Chemical Engineering Commons^™

Kinetics And Reactivity Of The 2,4-Tolyene Diiscoyanate With 2-Hydroxyethyl Methacrylate Reaction, Menq-Fong Shieh

Theses

The kinetics of the addition of 2-hydroxyethyl methacrylate(HEMA) to 2,4-Tolyene diisocyanate(2,4-TDI) were studied at the temperature of 25°C, 30°C and 38°C. Reactant and product concentrations were monitored by liquid chromatography.

The rate equations for the series-parallel second order reaction have been developed and integrated by the Runge Kutta-Gill method. The results show that the para

group is about 12 times more reactive than that of the corresponding ortho group with the HEMA hydroxyl group at 25°C, and small amount of HEMA diadduct invariably produced.

Mathematical Modeling Of The Unsteady State Glucose And Insulin Concentrations In Blood For Normal Subjects And Diabetics, Tung Shih

Theses

A mathematical model of the blood-glucose regulatory system has been developed. This model describes an oral glucose tolerance test adequately and simulates the behavior of the real physiological system using computer techniques.

Regression of the rate constants involved have been effected by conforming the theoretical functions to the data from glucose tolerance test in nonobese normal subjects, obese normal subjects, nonobese mild diabetics, obese mild diabetics, nonobese moderate diabetics and obese moderate diabetics measured by continuous sampling after oral ingestion. Most of the data were conformed within the limits of experimental error. The result of optimal parameters lead to a …

An Improvement In The Chemical Engineering Simulation System, Roman Andreyuk

Theses

The accurate design of chemical processing plants is important to the chemical engineer. The original version of CHESS (Chemical Engineering Simulation System) greatly reduced the amount of time which previously had to be spent on the design of such plants by providing the engineer with a package which simulated some of the more common pieces of chemical processing equipment found in a typical chemical plant.

The present version of the Chemical Engineering Simulation System (CHESS2) presents a significant improvement over the original version. The improvement was achieved by expanding the thermodynamic package, offering the user a choice of methods by …

Prediction Of Enthalpies Of Mixing With A Generalized Unifac Model, Steven Otto Hetzel

Theses

The UNIFAC model of Skjold-Jorgensen et al (1980), which incorporates a general temperature dependence for the coordination number is used in the correlation and prediction of heats of mixing for binary liquid mixtures. Correlation and prediction of n-alkanes and cyclic-alkanes with alkenes, ketones, aldehydes, esters, ethers, acids, nitriles, nitroalkanes, and aikynes have been performed in a temperature range of 0 to 100°C. Typical prediction and correlation errors of 5 to 20% are obtained using this model.

Steady State Heat Transfer From Two Concentric Rings Of Spheres, Kevin J. Fitzpatrick

Theses

The method of reflections was used to solve the steady state heat transfer problem for two concentric rings of spheres, all at equal surface temperature. The method results in a mathematical model for the three dimensional temperature profiles around the array of spheres. This model is used to develop an expression for heat transfer rate from the array. This work has resulted in a solution for dilute systems since no ring to ring interaction term was found.

Flow Tube Reactions Of Selected Chlorocarbons With Molecular Hydrogen Or Water Vapor In A Microwave Induced Plasma Reactor, Robert Benedict Barat

Theses

The reactions of various chlorinated hydrocarbons with molecular hydrogen or water vapor have been studied in a microwave plasma tubular flow reactor. The investigation of such reactions is desirable because the often toxic parent chlorocarbons are transformed to more thermodynamically stable and relatively non-toxic products by removal of' chlorine atoms as hydrogen chloride. Present detoxification technologies generally employ thermal oxidation as a means of disposal of chlorocarbons, which does not offer a thermodynamically stable sink for the chlorine atoms.

The experimental apparatus included feed introduction systems, a microwave plasma reactor, and full product analyses. The feed systems enabled use of …

Motion Of Viscous Liquid In Rotating Cylinder, Chicheng Wu

Dissertations

A computer model for the withdrawl and buildup of the fluid from the pool bounded on the horizontal, rotating, cylindrical surface has been developed. For a incompressible Newtonian fluid, the model is based upon the modified SOLA-SURF algorithm to solve the finite-difference form of Navier-Stokes equations on primitive variables. A hybird of centered and partial donor cell differencings is applied to the momentum convective flux. In each time cycle, the cell velocity is adjusted by the pressure corrector and iterates to satisfy the equation of continuity. The free surface position is approximated by a surface height function derived from kinematic …

Fractionation Of Multicomponent Mixtures By Staged Sequence Cyclic Process And Parametric Pumping, Charles Omotayo Kerobo

Dissertations

The continuous fractionation of multicomponent fluid mixtures has been experimentally and theoretically investigated by staged sequence cyclic process and parametric pumping operating in the direct thermal mode.

A multicolumn staged sequence cyclic process for the separation of solute mixtures was developed. The criteria necessary for the continuous fractionation of a system of n solutes with n+1 columns arranged in a series operated with n+1 cyclic variables is presented. The feasibility for practical application of this process was demonstrated by fractionating the model system, O-xylene-Anisole-n-heptane on silica gel. The separation was modeled by one column staged sequence experimental data and by …

Separation Of Proteins Via Ph Parametric Pumping With Electric Field, Helen Conway Hollein

Dissertations

A new semi-continuous parametric pumping process for the separation of protein mixtures has been developed, based on cyclic variation of pH and electric field. The model system used for this process consisted of a mixture of human serum albumin and human hemoglobin in contact with CM Sepharose cation exchanger. Experimental results show that the protein separation via the pH parapump with electric field is two to three times greater than the results which are obtained in batch chromatography or via either single-column or multi-column parapumps with cyclic variation of pH and ionic strength.

The separation in the new process depends …

A Modified Unifac Model For The Prediction Of Henry's Constants, Carlos Alberto Marques Antunes

Theses

A group-contribution model for the correlation and prediction of Henry's constants in single solvents is presented. The mode: involves a one-parameter per gas/ solvent group pair UNIFAC expression extended to incorcorate free volume effects. The model is applied to three gases, CH₄, N₂, and O₂ in alkane solvents and in water. Good results, including a successful description of the temperature dependency of the Henry's constants, are obtained with typical accuracy of ± 10%.

An Experimental Study Of Multiple Steady States In A Photopolymerization Reactor, Chih-Ning Kuan

Dissertations

An experimental study of photosensitized free radical polymerization of styrene in both batch and continuous stirred tank reactors is presented. Each reactor was run under both adiabatic and isothermal conditions. Multiple steady states were investigated. Exact multiplicity and uniqueness criteria for the above systems were derived and a mathematical model developed to correlate the results.

For both adiabatic and isothermal continuous stirred tank reactors operating in the metastable state regions, the conversion and polymer molecular weight are greater than the corresponding lower steady state operations. At a given conversion level, the reaction time for both adiabatic and isothermal continuous stirred …

The Entrainer Effect On Azeotropic Distillation Column Design, Charles Ming-Hsiao Tsai

Dissertations

A rigorous multistage distillation model was developed for use with non-ideal multicomponent systems. A subsidiary computer program was also developed to handle the problem of two liquid phases after condensation of a vapor.

Using the program developed, entrainer entry location and rate effects have been investigated via computer simulation for azeotropic distillation columns. The specific example used to verify the procedure was an ethanol dehydration column using benzene as the entrainer. The results indicate that the entrainer should enter the column two to five theoretical stages above the feed. The optimum entrainer rate was also determined.

The overhead vapor product …

Prediction Of Heats Of Mixing By Group Contribution Methods, William Walter Rupp

Theses

Three group contribution methods used to predict heats of mixing were tested: AGSM, UNIFAC with temperature dependent parameters and the modified UNIFAC of Skjold-Jor-gensen et al. The modified UNIFAC provided the best results and was adopted in this study. Primary parameters were obtained for ten groups with alkanes. The simultaneous correlation of cyclic and straight-chain alkanes gave poor results. Attempts to improve the error by changing the group area parameter for cyclic CH₂ failed.

A major problem in correlating the experimental data was the multiplicity of roots. The best set of parameters was obtained by using a grid approach …

Thermal Rearrangement Studies Of Deuterium Labeled Dibenzo [A,E] Cyclooctatetraenes, Charles W. Wenger

Theses

In an attempt to further substantiate the findings of Stiles and Salisbury on the rearrangement of aryl disubstiuted dibenzo [a, e] cyclooctatetraenes a new pair of derivatives were synthesized. The 5,6 and 5,11 dideuteriodibenzo-[a,e] cyclcoctetetraenes were prepared. The 5,6 derivative was prepared starting with dibenzo [a,e] cyclooctene-5,6-dione. The 5,11 derivative was prepared starting with o-tolualdehyde. In the case of the 5,6 derivative the deuterium was introduced by a LiAlD₄ reduction of the dibenzo [a,e]-cyclooctene-5,6-dione. The 5,11 derivative had been labeled with deuterium in the final step during the Wittig reaction. The use of methanol-d₁ as the solvent in …

Prediction Of Vapor-Liquid Equilibrium From Ternary Liquid-Liquid Equilibrium Data, David Kim Yee

Theses

Reasonable estimates of ternary vapor-liquid equilibrium can be obtained by using the corresponding liquid-liquid equilibrium (LLE) data with the NRTL, LEMF and UNIQUAC models. The overall average absolute deviation in vapor phase concentration for seven such systems is 0.028.: Use of the UNIFAC method gives erratic predictions suggesting caution when applied to such systems. Combination, however, of the LLE data and the UNIFAC method gives the best results with a deviation of 0.020 Prediction of binary VLE behavior from LLE data yields also reasonably good results.

Separation Technique On Proteins Via A Ph-Parametric Pump : A Theoretical And Experimental Study, Ura Pancharoen

Dissertations

The separation of protein mixtures via pH-parametric pumping was investigated both theoretically and experimentally. A simple system consisting of one column packed either with cation or anion exchanger was first considered. A system of parapumps was then developed with more columns which were connected in series and packed alternately with cation and anion exchangers. Various methods of operation of parapumps are discussed. Enrichment and spliting of protein mixtures were examined. In most cases, the separation factor was defined at a steady state condition and was improved by increasing the number of cycles and columns.

Computational methods for predicting both Batch …

An Experimental Study Of Comparison Between Ph-Parametric Pumping And Ph-Cycling Zone Adsorption Process On Protein Separation, Vincent P. Jajalla

Theses

In this thesis, an experimental investigation was conducted to compare the performance of the continuous pH-parametric pumping and the pH-cycling zone adsorption process on protein separation.

The model system studied was hemoglobin-water. on CM-Sepharose CL-6B (cation) exchanger in a single-column system. Various modes of operation were tried on both the pH-parametric pumping and the pH-cycling zone adsorption method. The separation factors for each mode of operation were computed and compared.

It is shown that the continuous pH-parametric pumping, with circulation to insure the pH uniformity inside the column, has the better separation factor than the pH-cycling zone adsorption method.

Reactions Of Atomic Hydrogen With Selected Halomethane, Sriram Chari

Theses

The kinetics of the reactions of atomic hydrogen with methylene chloride and carbon tetrachloride were studied spectroscopically and chromatographically using a 4 cm i.d. discharge flow reactor at pressures of 1 to 8 mm Hg absolute and room temperature. Hydrogen atom concentrations were measured by chemiluminescence titration with nitrogen dioxide. Evidence was found for the formation of atomic carbon intermediate in the reaction with carbon tetrachloride, but methane and HCl were the chief products in both reactions for reaction times of 150 ms and higher, showing that secondary reactions were so fast that almost all halomethane consumed went toward the …

Correlation And Prediction Of Vapor-Liquid Equilibrium In Electrolytic Solutions, Anil Krishna Rastogi

Dissertations

Two expressions for the excess Gibbs free energy are presented which correlate and predict vapor-liquid equilibrium and the mean molal activity coefficient of an electrolyte in a ternary mixture containing water and either MeOH or EtOH. The proposed equations take into account coulombic forces between ions and the physical interaction forces between ion-solvent and solvent-solvent molecules in a solution.

Model #1 is a combination of an extended Debye and Huckel equation and the local composition of non-random two liquid (NRTL) model. A ternary mixture requires six adjustable binary parameters to predict activity coefficients. These six parameters are evaluated from three …

Separation Of Proteins Via Continuous Ph Parametric Pumping, Steve Wu

Dissertations

This dissertation covers the separation of proteins via recuperative mode pH parametric pumping. Continuous pH parametric pumping separations using the model system haemoglobin and albumin on a CM-Sepharose cation exchanger have been experimentally and theoretically investigated.

The pH parametric pumping system has a feed containing the protein mixture to be separated, introduced alternately to the top and bottom of the column. The top and bottom products are withdrawn from the apparatus during the bottom and top feed, respectively. Both equilibrium and nonequilibrium cases were considered, and theoretical results agreed with the experimental data.

Buffer concentration, flow rate, reservoir displacement, and …

Parametric Pumping With Ph And Ionic Strength : Enzyme Purification, Zikri Mostafa Ahmed

Dissertations

The work on separation and purification of proteins by parametric pumping has been restricted so far to pH parametric pumping where the difference between the iso-electric points of the components to be separated is apparent. The present work establishes the foundations for the continuous separation and purification of proteins (including enzyms) that have similar or very close iso-electric points by using the ionic strength as a driving force for the separation process. This technique has commercial advantages over batch processes.

It was found that the most promising technique for separating alkaline phosphatase consists of the following three major steps: (I) …

Separation Via Multi-Column Ph Parametric Pumping, Wei Tai Yang

Dissertations

This thesis presents the study of multi-column pH parametric pumping, a separation technique which applies the principle of parametric pumping and uses pH as control variable. Studies emphasize the mass transfer and the capability of separation by multi-column pH parametric pumping. Many operation modes of multi-column pH parapump are developed for varied objectives of separation. A Two-pH Levels Parapump is capable of enriching the product stream with solute components; a Three-pH Levels Parapump is capable of splitting components into two product streams. The separation capability of multi-column parapump is greatly superior to that of single-column parapump. As compared to cycling …

Mathematical Modeling Of Jet Bubbling Reactor, Fred Jyh-Woei Cheng

Theses

A jet bubbling reactor for flue gas desulfurization is described by a mathematical model with the concept of two-stages mass transfer with chemical reactions. The Model consists of two coupling differential equations which are solved simultaneously. The result from the theoretical model is agreeable SO₂ removal data obtained from a pilot plant reactor.

The Heterogeneous Catalytic Decomposition Of Isopropyl Alcohol Over 0.5% Platinum On 4-8 Mesh Charcoal Catalyst Support, Thomas Michael Kudenchak

Theses

The heterogeneous catalytic decomposition of isopropyl alcohol vapor over 0.5% platinum on (4-8 mesh) charcoal support catalyst was studied at bench-top in a fixed-bed tubular micro-reactor of about 1 cm ID, six inches long containing one or two grams of catalyst. Reactor feed and exit gas analysis was obtained by gas chromatography.

Experimental runs aimed at determining the Arrhenius parameters and the reaction order (assuming the applicability of a simple power law model) were performed with 1 and 2 grams of catalyst at various residence times ranging from 0.24 to 2.3 seconds and temperatures of 150°, 175°, 200°, 225°, and …

Osmotic And Mean Activity Coefficients Of Libr And Lic In Methanol At 25, 35, And 45 Degrees C, Peggy Tomasula

Theses

Vapor pressure depression data of LiBr and LiCl in methanol at temperatures of 25,35, and 45°C were measured in the molality range 0.1-4.4m using a static method, where the difference in vapor pressure of the electrolytic solution is compared to that of pure methanol.

Osmotic coefficients were calculated from the vapor pressure data. This data was then correlated with both the one parameter Bromley equation and the three parameter Pitzer equation. For all systems at all temperatures, the data were better correlated by the Pitzer equation than with the Bromley equation. Mean activity coefficients of the two salts at the …

Correlation Of Thixotropic Parameters And Related Tests Of Blood From Human Subjects, Walter Fabisiak

Dissertations

The flow behavior of human blood is an important facet of the circulatory system as it affects all of the organs of the body. The rheological properties of whole blood provide a means of analyzing the flow of red cells and plasma through the microcirculation. A recently observed rheological characteristic of whole human blood is thixotropy, a time-dependent phenomenon. This phenomenon is caused mainly by the redistribution of an aggregated form of erythrocytes, known as rouleaux, and the non-aggregated, single erythrocytes. In order to further define and analyze the thixotropic properties of blood, the Huang model is used to quantitatively …

Thixotropic Properties Of Whole Human Blood, Jen An Su

Dissertations

The rheological property of whole blood from various human subjects was studied with a Weissenberg Rheogonio-meter, modified with a continuously variable speed drive. Experimental data showed a hysteresis loop in the shear stress versus the shear rate plot and a torque-decay in the shear stress versus the shearing time plot which is under a constant shear rate. The rheological equation previously developed by Huang was employed to define the thixotropic parameters of each whole blood sample based upon the recorded rheograms.

The altered thixotropic parameters for the blood from patients with open heart surgery at different clinical stages were quantitatively …

Temperature Dependency Of The Group Interaction Parameters In The Agsm And Unifac Models For The Prediction Of Heats Of Mixing, Ignatius Okoronkwo Ojini

Theses

A four-parameter group-contribution model (UNIFAC) has been developed for the prediction of heats of mixing of non-electrolyte mixtures. Both the UNIFAC and AGSM models are evaluated over a wide range of temperature dependencies of the group interaction parameters. The UNIFAC model has been chosen over the AGSM model and an optimum parameter-temperature relationship has been established.

Adopting the optimum temperature dependency, group inter-action parameters have been calculated using UNIFAC for the prediction of four types of mixtures: n-Alcohols/n-Alkanes; Benzene/n-Alkanes; Nitriles/n-Alkanes; Amines/n-Alkanes.

The Characterization Of The Oxygen Transfer Capabilities Of Fermentors, Joseph Stephen Adamca

Theses

A method of characterizing the oxygen mass transfer capabilities of fermentors was developed where volumetric oxygen mass transfer coefficients are obtained using a modified sulfite oxidation method in conjunction with on line digital data processing. Carboxymethylcellulose is used in the reaction media to simulate the viscosity of typical non-Newtonian fermentation broths. Using this method, instantaneous values of volumetric oxygen mass transfer coefficients can be obtained for various combinations of agitation and airflow rates in different fermentor configurations. This data is useful in the scale up or scale down of fermentors.

Data obtained using this method have revealed that for a …

Analysis Of Unsteady-State Heat Conduction In A Cylinder With The Finite Element Method, Richard F. Bernard

Theses

Unsteady-state heat conduction in a cylinder of finite dimensions with constant physical and thermal properties was analyzed with the finite element method. Symmetry of the cylinder and application of Newman's method reduced the problem to two independent one-dimensional problems. Finite element equations for the axial and radial dimensions were developed utilizing Galerkin's method of weighted residuals. Crank-Nicholson approximations were used for time derivatives. A computer program was written for solution of the finite element equations.

Solutions obtained were conditionally stable; dependent on the value of the ratio KΔt/ρCpl². For values of the ratio less than 1/3, errors in …