where 1 stands for

the CO2 and 2 for the ionic liquid This Table is divided in sections for each system studied The CO2 +

[C4mim][Ac] system determined by Shifflet et al1 was also investigated

Thermodynamic Modeling and Consistency

Valderrama and Aacutelvarez2 developed a thermodynamic consistency test for systems with

incomplete PTxy data cataloging them as thermodynamic consistent (TC) thermodynamic inconsistent

(TI) or not full consistent (NFC) The authors analyzed the difficulties normally found when modeling

this type of mixtures and proposed a methodology to analyze the experimental data concluding about

their thermodynamic consistency or inconsistency Recently Aacutelvarez and Aznar34 applied an extension

of this approach to several supercritical fluid + IL systems using a method based on the Gibbs-Duhem

equation on the fundamental phase equilibrium equation and on the Peng-Robinson equation of state 5

with the Wong-Sandler mixing rule6 using the UNIQUAC model7 for the activity coefficient The

NRTL (three adjustable parameters) and UNIQUAC (two adjustable parameters) models produce

similar fit results nonetheless the NRTL model is preferable when the data present a statistical quirk

caused by inaccurate measurements as shown in Aacutelvarez and Aznar publication3 Therefore the NRTL

model was selected in the present work

Similar to Van Ness-Byer-Gibbs test modeling procedure8 a thermodynamic model is used to

accurately fit the experimental data and thereafter apply the consistency test The experimental data fit

requires the calculation of several model parameters using an optimized objective function Although

the consistency test is model dependent good fitting does not guarantee that the data are consistent

since the proposed area test consequent from the GibbsndashDuhem equation must also be fulfilled

As described previously9 the test uses the Gibbs-Duhem equation expressed in the integral

form where the left-hand side is denoted as AP and the right-hand side as Aφ as it follows

A p=int1

Py2

dp (1)

Aφ=int1minus y2

y2 Zminus1

dφ1

φ1

int1

Zminus1

dφ2

φ2(2)

The values for AP are obtained with experimental Py2 data and the values for Aφ are obtained

with calculated values of Z φi and y2 The subscripts 1 and 2 denote CO2 and ionic liquid compounds

respectively The individual percent area deviation ∆Ai is given as

ΔAi=100 [ AφminusAP AP] i (3)

where the subscript i refer to the ith data point The quality of the correlation was analyzed

through the relative deviations in the calculated pressure in the gas phase for each point i defined as

Δpi=100 p icalminus pi

exp p iexp (4)

The method implies the minimization of the deviations of Eqs 3 and 4 setting as the objective

function OF for the consistency test the minimization of the deviations in VLE data and the individual

percent area deviation

OF=sumi=1

Nminus1

[ APminusAφ

σ A ] i

2

sumi=1

N

[ pcalminus pexp

σ P ]i2

sumi=1

N

[ y fluidcal minus1

σ y]i

2

(5)

where N is the number of data points p is the pressure yfluid is the vapor mole fraction of the

supercritical fluid for data point i the superscripts ldquoexprdquo and ldquocalrdquo refers to the experimental and

calculated values respectively and σA σP and σy are the standard deviations of those quantities The

experimental uncertainties in the pressure data were used for σP the value 10-4 for σy and the value of

AP for σA The minimization method was performed using a genetic algorithm code implemented and

fully explained in Alvarez et al10 The difference between experimental and calculated values was

calculated as the average percent deviation expressed in absolute form as follows

∣Δp∣=100

Nsumi=1

N

[∣picalminus p i

exp∣ p iexp ] (6)

The data set is considered consistent when the individual area deviation ∆Ai is within

acceptable defined deviations The difference between experimental and calculated individual area is

calculated as the average percent deviation expressed in absolute form as follows

∣ΔA∣=100

N [∣AφminusAP∣AP ] (7)

The isopleths for the CO2 + [C4mim][Ac] system and for the CO2+ [C4mim][TFA] system were

interpolated with the method proposed by Aacutelvarez and Aznar4 and the results are reported in supporting

information

The isopleths were interpolated with the method proposed by Aacutelvarez and Aznar4 and the results

are shown in Table 2 for the CO2 + [C4mim][Ac] system and for the CO2+ [C4mim][TFA] system

respectively

Detailed results are shown in Tables 3 through 6 The tables are divided in two parts the upper

part shows the original data set while the lower part shows the remaining data after removing some

experimental points that have been found to be thermodynamically inconsistent Tables 3 and 5 show

detailed results for the CO2 + [C4mim][Ac] systems at 3231 and 3481 K from Shifflet et al1 In Table

3 some data present deviations out the established limit for ∆Ai (bold and italic type) Nonetheless

deviations within the established limits are obtained by eliminating those points

The data for the CO2 + [C4mim][Ac] system at 3481 K from Shifflet et al1 presented in Table 5

presents deviations out the established limit for the values of ∆pi and thereafter the test could not be

applied In addition the data from this work at the same temperature was correlated with confidence

showing that the present data are more reliable In Table 6 detailed results for the system CO2 +

[C4mim][Ac] at 348 K show that for the upper part some data have deviations outside the established

limits in the final values of ∆Ai (bold and italic type) while for the lower part when two points from

the original data set are eliminated (the two with the highest area deviation highlighted in the upper

part) the deviations for the remaining eight points are within the defined limits of minus20 to +20

Therefore while the original set with nine data points is not fully consistent the new set with the

remaining eight points is thermodynamically consistent

The same procedure is applied for the data in Table 7 where detailed results for the system CO2

+ [C4mim][TFA] at 298 K are presented The original data are not fully consistent but after removing

one data point the remaining eight points are within the defined limits of minus20 to +20 which are

thermodynamically consistent

The results obtained for the CO2 + [C4mim][Ac] system denote greater deviations for the x1gt05

isopleths while the system CO2 + [C4mim][TFA] present greater deviations for the x1gt065 isopleths

leading to not fully consistent isotherms

Literature Cited(1) Shiflett M B Kasprzak D J Junk C P Yokozeki A J Chem Thermodyn 2008 40 25-31

(2) Valderrama J O Agravelvarez V H Fluid Phase Equilib 2004 226 149-159

(3) Alvarez V H Aznar M J Chin Inst Chem Eng 2008 39 353-360

(4) Alvarez V H Aznar M Open Thermodyn J 2008 2 25-38

(5) Peng D Robinson D B Ind Eng Chem Fund 1976 15 59-64

(6) Wong D S H Sandler S I AIChE J 1992 38 671-680

(7) Abrams D S Prausnitz J M AIChE J 1975 21 116-128

(8) Van Ness H C Byer S M Gibbs R E AIChE J 1973 19 238-244

(9) Carvalho P J Aacutelvarez V H Machado J J B Pauly J Daridon J Marrucho I M Aznar

M Coutinho J A P J Supercrit Fluids 2008 doi101016jsupflu200810012

(10) Alvarez V H Larico R Yanos Y Aznar M Braz J Chem Eng 2008 in press

Table 1 Results of the consistency test for all the experimental data

Reference NP T K kij α12g12-g22

kJ kmol

g21-g11

kJkmol

|∆p|

|∆A|

Result

CO2 + [C4mim][Ac]

1

5 28310 10000 02000 -112499893 -19335936 253 197 -

9 29810 -03274 02341 -281230098 60214521 122 138 NFC

9 32310 10000 03171 -111987109 30590808 104 146 NFC

9 34810 10000 03531 -91385596 245522227 141 172 -

[This work]

6 31310 -03284 02397 -406906016 174023555 16 197 NFC

9 32309 -03667 02469 -507822500 -15924650 15 235 NFC

8 33300 -04688 02635 -504495625 -16259657 10 131 NFC

8 34300 -04912 02876 -490086250 -17777466 15 152 NFC

8 34800 05083 03660 -392240273 -34830093 63 178 NFC

8 35298 -06875 02017 -889453125 -57540894 19 157 NFC

CO2 + [C4mim][TFA]

[This work]

7 29400 02188 02002 333105703 -30542261 32 111 NFC

7 29800 02188 02000 342718711 -29030513 31 146 NFC

7 30300 02188 02000 356836055 -26338701 31 190 NFC

7 31300 02192 02000 375824805 -23724836 35 308 NFC

7 32300 02120 02000 397375508 -20805359 37 901 NFC

6 33300 09596 02462 899501328 526753438 165 115 NFC

6 34300 02020 02018 426811992 -17578231 56 474 NFC

6 34800 01959 02001 446551328 -15524625 55 578 NFC

6 35300 01973 02018 449121094 -14944839 56 716 NFC

6 36300 01759 02036 457571133 -13674760 99 102 NFC

Table 2 Interpolated VLE data for the system supercritical CO2 (1) + [C4mim][Ac] (2) and CO2 (1) +

[C4mim][TFA] (2)

CO2 (1) + [C4mim][Ac] (2)x1

T(K)0201 0251 0300 0351 0402 0450 0500 055 06

31310 - 0496 1403 2593 4108 5731 - - 67371

32309 0228 0845 1908 3383 5213 7403 13515 34649 75526

33300 0380 1245 2502 4247 6509 9527 18058 41557 -

34300 0617 1705 3195 5243 8038 12142 22900 47955 -

34800 0779 1956 3576 5799 8892 13627 25417 50946 -

35298 0975 2220 3980 6400 9806 15224 27988 53863 -

CO2 (1) + [C4mim][TFA] (2)x1

T K0225 0300 0401 0502 0601 0650 0679

29400 1001 1579 2445 3527 8239 27010 44006

29800 1139 1771 2723 3956 10406 29326 46545

30300 1321 2025 3100 4538 13151 32175 49717

31300 1709 2586 3940 5856 18452 37715 56063

32300 2131 3216 4881 7382 22733 43047 62409

33300 2588 3915 5906 9117 28216 48169 -

34300 3080 4682 6999 11057 32537 53083 -

34800 3338 5092 7566 12102 34400 55462 -

35300 3606 5519 8143 13195 36498 57788 -

36300 4166 6425 9320 15521 42004 62284 -

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

Results and Discussion

The results of the application of the thermodynamic consistency test to the binary systems

containing ionic liquid is presented in Table 1 In this Table NP is the number of data points T is the

temperature k12 α12 g12-g22 and g21-g11 are the interaction parameters of the model where 1 stands for

the CO2 and 2 for the ionic liquid This Table is divided in sections for each system studied The CO2 +

[C4mim][Ac] system determined by Shifflet et al1 was also investigated

Thermodynamic Modeling and Consistency

Valderrama and Aacutelvarez2 developed a thermodynamic consistency test for systems with

incomplete PTxy data cataloging them as thermodynamic consistent (TC) thermodynamic inconsistent

(TI) or not full consistent (NFC) The authors analyzed the difficulties normally found when modeling

this type of mixtures and proposed a methodology to analyze the experimental data concluding about

their thermodynamic consistency or inconsistency Recently Aacutelvarez and Aznar34 applied an extension

of this approach to several supercritical fluid + IL systems using a method based on the Gibbs-Duhem

equation on the fundamental phase equilibrium equation and on the Peng-Robinson equation of state 5

with the Wong-Sandler mixing rule6 using the UNIQUAC model7 for the activity coefficient The

NRTL (three adjustable parameters) and UNIQUAC (two adjustable parameters) models produce

similar fit results nonetheless the NRTL model is preferable when the data present a statistical quirk

caused by inaccurate measurements as shown in Aacutelvarez and Aznar publication3 Therefore the NRTL

model was selected in the present work

Similar to Van Ness-Byer-Gibbs test modeling procedure8 a thermodynamic model is used to

accurately fit the experimental data and thereafter apply the consistency test The experimental data fit

requires the calculation of several model parameters using an optimized objective function Although

the consistency test is model dependent good fitting does not guarantee that the data are consistent

since the proposed area test consequent from the GibbsndashDuhem equation must also be fulfilled

As described previously9 the test uses the Gibbs-Duhem equation expressed in the integral

form where the left-hand side is denoted as AP and the right-hand side as Aφ as it follows

A p=int1

Py2

dp (1)

Aφ=int1minus y2

y2 Zminus1

dφ1

φ1

int1

Zminus1

dφ2

φ2(2)

The values for AP are obtained with experimental Py2 data and the values for Aφ are obtained

with calculated values of Z φi and y2 The subscripts 1 and 2 denote CO2 and ionic liquid compounds

respectively The individual percent area deviation ∆Ai is given as

ΔAi=100 [ AφminusAP AP] i (3)

where the subscript i refer to the ith data point The quality of the correlation was analyzed

through the relative deviations in the calculated pressure in the gas phase for each point i defined as

Δpi=100 p icalminus pi

exp p iexp (4)

The method implies the minimization of the deviations of Eqs 3 and 4 setting as the objective

function OF for the consistency test the minimization of the deviations in VLE data and the individual

percent area deviation

OF=sumi=1

Nminus1

[ APminusAφ

σ A ] i

2

sumi=1

N

[ pcalminus pexp

σ P ]i2

sumi=1

N

[ y fluidcal minus1

σ y]i

2

(5)

where N is the number of data points p is the pressure yfluid is the vapor mole fraction of the

supercritical fluid for data point i the superscripts ldquoexprdquo and ldquocalrdquo refers to the experimental and

calculated values respectively and σA σP and σy are the standard deviations of those quantities The

experimental uncertainties in the pressure data were used for σP the value 10-4 for σy and the value of

AP for σA The minimization method was performed using a genetic algorithm code implemented and

fully explained in Alvarez et al10 The difference between experimental and calculated values was

calculated as the average percent deviation expressed in absolute form as follows

∣Δp∣=100

Nsumi=1

N

[∣picalminus p i

exp∣ p iexp ] (6)

The data set is considered consistent when the individual area deviation ∆Ai is within

acceptable defined deviations The difference between experimental and calculated individual area is

calculated as the average percent deviation expressed in absolute form as follows

∣ΔA∣=100

N [∣AφminusAP∣AP ] (7)

The isopleths for the CO2 + [C4mim][Ac] system and for the CO2+ [C4mim][TFA] system were

interpolated with the method proposed by Aacutelvarez and Aznar4 and the results are reported in supporting

information

The isopleths were interpolated with the method proposed by Aacutelvarez and Aznar4 and the results

are shown in Table 2 for the CO2 + [C4mim][Ac] system and for the CO2+ [C4mim][TFA] system

respectively

Detailed results are shown in Tables 3 through 6 The tables are divided in two parts the upper

part shows the original data set while the lower part shows the remaining data after removing some

experimental points that have been found to be thermodynamically inconsistent Tables 3 and 5 show

detailed results for the CO2 + [C4mim][Ac] systems at 3231 and 3481 K from Shifflet et al1 In Table

3 some data present deviations out the established limit for ∆Ai (bold and italic type) Nonetheless

deviations within the established limits are obtained by eliminating those points

The data for the CO2 + [C4mim][Ac] system at 3481 K from Shifflet et al1 presented in Table 5

presents deviations out the established limit for the values of ∆pi and thereafter the test could not be

applied In addition the data from this work at the same temperature was correlated with confidence

showing that the present data are more reliable In Table 6 detailed results for the system CO2 +

[C4mim][Ac] at 348 K show that for the upper part some data have deviations outside the established

limits in the final values of ∆Ai (bold and italic type) while for the lower part when two points from

the original data set are eliminated (the two with the highest area deviation highlighted in the upper

part) the deviations for the remaining eight points are within the defined limits of minus20 to +20

Therefore while the original set with nine data points is not fully consistent the new set with the

remaining eight points is thermodynamically consistent

The same procedure is applied for the data in Table 7 where detailed results for the system CO2

+ [C4mim][TFA] at 298 K are presented The original data are not fully consistent but after removing

one data point the remaining eight points are within the defined limits of minus20 to +20 which are

thermodynamically consistent

The results obtained for the CO2 + [C4mim][Ac] system denote greater deviations for the x1gt05

isopleths while the system CO2 + [C4mim][TFA] present greater deviations for the x1gt065 isopleths

leading to not fully consistent isotherms

Literature Cited(1) Shiflett M B Kasprzak D J Junk C P Yokozeki A J Chem Thermodyn 2008 40 25-31

(2) Valderrama J O Agravelvarez V H Fluid Phase Equilib 2004 226 149-159

(3) Alvarez V H Aznar M J Chin Inst Chem Eng 2008 39 353-360

(4) Alvarez V H Aznar M Open Thermodyn J 2008 2 25-38

(5) Peng D Robinson D B Ind Eng Chem Fund 1976 15 59-64

(6) Wong D S H Sandler S I AIChE J 1992 38 671-680

(7) Abrams D S Prausnitz J M AIChE J 1975 21 116-128

(8) Van Ness H C Byer S M Gibbs R E AIChE J 1973 19 238-244

(9) Carvalho P J Aacutelvarez V H Machado J J B Pauly J Daridon J Marrucho I M Aznar

M Coutinho J A P J Supercrit Fluids 2008 doi101016jsupflu200810012

(10) Alvarez V H Larico R Yanos Y Aznar M Braz J Chem Eng 2008 in press

Table 1 Results of the consistency test for all the experimental data

Reference NP T K kij α12g12-g22

kJ kmol

g21-g11

kJkmol

|∆p|

|∆A|

Result

CO2 + [C4mim][Ac]

1

5 28310 10000 02000 -112499893 -19335936 253 197 -

9 29810 -03274 02341 -281230098 60214521 122 138 NFC

9 32310 10000 03171 -111987109 30590808 104 146 NFC

9 34810 10000 03531 -91385596 245522227 141 172 -

[This work]

6 31310 -03284 02397 -406906016 174023555 16 197 NFC

9 32309 -03667 02469 -507822500 -15924650 15 235 NFC

8 33300 -04688 02635 -504495625 -16259657 10 131 NFC

8 34300 -04912 02876 -490086250 -17777466 15 152 NFC

8 34800 05083 03660 -392240273 -34830093 63 178 NFC

8 35298 -06875 02017 -889453125 -57540894 19 157 NFC

CO2 + [C4mim][TFA]

[This work]

7 29400 02188 02002 333105703 -30542261 32 111 NFC

7 29800 02188 02000 342718711 -29030513 31 146 NFC

7 30300 02188 02000 356836055 -26338701 31 190 NFC

7 31300 02192 02000 375824805 -23724836 35 308 NFC

7 32300 02120 02000 397375508 -20805359 37 901 NFC

6 33300 09596 02462 899501328 526753438 165 115 NFC

6 34300 02020 02018 426811992 -17578231 56 474 NFC

6 34800 01959 02001 446551328 -15524625 55 578 NFC

6 35300 01973 02018 449121094 -14944839 56 716 NFC

6 36300 01759 02036 457571133 -13674760 99 102 NFC

Table 2 Interpolated VLE data for the system supercritical CO2 (1) + [C4mim][Ac] (2) and CO2 (1) +

[C4mim][TFA] (2)

CO2 (1) + [C4mim][Ac] (2)x1

T(K)0201 0251 0300 0351 0402 0450 0500 055 06

31310 - 0496 1403 2593 4108 5731 - - 67371

32309 0228 0845 1908 3383 5213 7403 13515 34649 75526

33300 0380 1245 2502 4247 6509 9527 18058 41557 -

34300 0617 1705 3195 5243 8038 12142 22900 47955 -

34800 0779 1956 3576 5799 8892 13627 25417 50946 -

35298 0975 2220 3980 6400 9806 15224 27988 53863 -

CO2 (1) + [C4mim][TFA] (2)x1

T K0225 0300 0401 0502 0601 0650 0679

29400 1001 1579 2445 3527 8239 27010 44006

29800 1139 1771 2723 3956 10406 29326 46545

30300 1321 2025 3100 4538 13151 32175 49717

31300 1709 2586 3940 5856 18452 37715 56063

32300 2131 3216 4881 7382 22733 43047 62409

33300 2588 3915 5906 9117 28216 48169 -

34300 3080 4682 6999 11057 32537 53083 -

34800 3338 5092 7566 12102 34400 55462 -

35300 3606 5519 8143 13195 36498 57788 -

36300 4166 6425 9320 15521 42004 62284 -

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

the consistency test is model dependent good fitting does not guarantee that the data are consistent

since the proposed area test consequent from the GibbsndashDuhem equation must also be fulfilled

As described previously9 the test uses the Gibbs-Duhem equation expressed in the integral

form where the left-hand side is denoted as AP and the right-hand side as Aφ as it follows

A p=int1

Py2

dp (1)

Aφ=int1minus y2

y2 Zminus1

dφ1

φ1

int1

Zminus1

dφ2

φ2(2)

The values for AP are obtained with experimental Py2 data and the values for Aφ are obtained

with calculated values of Z φi and y2 The subscripts 1 and 2 denote CO2 and ionic liquid compounds

respectively The individual percent area deviation ∆Ai is given as

ΔAi=100 [ AφminusAP AP] i (3)

where the subscript i refer to the ith data point The quality of the correlation was analyzed

through the relative deviations in the calculated pressure in the gas phase for each point i defined as

Δpi=100 p icalminus pi

exp p iexp (4)

The method implies the minimization of the deviations of Eqs 3 and 4 setting as the objective

function OF for the consistency test the minimization of the deviations in VLE data and the individual

percent area deviation

OF=sumi=1

Nminus1

[ APminusAφ

σ A ] i

2

sumi=1

N

[ pcalminus pexp

σ P ]i2

sumi=1

N

[ y fluidcal minus1

σ y]i

2

(5)

where N is the number of data points p is the pressure yfluid is the vapor mole fraction of the

supercritical fluid for data point i the superscripts ldquoexprdquo and ldquocalrdquo refers to the experimental and

calculated values respectively and σA σP and σy are the standard deviations of those quantities The

experimental uncertainties in the pressure data were used for σP the value 10-4 for σy and the value of

AP for σA The minimization method was performed using a genetic algorithm code implemented and

fully explained in Alvarez et al10 The difference between experimental and calculated values was

calculated as the average percent deviation expressed in absolute form as follows

∣Δp∣=100

Nsumi=1

N

[∣picalminus p i

exp∣ p iexp ] (6)

The data set is considered consistent when the individual area deviation ∆Ai is within

acceptable defined deviations The difference between experimental and calculated individual area is

calculated as the average percent deviation expressed in absolute form as follows

∣ΔA∣=100

N [∣AφminusAP∣AP ] (7)

The isopleths for the CO2 + [C4mim][Ac] system and for the CO2+ [C4mim][TFA] system were

interpolated with the method proposed by Aacutelvarez and Aznar4 and the results are reported in supporting

information

The isopleths were interpolated with the method proposed by Aacutelvarez and Aznar4 and the results

are shown in Table 2 for the CO2 + [C4mim][Ac] system and for the CO2+ [C4mim][TFA] system

respectively

Detailed results are shown in Tables 3 through 6 The tables are divided in two parts the upper

part shows the original data set while the lower part shows the remaining data after removing some

experimental points that have been found to be thermodynamically inconsistent Tables 3 and 5 show

detailed results for the CO2 + [C4mim][Ac] systems at 3231 and 3481 K from Shifflet et al1 In Table

3 some data present deviations out the established limit for ∆Ai (bold and italic type) Nonetheless

deviations within the established limits are obtained by eliminating those points

The data for the CO2 + [C4mim][Ac] system at 3481 K from Shifflet et al1 presented in Table 5

presents deviations out the established limit for the values of ∆pi and thereafter the test could not be

applied In addition the data from this work at the same temperature was correlated with confidence

showing that the present data are more reliable In Table 6 detailed results for the system CO2 +

[C4mim][Ac] at 348 K show that for the upper part some data have deviations outside the established

limits in the final values of ∆Ai (bold and italic type) while for the lower part when two points from

the original data set are eliminated (the two with the highest area deviation highlighted in the upper

part) the deviations for the remaining eight points are within the defined limits of minus20 to +20

Therefore while the original set with nine data points is not fully consistent the new set with the

remaining eight points is thermodynamically consistent

The same procedure is applied for the data in Table 7 where detailed results for the system CO2

+ [C4mim][TFA] at 298 K are presented The original data are not fully consistent but after removing

one data point the remaining eight points are within the defined limits of minus20 to +20 which are

thermodynamically consistent

The results obtained for the CO2 + [C4mim][Ac] system denote greater deviations for the x1gt05

isopleths while the system CO2 + [C4mim][TFA] present greater deviations for the x1gt065 isopleths

leading to not fully consistent isotherms

Literature Cited(1) Shiflett M B Kasprzak D J Junk C P Yokozeki A J Chem Thermodyn 2008 40 25-31

(2) Valderrama J O Agravelvarez V H Fluid Phase Equilib 2004 226 149-159

(3) Alvarez V H Aznar M J Chin Inst Chem Eng 2008 39 353-360

(4) Alvarez V H Aznar M Open Thermodyn J 2008 2 25-38

(5) Peng D Robinson D B Ind Eng Chem Fund 1976 15 59-64

(6) Wong D S H Sandler S I AIChE J 1992 38 671-680

(7) Abrams D S Prausnitz J M AIChE J 1975 21 116-128

(8) Van Ness H C Byer S M Gibbs R E AIChE J 1973 19 238-244

(9) Carvalho P J Aacutelvarez V H Machado J J B Pauly J Daridon J Marrucho I M Aznar

M Coutinho J A P J Supercrit Fluids 2008 doi101016jsupflu200810012

(10) Alvarez V H Larico R Yanos Y Aznar M Braz J Chem Eng 2008 in press

Table 1 Results of the consistency test for all the experimental data

Reference NP T K kij α12g12-g22

kJ kmol

g21-g11

kJkmol

|∆p|

|∆A|

Result

CO2 + [C4mim][Ac]

1

5 28310 10000 02000 -112499893 -19335936 253 197 -

9 29810 -03274 02341 -281230098 60214521 122 138 NFC

9 32310 10000 03171 -111987109 30590808 104 146 NFC

9 34810 10000 03531 -91385596 245522227 141 172 -

[This work]

6 31310 -03284 02397 -406906016 174023555 16 197 NFC

9 32309 -03667 02469 -507822500 -15924650 15 235 NFC

8 33300 -04688 02635 -504495625 -16259657 10 131 NFC

8 34300 -04912 02876 -490086250 -17777466 15 152 NFC

8 34800 05083 03660 -392240273 -34830093 63 178 NFC

8 35298 -06875 02017 -889453125 -57540894 19 157 NFC

CO2 + [C4mim][TFA]

[This work]

7 29400 02188 02002 333105703 -30542261 32 111 NFC

7 29800 02188 02000 342718711 -29030513 31 146 NFC

7 30300 02188 02000 356836055 -26338701 31 190 NFC

7 31300 02192 02000 375824805 -23724836 35 308 NFC

7 32300 02120 02000 397375508 -20805359 37 901 NFC

6 33300 09596 02462 899501328 526753438 165 115 NFC

6 34300 02020 02018 426811992 -17578231 56 474 NFC

6 34800 01959 02001 446551328 -15524625 55 578 NFC

6 35300 01973 02018 449121094 -14944839 56 716 NFC

6 36300 01759 02036 457571133 -13674760 99 102 NFC

Table 2 Interpolated VLE data for the system supercritical CO2 (1) + [C4mim][Ac] (2) and CO2 (1) +

[C4mim][TFA] (2)

CO2 (1) + [C4mim][Ac] (2)x1

T(K)0201 0251 0300 0351 0402 0450 0500 055 06

31310 - 0496 1403 2593 4108 5731 - - 67371

32309 0228 0845 1908 3383 5213 7403 13515 34649 75526

33300 0380 1245 2502 4247 6509 9527 18058 41557 -

34300 0617 1705 3195 5243 8038 12142 22900 47955 -

34800 0779 1956 3576 5799 8892 13627 25417 50946 -

35298 0975 2220 3980 6400 9806 15224 27988 53863 -

CO2 (1) + [C4mim][TFA] (2)x1

T K0225 0300 0401 0502 0601 0650 0679

29400 1001 1579 2445 3527 8239 27010 44006

29800 1139 1771 2723 3956 10406 29326 46545

30300 1321 2025 3100 4538 13151 32175 49717

31300 1709 2586 3940 5856 18452 37715 56063

32300 2131 3216 4881 7382 22733 43047 62409

33300 2588 3915 5906 9117 28216 48169 -

34300 3080 4682 6999 11057 32537 53083 -

34800 3338 5092 7566 12102 34400 55462 -

35300 3606 5519 8143 13195 36498 57788 -

36300 4166 6425 9320 15521 42004 62284 -

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

AP for σA The minimization method was performed using a genetic algorithm code implemented and

fully explained in Alvarez et al10 The difference between experimental and calculated values was

calculated as the average percent deviation expressed in absolute form as follows

∣Δp∣=100

Nsumi=1

N

[∣picalminus p i

exp∣ p iexp ] (6)

The data set is considered consistent when the individual area deviation ∆Ai is within

acceptable defined deviations The difference between experimental and calculated individual area is

calculated as the average percent deviation expressed in absolute form as follows

∣ΔA∣=100

N [∣AφminusAP∣AP ] (7)

The isopleths for the CO2 + [C4mim][Ac] system and for the CO2+ [C4mim][TFA] system were

interpolated with the method proposed by Aacutelvarez and Aznar4 and the results are reported in supporting

information

The isopleths were interpolated with the method proposed by Aacutelvarez and Aznar4 and the results

are shown in Table 2 for the CO2 + [C4mim][Ac] system and for the CO2+ [C4mim][TFA] system

respectively

Detailed results are shown in Tables 3 through 6 The tables are divided in two parts the upper

part shows the original data set while the lower part shows the remaining data after removing some

experimental points that have been found to be thermodynamically inconsistent Tables 3 and 5 show

detailed results for the CO2 + [C4mim][Ac] systems at 3231 and 3481 K from Shifflet et al1 In Table

3 some data present deviations out the established limit for ∆Ai (bold and italic type) Nonetheless

deviations within the established limits are obtained by eliminating those points

The data for the CO2 + [C4mim][Ac] system at 3481 K from Shifflet et al1 presented in Table 5

presents deviations out the established limit for the values of ∆pi and thereafter the test could not be

applied In addition the data from this work at the same temperature was correlated with confidence

showing that the present data are more reliable In Table 6 detailed results for the system CO2 +

[C4mim][Ac] at 348 K show that for the upper part some data have deviations outside the established

limits in the final values of ∆Ai (bold and italic type) while for the lower part when two points from

the original data set are eliminated (the two with the highest area deviation highlighted in the upper

part) the deviations for the remaining eight points are within the defined limits of minus20 to +20

Therefore while the original set with nine data points is not fully consistent the new set with the

remaining eight points is thermodynamically consistent

The same procedure is applied for the data in Table 7 where detailed results for the system CO2

+ [C4mim][TFA] at 298 K are presented The original data are not fully consistent but after removing

one data point the remaining eight points are within the defined limits of minus20 to +20 which are

thermodynamically consistent

The results obtained for the CO2 + [C4mim][Ac] system denote greater deviations for the x1gt05

isopleths while the system CO2 + [C4mim][TFA] present greater deviations for the x1gt065 isopleths

leading to not fully consistent isotherms

Literature Cited(1) Shiflett M B Kasprzak D J Junk C P Yokozeki A J Chem Thermodyn 2008 40 25-31

(2) Valderrama J O Agravelvarez V H Fluid Phase Equilib 2004 226 149-159

(3) Alvarez V H Aznar M J Chin Inst Chem Eng 2008 39 353-360

(4) Alvarez V H Aznar M Open Thermodyn J 2008 2 25-38

(5) Peng D Robinson D B Ind Eng Chem Fund 1976 15 59-64

(6) Wong D S H Sandler S I AIChE J 1992 38 671-680

(7) Abrams D S Prausnitz J M AIChE J 1975 21 116-128

(8) Van Ness H C Byer S M Gibbs R E AIChE J 1973 19 238-244

(9) Carvalho P J Aacutelvarez V H Machado J J B Pauly J Daridon J Marrucho I M Aznar

M Coutinho J A P J Supercrit Fluids 2008 doi101016jsupflu200810012

(10) Alvarez V H Larico R Yanos Y Aznar M Braz J Chem Eng 2008 in press

Table 1 Results of the consistency test for all the experimental data

Reference NP T K kij α12g12-g22

kJ kmol

g21-g11

kJkmol

|∆p|

|∆A|

Result

CO2 + [C4mim][Ac]

1

5 28310 10000 02000 -112499893 -19335936 253 197 -

9 29810 -03274 02341 -281230098 60214521 122 138 NFC

9 32310 10000 03171 -111987109 30590808 104 146 NFC

9 34810 10000 03531 -91385596 245522227 141 172 -

[This work]

6 31310 -03284 02397 -406906016 174023555 16 197 NFC

9 32309 -03667 02469 -507822500 -15924650 15 235 NFC

8 33300 -04688 02635 -504495625 -16259657 10 131 NFC

8 34300 -04912 02876 -490086250 -17777466 15 152 NFC

8 34800 05083 03660 -392240273 -34830093 63 178 NFC

8 35298 -06875 02017 -889453125 -57540894 19 157 NFC

CO2 + [C4mim][TFA]

[This work]

7 29400 02188 02002 333105703 -30542261 32 111 NFC

7 29800 02188 02000 342718711 -29030513 31 146 NFC

7 30300 02188 02000 356836055 -26338701 31 190 NFC

7 31300 02192 02000 375824805 -23724836 35 308 NFC

7 32300 02120 02000 397375508 -20805359 37 901 NFC

6 33300 09596 02462 899501328 526753438 165 115 NFC

6 34300 02020 02018 426811992 -17578231 56 474 NFC

6 34800 01959 02001 446551328 -15524625 55 578 NFC

6 35300 01973 02018 449121094 -14944839 56 716 NFC

6 36300 01759 02036 457571133 -13674760 99 102 NFC

Table 2 Interpolated VLE data for the system supercritical CO2 (1) + [C4mim][Ac] (2) and CO2 (1) +

[C4mim][TFA] (2)

CO2 (1) + [C4mim][Ac] (2)x1

T(K)0201 0251 0300 0351 0402 0450 0500 055 06

31310 - 0496 1403 2593 4108 5731 - - 67371

32309 0228 0845 1908 3383 5213 7403 13515 34649 75526

33300 0380 1245 2502 4247 6509 9527 18058 41557 -

34300 0617 1705 3195 5243 8038 12142 22900 47955 -

34800 0779 1956 3576 5799 8892 13627 25417 50946 -

35298 0975 2220 3980 6400 9806 15224 27988 53863 -

CO2 (1) + [C4mim][TFA] (2)x1

T K0225 0300 0401 0502 0601 0650 0679

29400 1001 1579 2445 3527 8239 27010 44006

29800 1139 1771 2723 3956 10406 29326 46545

30300 1321 2025 3100 4538 13151 32175 49717

31300 1709 2586 3940 5856 18452 37715 56063

32300 2131 3216 4881 7382 22733 43047 62409

33300 2588 3915 5906 9117 28216 48169 -

34300 3080 4682 6999 11057 32537 53083 -

34800 3338 5092 7566 12102 34400 55462 -

35300 3606 5519 8143 13195 36498 57788 -

36300 4166 6425 9320 15521 42004 62284 -

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

showing that the present data are more reliable In Table 6 detailed results for the system CO2 +

[C4mim][Ac] at 348 K show that for the upper part some data have deviations outside the established

limits in the final values of ∆Ai (bold and italic type) while for the lower part when two points from

the original data set are eliminated (the two with the highest area deviation highlighted in the upper

part) the deviations for the remaining eight points are within the defined limits of minus20 to +20

Therefore while the original set with nine data points is not fully consistent the new set with the

remaining eight points is thermodynamically consistent

The same procedure is applied for the data in Table 7 where detailed results for the system CO2

+ [C4mim][TFA] at 298 K are presented The original data are not fully consistent but after removing

one data point the remaining eight points are within the defined limits of minus20 to +20 which are

thermodynamically consistent

The results obtained for the CO2 + [C4mim][Ac] system denote greater deviations for the x1gt05

isopleths while the system CO2 + [C4mim][TFA] present greater deviations for the x1gt065 isopleths

leading to not fully consistent isotherms

Literature Cited(1) Shiflett M B Kasprzak D J Junk C P Yokozeki A J Chem Thermodyn 2008 40 25-31

(2) Valderrama J O Agravelvarez V H Fluid Phase Equilib 2004 226 149-159

(3) Alvarez V H Aznar M J Chin Inst Chem Eng 2008 39 353-360

(4) Alvarez V H Aznar M Open Thermodyn J 2008 2 25-38

(5) Peng D Robinson D B Ind Eng Chem Fund 1976 15 59-64

(6) Wong D S H Sandler S I AIChE J 1992 38 671-680

(7) Abrams D S Prausnitz J M AIChE J 1975 21 116-128

(8) Van Ness H C Byer S M Gibbs R E AIChE J 1973 19 238-244

(9) Carvalho P J Aacutelvarez V H Machado J J B Pauly J Daridon J Marrucho I M Aznar

M Coutinho J A P J Supercrit Fluids 2008 doi101016jsupflu200810012

(10) Alvarez V H Larico R Yanos Y Aznar M Braz J Chem Eng 2008 in press

Table 1 Results of the consistency test for all the experimental data

Reference NP T K kij α12g12-g22

kJ kmol

g21-g11

kJkmol

|∆p|

|∆A|

Result

CO2 + [C4mim][Ac]

1

5 28310 10000 02000 -112499893 -19335936 253 197 -

9 29810 -03274 02341 -281230098 60214521 122 138 NFC

9 32310 10000 03171 -111987109 30590808 104 146 NFC

9 34810 10000 03531 -91385596 245522227 141 172 -

[This work]

6 31310 -03284 02397 -406906016 174023555 16 197 NFC

9 32309 -03667 02469 -507822500 -15924650 15 235 NFC

8 33300 -04688 02635 -504495625 -16259657 10 131 NFC

8 34300 -04912 02876 -490086250 -17777466 15 152 NFC

8 34800 05083 03660 -392240273 -34830093 63 178 NFC

8 35298 -06875 02017 -889453125 -57540894 19 157 NFC

CO2 + [C4mim][TFA]

[This work]

7 29400 02188 02002 333105703 -30542261 32 111 NFC

7 29800 02188 02000 342718711 -29030513 31 146 NFC

7 30300 02188 02000 356836055 -26338701 31 190 NFC

7 31300 02192 02000 375824805 -23724836 35 308 NFC

7 32300 02120 02000 397375508 -20805359 37 901 NFC

6 33300 09596 02462 899501328 526753438 165 115 NFC

6 34300 02020 02018 426811992 -17578231 56 474 NFC

6 34800 01959 02001 446551328 -15524625 55 578 NFC

6 35300 01973 02018 449121094 -14944839 56 716 NFC

6 36300 01759 02036 457571133 -13674760 99 102 NFC

Table 2 Interpolated VLE data for the system supercritical CO2 (1) + [C4mim][Ac] (2) and CO2 (1) +

[C4mim][TFA] (2)

CO2 (1) + [C4mim][Ac] (2)x1

T(K)0201 0251 0300 0351 0402 0450 0500 055 06

31310 - 0496 1403 2593 4108 5731 - - 67371

32309 0228 0845 1908 3383 5213 7403 13515 34649 75526

33300 0380 1245 2502 4247 6509 9527 18058 41557 -

34300 0617 1705 3195 5243 8038 12142 22900 47955 -

34800 0779 1956 3576 5799 8892 13627 25417 50946 -

35298 0975 2220 3980 6400 9806 15224 27988 53863 -

CO2 (1) + [C4mim][TFA] (2)x1

T K0225 0300 0401 0502 0601 0650 0679

29400 1001 1579 2445 3527 8239 27010 44006

29800 1139 1771 2723 3956 10406 29326 46545

30300 1321 2025 3100 4538 13151 32175 49717

31300 1709 2586 3940 5856 18452 37715 56063

32300 2131 3216 4881 7382 22733 43047 62409

33300 2588 3915 5906 9117 28216 48169 -

34300 3080 4682 6999 11057 32537 53083 -

34800 3338 5092 7566 12102 34400 55462 -

35300 3606 5519 8143 13195 36498 57788 -

36300 4166 6425 9320 15521 42004 62284 -

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

(8) Van Ness H C Byer S M Gibbs R E AIChE J 1973 19 238-244

(9) Carvalho P J Aacutelvarez V H Machado J J B Pauly J Daridon J Marrucho I M Aznar

M Coutinho J A P J Supercrit Fluids 2008 doi101016jsupflu200810012

(10) Alvarez V H Larico R Yanos Y Aznar M Braz J Chem Eng 2008 in press

Table 1 Results of the consistency test for all the experimental data

Reference NP T K kij α12g12-g22

kJ kmol

g21-g11

kJkmol

|∆p|

|∆A|

Result

CO2 + [C4mim][Ac]

1

5 28310 10000 02000 -112499893 -19335936 253 197 -

9 29810 -03274 02341 -281230098 60214521 122 138 NFC

9 32310 10000 03171 -111987109 30590808 104 146 NFC

9 34810 10000 03531 -91385596 245522227 141 172 -

[This work]

6 31310 -03284 02397 -406906016 174023555 16 197 NFC

9 32309 -03667 02469 -507822500 -15924650 15 235 NFC

8 33300 -04688 02635 -504495625 -16259657 10 131 NFC

8 34300 -04912 02876 -490086250 -17777466 15 152 NFC

8 34800 05083 03660 -392240273 -34830093 63 178 NFC

8 35298 -06875 02017 -889453125 -57540894 19 157 NFC

CO2 + [C4mim][TFA]

[This work]

7 29400 02188 02002 333105703 -30542261 32 111 NFC

7 29800 02188 02000 342718711 -29030513 31 146 NFC

7 30300 02188 02000 356836055 -26338701 31 190 NFC

7 31300 02192 02000 375824805 -23724836 35 308 NFC

7 32300 02120 02000 397375508 -20805359 37 901 NFC

6 33300 09596 02462 899501328 526753438 165 115 NFC

6 34300 02020 02018 426811992 -17578231 56 474 NFC

6 34800 01959 02001 446551328 -15524625 55 578 NFC

6 35300 01973 02018 449121094 -14944839 56 716 NFC

6 36300 01759 02036 457571133 -13674760 99 102 NFC

Table 2 Interpolated VLE data for the system supercritical CO2 (1) + [C4mim][Ac] (2) and CO2 (1) +

[C4mim][TFA] (2)

CO2 (1) + [C4mim][Ac] (2)x1

T(K)0201 0251 0300 0351 0402 0450 0500 055 06

31310 - 0496 1403 2593 4108 5731 - - 67371

32309 0228 0845 1908 3383 5213 7403 13515 34649 75526

33300 0380 1245 2502 4247 6509 9527 18058 41557 -

34300 0617 1705 3195 5243 8038 12142 22900 47955 -

34800 0779 1956 3576 5799 8892 13627 25417 50946 -

35298 0975 2220 3980 6400 9806 15224 27988 53863 -

CO2 (1) + [C4mim][TFA] (2)x1

T K0225 0300 0401 0502 0601 0650 0679

29400 1001 1579 2445 3527 8239 27010 44006

29800 1139 1771 2723 3956 10406 29326 46545

30300 1321 2025 3100 4538 13151 32175 49717

31300 1709 2586 3940 5856 18452 37715 56063

32300 2131 3216 4881 7382 22733 43047 62409

33300 2588 3915 5906 9117 28216 48169 -

34300 3080 4682 6999 11057 32537 53083 -

34800 3338 5092 7566 12102 34400 55462 -

35300 3606 5519 8143 13195 36498 57788 -

36300 4166 6425 9320 15521 42004 62284 -

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

Table 1 Results of the consistency test for all the experimental data

Reference NP T K kij α12g12-g22

kJ kmol

g21-g11

kJkmol

|∆p|

|∆A|

Result

CO2 + [C4mim][Ac]

1

5 28310 10000 02000 -112499893 -19335936 253 197 -

9 29810 -03274 02341 -281230098 60214521 122 138 NFC

9 32310 10000 03171 -111987109 30590808 104 146 NFC

9 34810 10000 03531 -91385596 245522227 141 172 -

[This work]

6 31310 -03284 02397 -406906016 174023555 16 197 NFC

9 32309 -03667 02469 -507822500 -15924650 15 235 NFC

8 33300 -04688 02635 -504495625 -16259657 10 131 NFC

8 34300 -04912 02876 -490086250 -17777466 15 152 NFC

8 34800 05083 03660 -392240273 -34830093 63 178 NFC

8 35298 -06875 02017 -889453125 -57540894 19 157 NFC

CO2 + [C4mim][TFA]

[This work]

7 29400 02188 02002 333105703 -30542261 32 111 NFC

7 29800 02188 02000 342718711 -29030513 31 146 NFC

7 30300 02188 02000 356836055 -26338701 31 190 NFC

7 31300 02192 02000 375824805 -23724836 35 308 NFC

7 32300 02120 02000 397375508 -20805359 37 901 NFC

6 33300 09596 02462 899501328 526753438 165 115 NFC

6 34300 02020 02018 426811992 -17578231 56 474 NFC

6 34800 01959 02001 446551328 -15524625 55 578 NFC

6 35300 01973 02018 449121094 -14944839 56 716 NFC

6 36300 01759 02036 457571133 -13674760 99 102 NFC

Table 2 Interpolated VLE data for the system supercritical CO2 (1) + [C4mim][Ac] (2) and CO2 (1) +

[C4mim][TFA] (2)

CO2 (1) + [C4mim][Ac] (2)x1

T(K)0201 0251 0300 0351 0402 0450 0500 055 06

31310 - 0496 1403 2593 4108 5731 - - 67371

32309 0228 0845 1908 3383 5213 7403 13515 34649 75526

33300 0380 1245 2502 4247 6509 9527 18058 41557 -

34300 0617 1705 3195 5243 8038 12142 22900 47955 -

34800 0779 1956 3576 5799 8892 13627 25417 50946 -

35298 0975 2220 3980 6400 9806 15224 27988 53863 -

CO2 (1) + [C4mim][TFA] (2)x1

T K0225 0300 0401 0502 0601 0650 0679

29400 1001 1579 2445 3527 8239 27010 44006

29800 1139 1771 2723 3956 10406 29326 46545

30300 1321 2025 3100 4538 13151 32175 49717

31300 1709 2586 3940 5856 18452 37715 56063

32300 2131 3216 4881 7382 22733 43047 62409

33300 2588 3915 5906 9117 28216 48169 -

34300 3080 4682 6999 11057 32537 53083 -

34800 3338 5092 7566 12102 34400 55462 -

35300 3606 5519 8143 13195 36498 57788 -

36300 4166 6425 9320 15521 42004 62284 -

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

Table 2 Interpolated VLE data for the system supercritical CO2 (1) + [C4mim][Ac] (2) and CO2 (1) +

[C4mim][TFA] (2)

CO2 (1) + [C4mim][Ac] (2)x1

T(K)0201 0251 0300 0351 0402 0450 0500 055 06

31310 - 0496 1403 2593 4108 5731 - - 67371

32309 0228 0845 1908 3383 5213 7403 13515 34649 75526

33300 0380 1245 2502 4247 6509 9527 18058 41557 -

34300 0617 1705 3195 5243 8038 12142 22900 47955 -

34800 0779 1956 3576 5799 8892 13627 25417 50946 -

35298 0975 2220 3980 6400 9806 15224 27988 53863 -

CO2 (1) + [C4mim][TFA] (2)x1

T K0225 0300 0401 0502 0601 0650 0679

29400 1001 1579 2445 3527 8239 27010 44006

29800 1139 1771 2723 3956 10406 29326 46545

30300 1321 2025 3100 4538 13151 32175 49717

31300 1709 2586 3940 5856 18452 37715 56063

32300 2131 3216 4881 7382 22733 43047 62409

33300 2588 3915 5906 9117 28216 48169 -

34300 3080 4682 6999 11057 32537 53083 -

34800 3338 5092 7566 12102 34400 55462 -

35300 3606 5519 8143 13195 36498 57788 -

36300 4166 6425 9320 15521 42004 62284 -

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

Table 3 Detailed results for CO2 + [C4mim][Ac] at 3231 K from 1

Ap 107 Aφ 107 ∆Ai pexp pcal ∆p y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

00593 00957 6150 0010 0003 -6916 09999803 00000197 0108

0146 0172 1740 0050 0050 -001 09999992 00000008 0176

122 116 -500 0100 0113 1271 09999997 00000003 0204

154 138 -1010 0400 0420 523 09999999 00000001 0263

178 175 -191 0700 0697 -048 10000000 00000000 0292

207 207 010 1000 0987 -127 10000000 00000000 0315

154 168 872 1300 1284 -125 10000000 00000000 0334

456 513 1250 1500 1499 -001 10000000 00000000 0346

- - - 1999 2074 375 10000000 00000000 0373

(7 data points) kij = 10000 α12 = 03244 (g12-g22) = -112067412 (g21-g11) = 27633943 |∆P| () =34

0144 0172 2000 0050 0047 -628 09999992 00000008 0176

123 119 -317 0100 0108 763 09999997 00000003 0204

158 144 -880 0400 0411 299 09999999 00000001 0263

185 183 -069 0700 0687 -189 10000000 00000000 0292

216 218 119 1000 0978 -224 10000000 00000000 0315

161 177 980 1300 1275 -194 10000000 00000000 0334

- - - 1500 1491 -056 10000000 00000000 0346

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

Table 4 Detailed results for CO2 + [C4mim][Ac] at 32309 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03171 (g12-g22) = -111987109 (g21-g11) = 30590808 |∆P| () = 104

681E+13 687E+13 095 0228 0233 214 1000000 00000000 0201

748E+13 715E+13 -435 0845 0873 331 1000000 00000000 0251

401E+13 396E+13 -125 1908 1920 061 1000000 00000000 0300

109E+13 111E+13 216 3383 3401 054 1000000 00000000 0351

130E+12 142E+12 864 5213 5316 197 1000000 00000000 0402

709E+10 611E+10 -1380 7403 7793 527 1000000 00000000 0450

910E+05 341E+05 -6260 13515 14234 532 0999999 00000009 0500

621E+03 621E+03 000 34649 32819 -528 0999897 00001027 0550

- - - 75526 66592 -1183 0999418 00005825 0599

(7 data points) kij = -08433 α12 = 02261 (g12-g22) = -557553516 (g21-g11) = -5526208 |∆P| () = 40

297E+14 315E+14 620 0228 0223 -214 10000000 00000000 0201

257E+14 251E+14 -255 0845 0882 437 10000000 00000000 0251

845E+13 828E+13 -202 1908 1969 320 10000000 00000000 0300

114E+13 113E+13 -147 3383 3482 293 10000000 00000000 0351

561E+11 571E+11 177 5213 5374 309 10000000 00000000 0402

956E+09 877E+09 -828 7403 7717 424 10000000 00000000 0450

- - - 13515 14605 806 09998809 00001191 0500

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

Table 5 Detailed results for CO2 + [C4mim][Ac] at 3481 K from 1

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(9 data points) kij = 10000 α12 = 03531 (g12-g22) = -91385596 (g21-g11) = 245522227 |∆P| () = 142

00104 00097 -669 09999002 00000998 0063

00505 00555 998 09999855 00000145 0129

01 01185 1850 09999941 00000059 0161

04002 04206 510 09999988 00000012 0226

06994 06489 -721 09999993 00000007 0253

10003 08572 -1430 09999995 00000005 0272

12994 10532 -1895 09999996 00000004 0287

14997 11549 -2299 09999997 00000003 0294

19993 15237 -2379 09999998 00000002 0316

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

Table 6 Detailed results for CO2 + [C4mim][Ac] at 3480 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(8 data points) kij = 05083 α12= 03660 (g12-g22) = -392240273 (g21-g11) = -34830093 |∆P|() = 63

159E+11 158E+11 -108 0779 0779 000 10000000 00000000 0201

186E+11 186E+11 -011 1956 1939 -089 10000000 00000000 0251

170E+11 172E+11 103 3576 3547 -081 10000000 00000000 0300

105E+11 106E+11 014 5799 5800 001 10000000 00000000 0351

347E+10 320E+10 -781 8893 8983 102 10000000 00000000 0402

297E+09 154E+09 -4810 13627 13804 130 10000000 00000000 0450

252E+07 847E+06 -6630 25417 22318 -1219 10000000 00000000 0500

- - - 50946 33341 -3456 09999991 00000009 0550

(6 data points) kij = 07969 α12= 04229 (g12-g22) = -329205625 (g21-g11) = -35348833 |∆P|() = 12

276E+10 268E+10 -281 0779 0789 129 10000000 00000000 0201

410E+10 408E+10 -061 1956 1930 -133 10000000 00000000 0251

534E+10 544E+10 189 3576 3515 -172 10000000 00000000 0300

526E+10 540E+10 249 5799 5754 -077 10000000 00000000 0351

303E+10 285E+10 -594 8893 8955 070 10000000 00000000 0402

- - - 13627 13800 127 10000000 00000000 0450

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650

Table 7 Detailed results for CO2 + [C4mim][TFA] at 298 K from this work

Ap Aφ ∆Ai pexp pcal ∆P y1cal y2

cal x1

(7 data points) kij = 02188 α12 = 02000 (g12-g22) = 342718711 (g21-g11) = -29030513 |∆P| () = 31

308E+07 303E+07 -152 1140 1112 -24 10000000 00000000 0225

294E+07 340E+07 156 1771 1718 -30 10000000 00000000 0300

172E+07 207E+07 206 2723 2814 33 10000000 00000000 0401

211E+07 184E+07 -128 3956 4386 109 10000000 00000000 0502

220E+04 242E+04 103 10406 10274 -13 09999431 00000569 0601

981E+03 124E+04 265 29326 29156 -06 09999461 00000539 0650

- - - 46545 46501 -01 09999577 00000423 0679

(5 data points) kij = 02236 α12 = 02059 (g12-g22) = 340375859 (g21-g11) = -23545664 |∆P| () = 62

304E+07 287E+07 -555 1140 1226 758 10000000 00000000 0225

276E+07 304E+07 1010 1771 1862 518 10000000 00000000 0300

739E+07 718E+07 -293 2723 2985 961 10000000 00000000 0401

230E+04 229E+04 -035 10406 11321 879 09999449 00000551 0601

- - - 29326 29329 001 09999501 00000499 0650