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The study of zinc-copper cell¡Gusing zinc chloride and choline chloride ionic liquid as the electrolyteLiou, Ying-Chang 05 August 2008 (has links)
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Entanglement and decoherence in a trapped-ion quantum registerKielpinski, David. January 2001 (has links) (PDF)
Thesis (Ph. D.)--University of Colorado, 2001. / Includes bibliographical references.
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Determination of Young's modulus of carbon nanotube using molecular dynamics (MDSS) simulation /Oh, Jung Joo. January 2003 (has links) (PDF)
Thesis (M.S. in Applied Physics)--Naval Postgraduate School, December 2003. / Thesis advisor(s): Young W. Kwon, James H. Luscombe. Includes bibliographical references (p. 53-57). Also available online.
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Investigations of the electrochemical behaviour of room temperature ionic liquids2015 May 1900 (has links)
The existence of Room Temperature Ionic Liquids (RTILs) has been known for a long time, but only recently have they been pulled to the forefront of chemical research. This increase in attention can be attributed to a keen interest in their intrinsic properties for a wide variety of potential applications. RTILs have been used as alternative solvents for organic synthesis as well as catalysis, as well as supports for the purification or extraction of metals. Being ionic in nature and liquid at temperatures below 100°C, RTILs lend themselves to the electrochemist. As a result, they have been looked at for use in electrochemical systems such as high capacity batteries and supercapacitors. Due to their extremely high density of charge carriers relative to more well-known aqueous electrochemical systems, a new theoretical approach must be taken. Currently, a large gap exists between theoretical approaches and experimental results. The work contained within this thesis aims to provide insight into the interface between a RTIL and an electrified gold electrode.
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First principles-based atomistic modeling of the interfacial microstructure and capacitance of graphenePaek, Eunsu 04 March 2014 (has links)
Graphene has been extensively studied for possible future technical applications due to its unique electronic, transport, and mechanical properties. For practical applications, graphene often needs to be placed in a medium or on a substrate. The interfacial interaction between graphene and other materials can greatly affect the performance of graphene-based devices, but has not been well explored. My thesis research focused on developing a better understanding of the interface of pristine and chemically/mechanically modified graphene sheets with ionic liquids (ILs) as well as amorphous silica (a-SiO₂) surfaces using first principles-based atomistic modeling which combines density functional theory, classical molecular dynamics, and Metropolis Monte Carlo. The major focus of my thesis research was on investigating the interfacial structure and capacitance between graphene and ILs; graphene-based materials and ILs have been regarded as viable candidates for supercapacitor electrodes and electrolytes, respectively. Particular emphasis was placed on elucidating the relative contributions of the electric double layer (EDL) capacitance at the graphene/IL interface and the quantum capacitance of graphene-like electrodes. More specifically, we first determined the microstructure (such as orientation, packing density, cation-anion segregation) of chosen ILs near planar graphene electrodes with various surface charge densities. Based on the calculated IL microstructure for each system, the EDL capacitance was then evaluated with particular attention to the effect of cation-anion size difference. We also examined the influence of the chemical and mechanical modifications of graphene-like electrodes on the supercapacitor performance. Especially, mechanisms underlying chemical doping-induced enhancement of the total interfacial capacitance were addressed through analysis of electrode quantum capacitance changes resulting from electronic structure modifications. A part of my effort was also devoted to examining the binding interaction of graphene with a-SiO₂ (which is not yet clearly understood despite its scientific and technological importance). In particular, we attempted to evaluate quantitatively the adsorption strength of graphene on the a-SiO₂ surface, which has been under debate mainly due to the difficulty of direct measurement. / text
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Ionic liquid electrochemical processing of reactive metalsVaughan, James 05 1900 (has links)
Ionic liquids (ILs) were studied as solvents for electrochemical reactions with the intent to devise metallurgical processes for Al, Mg and Ti that are less energy intensive and operate at lower temperatures than current industrial practice. Tetra-alkyl phosphonium ILs are on the low end of the IL cost spectrum and are regarded as understudied compared with imidazolium and pyridinium ILs. They are also known to be more thermally stable.
The density, viscosity and conductivity of the phosphonium ILs and metal salt-IL mixtures were measured. The conductivity of the phosphonium ILs tested were found to be roughly an order of magnitude lower than imidazolium ILs; this is attributed to the relatively large cation size and localized charge. Linear density-temperature functions are presented. The viscosity and conductivity temperature relationship was modeled using the Vogel-Tamman-Fulcher (VTF) equation.
The electrochemical window of A10341'14,6,6,610 was studied on a Pt substrate over a wide range of A1C13 concentrations using cyclic voltammetry (CV). It was found that the tetra-alkyl phosphonium cation is on the order of 800 mV more electrochemically stable than the 1-ethyl-3-methyl imidazolium (EMI+).
Cathodic and anodic polarization of Al in A1C13-[P14,6,6,6]C1 (Xmc13 = 0.67) was studied at temperatures ranging from 347 to 423 K. The Butler-Volmer equation was fitted to the plots by varying the kinetic parameters. The cathodic reaction was found to be diffusion limited and the anodic reaction is limited by passivation at lower temperatures. The overpotential required for electrodissolution of Al was found to be higher than for electrodeposition.
Aluminium was electrodeposited using both an electrowinning setup (chlorine evolution anode reaction) and electrorefining setup (Al dissolution anode reaction). The deposits were characterized in terms of morphology, current efficiency and power consumption. A variety of deposit morphologies were observed ranging from smooth, to spherical to dendritic, and in some cases, the IL was occluded in the deposit. The current efficiency and power consumption were negatively impacted by the presence of H2O and HCl present in the as-received ILs and by C12(g) generated by the anode reaction in the case of the electrowinning setup. HC1 was removed by cyclic polarization or corrosion of pure Al, resulting in current efficiencies above 90%. Aluminium was electrodeposited using the electrorefining setup with anode-cathode spacing of 2 mm at power consumption as low as 0.6 kWhr/kg-Al. This is very low compared with industrial Al electrorefining and Al electroplating using the National Bureau of Standards bath, which require 15-18 kWhr/kg-Al and 18 kWhr/kg-Al, respectively. However, due to low solution conductivity the power consumption increases significantly with increased anode-cathode spacing.
Titanium tetrachloride was found to be soluble in [P14,6,6,6]Cl and increases the conductivity of the solution. Attempts to reduce the Ti(IV) included corrosion of titanium metal, corrosion of magnesium metal powder and cathodic polarization. Despite a few attempts, the electro-deposition of Ti was not observed. At this point, titanium electrodeposition from phosphonium based ILs does not appear feasible.
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DNA in Ionic Liquids and PolyelectrolytesKhimji, Imran January 2013 (has links)
DNA has been widely studied in a variety of solvents. The majority of these solvents consist of either aqueous or organic components. The presence of ions or salts in these solvents can further alter DNA properties by changing the melting point or helical structure. The size, charge, and concentration of these additional components can all affect the behaviour of DNA. A new class of solvents, known as ionic liquids have recently gained popularity. Ionic liquids are comprised of entirely of ions and can be liquid at room temperature. Due to their low volatility and ability to dissolve both polar and non-polar substances, they are generating high levels of interest as ‘green solvents’. Although the interaction between DNA and ionic liquids has been characterized, the potential of this interaction is still being studied. It was discovered that when DNA mixed with DNA intercalating dyes was added to ionic liquids, there was a large reduction in fluorescence. Although this fluorescence drop was believed to occur to removal of the dye molecule from the helix, the strength of this interaction has not been researched.
In this thesis, the interaction between different intercalating dyes and different ionic liquids was evaluated. We reasoned that perhaps the difference in interaction could be used as a method of separating the DNA-dye complex, which has previously never been accomplished. For example, it has been established that both DNA and cationic dyes have an affinity for ionic liquids. The relative strength of this affinity is undetermined, as well as the comparison to normal aqueous mediums. Although ionic liquids can drastically alter the stability of the DNA duplex by either raising or decreasing the melting point depending on the ionic liquid chosen, we found that the DNA actually has a higher affinity for the aqueous phase. Conversely, intercalating dyes prefer to partition into the ionic phase. The relative affinities of the two components are strong enough for their respective phases that the complex can be split apart and each component can be extracted, allowing for separation of the two.
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The measurement and application of transport properties of ion swarms in gasesHolleman, Franklin Benton 12 1900 (has links)
No description available.
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Structures of small organic cluster ions computed using self-consistent field semiempirical molecular orbital methodsVillanueva, Martha A. 08 1900 (has links)
No description available.
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Synthesis, characterization, and catalytic applications of metallic nanoparticles in Tetraalkylphosphonium ionic liquids2015 May 1900 (has links)
In recent years, ionic liquids have emerged as one of the most promising alternatives to traditional volatile organic solvents when it comes to catalytic reactions. Stable metal nanoparticles suspended in ionic liquids, are catalytic systems that mimic aspects of nanoparticles on solid supports, as well as traditional metal-ligand complexes used in organometallic catalysis. While alkylimidazolium ionic liquids, with or without appended functionalities, have been earmarked as the media of choice for the dispersal of nanoparticles,
the tetraalkylphosphonium family of ionic liquids has largely been overlooked, despite their facile synthesis, commercial availability, chemical resemblance to surfactants traditionally used
for nanoparticle stabilization, stability under basic conditions, and wide thermal as well as electrochemical windows. It is only recently that a number of research groups have given this family of novel alternative solvents the recognition it deserves, and used metal NPs dispersed in these ILs as catalysts in reactions such as hydrogenations, oxidations, C-C cross-couplings, hydrodeoxygenations, aminations, etc. This thesis investigates the synthesis, characterization, and catalytic applications of transition metal nanoparticles in tetraalkylphosphonium ionic liquids. The ionic liquids described in this thesis functioned as the reaction media as well as intrinsic nanoparticle
stabilizers during the course of the catalytic processes. Metallic nanoparticles synthesized in these ionic liquids proved to be stable, efficient and recyclable catalytic systems for reactions of industrial significance, such as hydrodeoxygenations, hydrogenations, and oxidations. It was demonstrated that stability and catalytic activity of these systems were profoundly dependent
on the properties of the ionic liquids, such as the nature of the alkyl chains attached to the phosphonium cation, and the coordination ability of the anion. Since heat-induced nanoparticle sintering was a problem, a procedure was devised to redisperse the aggregated and/or sintered
nanoparticles so as to restore their initial sizes and catalytic activities. The presence of halides as counter-ions in tetraalkylphosphonium ionic liquids was seen to facilitate the oxidative
degradation of agglomerated metal nanoparticles, which was a key step in our redispersion protocol. It was demonstrated that this redispersion protocol, when applied to heat-sintered
nanoparticles, produces nanostructures that resemble the freshly made nanoparticles not only in size but also in catalytic activities. The presence of by-products from the borohydride
reduction step used to generate the nanoparticles in the ionic liquids actually facilitated multistep reactions such as hydrodeoxygenation of phenol, where a Lewis Acid was necessary for a
dehydration step. Finally, an attempt was made to utilize nanoparticles of an earth-abundant metal (iron) as a hydrogenation catalyst in a variety of alternative solvents (including tetraalkylphosphonium ionic liquids) in order to enhance the “green”ness of the catalyst systems. X-ray absorption spectroscopy (XAS) of the iron- nanoparticles/ionic liquid systems at
the Canadian Light Source revealed significant details about the chemical interaction between iron and the ionic liquid matrices, which added to our understanding of this neoteric family of catalysts.
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