Submitted in fulfillment of the academic requirements for the Masters of Applied Science (Chemistry), Durban University of Technology, Durban, South Africa, 2016. / In this work, the thermodynamic properties for the binary mixtures containing the ionic liquid (IL): 1-ethyl-3-methylimidazolium ethyl sulphate ([EMIM] [EtSO4]) were calculated. The binary systems studied were {pyridine (Py) or ethyl acetoacetate (EAA) or thiophene (TS) + [EMIM] [EtSO4]}. The results were interpreted in terms of the intermolecular interactions between the (pyridine + IL), (ethyl acetoacetate + IL), and (thiophene + IL) molecules.
The physical properties: density, speed of sound, and refractive index were measured for the binary mixtures over the complete mole fraction range using an Anton Paar DSA 5000 M vibrating U- tube densimeter and an Anton Paar RXA 156 refractometer, respectively. The measurements were done at T = (298.15, 303.15, 308.15, 313.15, and 318.15) K and at p = 0.1 MPa. The experimental data was used to calculate the derived properties for the binary mixtures namely:- excess molar volume (V E ), isentropic compressibility (ks), molar refractions (R) and deviation in refractive
index (Δn).
For the binary mixtures, (Py or EAA or TS + IL),
V E was negative throughout the whole
composition range which indicates the existence of attractive intermolecular interaction between (pyridine + IL) and (ethyl acetoacetate + IL) for (thiophene + IL), V E was negative at low mole fraction of thiophene and became positive at high mole fraction of thiophene. For the binary mixtures (pyridine + IL), (ethyl acetoacetate + IL), ks was positive indicating that the binary
mixtures were more compressible than the ideal mixture. For the binary mixture (thiophene + IL)
ks was negative at low thiophene composition and positive at high composition indicating that the
binary mixture was less compressible than the ideal mixture at low thiophene composition and more compressible at high composition of thiophene. The molar refraction, R, is positive for the (Py or EAA or TS + IL) binary systems at T = (298.15 – 318.15) K, molar refraction decreases as the organic solvent composition increases. For the binary mixture (pyridine + [EMIM] [EtSO4]), Δn is negative at mole fractions < 0.75 of pyridine and positive at mole fractions >0.75 at all temperatures and decreases with an increase in temperature. For the binary system (ethyl acetoacetate + [EMIM] [EtSO4]), Δn values are positive over the entire composition range and at all temperatures and increases with an increase in temperature. Δn values for the (thiophene + IL) system are negative for mole fractions of thiophene < 0.62 and becomes positive for mole fractions of thiophene > 0.62 and Δn increases with an increase in temperature. The Redlich-Kister
smoothing equation was used successfully for the correlation of
V E and Δn data. The Lorentz-
Lorenz equation gave a poor prediction of V E , but a good prediction of density or refractive index. / M
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:dut/oai:localhost:10321/1727 |
| Date | January 2016 |
| Creators | Chule, Siyanda Brian |
| Contributors | Deenadayalu, Nirmala |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | 135 p |
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