Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2008
The green solvent ethyl lactate: an experimental and theoretical
characterization
Santiago Aparicio* and Rafael Alcalde
Department of Chemistry. University of Burgos. 09001 Burgos, Spain.
Fax: +34 947 258831; Phone: +34 947 258062; E-mail: sapar@ubu.es
Electronic Supplementary Information
S1
Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2008
H8
O7
(a)
ρBCP=0.0223
2ρBCP=0.0995
O10
(b)
O10
H8
▲C9
O7
▲
O11
▲
▲
C6
O11
Fig. S1. AIM analysis for EL monomer computed at the B3LYP/6-311++g** theoretical level. (a) Molecular graph; small red dots
represent bond critical points (BCP), pink lines represent bond paths, large dots represent attractors (atoms). (b) Contour plot for the
Laplacian of electron density,
 2  , in the vicinity of O7–H8 · · · O10 (atom numbering as in Fig. 1) hydrogen bonding; red dot
represents BCP for hydrogen bonding, black lines represent bond paths, red dashed line represent bond path for hydrogen bond, green
curves represent positive isosurface values of
values of electron density, ρ, and
 2  and black curves represent negative isosurface values of  2  . In Fig. 4b the
 2  (both in atomic units) for the BCP corresponding to the mentioned H-bond are reported. All
calculations for the gas phase structure reported in Fig. 1.
E(2)<0.5 kcal mol-1
LP (O10,1)
σ* (O7-H8)
E(2)=2.26 kcal mol-1
ΔE=0.71 a.u.
Fij=0.037 a.u.
LP (O10,2)
Fig. S2. Interaction among donor and acceptor NBO orbitals, nO  
*
OH
, in EL computed at the B3LYP/6-311++g** theoretical
level. Second order perturbation energy, E(2), energy difference among the donor and the acceptor, E , and Fock matrix element
between the donor and acceptor, Fij. Atom numbering as in Fig. 1. All calculations for the gas phase structure reported in Fig. 1.
S2
Supplementary Material (ESI) for Green Chemistry
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Table S1 Experimental density,
pressure,
 , and calculated isobaric thermal expansivity,  P , isothermal compressibility,  T , and internal
Pi , for EL, as a function of pressure and temperature
T /K
P / MPa 278.15
288.15
298.15
308.15
318.15
328.15
338.15
348.15
358.15
 / g cm-3
0.10
1.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
50.00
55.00
60.00
1.0498
1.0504
1.0531
1.0563
1.0594
1.0624
1.0653
1.0682
1.0710
1.0737
1.0764
1.0790
1.0815
1.0839
1.0392
1.0399
1.0427
1.0461
1.0494
1.0525
1.0556
1.0586
1.0616
1.0644
1.0672
1.0699
1.0726
1.0752
1.0283
1.0290
1.0320
1.0356
1.0391
1.0424
1.0457
1.0489
1.0520
1.0550
1.0579
1.0607
1.0635
1.0663
1.0175
1.0182
1.0213
1.0252
1.0289
1.0324
1.0358
1.0392
1.0424
1.0455
1.0486
1.0516
1.0545
1.0572
1.0064
1.0072
1.0106
1.0146
1.0186
1.0223
1.0259
1.0294
1.0328
1.0361
1.0392
1.0423
1.0454
1.0483
 P / kK-1
0.9953
0.9962
0.9998
1.0041
1.0082
1.0121
1.0159
1.0196
1.0231
1.0266
1.0300
1.0332
1.0363
1.0392
0.9841
0.9850
0.9888
0.9934
0.9977
1.0018
1.0059
1.0098
1.0135
1.0171
1.0206
1.0240
1.0273
1.0303
0.9726
0.9734
0.9771
0.9824
0.9870
0.9914
0.9957
0.9998
1.0037
1.0075
1.0112
1.0147
1.0182
1.0215
0.9609
0.9619
0.9663
0.9714
0.9764
0.9811
0.9855
0.9898
0.9939
0.9979
1.0017
1.0054
1.0090
1.0123
0.10
1.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
50.00
55.00
60.00
1.003
0.999
0.983
0.964
0.946
0.930
0.914
0.899
0.885
0.872
0.859
0.847
0.836
0.825
1.027
1.022
1.004
0.983
0.964
0.945
0.928
0.912
0.897
0.882
0.869
0.856
0.844
0.832
1.051
1.046
1.026
1.003
0.981
0.961
0.942
0.925
0.908
0.893
0.878
0.864
0.851
0.839
1.077
1.071
1.049
1.023
1.000
0.978
0.957
0.938
0.920
0.903
0.887
0.872
0.858
0.845
1.103
1.097
1.073
1.044
1.018
0.994
0.972
0.951
0.932
0.914
0.897
0.881
0.866
0.852
kT / TPa-1
1.131
1.125
1.097
1.066
1.038
1.011
0.987
0.965
0.944
0.925
0.907
0.890
0.874
0.860
1.160
1.153
1.123
1.089
1.058
1.030
1.004
0.980
0.958
0.937
0.919
0.901
0.884
0.869
1.191
1.183
1.150
1.113
1.080
1.049
1.022
0.997
0.973
0.952
0.932
0.914
0.897
0.880
1.222
1.214
1.179
1.139
1.103
1.071
1.042
1.016
0.992
0.970
0.949
0.930
0.913
0.896
0.10
1.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
50.00
55.00
60.00
641.94
637.90
620.54
600.20
581.20
563.42
546.75
531.09
516.33
502.42
489.27
476.82
465.02
453.82
686.34
681.72
661.94
638.84
617.38
597.37
578.68
561.18
544.76
529.31
514.76
501.02
488.03
475.73
735.87
730.55
707.89
681.55
657.19
634.58
613.56
593.94
575.60
558.41
542.26
527.06
512.74
499.21
791.10
784.96
758.86
728.68
700.92
675.29
651.56
629.51
608.97
589.79
571.84
555.00
539.18
524.27
852.64
845.52
815.32
780.60
748.85
719.70
692.83
667.99
644.95
623.52
603.53
584.85
567.34
550.90
921.09
912.79
877.69
837.61
801.19
767.95
737.48
709.44
683.55
659.57
637.30
616.55
597.17
579.03
996.95
987.23
946.32
899.91
858.05
820.07
785.47
753.79
724.69
697.85
673.03
649.99
628.55
608.54
1080.5
1069.1
5
1021.3
4
967.53
3
919.34
875.94
836.63
800.86
768.16
738.14
710.49
684.93
661.24
639.20
1171.9
1158.5
2
1102.6
1
1040.1
0
984.76
8
935.20
890.60
850.25
813.56
780.06
749.32
721.03
694.90
670.69
0.10
1.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
50.00
434.56
434.78
435.73
436.87
437.96
439.00
440.00
440.95
441.85
442.72
443.54
444.32
430.90
431.15
432.25
433.57
434.83
436.03
437.19
438.30
439.35
440.36
441.32
442.24
425.74
426.03
427.30
428.81
430.27
431.66
432.99
434.27
435.50
436.67
437.78
438.85
419.23
419.56
421.02
422.77
424.45
426.06
427.60
429.08
430.50
431.86
433.17
434.41
402.82
403.28
405.26
407.65
409.96
412.17
414.30
416.35
418.32
420.22
422.05
423.80
393.38
393.92
396.29
399.15
401.90
404.55
407.11
409.58
411.97
414.27
416.49
418.63
383.49
384.14
387.01
390.49
393.84
397.08
400.21
403.24
406.18
409.02
411.78
414.45
373.50
374.31
377.85
382.13
386.29
390.32
394.22
398.02
401.70
405.28
408.77
412.15
Pi / MPa
411.52
411.91
413.60
415.63
417.59
419.46
421.26
422.99
424.65
426.25
427.78
429.25
S3
Supplementary Material (ESI) for Green Chemistry
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55.00
60.00
445.07
445.78
443.12
443.95
439.88
440.85
435.61
436.75
430.66
432.02
425.50
427.13
420.70
422.70
417.04
419.55
415.45
418.66
Table S2 Fitting parameters of TRIDEN correlation of density, g cm-3, with pressure and temperature, and absolute average percentage
deviations, AAD, for EL. The parameters are valid for the 278.15 K – 358.15 K and 0.1 MPa – 60 MPa ranges. Parameters’ symbols as
in Ref. 34
Parameter
CT
b0 MPa 
b1 MPa 
b2 MPa 
b3 MPa 
ET K
A g cm 
3
R
BR
C R K 
DR
Value
0.083458
302.986
9.2502
-38.7835
5.33576
94.35
53.9032
6.437889
832.079
-0.267612
AAD
Table S3 Experimental dynamic viscosity,
0.0049
 / mPa s, for EL as a function of pressure and temperature
T/K
P / MPa
278.15
288.15
298.15
308.15
318.15
328.15
338.15
348.15
358.15
1.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
4.75
5.16
5.67
6.23
6.84
7.52
8.28
9.12
3.38
3.65
3.98
4.34
4.74
5.18
5.66
6.19
2.53
2.72
2.95
3.20
3.48
3.78
4.10
4.46
1.98
2.12
2.28
2.47
2.66
2.88
3.11
3.36
1.60
1.70
1.83
1.97
2.11
2.27
2.44
2.63
1.33
1.41
1.51
1.61
1.72
1.85
1.98
2.12
1.12
1.19
1.27
1.35
1.44
1.54
1.64
1.75
0.97
1.02
1.09
1.16
1.23
1.31
1.39
1.48
0.85
0.90
0.95
1.01
1.07
1.13
1.20
1.27
Table S4 Fitting parameters for correlation of viscosity, mPa s, with pressure and temperature, and absolute average percentage
deviations, AAD, for EL. The parameters are valid for the 278.15 K – 358.15 K and 0.1 MPa – 70 MPa ranges. Parameters’ symbols as
in Ref. 35
Parameter
Value
A (mPa s)
0.0818
B (K)
442.16
C (K)
169.08
D
-14.5080
E0 (MPa)
1006.72
-1
E1 (MPa K )
-7.010
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E2 (MPa K-2)
-0.008118
AAD
Table S5 Calculated pressure-viscosity,
1.10
  , and temperature-viscosity,  , coefficients for EL as a function of pressure and
temperature. Values calculated from parameters reported in Table S4.
T /K
P / MPa
278.15
288.15
298.15
308.15
318.15
328.15
338.15
348.15
358.15
7.1
7.1
7.2
7.2
7.2
7.3
7.3
7.3
6.7
6.7
6.8
6.8
6.8
6.9
6.9
6.9
6.3
6.4
6.4
6.4
6.4
6.5
6.5
6.5
6.0
6.0
6.1
6.1
6.1
6.1
6.2
6.2
5.7
5.7
5.7
5.8
5.8
5.8
5.8
5.9
19.9
20.3
20.7
21.2
21.6
22.1
22.5
23.0
17.5
17.9
18.2
18.6
19.0
19.4
19.8
20.2
15.5
15.8
16.2
16.5
16.9
17.2
17.6
18.0
13.8
14.1
14.4
14.7
15.1
15.4
15.7
16.1
12.4
12.7
12.9
13.2
13.5
13.8
14.1
14.4
 / GPa
1.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
9.2
9.3
9.4
9.4
9.5
9.5
9.6
9.7
8.6
8.7
8.7
8.8
8.8
8.9
8.9
9.0
8.0
8.1
8.1
8.2
8.2
8.3
8.3
8.4
7.5
7.6
7.6
7.7
7.7
7.7
7.8
7.8
1.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
37.2
37.8
38.5
39.2
39.9
40.7
41.4
42.1
31.2
31.8
32.4
33.0
33.6
34.2
34.9
35.5
26.6
27.1
27.6
28.1
28.7
29.2
29.8
30.4
22.9
23.3
23.8
24.3
24.8
25.3
25.8
26.3
1
 / kK 1
Table S6 MK Atomic charges for EL obtained from computations at B3LYP/6-311++g** theoretical level. Atom numbering as in Fig.
1.
Atom
MK
number
charge
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
0.077
0.114
0.058
-0.301
-0.008
0.428
-0.721
0.414
0.652
-0.571
-0.520
0.502
-0.005
-0.013
-0.479
0.104
0.140
0.129
S5
Supplementary Material (ESI) for Green Chemistry
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Table S7 Lennard–Jones OPLS–AA forcefield parameters used for molecular dynamics simulations in this work. Atom numbering as
in Fig. 1
Atom
σii / Å
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
εii /
kJ mol-1
1.403
1.403
1.403
1.964
1.403
1.964
1.751
0.000
2.105
1.661
1.684
1.964
1.403
1.403
1.964
1.403
1.403
1.403
0.126
0.126
0.126
0.276
0.126
0.276
0.711
0.000
0.439
0.879
0.711
0.276
0.126
0.126
0.276
0.126
0.126
0.126
Table S8 OPLS-AA bond stretching forcefield parameters used for molecular dynamics simulations in this work. Atom numbering as
in Fig. 1
Atom
Kr / kJ mol-1 Å-2
req /Å
1422.6
1422.6
1422.6
1121.3
1422.6
1338.9
1326.3
2313.8
2384.9
895.4
1338.9
1422.6
1422.6
1121.3
1422.6
1422.6
1422.6
1.090
1.090
1.090
1.529
1.090
1.410
1.522
0.945
1.229
1.327
1.410
1.090
1.090
1.529
1.090
1.090
1.090
number
1-4
2-4
3-4
4-6
5-6
6-7
6-9
7-8
9-10
9-11
11-12
12-13
12-14
12-15
15-16
15-17
15-18
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Table S9 OPLS-AA angle bending forcefield parameters used for molecular dynamics simulations in this work. Atom numbering as in
Fig. 1
Atom
Kθ / kJ mol-1 rad-2
θeq / deg
number
1-4-2
1-4-3
1-4-6
2-4-3
2-4-6
3-4-6
4-6-5
4-6-7
4-6-9
5-6-7
5-6-9
7-6-9
6-7-8
6-9-10
6-9-11
10-9-11
9-11-12
11-12-13
11-12-14
11-12-15
13-12-14
13-12-15
14-12-15
12-15-16
12-15-17
12-15-18
16-15-17
16-15-18
17-15-18
138.1
138.1
156.9
138.1
156.9
156.9
156.9
209.2
263.6
146.4
146.4
209.3
230.1
334.7
338.9
347.3
347.3
146.5
146.5
209.2
138.1
156.9
156.9
156.9
156.9
156.9
138.1
138.1
138.1
107.8
107.8
110.7
107.8
110.7
110.7
110.7
109.5
111.1
109.5
109.5
109.5
108.5
120.4
111.4
123.4
116.9
109.5
109.5
109.5
107.8
110.7
110.7
110.7
110.7
110.7
107.8
107.8
107.8
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Table S10 OPLS-AA dihedral torsion forcefield parameters used for molecular dynamics simulations in this work. Atom numbering
as in Fig. 1
Atom
number
1-4-6-5
1-4-6-7
1-4-6-9
2-4-6-5
2-4-6-7
2-4-6-9
3-4-6-5
3-4-6-7
3-4-6-9
4-6-7-8
5-6-7-8
9-6-7-8
4-6-9-11
5-6-9-11
7-6-9-10
7-6-9-11
6-9-11-12
10-9-11-12
9-11-12-13
9-11-12-14
9-11-12-15
11-12-15-16
11-12-15-17
11-12-15-18
13-12-15-16
13-12-15-17
13-12-15-18
14-12-15-16
14-12-15-17
14-12-15-18
Vn / kJ mol-1
phase / deg
n
1.255
1.958
-0.318
1.255
1.958
-0.318
1.255
1.958
-0.318
-1.490
-0.728
2.059
1.883
22.707
1.828
0.967
-2.314
0.552
12.163
8.979
0.540
12.163
8.979
0.540
19.535
21.439
21.439
0.828
0.828
-5.104
-0.527
1.766
1.958
1.958
1.958
1.255
1.255
1.255
1.255
1.255
1.255
0
0
0
0
0
0
0
0
0
0
180
0
0
180
0
0
0
0
180
0
0
180
0
0
0
180
180
0
0
0
180
0
0
0
0
0
0
0
0
0
0
3
3
3
3
3
3
3
3
3
1
2
3
3
1
2
3
3
3
1
2
3
1
2
3
1
2
2
3
3
1
2
3
3
3
3
3
3
3
3
3
3
S8