Chemical Engineering Commons^™

Potassium T-Butoxide-Initiated Elimination On Substrate 1,1,2-Trimethoxyethane, James Waldron

Theses

1-bromo-2,2-dimethoxyethane (I) was prepared in 68% yield from the addition of bromine to a solution of vinyl acetate and methanol. A Williamson ether synthesis, using sodium methoxide in methanol and I, gave 1,1,2-trimethoxyethane (II) in 48% yield. The compound (II) was the desired substrate for elimination reactions because it contains poor leaving alkoxide groups.

Many different reactions were investigated to convert II into 1,2-dimethoxyethylene. Among these were pyrolysis, acid catalyzed eliminations, and base initiated elimination reactions.

Best results were obtained using a bomb reactor, compound II as substrate, and potassium t-butoxide as the base. From this reaction, tertiary-butyl methyl ether, …

Ball Milling Of Non-Newtonian Dispersions, Barry S. Miller

Theses

This investigation attempts to obtain a better understanding of flow behavior of a pigmented dispersion in a ball mill.

A power-law fluid model was used to approximate the rheological behavior of the milled fluid. To correlate power data on each of 276 milled dispersions, this model was used together with power number, Reynolds number, Froude number; and some geometrical variables.

Laboratory size stainless steel jars containing stainless steel balls from 1/8 to 3/4 inches in diameter were used to Mill a pigment/binder/solvent system at various speeds for different periods of time.

A correlation of power number as a function of …

The Frequency Response Analysis Of A Reboiler-Condenser Under Condensate Control, Douglas F. Ready

Theses

In this investigation, the dynamics of a reboiler-condenser pair, with the reboiler operating under condensate control, were analyzed both theoretically and experimentally, and the results of the two analyses compared.

The theoretical analysis was performed using the standard method of Laplace transform transfer function synthesis.

The experimental study consisted of a frequency response analysis of the system response to sinusoidal variations of the steam condensate rejection rate.

Two mathematical models were developed, one quite rigorous but extremely cumbersome, the other neglecting all but the most important factors for the sake of simplicity.

The experimental data (in the form of Bode …

Carburizing Of Steel Using "Cracked" Methane, Robert Alvin Hesse

Theses

An attempt was made to carburize steel using cracked methane, industrial terminology for methane burned in air over a catalyst to give carbon monoxide and hydrogen, as the carburizing agent. Initial tests in a laboratory scale furnace using steel in chip form showed that, the feasibility of this method was excellent. These tests also indicated that a good method of control of the carburizing would be by a system that could measure the dew point of the gases introduced into the furnace. The next step was to apply the method of carburizing to small production size lots of bearing components. …

Melt Rheological Properties Of A Filled Polyethylene, George Lewis Levy

Theses

A procedure was developed to convert shear stress at various melt temperatures into a computed shear stress at a constant temperature in an isothermal system.

The isothermal shear stress was first analyzed at an equilibrium condition before time induced stress reduction for

1) the temperature dependency of shear stress

2) non-newtonian flow behavior

3) a relationship between the independent variables of shear rate, filler concentration and temperature, and shear stress.

A statistical analysis was performed on the data to find an empirical relationship between shear stress and the independent variables, at any time, under stress, for unfilled and filled high …

Kinetics Of The Lactic Acid-Butyl Alcohol Esterification Reaction, Joel Howard Kaplan

Dissertations

Kinetic and equilibrium data for the esterification reaction of monomeric lactic acid with normal butanol were determined in a series of experiments utilizing a batch stirred tank reactor. The variables studied were temperature and catalyst concentration. The kinetic data were successfully represented by the integrated equation for a second order reversible reaction.

Rate constants were obtained at three temperature levels and four catalyst levels. The observed rate constants in the catalytic reaction were linearly correlated with catalyst concentration and also satisfied the Arrhenius criterion. The activation energy and frequency factor for the uncatalyzed reaction were determined to be 13,190 calories …

Effects Of Non-Constant Molal Flow On Distillation Plate Separation, Joseph Lawrence Niedzwiecki, W. Weissman

Theses

This thesis presents new equations for predicting degree of separation on a distillation plate, recognizing non-constant molal flow effects. A FORTRAN program is included for solving the new equations. Experimental runs were made for comparison to theoretical predictions.

First an equation is derived for predicting separation at a point on a distillation plate. The derivation is analogous to Murphree's point efficiency equation except that the effects of flow between phases are included by applying the Colburn-Drew theory. Finally, an overall plate separation equation is derived analogous to the A.I.Ch.E. eddy diffusion model for Murphree plate efficiency, except that the rate …

Fugacity And Activity Coefficients For The N-Butane-Nitrogen System, Richard E. Walter

Theses

Fugacity and activity coefficients were calculated for the nitrogen-n-butane system at 310°, 340°, 370°, and 400°F. in 100 atmosphere pressure intervals from 100 to 700 atmospheres for the pure components and mixtures of 10, 30, 50, 70, and 90 mol% n-butane. Calculations were based on a method proposed by Van Ness. This calculation procedure combines an analytical solution utilizing the Redlich and Kwong equation of state with a graphically obtained correction factor.

Vapor-Liquid Equilibria System : Chloroform, Carbon Tetrachloride, Isopropanol, Barnet H. Bursack

Theses

A study was made of the vapor-liquid equilibria of the ternary system: Chloroform (CHCl₃), Carbon Tetra-chloride (CCl₄) and Isopropanol (C₃H₈O). An Othmer still was used for the equilibria determination. Refractive index and density measurements were used to determine liquid and vapor compositions. A comparison between experimental and theoretical values was made using the Margules 3-suffix ternary equations for the correlation.

It was necessary to investigate the vapor-liquid equilibria of each of the three binary systems to evaluate the techniques and equipment used and obtain new data. Only one previous investigation of the …

The Kinetics Of A Heterogeneous System, Francisco H. Fernandez-Ortega, Gonzalo D. Milian

Theses

The reaction between an acidic potassium dichromate solution and metallic copper has been studied at 25.0°C under batch quiescent and continuous flow conditions.

The effect of time of reaction, reactor diameter, acid, dichromate, and salt concentration upon reaction rate have been investigated for a quiescent batch reactor and found to influence the Reaction Velocity Constant of the system. As the reaction progressed, the Reaction Velocity Constant was observed to decrease. An increase in reactor diameter resulted in a Reaction Velocity Constant increase. Small increments in the dichromate concentration produced a decrease in the Reaction Velocity Constant. A maximum point of …

Kinetics Of Hydrolysis Of Butyl Lactate, Peter Pommers

Theses

The acid catalyzed hydrolysis of butyl lactate with water, using lactic acid to achieve a homogeneous solution, was studied.

Experiments at various temperatures were run under catalyzed and uncatalyzed conditions. The course of the hydrolysis was followed by titrating the acidity of the reaction mass at certain time intervals. From the results of these titrations and from the experimental determinations of the equilibrium constant, the reaction velocity constants for the hydrolysis of butyl lactate were calculated. The velocity constants were found to range from .8 x 10^-5 to 25 x 10^-5 liters/ (g-mole)(min), depending upon the reaction temperature …

Current-Potential Effects Of Trace Impurities In Manganese Electrowinning-Ii, Bipinchandra Govindlal Shah

Theses

The effects of trace non-metallic impurities, found in manganese electrowinning solutions, on cathode current-potential curves have been investigated. Five impurities, e.g., Sulfur-dioxide, Ammonium Sulphide, Urea, Thiourea, and Gelatine were studied.

In the first phase of the study the effect of individual impurity on the standard polarization curve was determined for a range of concentration. It was observed that these impurities did not affect the standard polarization curve.

In the second phase the above observation was confirmed by using cobalt as metallic impurity in addition to the non-metallic impurity. A marked effect on the standard polarization curve was observed due to …

Diffusion Coefficients In Alcohol - Water, Frank Gustav Meier

Theses

Diffusion coefficients of potassium, calcium and magnesium ions in ethanol-water solutions have been determined at 20°C. by means of Dowex 50W-X8 under experimental conditions that indicate that the transfer rate is controlled by film diffusion.

This investigation presents, for the first time, diffusion coefficients for these ions in ethanol solutions at concentrations below 0.01N.

The combined effect of viscosity and dielectric Constant of the solvent on the diffusion coefficient of Ions is demonstrated.

Hydrotropic Extraction Of Hydrocarbon Mixtures, Michael Jay Ram

Dissertations

The solubilities at 25°C of selected aromatics and straight chain alkanes in hydrotropic solutions of sodium xylene sulfonate and sodium cymene sulfonate were studied. The results of this investigation are shown on distribution diagrams relating the solubilities of alkane and aromatic in each phase.

Two methods were investigated to predict the experimentally determined solubilities. The semi-empirical solubility parameter approach resulted in answers that were extremely low. A purely theoretical approach involves the calculation of dispersion forces between molecules. An equation for predicting solubilities has been derived so that it is applicable to four component systems. This method results in values …

Correlation And Coordination Of Engineering Properties Of Zirconium And Zirconium Alloys, Rasiklal Jethalal Shah

Theses

This thesis is a report on the mechanical, nuclear, electrical and chemical properties of the zirconium and five zirconium-base binary alloys: zirconium-tin alloys, zirconium-aluminium alloys, zirconium-titanium alloys, zirconium-niobium alloys, and zirconium-hafnium alloys. The peculiarities of these alloys, as related to its history, heat treatment and composition, are discussed. This work discusses the effect of temperature and impurities such as carbon, oxygen, nitrogen and hydrogen on mechanical properties and corrosion resistance of zirconium and zirconium alloys. Zirconium metal production is briefly discussed. Empirical formula, by which the thermal conductivity of zirconium alloys can be calculated by the measurements of thermal resistivity, …

A Systematic Evaluation Of Alternate Chemical Routes, Arthur H. Bobis

Dissertations

A systematic method for selecting from among alternative routes for chemical synthesis is developed and presented. Consideration is given not only to making the best decision, but of reaching that decision with a minimum of experiments.

A method is developed whereby the calculated differences in process cost due to variations in the levels of such responses as chemical yield, usage and recovery are displayed graphically. Such a representation by indicating the potential worth of any experiment focuses attention on those parts of the synthesis which have an economic bearing on the ultimate process cost.

The probability of achieving a particular …

Prediction Of Batch Heat Transfer Coefficients For Pseudoplastic Fluids In Agitated Vessels, Donald William Hagedorn

Dissertations

Experimental batch heat-transfer data were obtained for both Newtonian and pseudoplastic liquids in a baffled agitated vessel. The fluids tested had flow behavior in-dexes between 0.36 and 1.0; and the apparent viscosity ranged from 1 to 1200 centipoise. Four types of impellers (anchor, paddle, propeller, and disk and vane turbine) were studied using eleven separate impellers. The probable error in the measured heat transfer coefficient was ± 20 percent.

The effects of the generalized Reynolds number, generalized Prandtl number, and viscosity ratio were studied. In addition the effect of impeller diameter was studied for paddles, propellers, and turbines; and the …

The Electrochemical Oxidation Of Cholesteryl Acetate Dibromide, Abraham Cooper

Dissertations

Cholesteryl Acetate Dibromide was dissolved in carbon tetrachloride, suspended with mixing in 4.5 molar solution of sulfuric acid and electrolyzed at a lead dioxide anode. The anodically prepared film of lead dioxide, when maintained at potentials (relative to a calomel electrode) above 1.5 volts, was a catalyst for the oxidation. A new and mild oxidation took place at the catalytic electrode surface that resulted in attack on the tertiary hydrogen atom at the 25 carbon. The mildness of the oxidation prevented the decomposition of the unconverted raw material and permitted the recovery of up to 96% of the cholesteryl acetate …

Current-Potential Effects Of Trace Impurities In Manganese Electrowinning, George Robert Ferment

Dissertations

The purpose of this investigation was to study the effects of trace metallic impurities, found in manganese electro-winning solutions, on cathode current-potential curves.

This investigation led to the development of a novel analytical tool, emphasizing polarization curves as a means of detecting trace metallic impurities in manganese sulfate electrolytes. The method possesses two distinguishing features: (a) it uses the competing hydrogen evolution reaction as a means of detecting metallic impurities, and (b) it enables one to establish if the electrolyte is sufficiently pure for efficient electrolysis.

Nine metallic impurities were studied, consisting of: nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, …

Use Of Gas Chromatography To Determine The Mutual Solubility Of Water And Toluene, John Orshich

Theses

The possibility of determining the water traces in water saturated toluene as well as the traces of toluene in toluene saturated water by means of gas chromatography was investigated.

A 15 feet long, 1/4 inch copper column, attached to F & M Chromatograph 500, was used; the column was packed with 5 Armeen SB on Haloport F (Teflon).

The determination of toluene in toluene saturated water did not appear to be feasible, since the retention time for toluene with the used column was too short to allow the base line of the recorder to become steady at the attenuation value …

The Effect Of Column Diameter On The Efficiency Of Packed Fractioning Towers, William Lintner

Theses

The object of this work was to study the effect of packed column diameter on the fractionation efficiency so that a more reliable engineering approach could be employed in the scaling up of fractionating columns.

The height equivalent to a theoretical plate (HETP) was employed to compare column efficiencies in this study. The HETP was calculated for several gas mass velocities through columns of one-inch, two-inch and three-inch diameter, packed with one-quarter inch Berl saddles. All data were collected at total reflux conditions employing the standard n-heptane-methylcyclohexane binary.

The results indicated that the efficiencies of the one-inch and two-inch diameter …

Factors Affecting The Biodegradation Of Linear Alkylbenzene Sulfonates In River Die-Away Studies, Neil M. Mchugh

Theses

The determining factors in the biodegradation of linear alkylbenzene sulfonates have been investigated using the river die-away technique. Emphasis was placed on finding the correlation between biodegradability and each of the following: surfactant structure, inoculation of basic water medium with activated sludge, and acclimation of bacteria to a given surfactant. It has been shown that the lower the molecular weight of linear alkylate, down to C8, the faster the rate of biodegradation. It was further shown that there is no direct relationship between phenyl position distribution and biodegradability, nor is there any direct correlation between the amount of surfactant remaining …

A Study Of Emulsion Viscosities, Frederick R. Cummings

Theses

The apparent viscosity of stable emulsions has been measured and evaluated. The systems studied consisted of various oil in water emulsions, utilizing a series of six n-paraffins from heptane to octadecane. The system was stabilized with a conventional emulsifying agent. The apparent viscosity of these emulsions was studied in relation to (a) the concentration of the disperse phase and, (b) the viscosity of the hydrocarbon used as the continuous phase.

It was established that the volume concentration of the disperse phase had considerable effect on the apparent viscosity of the emulsion. An increase in the concentration of the disperse phase …

Effect Of Particle Size And Particle Size Distribution On The Burning Rate Of Barium Chromate-Boron Pyrotechnic Delay Compositions, Donald J. Freeman

Theses

The burning rate of barium chromate-boron delay compositions is shown to be related to the 10 percent particle size point on the particle size distribution curve (particle size vs. percent greater than size) for either of the components. The burning rate is also shown to be inversely proportional to the 10 percent point of the barium chromate; and to follow a hyperbolic type relationship with the 10 percent of the boron, decreasing asymptotically as the 10 percent point increases. No correlations were found between the burning rate of the compositions and the average particle diameter, the mean particle diameter, or …

Investigation Of The Octene-Decane-Urea Adduct Equilibrium System, Frederick Charles Guest

Theses

Concentrations of equilibrium mixtures formed by adding increments of octene to a solution of urea in methanol to form adduct are reported.

Calorimetric studies indicate that the addition of octene to a urea-methanol solution shows an endothermic heat effect prior to the formation of solid adduct. The heat effect becomes exothermic as solid adduct is formed.

Addition of decane to an equilibrium octene-urea adduct system increased octene concentration in the supernatent liquid, indicating an octene release from the original adduct as decane adduct was formed.

The order in which decane and octene were added to form the decane-octene-urea adduct system …

Cation Exchange Between Solutions Of Ferric Nitrate And Dowex 50x-8 Resin, Michael H. Mansky

Theses

The rate of exchange of ferric ions from solutions of ferric nitrate and hydrogen ions from Dowex 50X-8 has been studied in an agitated bed ion exchange column over a range of bed loading conditions. Agitation has been maintained in a regime known to indicate film diffusion control of rate in small scale batch reactors.

Calculated diffusion coefficients for the column are slightly higher than those determined in the batch reactor because of greater turbulence of agitation in the column.

The assumption of previous investigators concerning linearity of equilibrium data has been found to be invalid for the system studied. …

Activity Coefficient For Infinite Dilute Solution By Gas-Liquid Chromotography, Suresh Jivabhai Patel

Theses

Gas-liquid partition chromatography has been used to determine the activity coefficient for very dilute solutions of solute in non-volatile solvents.

Other, more classical methods of determining the activity coefficient are laborious and are neither as accurtate nor as precise as desired.

The systems studied were:

(1) Benzene-Dinonyl Phthalate

(2) Cyclohexane-Dinonyl Phthalate

(3) Benzene-Squalane

(4) Cyclohexane-Squalane

All systems were studied over the column temperature range of 50° to 110°C with constant pressure and sample size. A study was also made on the effect of column pressure at constant temperature and sample size. One system was studied with variable sample size but …

Heat Transfer To Non-Newtonian Fluids In Turbulent Flow, Donald S. Smalley, George Vassil

Theses

An investigation of the heat transfer characteristics of non-Newtonian solutions in turbulent flow is presented. The range of flow behavior indices (n) was examined from 0.69 to 0.88. The consistency index (K) was investigated over the range of 0.00008 to 0.002 lbsf x sec^n'/ft². The Reynolds number varied between 2200 to 25,000.

Two methods of correlating film coefficients which have been previously developed were examined. Improvement in the reliability of correlation is demonstrated by modifications proposed in this work.

Brittle Fracture Of Carbon Steel, Ronald Robert Stang

Theses

This thesis is a report on the research and engineering efforts made, since 1957, to further define the causes and means for the prevention of catastrophic brittle fracture of carbon steels at ambient temperatures. All of the data based on the literature published from 1958 to 1965 has been critically examined and correlated.

Included are discussions of the factors affecting brittle fracture and the tests used to predict resistance Of steels to brittle fracture. Correlations of tests with actual service performance and relationships between tests are discussed. A review and critical evaluation of present day steel specifications as they affect …

The Thermal Conductivity With Vapor Pressure For N-Paraffin Hydrocarbons, Jacob Tolsma

Theses

A literature search of the thermal conductivity of pure liquids has been made and experimental values have been compiled. Study of the theory of the thermal conductivity of liquids indicated that a relationship exists between thermal conductivity and viscosity. Previous investigations have found an almost linear relationship between the logarithms of viscosity and vapor pressure for n-paraffin hydrocarbons. In this investigation the logarithm of thermal conductivity plotted versus the logarithm of vapor pressure for the same series was also found to be almost linear. The equation of the line when combined with a linearized Antoine equation in terms of the …