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 …

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%.

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.

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 …

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 …

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 …

An Experimental Study Of Photopolymerization In A Continuous Stirred Tank Reactor, Songvit Setthachayanon

Theses

An experimental study was carried out on the control of CSTR by on-off regulation of light intensity for the photo-sensitized polymerization of styrene. The controllability of the reaction temperature, the advantages of operating at metastable states, and the molecular weights of the polymer formed were discussed. The influence of feed temperatures, sensitizer concentrations, and residence times on the reactor performance characteristics were also discussed. Experimental results showed that polymer formed at the metastable state had a higher average chain length and narrower molecular weight distribution than that formed at the low stable state. While increasing the residence time shifted the …

Continuous Fractionation Of Protein Mixtures By Ph-Parametric Pumping, Yuk-Wei Wong

Theses

Continuous pH-parametric pumping separations of a haemoglobin - albumin - CM Separose system were experimentally investigated. The parapump system has a feed, containing the protein mixture to be separated, introduced alternately to the top and bottom of the chromatographic column. The top and bottom products are withdrawn from the apparatus during the bottom and top feed respectively. It is shown that under certain conditions the pH-driven parametric pump has the capacity for removal of a protein component from one product fraction and large enrichment in the other fraction. Moreover, the continuous process can be operated with a large feed throughput.

A Study On The Growth And Asparaginase Production Of Vibrio Succinogenes In A Chemostat, Preston David Krautheim

Theses

A continuous fermentation assembly was constructed and studies on the growth of the organism, Vibrio succinogenes, and its production of asparaginase was conducted. Results were compared with that already performed on a batch system and showed that a continuous fermentation produced 31.83 I.U. enzymes/mM ammonium formate compared to 17.4 I.U. enzyme/mM formate for batch.

Some of the runs performed indicated that the organism was washing out or giving very low specific growth rates. It was decided that this was not due to operational parameters of the chemostat, but possible chemical contamination in the medium. With all things considered, a continuous …

Calculations Of Isobaric Phase Enthalpy Differences For Binary Systems From Vapor-Liquid Equilibrium Data, Steven Merrill Harvey

Theses

Equations relating isobaric vapor-liquid equilibrium data to heats of vaporization are useful in testing the thermodynamic consistency of experimental VLE data and in the design of distillation equipment. Several researchers have proposed such equations based on the Gibbs-Duhem equation. At low pressures, simplified versions of these equations were successfully used to test the consistency of published VLE and enthalpy data. At high pressures, equilibrium phase enthalpy differences were calculated from rigorous equations using a modified form of the Redlich-Kwong equation to calculate fugacity coefficients. As expected, the relative error of using the simplified equations was found to increase with increasing …

The Preparation, Spectra, And Conformations Of Cis, Cis-, Cis, Trans-, And Trans, Trans- Dipropenyl Ethers, Helen C. Hollein

Theses

Cis,cis-dipropenyl ether was prepared by potassium t-butoxide catalyzed rearrangement of diallyl ether in diglyme solution. Pyrolysis was used in an attempt to produce an isomeric dipropenyl ether mixture with a high percentage of the less stable trans,trans isomer; 21.6% trans,trans-dipropenyl ether was produced by pyrolysis at 395°C, but formation of an azeotropic byproduct in significant quantities negated the feasibility of this synthesis. A mixture of 45.7% cis,cis-, 43.6% cis,trans-, and 10.7% trans,trans-dipropenyl ether was produced by mercuric acetate catalyzed isomerization at 80°C, and the mixture was separated on a Nester/Faust spinning band column of two hundred theoretical plates.

Physical properties, …

An Equilibrium Theory Of The Ph-Parametric Pump, Charles Omotayo Kerobo

Theses

Parametric pumping, both batch and continuous, and cycling zone adsorption are theoretically scrutinized for various operating conditions by using the concept of equilibrium stages. The model system is Haemoglobin-Albumin-CM sepharose, a physical system in which a local equilibrium between liquid and sorbent in the layers of the separating medium in the column is characterized. For the batch process, the steady-state concentrations in both top and bottom reservoirs are found to be independent of the number of equilibrium stages, provided that a = 1 (i.e., number of transfer steps/number of stages).. For continuous parapump process, separation is enhanced with decreasing top …

Effect Of Concentration And Ph On Parametric Pumping Separations, Tsu-Kun S. Hsieh

Theses

The technique of parametric pumping represents a new and valuable development in the separation science of proteins. Many conventional protein separation are often processed batchwise. However, parametric pumping offers the possibility of continuous processing; the continuous process provides both the advantages of decreasing the processing time and of minimizing degradation.

Preliminary step testing experiments were conducted to study the equilibrium of protein between the stationary and mobile phase of the sephadex ion exchanger.

It was the purpose of this research to study the feasibility of operating a semi-continuous parametric pump with a sephadex ion exchanger for the separation of a …

The Countercurrent Multistage Desorption Of The Acetic Acid/Water Solution With An Inert Vapor, Michael John Danko

Theses

The desorption of a acetic acid and water solution with an inert gas was experimentally investigated using a perforated plate distillation column having 17 actual trays. An inert air stream flowing countercurrent was used to strip the water from the acetic acid and water solution.

The feed composition was 0.2509 mole fraction acetic acid. The experimental results showed the best obtainable separation to be 0.16118 and 0.3965 mole fraction acetic acid in the overhead condensate and bottoms respectively, at an average column operating temperature of 56.0 degrees centigrade. The concentration of acetic acid predicted by calculation is 0.003917 and 0.9860 …

Semicontinous Ph-Parametric Pump : Experimental Study, Hsien-Chih Lee

Theses

Voidage of SP Sephadex (C-50) ion exchanger at different aqueous buffer concentration and the pH have been estimated from draining the interstitial aqueous. Experimental results of the SP Sephadex (C-50) voidage at pH cycling zone are in quantitative agreement with previous test method, so the voidage estimated from draining the interstital aqueous can be used in pH-parametric pumping. The optional displacement volume in semicontinuous pH-parametric pump of different buffer concentration can be predicted from voidage. A semicontinuous pH-parametric pump for separating proteins has been experimentally investigated using the model system haemoglobin and albumin on a. SP Sephadex (C-50) ion exchanger. …

A Kinetic Study Of The Reactions Of Poly-L-Lysine With 1-Halo-2, 4-Dinitrobenzenes, Raymond K. Rakowitz

Theses

The kinetics of the reactions of poly-L-lysine with 1-Fluoro, 1-Chloro, 1-Bromo, and 1-Iodo-2,4-Dinitrobenzenes have been studied. The investigation was done at 25°C as a function of pH and concentration. In all cases the rate of reaction increased as pH increased. In the reactions of Chloro, Bromo, and Iododinitrobenzenes with Polylysine the reaction rate is the composite of two rates; one associated with the random coil and one associated with the helical conformation. For the reaction of Fluorodinitrobenzene with Polylysine the reaction rate is the composite of four rates; two associated with the random coil and two associated with the helical …

Possible Efficiency Improvements In Residential, Gas Fired Furnances, Philip Louis Rinaldi

Theses

This project examines the problem of how to improve energy utilization in a residential space heating environment. Techniques for lowering unit energy consumption are developed and the feasibility of their implementation is discussed.

The project development first establishes the magnitude of the energy wastage problem for the individual consumer and its impact on the national scale. It must be emphasized that these represent two, sometimes distinctly different justifications for reducing energy use in the home. What may be considered only a small personal waste of $50 to $100 per year may indeed--when viewed in aggregate--represent a significant burden on the …

The Slow Settling Of A Sphere In A Viscous Fluid In The Proximity Of A Corner, Joseph Kisutcza

Theses

Experimental settling velocities for three different sizes of Delrin spheres in Ucon lubricant were determined at 20.2 degrees Celsius in order to confirm the validity of a theoretically derived equation for the settling of a sphere in the proximity of a corner. The experiments were conducted in a wedge shaped column with a circular sector base, filled with the viscous fluid, where the angle of the wedge was varied for experimental purposes. The distance from the wedge apex to the particle was also changed for the different runs.

The experimental data gave a good approximation of the values evaluated by …