Title:
Study of Lithium Solvation Environments in Water-saturated Nitrobenzene

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dc.contributor.advisor Janata, Jiří
dc.contributor.author Moakes, Greg en_US
dc.contributor.committeeMember Bottomley, Lawrence
dc.contributor.committeeMember Eckert, Charles
dc.contributor.committeeMember Gelbaum, Leslie
dc.contributor.committeeMember Lyon, Louis Andrew
dc.contributor.department Chemistry and Biochemistry en_US
dc.date.accessioned 2007-03-27T18:24:14Z
dc.date.available 2007-03-27T18:24:14Z
dc.date.issued 2006-11-14 en_US
dc.description.abstract It was found that there exist three major water environments when water is dissolved in nitrobenzene. 2H NMR has proved that these solvatomers exist irrespective of whether lithium salt is added to the system. 7Li NMR experiments suggested that the first solvatomer is majority nitrobenzene, the second a mixed solvation shell consisting of nitrobenzene and water and the third solvatomer is a large water aggregated at the glass surface. The mixed solvation state is short lived and is promoted by addition of water of by supersaturating the system upon cooling. This is a high energy state and decays either into the homogenous bulk NB state or to the surface of the glass wall, depending on if glass surface is present. In the 7Li NMR experiments, the hydrophobicity of the salt, determined by the anion, affects the relative intensity of the three 7Li resonances. Addition of lithium serves to promote hydrogen bonding in the majority nitrobenzene solvatomer, as confirmed by FTIR and neutron diffraction studies. There is no evidence that it has an effect on the size of the mixed solvatomer or the water aggregate immobilized on the glass surface. A reasonable hypothesis is that lithium exchanges between the water species which are formed independent of lithium involvement. The system is summarized as follows: Below critical water concentration (~200mM) nitrobenzene/water is a homogeneous distribution of water molecules in nitrobenzene. Addition of lithium salt to such a system has two main affects. First, the lithium promotes hydrogen bonding between the dissolved water molecules, as confirmed by FTIR and neutron scattering. Second, the hydrogen bonded water may precipitate causing microheterogeneity of the system, leading to a second resonance observed in both the 2H and 7Li NMR spectra (LiNB/W). In the presence of glass, a third solvation state can nucleate at the glass surface; this solvation state has character even closer to that of bulk water (LiW). These two supplementary solvation states can be artificially induced by either adding aliquots of water or cooling. en_US
dc.description.degree Ph.D. en_US
dc.format.extent 2125381 bytes
dc.format.mimetype application/pdf
dc.identifier.uri http://hdl.handle.net/1853/14105
dc.language.iso en_US
dc.publisher Georgia Institute of Technology en_US
dc.subject Electrochemistry en_US
dc.subject Liquid-liquid interface en_US
dc.subject Solvation en_US
dc.subject FTIR en_US
dc.subject NMR en_US
dc.subject ITIES en_US
dc.subject.lcsh Solvation en_US
dc.subject.lcsh Surface chemistry en_US
dc.subject.lcsh Electrochemistry en_US
dc.subject.lcsh Interfaces (Physical sciences) en_US
dc.subject.lcsh Lithium silicates en_US
dc.subject.lcsh Nitrobenzene en_US
dc.subject.lcsh Solution (Chemistry) en_US
dc.title Study of Lithium Solvation Environments in Water-saturated Nitrobenzene en_US
dc.type Text
dc.type.genre Dissertation
dspace.entity.type Publication
local.contributor.advisor Janata, Jiří
local.contributor.corporatename School of Chemistry and Biochemistry
local.contributor.corporatename College of Sciences
relation.isAdvisorOfPublication bdd9601d-9df0-4a6e-90dc-5e5b222dcee3
relation.isOrgUnitOfPublication f1725b93-3ab8-4c47-a4c3-3596c03d6f1e
relation.isOrgUnitOfPublication 85042be6-2d68-4e07-b384-e1f908fae48a
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