Numerical Solution and Sensitivity Analysis of Pore Liquid Pressure and Cake Porosity to Model Parameters

Filter cake formation is important in groundwater and oil wells where drilling contains suspended mud particles. The accumulation of these mud particles on the borehole wall creates a pressure drop in the well. Furthermore, the migration of colloidal particles into adjacent porous rock could damage the formation and cause productivity decline. In this study, numerical solutions for pore liquid pressure variation across the cake with variable total stress and associated porosity variation are obtained. Mass equations for captured and suspended particles are averaged along the mud cake thickness, taking into account conditions on the cake surface and at the filter septum. The variability of total stress in soil consolidations problem is considered to determine the pore liquid pressure along the mud cake thickness. Then, the relation between porosity and pressure is studied to determine the mud cake porosity. Experimental data obtained by various researchers is used to compare and test the validity of numerical solutions to develop guidelines for model applications. Results show that the pore liquid pressure increases with the decrease of membrane impedance value (i.e. less pervious membrane). Also, the pressure profile has a cubic function of dimensionless cake thickness. The conclusions from the sensitivity analysis conducted in this study agree with earlier conclusions.     

The intramolecular Morita-Baylis-Hillman-type alkylation reaction

From the initial development of a homologous Morita-Baylis-Hillman reaction utilizing epoxides as electrophiles, the method was expanded to enable the exclusively organocatalyzed intramolecular allylation of enones and to develop the intramolecular MBH-type alkylation of activated alkenes. We successfully utilized both enones and unsaturated thioesters as the activated alkene component. This work, carried out using stoichiometric amounts of the trialkylphosphine, gave an array of functionalized five- and six-membered carbocycles in high yields. With the cycloalkylation of enones and thioesters, conditions that allowed the use of substoichometric amounts of the phosphine catalyst were developed. As a result both five- and six-membered rings can be formed efficiently with little to no loss in yield upon comparison to yields obtained when stoichiometric amounts of trialkylphosphines were employed. We isolated, for the first time, an MBH-type intermediate exhibiting unprecedented trans geometry of the phosphonium salt and acyl group.     

Self-assembly approach toward chiral bimetallic catalysts: bis-urea-functionalized (salen)cobalt complexes for the hydrolytic kinetic resolution of epoxides

A series of novel bis-urea-functionalized (salen)Co complexes has been developed. The complexes were designed to form self-assembled structures in solution through intermolecular urea-urea hydrogen-bonding interactions. These bis-urea (salen)Co catalysts resulted in rate acceleration (up to 13 times) in the hydrolytic kinetic resolution (HKR) of rac-epichlorohydrin in THF by facilitating cooperative activation, compared to the monomeric catalyst. In addition, one of the bis-urea (salen)Co(III) catalyst efficiently resolves various terminal epoxides even under solvent-free conditions by requiring much shorter reaction time at low catalyst loading (0.03-0.05 mol %). A series of kinetic/mechanistic studies demonstrated that the self-association of two (salen)Co units through urea-urea hydrogen bonds was responsible for the observed rate acceleration. The self-assembly study with the bis-urea (salen)Co by FTIR spectroscopy and with the corresponding (salen)Ni complex by (1)H NMR spectroscopy showed that intermolecular hydrogen-bonding interactions exist between the bis-urea scaffolds in THF. This result demonstrates that self-assembly approach by using non-covalent interactions can be an alternative and useful strategy toward the efficient HKR catalysis.     

Q-admissibility of certain nonsolvable groups

A finite groupG is calledQ-admissible if there exists a finite dimensional central division algebra overQ, containing a maximal subfield which is a Galois extension ofQ with Galois group isomorphic toG. It is proved thatS ₅ ⁻ , one of the two nontrivial central extensions ofS ₅ byZ/2Z, isQ-admissible. As a consequence of that result and previous results of Sonn and Stern, every finite Sylow-metacyclic group, havingA ₅ as a composition factor, isQ-admissible. This paper is part of a M.Sc. thesis written at the Technion — Israel Institute of Technology, under the supervision of Professor J. Sonn, whom the author wishes to thank for his valuable guidance.     

Design of axially super-resolving phase filters using the method of generalized projections

The design of pupil phase filters that super-resolve the axial intensity distribution with controlled side-lobe peak intensity under high numerical aperture conditions can be accomplished by incorporating the theory of electromagnetic diffraction in the method of generalized projections (MGP). The MGP results are however strongly dependent on the starting conditions and the applied constraints. In this report we study this dependence by investigating different starting pupil functions and introducing modifications to the applied constraints. Methods are described and implemented to generate a systematic set of starting conditions that enable a more thorough search of the solutions space. This approach generated results for which 95% have a super-resolved central-lobe, yet only a subset of those solutions offer a satisfactory compromise between super-resolution of the central-lobe and increased intensity of the axial side-lobes. These solutions are presented and discussed in the context of specific applications.     

The Markovian Two-echelon Repairable Item Provisioning Problem

A repairable-item provisioning system with two levels of repair is presented. Under the assumption that the machine time-to-failure and the repair times are exponentially distributed, a new algorithm is developed to compute the long-run average number of machines operating. Using the new algorithm we determine the optimal number of machines and repair channels at the two repair centres to minimize cost and meet a service-level constraint. The algorithm, which is based on Little's result in queueing theory and the theory of regenerative processes, is extremely efficient in terms of computer storage and execution time.     

Why Does Pivalaldehyde (Trimethylacetaldehyde) Unexpectedly Seem More Basic Than 1‐Adamantanecarbaldehyde in the Gas Phase? FT‐ICR and High‐Level Ab Initio Studies

Fourier transform ion cyclotron resonance spectroscopy (FT ICR) techniques, including collision-induced dissociation (CID) methodology, were applied to the study of the gas-phase protonation of pivalaldehyde (1) and 1-adamantanecarbaldehyde (2). A new synthetic method for 2 was developed. The experiments, together with a thorough computational study involving ab initio and density functional theory (DFT) calculations of high level, conclusively show that upon monoprotonation in the gas phase, compound 1 yields monoprotonated methyl isopropyl ketone 3. The mechanism of this gas-phase acid-catalyzed isomerization is different from that reported by Olah and Suryah Prakash for the reaction in solution. In the latter case, isomerization takes place through the diprotonation of 1.