Physical Sciences and Mathematics Commons^™

Nmr Characterization Of Parathion: Properties, Transport, And Reaction Kinetics, Emma Catherine Baker

Boise State University Theses and Dissertations

The hydrolysis reaction of parathion (PTH) to produce para-nitrophenolate (pNP) and O,O-diethylthiophosphate (DETP) was examined in a minimally disturbed liquid-liquid biphasic reaction system by proton and phosphorous nuclear magnetic resonance spectroscopy. The effect of the micellar cationic surfactant, cetyltrimethylammonium chloride (CTAC), on PTH transport, hydrolysis, and system characteristics including reactant-product concentrations, pNP partition coefficients, pNP surface activity, ultraviolet degradation of pNP, oxidation of pNP, and impurities in PTH are reported. Surfactant reaction systems resulted in a 2.5 order of magnitude increase in the amount of PTH transported into the aqueous layer as compared to the control system at 2100 …

The Kinetics And Mechanisms Of Some Fundamental Organic Reactions Of Nitro Compounds, Zhao Li

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

In chemistry, kinetics is the study of the rates of chemical reactions. A reaction mechanism describes in detail exactly what takes place at each stage of an overall chemical reaction from reactants to products. The work outlined in this dissertation was carried out in order to find out the true mechanisms of some fundamental organic reactions of nitro compounds by means of a series of novel kinetic techniques and analysis methods.

The target reactions include (1) the proton transfer reactions of nitroalkanes and (2) the aromatic nucleophilic reactions of trinitroarenes, both of which are undeniably among the most elementary and …

Removal Of Heavy Metals Using Modified Limestone Media: Zinc And Cadmium, Keerthy Mandadi

Masters Theses & Specialist Projects

Heavy metal contamination is a serious concern throughout the world. Increased concentrations in drinking water have many negative impacts on human health. Limestone is an inexpensive and simple media for removing high concentrations of heavy metals from drinking water supplies. Ferric based media is commonly used to remove zinc, cadmium, lead, arsenic and other heavy metals. The drinking water standards set by the US EPA for cadmium, zinc and arsenic are 0.005 mg/L, 5 mg/L and 0.010 mg/L respectively. Bangladesh, parts of India, China and the United States have high concentrations of arsenic in drinking water. Although many technologies exist …

Kinetics Of O2 Reduction On Oxide-Covered Ni-Cr-Mo Alloys, Xiangrong (Sarah) Zhang

Electronic Thesis and Dissertation Repository

Ni-Cr-Mo alloys exhibit exceptional corrosion resistance and are widely used in chemical processing industries. The reliable performance of these alloys under extreme industrial conditions, are generally attributed to the presence of a passive film on the alloy surface. O₂ reduction is the most likely cathodic process able to sustain metal oxidation (corrosion) in industrial environments. However, the kinetics of O₂ reduction on these oxide-covered alloys has hardly been studied, despite the possibility it may be the rate controlling process for corrosion, especially localized corrosion. The objectives of this research are to characterize the properties of the oxide film …

Transient Ru-Methyl Formate Intermediates Generated With Bifunctional Transfer Hydrogenation Catalysts, Richard H. Perry, Kristen R. Brownell, Konstantin Chingin, Thomas J. Cahill Iii, Robert M. Waymouth, Richard N. Zare

Chemistry and Physics Faculty Articles

Desorption electrospray ionization (DESI) coupled to high-resolution Orbitrap mass spectrometry (MS) was used to study the reactivity of a (β-amino alcohol)(arene)RuCl transfer hydrogenation catalytic precursor in methanol (CH₃OH). By placing [(p-cymene)RuCl₂]₂ on a surface and spraying a solution of β-amino alcohol in methanol, two unique transient intermediates having lifetimes in the submillisecond to millisecond range were detected. These intermediates were identified as Ru (II) and Ru (IV) complexes incorporating methyl formate (HCOOCH₃). The Ru (IV) intermediate is not observed when the DESI spray solution is sparged with Ar gas, indicating that …

Dynamics Of The Solvent Exchange Reaction Of Weakly Bound Organic Solvents To Group 6 Transition Metal Carbonyls And The Molybdenum Hexacarbonyl Mediated Pauson-Khand Reaction, Richard J. Gates

Theses and Dissertations

Many organometallic reactions are solvent-dependent, suggesting solvent molecules interact with reaction intermediates. Studies of the solvent exchange reaction of group 6 transition metal carbonyls with moderately binding ligands have provided insight into these interactions, however, studies of the mechanism for this reaction with weakly binding ligands have not been performed. Experiments were conducted on the nanosecond time scale in methylcyclohexane over the temperature range of 4 to 44 °C using Step Scan FTIR (SS FTIR) spectroscopy with weakly binding ligands benzene and mesitylene. Upon photolysis of the metal hexacarbonyls, the kinetically favored product (M(CO)5(solv)), decays following pseudo-first-order kinetics to the …

Nmr Line Shapes And Multi-State Binding Equilibria, Evgeni Kovrigin

Chemistry Faculty Research and Publications

Biological function of proteins relies on conformational transitions and binding of specific ligands. Protein-ligand interactions are thermodynamically and kinetically coupled to conformational changes in protein structures as conceptualized by the models of pre-existing equilibria and induced fit. NMR spectroscopy is particularly sensitive to complex ligand-binding modes—NMR line-shape analysis can provide for thermodynamic and kinetic constants of ligand-binding equilibria with the site-specific resolution. However, broad use of line shape analysis is hampered by complexity of NMR line shapes in multi-state systems. To facilitate interpretation of such spectral patterns, I computationally explored systems where isomerization or dimerization of a protein (receptor) molecule …

Kinetic Studies On Lactonization Of Quinone Propionic Acid Derivatives For The Development Of Redox Responsive Liposomes, K. L. Iresha Sampathi Perera

LSU Master's Theses

ABSTRACT Stimuli-responsive liposome systems that utilize endogenous triggers of tumor microenvironment have generated great attention in recent drug delivery research. Among such formulations, redox-responsive liposomes seem highly promising for cancer treatment due to their potential to release high drug concentrations upon reduction (by reductase enzymes). The research described in this thesis involved the evaluation of kinetics of trimethyl-lock quinone propionic acid reduction and lactonization, which accounts for payload release from trimethyl-lock quinone propionic acid-decorated liposomes. To achieve the ultimate goal of this research, several trimethyl-lock quinone propionic acid-based amide compounds were synthesized and characterized. Kinetic studies were carried out with …

Atr-Ftir Studies On The Kinetics Of Dimethylarsinic Acid (Dma) Surface Complexation With Iron(Oxyhydr)Oxides, Julia Tofan-Lazar Miss

Theses and Dissertations (Comprehensive)

Dimethylarsinic acid (DMA) is an organoarsenical compound that, along with monomethylarsonic acid, poses a health and an environmental risk, and a challenge to the energy industry. Little is known about the surface chemistry of DMA at the molecular level with materials relevant to geochemical environments and industrial sectors. The surface chemistry of phosphorus and arsenic compounds in their organic and inorganic forms is of great interest due to its role in controlling their transport, bioaccessibility and speciation. This thesis reports the first in-situ and surface-sensitive rapid kinetic studies on the adsorption and desorption of DMA to and from Fe-(oxyhydr)oxide films …

Extractive Metallurgy Of Copper, Fathi Habashi

Fathi Habashi