Supplementary Information

Deep Eutectic Solvents Formed Between Choline Chloride and Carboxylic Acids:
Versatile Alternatives to Ionic Liquids

Andrew P. Abbott*, David Boothby, Glen Capper, David L. Davies, and Raymond K.
Rasheed
Chemistry Department, University of Leicester, Leicester, LE1 7RH, U K

Table 1 supp: Energy for activation of viscous flow Eη and conductivity EΛ obtained by

fitting the data in Figure 4 to Equation 1 and those in Figure 7 to equation 5.

Acid ln η0 Eη ln σo EΛ
/ kJ mol-1 / kJ mol-1
Citric -15.5 ± 0.2 66.7 ± 0.6 17.8 ± 0.2 -53.2 ± 0.5
Malonic -10.6 ± 0.3 44.6 ± 0.8 11.4 ± 0.4 -29.0 ± 1.2
Oxalic -15.2 ± 0.9 59.2 ± 2.4 13.0 ± 0.5 -34.6 ± 1.5
Phenyl acetic -15.3 ± 4.7 52.5 ± 3.8 11.4 ± 0.2 -30.5 ± 0.6
Phenylpropionic -12.5 ± 1.2 51.6 ± 3.0 10.8 ± 0.3 -30.1 ± 0.9
Succinic -20.3 ± 0.8 74.1 ± 2.1 19.5 ± 1.5 -54.3 ± 4.1

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Table 2 supp: Data Used to Produce Figure 6

Salt γ / dyne/cm <r> / Å <r+> / Å <r-> / Å rs/rh Eη Refs
Imidazolium
bmim BF4 46.6 1.57 3.55 2.50 1.93 38.8 1,2
bmim PF6 48.8 1.53 3.55 2.78 2.06 44 1,2
hmim PF6 43.4 1.62 3.81 2.78 2.02 46.3 1,2
omim BF4 30 2.07 4.03 2.50 1.57 45.5 1,2
omim PF6 36.5 1.77 4.03 2.78 1.92 53.8 1,2
AcChCl Tf2N 38.6 1.77 3.7 3.62 2.07 47.4 3
BzAcCh Tf2N 37.71 1.79 3.96 3.62 2.12 84.1 3
(C4H9)4N+ picrate 26.4 2.13 4.13 3.66 1.82 32.6 4
DES
zncl2:cc 50.9 1.53 3.29 3.38 2.18 55.6 5
ChCl/malonic acid 65.68 1.32 3.29 1.81 1.93 44.6 6
ChCl/phenylacetic acid 41.86 1.65 3.29 3.63 2.09 52.5 6
ChCl/urea 52.02 1.48 3.29 2.75 2.03 59.6 6
Molten Salts
NaCl 107.1 1.70 0.94 1.81 0.80 2.18 7,8
NaBr 90.5 1.90 0.94 1.95 0.76 1.91 7,8
KCl 89.5 1.90 1.33 1.81 0.82 1.87 7,8
KBr 77.3 2.10 1.33 1.95 0.78 1.79 7,8
CsCl 72.7 2.20 1.67 1.81 0.79 2.35 7,8
NaI 66.4 2.30 0.94 2.16 0.67 1.77 7,8
KI 60.3 2.30 1.33 2.16 0.75 2.2 7,8
CsI 63 2.58 1.67 2.16 0.74 1.36 7,8
Hydrocarbons
naphthalene 31.8 2.12 3.37 1.58 24.98 9
benzene 28.2 2.02 2.94 1.45 10.14 9
cyclohexane 24.65 2.16 3.11 1.44 12.12 9
2,2-dimethyl butane 15.81 2.69 3.21 1.19 8.26 9
hexane 17.94 2.53 3.22 1.27 7.06 9
pentane 15.48 2.72 3.06 1.12 6.28 9
2-methyl butane 14.46 2.81 3.06 1.08 6.47 9

References

1. Branco, L. C.; Rosa, J. N.; Ramos, J. J. M.; Afonso, C. A. M. Chem. Eur. J. 2002, 8,
3671-3677
2. Huddleston, J. G.; Visser, A. E.; Reichert, W. M.; Willauer, H. D.; Broker, G. A.;
Rogers, R. D., Green Chem. 2001, 3, 156-164
3. Abbott, A.P.; Capper, G.; Davies, D. L.; Rasheed, R. K.; manuscript in preparation:
AcChCl Tf2N = acetylcholine triflamide, BzAcCh Tf2N = BzCOOC2H4N+(CH3)3
(CF3SO3)2N-

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Supplementary Information

4. Kumar, A. J J. Am. Chem. Soc. 1993, 115, 9243-9248

5. Abbott, A. P.; Capper, G.; Davies, D. L.; Rasheed, R. K.; Inorg. Chem. 2004, 43, in
press
6. This manuscript
7. Bockris, J. O’M.; Reddy, A. K. N. Modern Electrochemistry, Plenum Press, New
York, 1970; Vol.1, Chapter 6.
8. Janz, G. J. Molten Salt Handbook, Academic Press, New York, 1967
9. Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Organic Solvents: Solvent Properties
and Methods of Purification, 4th Edition, J. Wiley and Sons, New York, 1986.

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