Supporting Information
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2009
Ionic Liquids in Microemulsions—A Concept to Extend the Conventional
Thermal Stability Range of MicroACHTUNGREemulsions
Oliver Zech,[a] Stefan Thomaier,[a] Agnes Kolodziejski,[a] Didier Touraud,[a]
Isabelle Grillo,[b] and Werner Kunz*[a]
chem_200901101_sm_miscellaneous_information.pdf
Density measurements
Densities, ρ, of the pure EAN, dodecane and the densities of the [C16mim][Cl]+decanol mixture (1:4, molar ratio) were measured with a
pyknometer between 30 °C and 150 °C in steps of 10 °C. The following linear density-temperature relationships were obtained:
ρΕΑΝ / gcm-³ = 1.223-0.00055 θ / °C
ρ[C16mim][Cl]+decanol / gcm-³ = 0.884 – 0.00063 θ / °C
ρdodecane / gcm- ³ = 0.763 – 0.00073 θ / °C
The temperature dependent droplet volume fraction φ was calculated with the assumption of ideal mixing according to equation 1, where Vi is
the volume of compound i.
φ=
VEAN + V[C16 mim][ Cl ]+ decanol
VEAN + V[ C16 mim ][ Cl ]+ decanol + Vdodecane
(1)
Conductivity measurements
The curves log(κ) = f(φ) exhibit a sigmoid shape as shown in Figure S1. A fourth order polynomial was fitted to the curves, the percolation
threshold volume fraction φP was calculated from the inflection point of the fit curve.
.
Figure S1 Determination of the percolation threshold volume fraction at various temperatures (30 °C (? ), 60 °C (+), 90 °C (×), 120 °C (∗) and 150 °C(? )),
lines are fourth order polynomial fits, data points that were not used for the fit are marked grey.
Misciblity of EAN in dodecane
1.2527
1.2280
1.2042
3.0000
2.0195
3.2
3.0
1.5
2.8
1.0
(ppm)
8.0
7.5
7.0
6.5
6.0
Figure S2a. 1H-NMR of EAN in acetonitrile-d3.
5.5
5.0
4.5
(ppm)
4.0
3.5
3.0
3.0000
2.0195
3.0206
Integral
(ppm)
8.5
1.2527
1.2280
1.2042
1.9641
1.9559
1.9476
1.9394
1.9312
1.9230
3.0797
3.0550
3.0312
3.0065
3.0797
3.0550
3.0312
3.0065
7.3856
The immiscibility of the polar phase EAN with dodecane over the whole temperature range was confirmed by 1H-NMR and refractive index
measurements. To this purpose, 5 g EAN were added to 5g dodecane and stirred at ambient temperature and at 150 °C, respectively, for three
hours. Then, 2 mL of the upper phase (dodecane) were removed and cooled down to room temperature. By cooling down, no phase separation
occurred. As the refractve indices of dodecane (nD20= 1.4221)1 and EAN (nD25= 1.4524)2 differ significantly a partial miscibility of the
compounds would be detectable. The refractive indices of pure dodecane and the oil phase of the dodecane-EAN mixture were identical within
the uncertainty limits indicating the immiscibility of EAN in dodecane. The phases were further characterized by means of 1H-NMR
measurements. Within the detection limits, EAN could not be detected with 1H-NMR in the apolar phase at both temperatures, 30 °C and 150 °C.
The spectra of the pure substances and the upper phases are given in Figures S2 and S3, respectively. Therefore, we can assume with good
confidence that EAN is not miscible in dodecane over the whole investigated temperature range.
2.5
2.0
1.5
1.0
0.5
10.007
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
(ppm)
4.0
3.5
3.0
2.5
2.0
1.5
3.0000
1.3048
0.9400
0.9190
0.8952
7.2612
Integral
8.5
1.0
0.5
0.0
Integral
1.6124
1.2277
1.2112
1.1930
Figure S2b. 1H-NMR of dodecane in chloroform-d.
3.2
(ppm)
3.0
10.020
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
3.0000
3.4
Integral
3.6
1.5
1.0
0.5
(ppm)
Figure S3a. 1H-NMR of dodecane saturated with EAN at 30 °C, the quartet from CH3-CH2 -NH4+ NO3- could not be detected demonstrating the
immiscibility of EAN in dodecane.
1.6138
1.2291
1.2124
1.1942
Integral
3.6
3.2
2.8
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
(ppm)
4.0
3.5
3.0
2.5
2.0
3.0000
9.9850
Integral
(ppm)
1.5
1.0
0.5
0.0
Figure S3b. 1H-NMR of dodecane saturated with EAN at 150 °C, the quartet from CH3 -CH2-NH4+ NO3- could not be detected demonstrating the
immisciblity of EAN in dodecane.
[1]
G. Körösl, E. sz. Kováts, J. Chem. Eng. Data 1981, 26, 323-332.
[2]
T. L. Greaves, A. Weerawardena, C. Fong, I. Krodkiewska, C. J. Drummond, J. Phys Chem B 2006, 110, 22479-22487.