Global ETD Search
Search theses and dissertations gathered from participating repositories worldwide. Every result links back to the library that holds it. No account is needed.
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Showing 1 to 20 of 35 for “"outer-sphere"”.
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Nuclear magnetic resonance investigation of mineral surface reactions involving inner-sphere and outer-sphere complexes
… Phosphate and Cs are good examples of inner-sphere and outer-sphere complexes, respectively, and this study shows that NMR is in many ways a more useful tool to investigate surface adsorbed species than other spectroscopic methods. Chapter 1 reviews mineral surface reactions which involve …
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Catalytic consequences of inner- and outer-sphere interactions at the solid-liquid interface in zeolites
… to an active site are referred to as “inner-sphere” interactions, while those involving molecules within the second shell are known as “outer-sphere” interactions. This dissertation explores both inner- and outer-sphere interactions that influence the stability of catalytically relevant …
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Magnetic Exchange Effects in Outer-Sphere Associated Metal Dimers and in Oxidized Manganese(ii) Schiff Base Complexes
Made available in DSpace on 2014-12-13T20:09:58Z (GMT). No. of bitstreams: 1 7709065.pdf: 13092680 bytes, checksum: e1eab93c7e72699be794c549fbe95218 (MD5) Previous issue date: 1976
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The role of outer-sphere residues and substrate-binding at the 3-mercaptopropionic acid dioxygenase (3mdo) active site: a combined spectroscopic and computational investigation
Thiol Dioxygenases (TDOs) are non-heme iron enzymes that catalyze the O2-dependent oxidation of thiol-bearing amino acid derivatives to their corresponding sulfinic acid. Recently, considerable work has been focused on this class of enzymes, as sulfur metabolite imbalances have been correlated with …
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Kissing the Archimedeans
… polyhedra presented their vertices will have spheres expanding such that the center of each of these outer spheres are the vertices of the polyhedron, and these outer spheres will continue to expand until they become tangent to each other. The ratio will be found between the radius of each …
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Understanding cation catalytic effects in electron transfer reactions at molecular scale
… display no cation specific trend in outer-sphere reorganization energy for both homogeneous ET case and heterogeneous ET case. Further investigation into the effects of redox charge distribution reveals that charge distribution has significant effect on outer-sphere reor- ganization …
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Kinetic and Thermodynamic Aspects of Voltage as a Driving Force for Ammonia Activation
… I find that the reaction proceeds via an inner-sphere route at heterogeneous metal surfaces, in contrast to most previous work on outer-sphere electrochemical reductive amination systems. I then investigate the kinetics of activating ammonia by breaking the nitrogen-hydrogen bond oxidatively, …
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Formation and transformation kinetics of iron oxy-hydroxides and effects of adsorbed oxyanions
… Results show that AsO43- and SO42- inner-sphere complexes decrease the rate of Fh transformation and induce the formation of Hm. In contrast, NO3- outer-sphere complexes promote the formation of Gt. We then investigated the impact of oxyanion (AsO43- and PO43-) surface loading on the rate …
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Untersuchung von Ladungstransfermechanismen an Galliumarsenid- und Indiumphosphid-Elektrolyt-Grenzflächen mittels Impedanz- und phasensensitiver Photostrom-Spektroskopie
… Metallocene seien nicht-adsorbierende, ideale outer-sphere Redoxsysteme. Es wurde daher ein umfangreiches kinetisches Modell entwickelt, in dem von der Adsorption des Redoxsystems und einem Ladungstransfer über einen Selbstaustauschprozeß ausgegangen wird. Die gute Übereinstimmung der nach …
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Investigation into the unique coordination and spectroscopic properties of lanthanide ions with dipyridylamine and dipicolylamine based ligands.
… rather the ligand participated in unprecedented outer-sphere anion-pi interactions with lanthanide chloride and lanthanide nitrate moieties. In addition to solid-state structures, extensive solution studies were carried out with the dipicolylamine triazine molecule in order to probe the …
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Environmental tuning of the reactivity of molecules confined to polarized interfaces
… However, recent work has established that outer-sphere effects such as the surface structure and ligation method can impact reactivity as much as catalyst structure. This thesis explores these environmental contributions to reactivity with a particular focus on exploring the impact of …
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Flow of power law fluids with application to oil drilling
… These are: 1. The creeping motion of a sphere moving through an expanse of liquid. 2. The combined steady and oscillatory flow of a liquid through a straight tube of circular cross section. The first part of the work is devoted to the prediction of the drag correction factor for a sphere …
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Determination of the Activation Parameters of Reaction Between [Fe(CN<sub>6</sub>]<sup>-4</sup> and K[Co(HEDTA)NO<sub>2</sub>].
… conditions. Based on previous results, an outer-sphere electron-transfer pathway and a first order rate of reaction for each of the reacting species <sup>1</sup> have been proposed.</p>
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Computing the energetic component of the charge-transfer symmetry factor
… the reaction free energy. The model mimics an outer-sphere electron-transfer reaction that obeys Marcus theory to a good approximation. This theory uses the energy difference between the two empirical valence bond states as the reaction coordinate and quantitatively predicts the location of the …
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Study of Chemical States, Composition and Adsorption Behavior of Iron Coated Granular Activated Carbon (Fe-GAC) for Selenate Removal and Feasible Adsorbent Modifications
… M ionic strength. The results showed that inner-sphere and outer-sphere complexes were formed at pH 5 and 8, respectively. Additionally, mixture of mono-dentate and bi-dentate binding was observed at pH 5 with selenate. In comparison, selenite was only observed to form bi-dentate inner sphere …
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Electrochemical mechanisms in nano-structured graphitic and redox-active polymeric architectures
… and physically impermeable interface. Outer-sphere reactions on metal substrate-modulated graphene prove the electronic transparency of the graphene interface. Inner-sphere oxygen reduction reaction activity changes demonstrate the electronic coupling between metal substrates and …
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Ultrasonic backscatter coefficient quantitative estimates from Chinese hamster ovary and BALB/3T3 cell pellet biophantoms
… to eukaryotic cells, is a concentric sphere scattering model. BSC estimates from cell pellet biophantoms of known number density were performed with 20, 40 and 80 MHz focused transducers (overall bandwidth: 20-100 MHz). These biophantoms were histologically processed and then evaluated …
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Steric and kinetic measurements at well-defined surface sites
… first chapter demonstrates passivation of inner-sphere ET processes on glassy carbon via deposition of a fluorinated aryl film onto the electrode. At sufficiently thin deposition layers, outer-sphere ET rates are preserved. The second chapter describes condensation of crown ethers onto the …
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Reductive and oxidative dissociative electron transfers: transition between the concerted and stepwise mechanistic pathways
… experiments do not proceed through an outer sphere electron transfer. Additionally, it is shown that the difference between the direct oxidation of acetate in anhydrous and wet acetonitrile is unlikely to be the result of transition from a purely concerted mechanism to a purely stepwise …
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The sorption of uranium(VI) and neptunium(V) onto surfaces of selected metal oxides and alumosilicates studied by in situ vibrational spectroscopy
… solutions of U(VI) and Np(V/VI) at ambient atmosphere has been characterized for the first time, by a combination of ATR FT-IR spectroscopy, near infrared (NIR) absorption spectroscopy, and speciation modeling applying updated thermodynamic databases. From the infrared spectra, a significant …
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