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Isothermal Titration Calorimetric Study of Ionic Liquid Solutions in Alcohols in Extreme

Dilutions: An Investigation of Ion-Solvent Interactions

Gitanjali Rai1 · Preeti Jain1 ·Anil Kumar1

1Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Pune-411 008, India

Sample of Calculations

Table S1 The experimental H ILE

values and the calculated relative apparent molar enthalpy φL values

for [C2mim][BF4]–1-ethanol

106 m / mol·kg–1

H ILE

/ J·mol–1φL / J·mol–1

0 0 0

4.854 –375953 –8227

9.707 –167689 –16392

14.561 –101988 –24519

19.415 –67978 –32613

24.269 –48290 –40680

29.122 –32186 –48722

33.976 –19253 –56742

38.830 –17069 –64741

43.6834 –14474 –72721

48.537 –13808 –80682

53.391 –12601 –88626

58.245 –10905 –96554

63.099 –10428 –104465

67.952 –9025 –112362


values and the calculated relative apparent molar enthalpy φL values for [C2mim][BF4]–1-butanol

106 m / mol·kg–1 H ILE


0 0 0

4.783 –958728 –21761

9.567 –421151 –43360

14.350 –257748 –64855

19.133 –175842 –86264

23.916 –123954 –107601

28.700 –83414 –128872

33.483 –59401 –150084

38.266 –47596 –171240

43.050 –42334 –192345

47.833 –39012 –213401

52.616 –35944 –234411

57.400 –32572 –255377

62.183 –30051 –276300

66.967 –26829 –297184



for [C2mim][BF4]–1-hexanol



0 0 0

4.708 –315438 –10820

9.416 –108799 –21554

14.125 –64835 –32233

18.833 –54761 –42867

23.541 –48867 –53462

28.249 –35119 –64022

32.958 –22747 –74551

37.666 –21106 –85050

42.374 –19996 –95522

47.082 –12379 –105968

51.791 –7018 –116390

56.499 –4837 –126788

61.207 –3758 –137164

65.916 –3492 –147519



for [C2mim][BF4]–1-octanol



0 0 0

4.373 –247296 –6457

8.746 –103378 –12865

13.118 –62315 –19242

17.491 –40862 –25593

21.864 –33954 –31922

26.237 –23852 –38231

30.610 –20493 –44523

34.982 –16862 –50798

39.355 –13876 –57057

43.728 –11258 –63301

48.101 –10017 –69532

52.474 –9232 –75749

56.847 –7456 –81954

61.220 –7189 –88147






0 0 0

4.497 –279759 –7621

8.995 –111577 –15185

13.492 –62816 –2272

17.990 –39184 –30208

22.487 –26618 –376784

26.985 –18916 –45125

31.482 –14980 –52550

35.980 –11068 –59956

40.477 –8621 –67344

44.975 –6826 –74714

49.472 –5211 –82068

53.970 –4680 –89406

58.467 –3813 –96729

62.965 –3120 –104038



for [C4mim][BF4]–1-butanol



0 0 0

4.489 –727514 –18728

8.978 –318376 –37315

13.467 –193761 –55810

17.956 –136847 –74232

22.445 –105292 –92589

26.934 –86480 –110888

31.423 –70936 –129136

35.912 –61653 –147335

40.401 –50664 –165490

44.890 –43573 –183601

49.378 –38197 –201672

53.867 –34177 –219705

58.357 –29689 –237701

62.846 –26740 –255662



for [C4mim][BF4]–1-hexanol



0 0 0

4.535 –477187 –13975

9.070 –186378 –27843

13.604 –107119 –41642

18.139 –69519 –55385

22.674 –53986 –69080

27.209 –41402 –82731

31.743 –32110 –96343

36.278 –27993 –109919

40.813 –25366 –123461

45.348 –19846 –136970

49.883 –18767 –150450

54.418 –14632 –163900

58.952 –15057 –177322

63.487 –12964 –190718



for [C4mim][BF4]–1-octanol



0 0 0

5.648 –184730 –4403

11.296 –74641 –8772

16.944 –64350 –13119

22.592 –43056 –17447

28.240 –27310 –21760

33.888 –19904 –26058

39.536 –16438 –30344

45.184 –14837 –34618

50.832 –13411 –38881

56.480 –11940 –43134

62.128 –10375 –47377

67.777 –9324 –51610

73.425 –7977 –55835

79.073 –7056 –60051






0 0 0

4.543 –472757 –11210

9.085 –212767 –22335

13.628 –135269 –33405

18.171 –94822 –44432

22.713 –74480 –55420

27.256 –58139 –66373

31.799 –47852 –77296

36.341 –39114 –88190

40.884 –33016 –99057

45.427 –30607 –109898

49.970 –25933 –120715

54.512 –23204 –131510

59.055 –20878 –142282

63.598 –18936 –153033


values and the calculated relative apparent molar enthalpy φL

values for [C6mim][BF4]–1-butanol



0 0 0

4.401 –518459 –14000

8.802 –210498 –27895

13.203 –123723 –41721

17.605 –83148 –55491

22.006 –58964 –69214

26.407 –44952 –82893

30.808 –39324 –96534

35.209 –29190 –110139

39.610 –26460 –123709

44.012 –22448 –137248

48.413 –19410 –150757

52.814 –17099 –164237

57.215 –15648 –177689

61.617 –13585 –191115



values for [C6mim][BF4]–1-hexanol



0 0 0

4.379 510640 –8038

8.758 283768 –16132

13.137 195040 –24262.2

17.516 145190 –32423

21.895 115242 –40609

26.274 92484 –48817

30.653 81151 –57047

35.032 71772 –65296

39.410 64558 –73563

43.790 56013 –81847

48.169 51135 –90148

52.548 45129 –98463

56.927 42248 –106794

61.306 37392 –115138



values for [C6mim][BF4]–1-octanol



0 0 0

4.350 2.15 x 106 55630

8.700 980781 110862

13.049 313097 165835

17.398 166997 220600

21.748 73414 275184

26.098 46831 329606

30.447 34160 383882

34.797 24399 438021

39.147 25551 492033

43.496 42057 545926

47.846 60076 599704

52.196 70733 653374

56.545 70217 706940

60.895 66817 760407



values for [C8mim][BF4]–1-ethanol



0 0 0

4.513 –257195 –6976

9.026 –105014 –13900

13.539 –61876 –20790

18.052 –40597 –27651

22.565 –29405 –34489

27.077 –20987 –41305

31.590 –17376 –48102

36.103 –14663 –54881

40.616 –12471 –61643

45.129 –10157 –68389

49.642 –8481 –75120

54.155 –7393 –81836

58.668 –6098 –88539

63.181 –5122 –95228



values for [C8mim][BF4]–1-butanol



0 0 0

4.452 –691398 –17959

8.905 –294180 –35783

13.357 –171692 –53519

17.810 –118021 –71185

22.262 –88598 –88789

26.714 –68374 –106339

31.167 –55032 –123839

35.619 –45886 –141293

40.072 –39952 –158704

44.524 –35119 –176074

48.977 –30343 –193406

53.429 –27056 –210701

57.882 –24474 –227961

62.334 –22390 –245187



values for [C8mim][BF4]–1-hexanol



0 0 0

4.543 –37605 –3708

9.087 19190 –7388

13.630 24184 –11048

18.174 26655 –14692

22.717 22989 –18324

27.261 21652 –21943

31.804 19791 –25552

36.348 17014 –29151

40.891 16552 –32740

45.435 15178 –36320

49.978 13549 –39892

54.522 12756 –43456

59.065 11340 –47013

63.609 10891 –50562



values for [C8mim][BF4]–1-octanol



0 0 0

4.436 343084 –68304

8.872 298736.3 –135980

13.309 202619 –203248

17.745 131852 –270185

22.181 83030 –336837

26.617 114548 –403234

31.053 156816 –469399

35.490 193918 –535350

Table S17 The Experimental H ILE

values for the [C2mim][NTf2]–ethanol system


/ J·mol–1

0 0

5.276 9077

7.034 7978

8.793 7615

10.552 7204

12.310 6674

14.069 6204

15.828 5695

17.587 5194


values for the [C8mim][NTf2]–ethanol system


/ J·mol–1

0 0

0.721 134123

1.442 78623

2.164 45720

2.885 18827

4.327 –17340

5.048 –29262

5.770 –34339

Table S19 Adjustable parameters for fitting excess partial molar enthalpy data (H ILE

/

kJ·mol–1) of different ionic liquid–alcohol systems using Eq. 1

IL/Solvent a0 /J·mol–1 a1 / J·mol–1 a2 / J·mol–1

[C2mim][BF4]

Ethanol(5.37 ± 0.42) 108 –(8.14 ± 0.85) 1010 (4.11 ± 0.54) 1012

1-Butanol (1.39 ± 0.115) 109 –(2.15 ± 0.23) 1011 (1.10 ± 0.15) 1013

1-Hexanol (5.29 ± 0.74) 108 –(8.75 ± 0.15) 1010 (4.79 ± 0.97) 1012

1-Octanol (4.03 ± 0.37) 108 –(6.68 ± 0.78) 1010 (3.68 ± 0.52) 1012

[C4mim][BF4]

Ethanol (4.69 ± 0.40) 108 –(7.68 ± 0.835) 1010 (4.16 ± 0.55) 1012

1-Butanol (1.14 ± 0.99) 108 –(1.86 ± 0.21) 1011 (1.01 ± 0.135) 1013

1-Hexanol (8.10 ± 0.75) 108 –(1.34 ± 0.16) 1011 (7.29 ± 1.01) 1012

1-Octanol (2.30 ± 0.32) 108 –(3.25 ± 0.59) 1010 (1.54 ± 0.35) 1012

[C6mim][BF4]

Ethanol (7.02 ± 0.61) 108 –(1.13 ± 0.13) 1011 (6.03 ± 0.83) 1012

1-Butanol (8.65 ± 0.76) 108 –(1.44 ± 0.16) 1011 (7.88 ± 1.07) 1012

1-Hexanol –(6.26 ± 0.34) 108 (9.71 ± 0.72) 1010 –(5.12 ± 0.48) 1012

1-octanol –(4.02 ± 0.21) 109 (6.66 ± 0.46) 1011 –(3.59 ± 0.30) 1013

[C8mim][BF4]

Ethanol(4.23 ± 0.36) 108 –(6.92 ± 0.75) 1010 (3.75 ± 0.49) 1012

1-Butanol (1.12 ± 0.09) 109 –(1.83 ± 0.20) 1011 (9.97 ± 1.29) 1012

1-Hexanol (1.68 ± 0.21) 108 –(3.05 ± 0.44) 1010 (1.74 ± 0.29) 1012

1-Octanol –(3.25 ± 0.65) 108 (3.37 ± 0.75) 1010 -

Table S20 Values of hydrogen bond acidity (α) and hydrogen acceptor basicity (β) of the studied

ionic liquids and solvents

Ionic liquids and solvent α β

[C2mim][BF4] 0.70 0.26

[C4mim][BF4] 0.63 0.38

[C6mim][BF4] 0.44 0.60

[C8mim][BF4] 0.62 0.41

Ethanol 0.83 0.75

1-Butanol 0.84 0.84

1-Hexanol 0.80 0.84

1-Octanol 0.77 0.81

Table S21 Pitzer–Debye–Hückel limiting AL values at 298.15 K for solvents used in the present study

Solvent AL (J·kg0.5·mol–1.5)

Ethanol 33183

1-Butanol 53748

1-Hexanol 83217

1-Octanol 121397

1H NMR of Ionic Liquids

Fig. S1 [C2mim][BF4] 1H NMR, 200 MHz, DMSO-d6

Fig. S2 [C4mim][BF4] 1H NMR, 200 MHz, CDCl3


1.50

1.52

1.48

4.254.

284.

31

7.50

8.67

Fig. S5 [C2mim][NTf2] 1H NMR, 200 MHz, CDCl3

3.89

7.45

Fig. S6 [C8mim][NTf2] 1H NMR, 200 MHz, D2O capillary

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