CELS-D-13-00474-Second Revision
Electronic Supplementary Material Electronic Supplementary Material for
Mixed solvents for cellulose derivatization under homogeneous conditions: Kinetic, spectroscopic, and theoretical studies on the acetylation of the biopolymer in binary mixtures of an ionic liquid and molecular solvents.
Haq Nawaz; Paulo A. R. Pires; Thaís A. Bioni, Elizabeth P. G. Arêas, Omar A. El Seoud,*
Institute of Chemistry, University of São Paulo, P. O. B. 26077,
05513-970 São Paulo, S. P., Brazil;
E-mail <>; Phone/Fax: 55-11-3091-3874
Figure ESM-1 Plots for calculation of the pseudo first-order rate constant (kobs) for the reaction in mixtures IL-DAS. The symbols (l¥) and (lt) refer to the conductivity at “infinity”- and any time (t), respectively. Part (A) is for AlMeImCl-DMAC at [IL] = 1.887 mol/L, and T (from bottom up) = 30, 40, 50, and 60 °C, respectively. Part (B) is for AlMeImCl-MeCN at [IL] = 3.025 mol/L, and T (from bottom up) = 30, 40, 50, and 60 °C, respectively.
Table ESM-1 Observed rate constants of the reaction, kobs in s-1, and k3, L2 mol-2 s-1, at different temperatures and [AlMeImCl] for the acetylation of MCC in binary mixtures of AlMeImCl with DMAC.
°C / kobs,
s-1 / k3 = kobs/[Ac2O] [IL];
L2 mol-2 s-1
AlMeImCl
1.887 mol/L;
30 v % L / 30 / 5.776× 10-4 / 2.897× 10-4
40 / 7.670× 10-4 / 3.847× 10-4
50 / 1.001× 10-3 / 5.024× 10-4
60 / 1.274× 10-3 / 6.392× 10-4
2.269 mol/L;
36 v % / 30 / 9.052× 10-4 / 3.775× 10-4
40 / 1.172× 10-3 / 4.891× 10-4
50 / 1.506× 10-3 / 6.283× 10-4
60 / 1.910× 10-3 / 7.968× 10-4
2.647 mol/L;
42 v % / 30 / 1.240× 10-3 / 4.436× 10-4
40 / 1.593× 10-3 / 5.696× 10-4
50 / 2.009× 10-3 / 7.185× 10-4
60 / 2.509× 10-3 / 8.973× 10-4
3.025 mol/L;
48 v % / 30 / 1.599× 10-3 / 5.286× 10-4
40 / 2.145× 10-3 / 6.712× 10-4
50 / 2.665× 10-3 / 8.337× 10-4
60 / 3.121× 10-3 / 1.032× 10-3
3.404 mol/L;
54 v % / 30 / 2.273× 10-3 / 6.320× 10-4
40 / 2.835× 10-3 / 7.882× 10-4
50 / 3.488× 10-3 / 9.695× 10-4
60 / 4.263× 10-3 / 1.185× 10-3
3.782 mol/L;
60 v % / 30 / 2.758× 10-3 / 7.293× 10-4
40 / 3.642× 10-3 / 9.114× 10-4
50 / 4.456× 10-3 / 1.115× 10-3
60 / 5.351× 10-3 / 1.339× 10-3
CHM / 60 / 1.410× 10-3 / 7.071× 10-4
CHD / 60 / 8.425× 10-4 / 4.225× 10-4
Table ESM-2 Observed rate constants of the reaction, kobs in s-1, and k3, L2 mol-2 s-1, at different temperatures and [AlMeImCl] for the acetylation of MCC in binary mixtures of AlMeImCl with MeCN.
Ac2O (1.057mol/L) / Temperature,°C / kobs,
s-1 / k3 = kobs/[Ac2O] [IL];
L2 mol-2 s-1
AlMeImCl
2.647 mol/L;
42 v % / 30 / 2.316× 10-4 / 0.828× 10-4
40 / 3.219× 10-4 / 1.151× 10-4
50 / 4.388× 10-4 / 1.569× 10-4
60 / 5.842× 10-4 / 2.088× 10-4
3.025 mol/L;
48 v % / 30 / 3.218× 10-4 / 1.006× 10-4
40 / 4.354× 10-4 / 1.362× 10-4
50 / 5.824× 10-4 / 1.822× 10-4
60 / 7.592× 10-4 / 2.375× 10-4
3.404 mol/L;
54 v % / 30 / 4.332× 10-4 / 1.204× 10-4
40 / 5.778× 10-4 / 1.606× 10-4
50 / 7.559× 10-4 / 2.101× 10-4
60 / 9.685× 10-4 / 2.692× 10-4
3.782 mol/L;
60 v % / 30 / 5.710× 10-4 / 1.428× 10-4
40 / 7.454× 10-4 / 1.865× 10-4
50 / 9.532× 10-4 / 2.385× 10-4
60 / 1.201× 10-3 / 3.004× 10-4
Figure ESM- 2 Relationship between k3 and molar concentration of ionic liquid for the acetylation of CHM in binary mixtures of AlMeImCl with DMAC at 60 °C.
Table ESM-3 Overall third order rate constants k3, and activation parameters calculated for the acetylation of microcrystalline cellulose in binary mixtures of AlMeImCl with DMAC and MeCN.a,b
(IL), mol/L/ Temperature / 30 °C / 40 °C / 50 °C / 60 °C / DH¹,kcal mol-1 / TDS¹,
kcal mol-1 / DG¹,
kcal mol-1
Acetylation in IL-DMAC
104 x (overall k3), L2 mol-2 s-1
1.887 / 2.897 / 3.847 / 5.024 / 6.392 / 4.64 / -19.79 / 24.44
2.269 / 3.775 / 4.891 / 6.283 / 7.968 / 4.33 / -19.95 / 24.30
2.647 / 4.436
(5.36) / 5.696
(4.95)c / 7.185
(4.58) / 8.973
(4.30) / 4.04 / -20.16 / 24.22
3.025 / 5.286
(5.25) / 6.712
(4.93) / 8.337
(4.58) / 10.32
(4.34) / 3.80 / -20.31 / 24.12
3.404 / 6.320
(5.25) / 7.882
(4.91) / 9.695
(4.61) / 11.85
(4.40) / 3.53 / -20.48 / 24.03
3.782 / 7.293
(5.10) / 9.114
(4.89) / 11.15
(4.68) / 13.50
(4.49) / 3.45 / -20.53 / 23.94
Acetylation in IL-MeCN
104 x (overall k3), L2 mol-2 s-1
(IL), M/ Temperature / 30 °C / 40 °C / 50 °C / 60 °C / DH¹,
kcal mol-1 / TDS¹,
kcal mol-1 / DG¹,
kcal mol-1
2.647 / 0.828 / 1.151 / 1.569 / 2.088 / 5.53 (1.49) / -19.64 (0.52) / 25.18 (0.96)
3.025 / 1.006 / 1.362 / 1.822 / 2.375 / 5.09 (1.29) / -19.99 (0.32) / 25.09 (0.97)
3.404 / 1.204 / 1.606 / 2.101 / 2.692 / 4.72 (1.19) / -20.27 (0.21) / 25.01 (0.98)
3.782 / 1.428 / 1.865 / 2.385 / 3.004 / 4.31 (0.86) / -20.42 (0.11) / 24.94 (1.00)
a-Except for the overall k3 of MCC, the remaining rate constants refer to a single OH group. The values of k3 for the discrete (OH) groups of the AGU of MCC were calculated as indicated in the text, i.e., k3 = k3,Prim(OH) + 2 k3,Sec(OH) and k3,Prim(OH) / k3,Sec(OH) = 5
b- All activation parameters were calculated at 60 °C. The uncertainties in the activation parameters are ± 0.1 kcal mol-1 (DH¹, and DG¹) and 0.5 cal K-1 mol-1 (DS¹).
c- The numbers within parenthesis refer to: (overall k3 IL-DMAC/overall k3 IL-MeCN); (DDH¹ = DH¹ IL-MeCN - DH¹ IL-DMAC); (DTDS¹ = TDS¹ IL-MeCN - TDS¹ IL-DMAC), and (DDG¹ =DG¹ IL-MeCN- DG¹ IL-DMAC).
Table ESM-4 Partial third order rate constants k3, and activation parameters calculated for the acetylation of microcrystalline cellulose in binary mixtures of AlMeImCl with DMAC using different (1.30, 3.15 and 5.00) split ratios.
[IL] / 30 °C / 40 °C / 50 °C / 60 °C / DH¹,kcal mol-1 / TDS¹,
kcal mol-1 / DG¹,
kcal mol-1
k3,Prim(OH) / k3,Sec(OH) = 1.30
104 x k3; Prim(OH), L2 mol-2 s-1
1.887 / 1.141 / 1.515 / 1.979 / 2.518 / 4.64 / -20.42 / 25.06
2.269 / 1.487 / 1.927 / 2.475 / 3.139 / 4.34 / -20.58 / 24.92
2.647 / 1.748 / 2.244 / 2.830 / 3.535 / 4.05 / -20.79 / 24.84
3.025 / 2.082 / 2.644 / 3.284 / 4.065 / 3.80 / -20.94 / 24.74
3.404 / 2.490 / 3.105 / 3.819 / 4.668 / 3.54 / -21.12 / 24.65
3.782 / 2.873 / 3.590 / 4.392 / 5.318 / 3.45 / -21.11 / 24.56
104 x k3; Sec(OH), L2 mol-2 s-1
1.887 / 0.878 / 1.166 / 1.522 / 1.937 / 4.64 / -20.59 / 25.23
2.269 / 1.144 / 1.482 / 1.904 / 2.415 / 4.34 / -20.75 / 25.09
2.647 / 1.344 / 1.726 / 2.177 / 2.719 / 4.05 / -20.96 / 25.01
3.025 / 1.602 / 2.034 / 2.526 / 3.127 / 3.80 / -21.12 / 24.92
3.404 / 1.915 / 2.388 / 2.938 / 3.591 / 3.54 / -21.29 / 24.83
3.782 / 2.210 / 2.762 / 3.379 / 4.091 / 3.45 / -21.29 / 24.74
k3,Prim(OH) / k3,Sec(OH) = 3.15
104 x k3; Prim(OH), L2 mol-2 s-1
1.887 / 1.772 / 2.353 / 3.073 / 3.910 / 4.64 / -20.13 / 24.77
2.269 / 2.309 / 2.992 / 3.843 / 4.874 / 4.34 / -20.29 / 24.62
2.647 / 2.713 / 3.484 / 4.395 / 5.488 / 4.04 / -20.51 / 24.55
3.025 / 3.233 / 4.105 / 5.099 / 6.312 / 3.80 / -20.65 / 24.45
3.404 / 3.866 / 4.821 / 5.930 / 7.248 / 3.54 / -20.82 / 24.36
3.782 / 4.461 / 5.575 / 6.820 / 8.257 / 3.45 / -20.82 / 24.27
104 x k3; Sec(OH), L2 mol-2 s-1
1.887 / 0.563 / 0.747 / 0.976 / 1.241 / 4.64 / -20.89 / 25.53
2.269 / 0.733 / 0.950 / 1.220 / 1.547 / 4.34 / -21.05 / 25.38
2.647 / 0.861 / 1.106 / 1.395 / 1.742 / 4.05 / -21.26 / 25.30
3.025 / 1.026 / 1.303 / 1.619 / 2.004 / 3.80 / -21.41 / 25.21
3.404 / 1.227 / 1.530 / 1.883 / 2.301 / 3.54 / -21.58 / 25.12
3.782 / 1.416 / 1.770 / 2.165 / 2.621 / 3.45 / -21.58 / 25.03
k3,Prim(OH) / k3,Sec(OH) = 5.00
104 x k3; Prim(OH), L2 mol-2 s-1
1.887 / 2.069 / 2.748 / 3.589 / 4.566 / 4.64 / -20.02 / 24.66
2.269 / 2.696 / 3.494 / 4.488 / 5.691 / 4.34 / -20.18 / 24.52
2.647 / 3.169 / 4.069 / 5.132 / 6.409 / 4.05 / -20.40 / 24.44
3.025 / 3.776 / 4.794 / 5.955 / 7.371 / 3.80 / -20.55 / 24.35
3.404 / 4.514 / 5.630 / 6.925 / 8.464 / 3.54 / -20.72 / 24.26
3.782 / 5.209 / 6.510 / 7.964 / 9.643 / 3.45 / -20.72 / 24.17
104 x k3; Sec(OH), L2 mol-2 s-1
1.887 / 0.414 / 0.550 / 0.718 / 0.913 / 4.64 / -21.09 / 25.73
2.269 / 0.539 / 0.699 / 0.898 / 1.138 / 4.34 / -21.25 / 25.59
2.647 / 0.634 / 0.814 / 1.026 / 1.282 / 4.05 / -21.46 / 25.51
3.025 / 0.755 / 0.959 / 1.191 / 1.474 / 3.80 / -21.61 / 25.42
3.404 / 0.903 / 1.126 / 1.385 / 1.693 / 3.54 / -21.79 / 25.32
3.782 / 1.042 / 1.302 / 1.593 / 1.929 / 3.45 / -21.79 / 25.24
Table ESM-5 Partial third order rate constants k3, and activation parameters calculated for the acetylation of microcrystalline cellulose in binary mixtures of AlMeImCl with MeCN using different (1.30, 3.15 and 5.00) split ratios.
[IL] / 30 °C / 40 °C / 50 °C / 60 °C / DH¹,kcal mol-1 / TDS¹,
kcal mol-1 / DG¹,
kcal mol-1
k3,Prim(OH) / k3,Sec(OH) = 1.30
104 x k3; Prim(OH), L2 mol-2 s-1
2.647 / 0.326 / 0.453 / 0.618 / 0.823 / 5.53 / -20.27 / 25.80
3.025 / 0.396 / 0.537 / 0.718 / 0.936 / 5.10 / -20.62 / 25.72
3.404 / 0.474 / 0.633 / 0.828 / 1.060 / 4.72 / -20.91 / 25.63
3.782 / 0.563 / 0.735 / 0.940 / 1.183 / 4.31 / -21.25 / 25.56
104 x k3; Sec(OH), L2 mol-2 s-1
2.647 / 0.251 / 0.349 / 0.475 / 0.633 / 5.53 / -20.44 / 25.97
3.025 / 0.305 / 0.413 / 0.552 / 0.720 / 5.10 / -20.79 / 25.89
3.404 / 0.365 / 0.487 / 0.637 / 0.816 / 4.72 / -21.08 / 25.81
3.782 / 0.433 / 0.565 / 0.723 / 0.910 / 4.31 / -21.42 / 25.73
k3,Prim(OH) / k3,Sec(OH) = 3.15
104 x k3; Prim(OH), L2 mol-2 s-1
2.647 / 0.506 / 0.704 / 0.960 / 1.277 / 5.53 / -19.98 / 25.51
3.025 / 0.615 / 0.833 / 1.114 / 1.453 / 5.10 / -20.33 / 25.42
3.404 / 0.736 / 0.982 / 1.285 / 1.647 / 4.72 / -20.62 / 25.34
3.782 / 0.873 / 1.141 / 1.459 / 1.837 / 4.31 / -20.96 / 25.27
104 x k3; Sec(OH), L2 mol-2 s-1
2.647 / 0.161 / 0.223 / 0.305 / 0.405 / 5.53 / -20.74 / 26.27
3.025 / 0.195 / 0.264 / 0.354 / 0.461 / 5.10 / -21.09 / 26.18
3.404 / 0.234 / 0.312 / 0.408 / 0.523 / 4.72 / -21.38 / 26.10
3.782 / 0.277 / 0.362 / 0.463 / 0.583 / 4.31 / -21.72 / 26.03
k3,Prim(OH) / k3,Sec(OH) = 5.00
104 x k3; Prim(OH), L2 mol-2 s-1
2.647 / 0.591 / 0.822 / 1.121 / 1.491 / 5.53 / -19.88 / 25.41
3.025 / 0.719 / 0.973 / 1.301 / 1.696 / 5.09 / -20.23 / 25.32
3.404 / 0.860 / 1.147 / 1.501 / 1.923 / 4.72 / -20.51 / 25.24
3.782 / 1.020 / 1.332 / 1.704 / 2.146 / 4.31 / -20.86 / 25.17
104 x k3; Sec(OH), L2 mol-2 s-1
2.647 / 0.118 / 0.164 / 0.224 / 0.298 / 5.53 / -20.94 / 26.47
3.025 / 0.144 / 0.195 / 0.260 / 0.339 / 5.10 / -21.29 / 26.39
3.404 / 0.172 / 0.229 / 0.300 / 0.385 / 4.72 / -21.58 / 26.30
3.782 / 0.204 / 0.266 / 0.341 / 0.429 / 4.31 / -21.92 / 26.23
Table ESM-6 Solvatochromic parameters for IL/DMAC and MCC-IL/DMAC, and their pure components.a
IL/DMAC; 40 oCSolvent; Molarity of IL (mol/L) in DAS / ET (33), kcal mol-1 / SA / SB
Pure DMACb / 51.50 / 0.024 / 0.804
1.887 / 58.80 / 0.120 / 0.829
2.520 / 59.02 / 0.133 / 0.798
3.150 / 59.18 / 0.148 / 0.777
3.782 / 59.39 / 0.166 / 0.753
Pure IL / 59.85 / 0.131 / 0.651
MCC-IL/DMAC; 40 oC
1.887 / 58.65 / 0.144 / 0.841
2.520 / 58.81 / 0.161 / 0.809
3.150 / 58.99 / 0.180 / 0.785
3.782 / 59.14 / 0.201 / 0.763
a- ET33, SA, SB refer to the empirical polarity, acidity, and basicity, respectively, of the solvent or binary solvent mixture (Reichardt et al. 2011).
b- Solvatochromic parameters for pure DMAC were taken from literature (Antonious et al. 2002; Catalán 2009). The corresponding values for pure MeCN are: 55.4, 0.044, and 0.356, for ET (33), SA, and SB, respectively (Antonious et al. 2002; Catalán 2009). All other solvatochromic parameters were determined in the present work.
References
Antonious MS, Tada EB, El Seoud OA (2002) Thermo-solvatochromism in Aqueous Alcohols: Effects of the Molecular Structures of the Alcohol and the Solvatochromic Probe. J Phys Org Chem 15:403-412
Catalán J (2009) Toward a Generalized Treatment of the Solvent Effect Based on Four Empirical Scales: Dipolarity (SdP, a New Scale), Polarizability (SP), Acidity (SA), and Basicity (SB) of the Medium. J Phys Chem B 113:5951–5960
Reichardt C, Welton T (2011) Solvents and Solvent Effects in Organic Chemistry. 4 ed. Weinheim: Wiley: VCH