There has been an increasing interest in probabilistic modeling of hydrogeologic systems. The classical approach to groundwater modeling has been deterministic in nature, where individual layers and formations are assumed to be uniformly homogeneous. Even in the case of complex heterogeneous systems, the heterogeneities describe the differences in parameter values between various layers, but not within any individual layer. In a deterministic model a single-number is assigned to each hydrogeologic parameter, given a particular scale of interest. However, physically there is no such entity as a truly uniform and homogeneous unit. Single-number representations or deterministic predictions are subject to uncertainties. The approach used in this work models such uncertainties with probabilistic parameters. The resulting statistical distributions of output variables are analyzed. A numerical algorithm, based on axiomatic principles of probability theory, performs arithmetic operations between probability distributions. Two subroutines are developed from the algorithm and incorporated into the computer program TERZAGI, which solves groundwater flow problems in saturated, multi-dimensional systems. The probabilistic computer program is given the name, PROGRES. The algorithm has been applied to study the following problems: one-dimensional flow through homogeneous media, steady-state and transient flow conditions, one-dimensional flow through heterogeneous media, steady-state and transient flow conditions, and …

Hourly Wangara boundary layer data (Clark et al., 1971) was used to substantiate previously derived empirical equations of the surface radiation budget. These equations only require measurements taken by a surface observer in order to be evaluated. A parameterization was made for infrared (IR) radiation. From this procedure, a residual radiation was obtained from the measured daytime net radiation data in order to approximate short wave (SW) radiation. Diurnal trends in radiation and other related meteorological parameters were also evaluated. For IR radiation, the Brunt equation was found to adequately represent effective radiation without clouds. IR attenuation (K-values) of 0.89, 0.64, and 0.51 were calculated for low, middle, and high clouds, respectively. A modification of Beer's Law was derived to evaluate the residual radiation under clear skies as suggested by Flowers et al. (1969) for SW radiation. With the surface albedo assumed at 0.15, a mean turbidity coefficient of 0.16 was determined. Also, the square root of the optical air mass was found to best represent the data in this equation. An analysis of SW cloud attenuation coefficients (C-values) from the residual radiation proved inconclusive. Of considerable importance is the finding that cloud attenuation of the residual radiation behaved nonlinearly. …

Techniques for applying ab-initio calculations to the is of atomic spectra are investigated, along with the relationship between the semi-empirical and ab-initio forms of Slater-Condon theory. Slater-Condon theory is reviewed with a focus on the essential features that lead to the effective Hamiltonians associated with the semi-empirical form of the theory. Ab-initio spectroscopic parameters are calculated from wavefunctions obtained via self-consistent field methods, while multi-configuration Hamiltonian matrices are constructed and diagonalized with computer codes written by Robert Cowan of Los Alamos Scientific Laboratory. Group theoretical analysis demonstrates that wavefunctions more general than Slater determinants (i.e. wavefunctions with radial correlations between electrons) lead to essentially the same parameterization of effective Hamiltonians. In the spirit of this analysis, a strategy is developed for adjusting ab-initio values of the spectroscopic parameters, reproducing parameters obtained by fitting the corresponding effective Hamiltonian. Secondary parameters are used to "screen" the calculated (primary) spectroscopic parameters, their values determined by least squares. Extrapolations of the secondary parameters determined from analyzed spectra are attempted to correct calculations of atoms and ions without experimental levels. The adjustment strategy and extrapolations are tested on the K I sequence from K{sup 0+} through Fe{sup 7+}, fitting to experimental levels for V{sup 4+}, …

I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl~ acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that …

To determine the activity of zinc in Zn-Al alloys, the electromotive force (emf) of the cell: Zn/ZnCl/sub 2/-KC1 (eut)/Zn,Al was measured at temperatures between 569.5 K (296.5C) and 649.5 K (376.5C). The applicability of a two-suffix Margules equation was demonstrated, in good agreement with theoretical expectations. The diffusion coefficient of Zn in Al determined from a planar diffusion model for the experimental data was about 3 x 10/sup -10/ cm/sup 2//sec to 2 x 10/sup -9/ cm/sup 2//sec in the range of temperature studied. This is higher than that found in the literature. The most plausible reason appears to be the high alumina concentration in the working electrode because of partial oxidation. Oxidation of the alloying metals was the primary cause of poor alloying between calcium/or zinc and aluminum, thereby frustrating similar measurements at a Ca-Al/or Zn-Al alloy. The literature on the activity of calcium and zinc is aluminum is reviewed.

A deterministic analysis of the computational cost associated with geometric splitting/Russian roulette in Monte Carlo radiation transport calculations is presented. Appropriate integro-differential equations are developed for the first and second moments of the Monte Carlo tally as well as time per particle history, given that splitting with Russian roulette takes place at one (or several) internal surfaces of the geometry. The equations are solved using a standard S/sub n/ (discrete ordinates) solution technique, allowing for the prediction of computer cost (formulated as the product of sample variance and time per particle history, sigma/sup 2//sub s/tau p) associated with a given set of splitting parameters. Optimum splitting surface locations and splitting ratios are determined. Benefits of such an analysis are particularly noteworthy for transport problems in which splitting is apt to be extensively employed (e.g., deep penetration calculations).

The objectives of this work were: (1) to investigate formation and destruction reactions of peroxynitric acid, HO{sub 2}NO{sub 2} and (2) to study the photochemistry and kinetics of the HO{sub x} - NO{sub x} - CO{sub x} system were also studied. Investigations were done using infrared spectroscopy to observe the behavior of species involved with the reactions of interest. Several techniques were used, including expansion of reactants into an evacuated cell, static cell decays under constant illumination, and periodic photolysis of flow systems, Infrared absorption cross sections were obtained for CO, CO{sub 2}, NO, NO{sub 2}, N{sub 2}O{sub 5}, HNO{sub 3}, H{sub 2}O{sub 2}, and H{sub 2}O. The spectroscopic measurements were used to derive kinetic information on the systems under study,

The spectra of Sc I, Sc II, Sc III, and Sc IV are analyzed through the use of the Zeeman effect. A sliding spark of the author's design is used in conjunction with a 27 kilogauss electromagnet. The spectra have (reciprocal) dispersions of 0.2 to 0.5 A/mm. 10 Sc I levels, 16 Sc II levels and 5 Sc III levels show Zeeman splitting. No Sc IV Zeeman patterns were observed. 2 Sc I, 4 Sc II, and all of the Sc III level data are new.

As a part of the continuing research on aluminum recovery from fly ash by HiChlor process, a plexiglass fluidization column system was constructed for measurement of fluidization parameters for power-plant fly ashes and fly ash-charcoal mixtures. Several bituminous and subbituminous coal fly ashes were tested and large differences in fluidization characteristics were observed. Fly ashes which were mechanically collected fluidized uniformly at low gas flow rates. Most fly ashes which were electrostatically precipitated exhibited channeling tendency and did not fluidize uniformly. Fluidization characteristics of electrostatically collected ashes improve when the finely divided charcoal powder is added to the mixture. The fluidization of the mixture was aided initially by a mechanical stirrer. Once the fluidization had succeeded, the beds were ready to fluidize without the assistance of a mechanical action. Smooth fluidization and large bed expansion were usually observed. The effects of charcoal size and aspect ratio on fluidization characteristics of the mixtures were also investigated. Fluidization characteristics of a fly ash-coal mixture were tested. The mixture fluidized only after being oven-dried for a few days.

A model for simulating the transient behavior of solid electrodes undergoing deposition or dissolution has been developed. The model accounts for ohmic drop, charge transfer overpotential, and mass transport limitations. The finite difference method, coupled with successive overrelaxation, was used as the basis of the solution technique. An algorithm was devised to overcome the computational instabilities associated with the calculations of the secondary and tertiary current distributions. Simulations were performed on several model electrode profiles: the sinusoid, the rounded corner, and the notch. Quantitative copper deposition data were obtained in a contoured rotating cylinder system, Sinusoidal cross-sections, machined on stainless steel cylinders, were used as model geometries, Kinetic parameters for use in the simulation were determined from polarization curves obtained on copper rotating cylinders, These parameters, along with other physical property and geometric data, were incorporated in simulations of growing sinusoidal profiles. The copper distributions on the sinusoidal cross-sections were measured and found to compare favorably with the simulated results. At low Wagner numbers the formation of a slight depression at the profile peak was predicted by the simulation and observed on the profile. At higher Wagner numbers, the simulated and experimental results showed that the formation of a depression …

Nucleation of bubbles, their growth by diffusion of dissolved gas to the bubble surface and by coalescence, and their detachment from the electrode are all very fast phenomena; furthermore, electrolytically generated bubbles range in size from ten to a few hundred microns; therefore, magnification and high speed cinematography are required to observe bubbles and the phenomena of their growth on the electrode surface. Viewing the action from the front side (the surface on which the bubbles form) is complicated because the most important events occur close to the surface and are obscured by other bubbles passing between the camera and the electrode; therefore, oxygen was evolved on a transparent tin oxide "window" electrode and the events were viewed from the backside. The movies showed that coalescence of bubbles is very important for determining the size of bubbles and in the chain of transport processes; growth by diffusion and by coalescence proceeds in series and parallel; coalescing bubbles cause significant fluid motion close to the electrode; bubbles can leave and reattach; and bubbles evolve in a cycle of growth by diffusion and different modes of coalescence. An analytical solution for the primary potential and current distribution around a spherical bubble in …

Part I of this dissertation is a study of the magnetic isotope effect, and results are presented for the separation of /sup 13/C and /sup 12/C isotopes. Two models are included in the theoretical treatment of the effect. In the first model the spin states evolve quantum mechanically, and geminate recombination is calculated by numerically integrating the collision probability times the probability the radical pair is in a singlet state. In the second model the intersystem crossing is treated via first-order rate constants which are average values of the hyperfine couplings. Using these rate constants and hydrodynamic diffusion equations, an analytical solution, which accounts for all collisions, is obtained for the geminate recombination. The two reactions studied are photolysis of benzophenone and toluene and the photolytic decomposition of dibenzylketone (1,3-diphenyl-2-propanone). No magnetic isotope effect was observed in the benzophenone reaction. /sup 13/C enrichment was observed for the dibenzylketone reaction, and this enrichment was substantially enhanced at intermediate viscosities and low temperatures. Part II of this dissertation is a presentation of theory and results for the use of Zeeman spin-lattice relaxation as a probe of methyl group rotation in the solid state. Experimental results are presented for the time and angular …

A positive relationship was found between the photodynamic activity of 24 polycyclic aromatic hydrocarbons versus published results on the mutagenicity, carcinogenicity, and initiation of unscheduled DNA synthesis. Metabolic activation of benzo(a)pyrene resulted in detection of increased mutagenesis in Paramecium tetraurelia as found also in the Ames Salmonella assay. The utility of P. tetraurelia as a biological detector of hazardous polycyclic aromatic hydrocarbons is discussed.

The observation of multiple-quantum nuclear magnetic resonance transitions in isotropic or anisotropic liquids is shown to give readily interpretable information on molecular configurations, rates of motional processes, and intramolecular interactions. However, the observed intensity of high multiple-quantum transitions falls off dramatically as the number of coupled spins increases. The theory of multiple-quantum NMR is developed through the density matrix formalism, and exact intensities are derived for several cases (isotropic first-order systems and anisotropic systems with high symmetry) to shown that this intensity decrease is expected if standard multiple-quantum pulse sequences are used. New pulse sequences are developed which excite coherences and produce population inversions only between selected states, even though other transitions are simultaneously resonant. One type of selective excitation presented only allows molecules to absorb and emit photons in groups of n. Coherent averaging theory is extended to describe these selective sequences, and to design sequences which are selective to arbitrarily high order in the Magnus expansion. This theory and computer calculations both show that extremely good selectivity and large signal enhancements are possible.

A study of the forms of trace elements occurring in Solvent Refined Coal has been performed by chemical separation of the Solvent Refined Coal based on differences in the functionality and molecular weight of the organic matrix. Analysis of the fractions separated for various trace elements has revealed associations of certain elements with other elements as well as with certain fractions. The analysis of Solvent Refined Coal I by these methods provided data on the distribution of Ti, V, Ca, S, Al, Mn, As, Se, Cr, Fe, Ni, Zn, Sc, and Ga in the fractions generated. Because of the low trace element content of Solvent Refined Coal II only As, Se, and Cr could be detected in the silica fractions. Based on the distributions three different groups of elements have been based on the association of elements with each other and with certain fractions. The first group is composed of As, Se, and Cr associated with silica fractions of relatively low functionality; these elements have a high percent solubility in the starting Solvent Refined Coal II oil. The second group composed of Ti, V, and to a lesser extent a second form of Cr, is associated with fractions that have …