Bowser, Sage R
(2014)
STRUCTURE AND TRANSPORT IN TRIALKYLTRIAZOLIUM IONIC LIQUIDS: A COMBINED PFG-NMR DIFFUSION AND CONDUCTIVITY STUDY.
Master's Thesis, University of Pittsburgh.
(Unpublished)
Abstract
Ionic liquids (ILs), the class of salts with melting points below 100 °C, are promising alternatives to molecular solvents. Their great chemical tuneability opens the possibility of tailoring ILs for specific tasks; however, data from systematic structure-property studies of ILs, as well as a more complete understanding of the liquid structure and interionic interactions within ILs, are required for the rational design of ILs.
In this thesis, a systematic study of the effect of alkyl chain length and alkyl chain branching on the transport properties and carbon dioxide solubility in trialkyltriazolium ionic liquids is described. The viscosities, diffusion coefficients, and conductivities of 15 1,2,4-trialkyl-1,2,3-triazolium bis(trifluoromethylsulfonyl)imide ILs are reported, and are found to be greatly reduced in ILs that incorporate multiple branched alkyl groups on the cation. The interrelationships among the transport properties are analyzed by comparing the deviations of the transport properties of each IL from Walden’s Rule, the Stokes-Einstein equation, and the Nernst-Einstein equation. Preliminary evidence is given for a connection between the formation of polar and non-polar nanodomains within ILs, and the Nernst-Einstein deviation ratio. Henry’s Law constants for the solubility of carbon dioxide in the ILs are reported and found to be most strongly correlated to the molar volume of the IL; evidence supporting a relationship between the Nernst-Einstein deviation ratio and carbon dioxide solubility for a given IL is not found.
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Details
| Item Type: |
University of Pittsburgh ETD
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| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
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| Date: |
27 January 2014 |
| Date Type: |
Publication |
| Defense Date: |
30 August 2013 |
| Approval Date: |
27 January 2014 |
| Submission Date: |
17 September 2013 |
| Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
| Number of Pages: |
92 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
MS - Master of Science |
| Thesis Type: |
Master's Thesis |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
NMR, ionic liquids, ionicity, diffusion, Nernst-Einstein |
| Date Deposited: |
27 Jan 2014 16:38 |
| Last Modified: |
15 Nov 2016 14:15 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/19790 |
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