Engineering Commons^™

The Kinetics And Mechanism Studies Of Cathodic Electro-Initiated Crosslinking Polymerization Of Unsaturated Polyester Prepolymer, Joseph Yuan-Ji Sheng

Theses

The cathodic electro-initiated polymerization reaction of the unsaturated polyester prepolymer has been found to have the characteristics of the first order ionic initiation polymerization mechanism. The rate of polymer formation is directly proportional to the current intensity and voltage supplied, but inversely proportional to the reaction temperature. The rate of initiation can be expressed as a function of the initial concentration of the prepolymer, residence time and reaction temperature. The rate expression of the initiation step has been derived based upon the experimental data collected as follows:

ln W = k0 exp[-Ea/RT] Ca0 ln t + ln b

where k0 …

High Temperature Reactions Of Chloroform With Methane, Thomas Siozopoulos

Theses

The reactions of Chloroform with Methane were studied at atmospheric pressure in the temperature range of 550-800 deg C, and using three different reactor diameters.

The reaction was found to follow pseudo-first order kinetics in the presence of excess Methane and Argon, and the kinetic parameters were determined for each of the reactor sizes.

The resulting global Arrhenius expressions are:

For 0.4 cm ID Kexp = 2.03 * 10⁸ exp (-34000/RT)

For 1.05 cm ID Kexp = 9.86 * 10⁸ exp (-37950/RT)

For 1.6 cm ID Kexp = 4.17 * 10⁸ exp (-36760/RT)

An increase in the …

Letters To The Editor, Partho Neogi

Chemical and Biochemical Engineering Faculty Research & Creative Works

No abstract provided.

Modeling And Analysis Of Biospecific Adsorption In A Finite Bath, B. H. Arve, Athanasios I. Liapis

Chemical and Biochemical Engineering Faculty Research & Creative Works

A general model is presented and used to predict the dynamic behavior of the adsorption and wash stages of bio specific adsorption (affinity chromatography) in a finite bath. The model accounts for film and diffusional mass transfer resistances as well as for the rates of interaction between adsorbates and ligands. The model is applicable to single and multicomponent bio specific as well as nonspecific adsorption, and the adsorbates may be monovalent or multivalent. The predictions of the model are compared with the experimental data of the adsorption of β‐galactosidase onto immobilized anti‐β‐galactosidase. The results of bio specific adsorption of bivalent …

A Mathematical Model For The Initial Corrosion Rate Of A Porous Layer On A Rotating Disk Electrode, William E. Ryan, Ralph E. White, S. L. Kelly

Faculty Publications

A mathematical model is presented for the initial corrosion rate of a porous layer on a rotating disk electrode. The model is used to predict the corrosion potential and corrosion current density for a porous electrode made of pure iron in aerated caustic solutions. The dependence of these predictions on some of the properties of the porous layer is presented. It is shown that the corrosion rate depends significantly on the specific surface area of the porous electrode.

Performance Predictions For Oil Reservoirs Under Water Influx, Briareus Mitchell Wilkinson

Masters Theses

"The intent of this thesis is to develop a program that will give reasonable recovery predictions for oil reservoirs under water influx. The main advantage is to avoid the massive storage and computational requirements of numerical simulators while achieving roughly comparable results. There are many methods already in existence that have not received their full benefit, mainly because they were developed prior to the recent advances of the computer age. This thesis therefore brings some already proven methods together with new techniques in a program which, with the aid of the computer, stimulates new life in these methods. The main …

Enthalpies Of Solution Of Co2 In Aqueous Methyldiethanolamine Solutions, Keith E. Merkley

Theses and Dissertations

The enthalpies of solution, H^S, of carbon dioxide in aqueous methyldiethanolamine were measured with an isothermal flow calorimeter over wide ranges of temperature, pressure, weight percent MDEA, and loading (gmole CO₂/gmole MDEA). The values of H^S (kJ/gmole CO₂) were found to be constant up to the saturation concentration of CO₂ in the aqueous solution. In addition, experimental data showed that H^S was independent of the total pressure over the solution, but linearly dependent upon both temperature and weight percent MDEA as was given by a correlation. A computer program based upon …

Statistical Analysis Of A Compound Power-Law Model For Repairable Systems, Max Engelhardt, Lee J. Bain

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

Conclusions - A compound (mixed) Poisson distribution is sometimes used as an alternative to the Poisson distribution for count data. Such a compound distribution, which has a negative binomial form, occurs when the population consists of Poisson distributed individuals, but with intensities which have a gamma distribution. A similar situation can occur with a repairable system when failure intensities of each system are different. A more general situation is considered where the system failures are distributed according to nonhomogeneous Poisson processes having Power Law intensity functions with gamma distributed intensity parameter. If the failures of each system in a population …

The Effect Of The Tribromide Complex Reaction On The Oxidation/Reduction Current Of The Br2/Br– Electrode, P K. Adanuvor, Ralph E. White, S. E. Lorimer

Faculty Publications

The Br₂/Br^– electrode reaction with tribromide complex formation reaction in the solution, a chemical-electrochemical (C-E) type reaction, has been investigated in order to determine the effect of the chemical reaction on the electrode kinetics. It is shown that the chemical reaction has little effect on the electrode kinetics at very slow homogeneous reaction rates, but has a more drastic effect on the electrode kinetics at faster homogeneous reaction rates. Also, the kinetics at the electrode are affected by changes in the concentrations of the active species (Br₂, Br^–, and Br₃^–) …

Modeling The Rotating Disk Electrode For Studying The Kinetics Of Electrochemical Reactions, P K. Adanuvor, Ralph E. White, S E. Lorimer

Faculty Publications

A general mathematical model for studying the kinetics of electrochemical reactions at a rotating disk electrode under steady-state potentiostatic conditions is presented. The model, apart from predicting the net and partial current densities at given values of the applied potential, the ohmic potential drop, and the concentration and potential profiles in the solution, also accounts for homogeneous reactions of any order in the solution and noncharge transfer reactions at the electrode surface. The versatility of the model is demonstrated by the application of the model to a variety of complex reaction schemes.

A Mathematical Model Of A Zinc/Bromine Flow Cell, T. I. Evans, Ralph E. White

Faculty Publications

A mathematical model is presented for a zinc/bromine flow cell. The model includes a thin porous layer on the bromine electrode and a porous separator. The independent parameters of the porous layer are defined, and their effect on cell performance during charge and discharge is investigated. The dependence of the round trip energy efficiency on the thickness of the porous layer and mode of discharge is presented. The predictions of the model show that a maximum round trip energy efficiency of 70% should be possible under the design conditions considered.

Simulation Of The Polarization Curves For Oxygen Reduction At A Rotating Disk Electrode, P. K. Adanuvor, Ralph E. White

Faculty Publications

The electrochemical reduction of oxygen in 1M NaOH solution is simulated at a rotating disk electrode. Steady-state polarization curves are presented for possible reaction schemes for the reduction process. The effect of changes in the kinetic parameters on the polarization curves is demonstrated and special attention is focused on the production of hydrogen peroxide.

Utility Of An Empirical Method Of Modeling Combined Zero Gap/Attached Electrode Membrane Chlor-Alkali Cells, Clifford W. Walton, Ralph E. White

Faculty Publications

An extensive survey of the Docktor-Ingenieur Dissertationen of Jakob Jörissen and Klaus-R. Menschig, both originally from the Universität Dortmund, is presented in regard to the empirical modeling of membrane chlor-alkali cells and how it can be applied to a combined zero gap/attached porous electrode layer membrane cell. Particular emphasis isplaced on Menschig's work on zero gap (ZG) and attached porous electrode layer (APEL) membrane chlor-alkali cells, the first such research to appear in the open literature. Menschig developed various computer programs to characterize these ZG and APEL membrane chlor-alkali cells. He characterized these cells by using the following parameters: the …

A Review Of Mathematical Modeling Of The Zinc/Bromine Flow Cell And Battery, T. I. Evans, Ralph E. White

Faculty Publications

Mathematical models which have been developed to study various aspects of the zinc/bromine cell and stack of cells are reviewed. Development of these macroscopic models begins with a material balance, a transport equation which includes a migration term for charged species in an electric field, and an electrode kinetic expression. Various types of models are discussed: partial differential equation models that can be used to predict current and potential distributions, an algebraic model that includes shunt currents and associated energy losses and can be used to determine the optimum resistivity of an electrolyte, and ordinary differential equation models that can …

A Mathematical Model Of A Lead-Acid Cell: Discharge, Rest, And Charge, Hiram Gu, T. V. Nguyen, Ralph E. White

Faculty Publications

A mathematical model of a lead-acid cell is presented which includes the modeling of porous electrodes and various physical phenomena in detail. The model is used to study the dynamic behavior of the acid concentration, the porosity of the electrodes, and the state of charge of the cell during discharge, rest, and charge. The dependence of the performance of the cell on electrode thicknesses and operating temperature is also investigated.

Phase Equilibria From Pvt Measurements For Carbon Dioxide, Water And N-Decane, Michael Nduka Okafor

Doctoral Dissertations

"Phase equilibrium properties for the carbon dioxide - water - n-decane system were determined from pressure-temperature-volume (PVT) measurements. PVT properties were also obtained for pure carbon dioxide and water, and the binary mixtures of carbon dioxide - water and carbon dioxide - n-decane. The experiments were conducted at temperatures of 313.17, 353.15 and 393.15 Kelvin, and at pressures from 37 to 416 bar. Measurements for the mixtures were terminated when complete miscibility was observed.

The Perturbed-Hard-Chain (PHC) equation of state developed by Gmehling et al. (1979) was chosen to correlate the measured data because of its ability to handle the …

Experimental Vapor-Liquid Equilibria Of Propyne With Propane, Propene And Propadiene, Edward Allen Kyser

Doctoral Dissertations

"Vapor pressures for pure propane, pure propene, impure propadiene and pure propyne and 19 binary mixtures of propane, propene, and propadiene with propyne are reported at -20, 5, 30, 55 and 80° C. An equation of state utilizing pure component saturated vapor and liquid densities is used to correlate all the data and the effect of the propadiene impurities was theoretically removed. The data of Burcham (1981) are recorrelated using new information about the impurities, and different results are obtained. Calculated relative volatilities and saturated densities are reported for the systems propane-propyne, propene-propyne, propadiene-propyne and propane-propadiene"-- Abstract, p. ii

The Use Of Pure Cultures As A Means Of Understanding The Performance Of A Mixed Culture In The Biodegradation Of Phenol, Chirasakdi Varuntanya

Dissertations

In an effort to gain a more fundamental understanding of the performance of mixed microbial cultures in the biodegradation of toxic organic chemicals, studies have been conducted using three phenol degrading species isolated from a municipal treatment plant. The rate of phenol degradation was investigated for each of the three pure phenol degrading species, and various combinations of the three species. A simple competitive model was used to predict the behavior of the mixed cultures by using the pure culture Monod rate constants. The model fit the growth data for total biomass very well, although (as with the pure culture …

The Biochemical Fuel Cell : Conversion Of Waste To Energy, Charles August Mielke

Theses

A batch biochemical-fuel cell was constructed and studies on the production of bioelectric energy using an alga Scenesdesmus quadricauda, and a bacterium Desulfovibrio desulfuricans, were conducted. Results were compared for a steady state cell using various concentrations of media components and showed that a 1000-fold increase in the concentration of media components produced a net potential output of 0.03mv/ml compared to an initial output of 0.02mv/ml. Further studies showed the biochemical net potential output using activated sludge from a waste treatment facility was 0.01mv/ml compared to 0.02mv/ml for the cell using the initial media concentration.

The system exhibited steady state …

A New Density-Dependent Mixing Rule For Equations Of State, Theodore John Shatynski

Theses

A general procedure for the development of density-dependent mixing rules is demonstrated. This method is used to obtain a density-dependent local-composition mixing rule based on an extention of the work of Knox et al (1984). The resulting expression is tested with the Soave-Redlich-Kwong equation of state. Results for normal and cryogenic vapor-liquid systems for both one-parameter and three-parameter versions of the mixing rule are compared with results using the classical mixing rules.

Gas-Phase Reaction Of 1,2-Dichloroethane With Hydrogen In A Tubular Flow Reactor, Wei-Lian Lee

Theses

We have studied the reaction of 1,2-dichloroethane with H₂ in three tubular flow reactors of different diameters at atmospheric pressure in the temperature range of 550° C to 1000°C. The kinetic parameters and product distribution were experimentally determined for each size reactor. The wall and bulk reaction rate constants were decoupled via analysis of three different surface to volume reaction data.

The experimental reactor was an isothermal tubular flow reactor that operated within the domain of plug flow region. The reaction was found to follow first-order kinetics with respect to 1,2-dichloroethane when in the presence of excess hydrogen. The …

Thermal Decomposition Of Chlorobenzene In An Atmosphere Of Hydrogen, Edward Robert Ritter

Theses

The thermal decomposition of chlozobenzene was investigated in a tubular flow reactor at 1 atmosphere total pressure and average residence times of 0.02 - 2.5 seconds. The temperature range from 800 - 1010°C was studied in both a reductive atmosphere of hydrogen and an inert atmosphere of heIium. Complete destruction of chlorobenzene occurs at about 1000°C for an average residence time of 1 second in hydrogen gas. In the inert gas, the complete destruction of the reagent was not observed in the range of conditions which were studied. The major products observed for pyrolysis in hydrogen were benzene, HCl, and …

Heats Of Transport From The Diffusion Thermoeffect In Binary Liquid Mixtures Of Toluene, Chlorobenzene, And Bromobenzene, Richard L. Rowley, M. D. Hall

Faculty Publications

Measurements of heats of transport in binary liquid mixtures of toluene, chlorobenzene, and bromobenzene utilizing the diffusion thermoeffect, or Dufour effect, are reported at 298 and 308 K. The corresponding heat-mass Onsager doefficients are also reported, from which thermal diffusion ratios have been calculated based on Onsager reciprocity. The resultant binary thermal diffusion ratios have been correlated as a function of composition in an attempt to study the relationship between values in binary and ternary mixtures. It was found that the single independent binary values can be used to estimate the two independent thermal diffusion ratios previously reported in toluene …

Zeta Potential Measurements Of Biological Flocs Using A Streaming Potential Cell, Wayne James Gallagher

Theses

A streaming potential apparatus was assembled and tested. Its purpose was to characterize the surface of biological flocs in a wastewater environment. Samples of mixed liquor were obtained from the Passaic Valley Sewerage Commissioners wastewater treatment plant in Newark, New Jersey. Filtered mixed liquor was passed through a bed of the floc particles in the streaming potential cell, and the electric potential across the cell was measured as a function of the differential pressure drop. From these data, the zeta potential was calculated using the Helmholtz equation. Values of -0.88 and -0.44 millivolts were obtained for two mixed liquor samples.

A Theoretical Study Of Pure And Simple Competition Between Two Microbial Species In Configurations Of Two Interconnected Chemostat, Cheng-Ming Kung

Theses

It is known that two microbial populations competing purely and simply for a common substrate cannot coexist in a steady state in an environment which is spatially homogeneous. Hence they cannot coexist in a chemostat something which implies that a mixed culture of two pure and simple competitors cannot be maintained in a single ideal reactor in a steady state. The present study investigates theoretically pure and simple competition between two populations in two interconnected chemostats. Three reactor configurations are considered and analyzed. It is proved that two pure and simple competitors can coexist in a steady state in both …

Hydrocarbon Fuel Additives And Method For Preparing Same, G. David Mendenhall, Hsiang T. Chen

Michigan Tech Patents

A compound having the general formula R*COH[- CORJj,, wherein R is a lower alkyl hydrocarbon radical, y is 0 or 1, and x is 2 when y is 1 and 3 when y is 0, is prepared by admixing carbon monoxide, a transition metal halide, and an organomonolithium compound or an anionic equivalent thereof.

Fluid Flow And Gas Absorption In An Ejector Venturi Scrubber, Iclal Atay

Dissertations

Empirical models were developed to describe the fluid flow characteristics and gas absorption efficiency of an ejector venturi scrubber. The empirical constants were determined experimentally using stop action photographs of the spray, static pressure measurements, and sulfur dioxide absorption efficiencies.

To take photographs of the spray, a 2 foot high, clear plastic ejector venturi scrubber was used, with a 4 inch diameter gas entrance port. Photographic equipment included a Hasselblad camera, Xenon flash lamp, and Polaroid 667 ASA 3000 film. Exposure duration was about 1 microsecond, resulting in complete stop-action of the spray droplets at liquid rates up to 6 …

The Kinetics And Mechanism Studies Of A Polymer Powder Coating On Metal Surface By Cathodic Electrodeposition Process, Wen-Lin Wu

Theses

A polymer dispersion of fluorocarbon with solid constent in the range of 10-25% were prepared from white powder polytetrafluorethylene (PTFE), emulsifier combination of dodecylbenzyldimetlyl sulfonium chloride and Trition N-150, and other components or additives. Such a fluorocarbon dispersion is very stable against coagulation and has a pH in the range of 8-10, which is especially suitable for powder coating purpose.

A new electrocoating technique, which is called cathodic electrodeposition powder coating method, was conducted in this study. This new coating method includes four steps: pretreatment, electrocoating, drying and baking. Two kinds of degreased metal substrates, aluminum and steel plates, were …

An Analysis Of Carrier Facilitated Transport In Liquid Surfactant Membranes, Pei-Jen Tsai

Theses

Mathematical models describing the mass transfer through facilitated liquid membranes are proposed and solved analytically. A self-adjoint operator method is applied to solve the coupled differential equations with discontinuity in the boundary conditions. It is assumed that equilibrium of the solute at the interfaces is maintained during the separation process. The effects of film resistance are studied/ and a first order kinetic model is used to simulate the reaction which takes place at the membrane-internal phase interface.

Experimental results indicate that the model with external film resistance consideration is in good agreement with the experimental data. This shows that most …

Computer Aided Mathematical Modeling Of A Once Through Claus Type Sulfur Recovery Process, Yuriy Osyp Kutny

Theses

The computer aided mathematical modeling of the once through Claus process for hydrogen sulfide conversion to sulfur is presented herein. This vapor phase oxidation reaction is carried out using one thermal reactor and up to three bauxite catalytic reactors with sulfur condensers in between. The method of catalytic reactor feed reheat and its ramifications upon reactor performance and total model convergence is of major importance.

The reactor feed preheat can be carried out in either of the following ways: (1) indirect heat exchange using some external heat source; (2) indirect heat exchange using other hot process streams as heat source; …