Thesis (Ph. D.)--University of Chicago, 1905. / Includes bibliographical references. Also available on the Internet.

The manufacture of hydroxylamine by electrolytic reduction of nitric oxide was experimentally investigated. The experiments were carried out in a two-compartment packed bed electrochemical reactor consisting of a cathodic bed of tungsten carbide and a lead plate anode. The compartments were separated by an anion exchange membrane which was supported by a bed of glass beads on the anode side. The reduction occurred as the nitric oxide gas and sulphuric acid electrolyte trickled down cocurrently over the tungsten carbide bed. Sulphuric acid was also circulated separately through the anode chamber. The efficiency of tungsten carbide particles for nitric oxide reduction was observed to drop between successive runs. When in operation the activity remained fairly stable for a period of twelve hours. The drop in activity between the runs appeared to be the result of surface oxidation of the particles by dissolved or free oxygen. Tungsten carbide nevertheless gave better performance than a graphite bed electrode. The operating parameters studied over the stabilized portion of the activity of fresh tungsten carbide included catholyte flowrate and composition, catholyte recycle, gas flowrate and composition, particle size, bed dimensions and reactor pressure and temperature. In typical operation at atmospheric pressure, a current efficiency of 62% and a hydroxylamine concentration of 0.03 M were obtained under a current density of 213 A m⁻² . Doubling the pressure approximately doubled the current density under which similar current efficiencies were observed. The hy-droxylamine concentration decreased sharply with increase in catholyte flowrate. Increases in gas flow-rate produced only a moderate increase in current efficiency above a certain current density. In recycling catholyte, the hydroxylamine concentration was built up almost linearly with number of passes of catholyte through the reactor without appreciable drop of current efficiency. The rate of reduction of nitric oxide to hydroxylamine appeared to be controlled by mass transfer. Appropriate mass transfer correlations for trickle-bed reactors were suitably corrected for the present system and applied to predict the theoretical limiting current densities. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Thesis (Ph. D.)--Princeton University, 1926.

Thesis (Ph. D.)--Princeton University, 1922. / "Reprinted from the Journal of the American Chemical Society, vol. XLIV, no.10. October, 1922."

No description available.

P.A.S. Smith's Thesis--University of Michigan. / "Contribution from the Chemistry Laboratory of the University of Michigan." Two articles, by R.N. Keller an P.A.S. Smith, reprinted from the Journal of the American Chemical Society, v. 66, 1944, and v. 68, 1946.

Mitochondrial dysfunction and oxidative stress have been linked with many pathological conditions. Studies suggest that antioxidants able to accumulate in the inner regions of the mitochondria as well as possessing the chemical entities to cross membranes such as the blood brain barrier, could potentially overcome many of the limitations found with current antioxidants. Nitrones have demonstrated great antioxidant potential due to their free radical scavenging properties, cardio and neuro-protective activities. In this research, several synthetic studies were performed with the aim of synthesizing a novel hydroxylamine of potential utility for the preparation of mitochondria targeted nitrones. These studies resulted in the generation of a synthetic intermediate, N-(3-(1H-imidazol-1-yl)propyl)-2,2,3-trimethyl-3-nitrobutaminde, that although lacking the desired hydroxyl- amino functionality, this intermediate is, in theory, an immediate precursor to a molecule that is endowed with the structural characteristics to deliver tethered nitrones to the inner regions of the mitochondria.

No description available.

Hydroxylamine nitrate (HAN), an important agent for the nuclear industry and the U.S. Army, has been involved in several costly incidents. To prevent similar incidents, the study of HAN safe storage and handling boundary has become extremely important for industries. However, HAN decomposition involves complicated reaction pathways due to its autocatalytic behavior and therefore presents a challenge for definition of safe boundaries of HAN storage and handling. This research focused on HAN decomposition behavior under various conditions and proposed isothermal aging testing and kinetic-based simulation to determine safety boundaries for HAN storage and handling. Specifically, HAN decomposition in the presence of glass, titanium, stainless steel with titanium, or stainless steel was examined in an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC). n-th order kinetics was used for initial reaction rate estimation. Because stainless steel is a commonly used material for HAN containers, isothermal aging tests were conducted in a stainless steel cell to determine the maximum safe storage time of HAN. Moreover, by changing thermal inertia, data for HAN decomposition in the stainless steel cell were examined and the experimental results were simulated by the Thermal Safety Software package. This work offers useful guidance for industries that manufacture, handle, and store HAN. The experimental data acquired not only can help with aspects of process safety design, including emergency relief systems, process control, and process equipment selection, but also is a useful reference for the associated theoretical study of autocatalytic decomposition behavior.

Thesis (Ph. D.)--Oregon State University, 1986. / Includes bibliographical references (leaves 169-181).