Chemical Engineering Commons^™

The Reaction Of O-Propylphenyl Azide With Di-N-Propylamine, Seyed Ziaeddin Razavi

Theses

Nitration of n-propylbenzene resulted in O-nitro-n-propylbenzene. Reduction of this compound gave o-n-Propylphenyl azide was prepared by diazotization of o-n-propylaniline followed by treatment with sodium azide.

Photolysis of o-n-propylphenyl azide in di-n-propyl-amine yielded two new azepines, 2-di-n-propylamino-3n-propyl-3H azepine and 2-di-n-propylamino-7-n-propy1-7H-azepine. Their structures were assigned on the basis of their physical properties (i.e. I.R., U.V., N.M.R., N.S. and elemental analysis).

Photolysis of the azide at room temperature gave 26.9% o-n-propylaniline and 4.3% 2-di-n-propylamino-3-n-propy1-3H azepine, but when the photolysis was carried out in the presence of the triplet photosensitizer (xanthen-9-one) the yield of o-n-propylaniline was increased to 34.6% and the yield of 2-di-n-propylamino-3n-propy1-3H-azepine …

Development Of An Apparatus To Obtain Temperature Profiles Of Molten Flowing Polymers, Ismail Kemal Saltuk

Theses

The object of this investigation is to develop and test an apparatus to predict temperature profiles of polymer melts in laminar flow in a heat exchanger, with non-isothermal wall conditions.

A commercial polyethylene melt is pumped at various flow rates through a smooth 0.957 in. I.D. pipe. The entrance temperature of polymer is maintained uniform.

Radially distributed six thermocouples (0.062 in. 0.D.) are placed at 2.5 ft. intervals from the entrance of heat exchanger. Immersion of these probes parallel to the flow direction, reduced the errors due to the conduction of heat from the tube wall to the thermocouple stems. …

A Digital Computer Simulation Of A Batch Or Semi-Batch Reactor, Robert Edward Viczorek

Theses

A digital computer simulation of a batch or semi-batch reaction was developed. The system consisted of a jacketed, agitated vessel equipped with a temperature controller modulating a control valve in the stream to the jacket. The reaction was liquid phase, and the jacket medium was liquid.

The program was written in a general form so as to be applicable to any liquid phase reaction with minimum modification.

A numerical technique was employed using initial values of the process variables in the first cycle of calculations for a time interval, and then using average values for further iterations. The simulation proceeded …

Phosphate Removal From Sewage Using A Combination Of Ferric Chloride And A Polymeric Flocculant, Ravindra C. Patel

Theses

The present work is concerned with a newer technique and approach to the problem of phosphate removal from waste water. This includes the removal of phosphate from the sample of activated sludge, i.e., a sample from the aeration tank of the secondary sewage treatment. The phosphate is removed by using ferric chloride as a precipitating agent and a cationic polyelectrolyte (P.E.) as a flocculating agent. Results of this study showed that: (a) P.E. addition gives a significant improvement in phosphate removal over that obtained by ferric chloride alone. In some cases the phosphate removal increased from 92 to 96.5 per …

A Computer Program For The Design Of Packed Extraction Columns, George P. Gaccione

Theses

A computer program for the design of packed extraction columns has been developed. This program can operate with a minimum of data of the type that can easily be determined or estimated. The program can be used to investigate design alternates during the preparation of project cost estimates and for the final design of extraction columns.

Correlation And Prediction Of Diffussion Coefficients In Binary Gas Systems, Raymond Gerald Bailey

Theses

A correlation was developed for estimating binary gas diffusion coefficients by the reference substance method, in this case using the viscosity of air and subsequently its corresponding temperature. The derivation was made by the linear least square analysis of 65 different binary systems comprising 161 separate data points at temperatures ranging from 193°K. to 1200°K. At any given temperature only the critical molal volume and the molecular weights of the two gases of interest are required to calculate the diffusion coefficient. The correlation based on the viscosity of air had an average error of 7.67%. The correlation using temperature had …

The Transferability Of Force Constants Among Olefins, John Martin Comerford

Theses

A normal coordinate analysis of the in-plane vibrations of ethylene was performed using a modified valence force field, a modified Urey-Bradley force field and a hybrid orbital force field. The B_2u species of isobutene was also analyzed. An attempt was made to transfer force constants from ethylene and thereby solve the A₁ species of isobutene, but a solution could not be obtained. This suggests that simple transference of force constants is not feasable in this case.

The potential energy distributions obtained for ethylene are discussed. The normal coordinates calculated in this work are appended.

The Absorption Of Hydrogen Chloride From Dilute Air Mixtures, Edgar L. Demarest

Theses

A study was made of the absorption of hydrogen chloride from air mixtures containing from 1 to 40 mgm. HCl/liter (1000 to 40000 mgm./m.³), using a.4" diameter tower packed with 2" Intalox saddles, irrigated with water or with sodium hydroxide solutions of 0.3% to 3.8% concen?tration. Gas flow rates of 177 to 752 lbs./(hr.)(ft.²) were investigated at three liquid rates: 2960 ; 4260, and 5700 lbs./(hr/)(ft.²). All data were collected below the flooding point.

Correlations of the height of a transfer unit with the superficial gas velocity were prepared for water and for sodium …

Aiir Pollution Emissions From Turbine Powered Aircraft, Raymond Arthur Filippini

Theses

The major pollutants that are emitted by jet aircraft include: particulate matter (soot), carbon monoxide, aldehydes, hydrocarbons, and nitrogen oxides. The first of the pollutants, particulate matter (smoke), constitutes not only a visual nuisance but is also a potential health problem. The rest, which are not visible, are irritants and in high enough concentrations can be toxic.

Since pollutants emitted by jet aircraft are of the same type as those given off by a car, a direct comparison is possible. In one landing take off cycle (LTO), a four engine jet aircraft emits the same amount of particulate matter as …

The Relation Of Heat Transfer To Power Consumption Of Liquids In Turbulent Flow, John D. Bien

Theses

The relationship between the heat transfer ability and the power input requirement of liquid coolants in a turbulent heat transfer condition was investigated. A correlation in terms of the liquid physical properties and the required volumetric flow was proposed and the use of this correlation in selection of liquids as coolant was discussed. The optimum condition for a high heat transfer/power input ratio was also discussed.

Viscoelastic Properties Of Polymer Melts, Wu-Shiong Lee

Theses

Thirteen samples of molten polymers were used to test Spriggs and Careau Models. Two empirical equations, one for apparent viscosity and the other which is new, for primary normal stress difference, were checked with these samples also.

In order to test the models, material functions were sought for some specific flow patterns under which the experimental data were collected, and then these functions were compared with data.

Careau Model was found to be better than Spriggs Model in representing molten polymer properties but still yield large deviations. Two empirical equations fitted data quite well and were expected to be useful …

Combined Feedforward-Feedback Control Of A Fluidized-Bed Reactor, Reginald Eugene Mitchell

Theses

Feedforward control, feedback control, and combined feedforward-feedback control were studied on an analog computer to evaluate their effectiveness in controlling a fluidized-bed reactor used for the decomposition of cumene. Proportional, proportional-integral, proportional-derivative, and proportional-integral-derivative modes of control were investigated. Step changes in set-point and load were used as disturbances. The Ziegler-Nichols method and the process reaction curve method of Cohen and Coon were compared in determining values of KC, Ti, and Td which gave optimum control of the fluidized-bed reactor.

Control equation were obtained from the block diagrams of the systems and solved on an EAI TR-20 Analog Computer.

It …

A Modified Redlich-Kwong Equation For Nonpolar And Slightly Polar Gases, David G. Skamenca

Theses

The PVT prediction capability of the Redlich-Kwong equation is substantially improved through the use of a generalized correlation based on the acentric factor. No experimental data is required to obtain the improved constants. Only the acentric factor and the critical properties of the pure gas are needed. The correlation of improved constants is limited to non-polar and slightly polar pure gases and mixtures in the supercritical temperature range.

The correlation applies to a reduced temperature range 1.00 le; T_R le; 1.60 and a reduced pressure range of 0.030 le; P_R le; 3.00. The correlation reduces deviations by as …

Heat And Mass Transfer In The Lyophilizatiuon Of Pharmaceuticals In Vials By Conduction Heating, William Warren Walsh

Theses

This thesis investigates the lyophilization of pharmaceuticals in vials by conductive heat transfer. The process phase diagram and methods of determining the solution eutectic temperature are reviewed. The theoretical considerations of heat and mass transfer pertaining to this process are discussed.

Lyophilization tests of distilled water and of mannitol solutions are used to indicate the relationship between vacuum chamber total pressure and the product/vial interface temperature. Experiments with 10% lactose solutions are used to determine the effect of shelf fluid temperature, product height and chamber vacuum on product/vial interface temperature. Test on a pharmaceutical product are used to confirm the …

Packed Column Simulation, Frederick W. Schmidt

Theses

The most difficult and time consuming aspect of the design of packed columns is the hydraulic part. If the designer wants to try many different conditions, many repetitive calculations will have to be performed. Also, some inaccuracy is incurred when trying to use the U.S. Stoneware curves. The graphs are hard to read and almost impossible to interpolate between the parametric lines. The purpose of the program is to give a more accurate calculation by using equations for the pressure drop lines, interpolating between them and correcting for gas density for each foot of packing. The program also allows changes …

An Economic Evaluation Of A Pressure Sulfuric Acid Manufacturing Plant, Daniel A. Marlin

Theses

The production of Sulfuric Acid at elevated pressures is presented with the economics for operating at one, three, five, seven, nine and thirteen atmospheres. The conventional and pressure plants are compared operating on the same basis.

The basis for a pressure plant design is obtained from an I.B.M. 1130 computer program developed for One Thousand Net Tons per Day of Sulfuric Acid. Recognized operating conditions for a conventional acid plant are incorporated in the pressure plant design program.

Sulfuric Acid manufacture with operating pressures higher than atmospheric, but less than five atmospheres, results in maximum rate of return on investment …

The Application Of A Non-Newtonian Rheological Equation To Low-Density Polyethylene, Jeffrey N. Goldstein

Theses

A generalized non-Newtonian equation describing the rheology of molten thermoplastics is verified for low-density polyethylenes. The equation is extended to account for both rheological temperature dependency and polyethylene molecular weight dependency. The prediction of the rheology of new polyethylenes without additional experimentation is thus possible.

The Oxidation Of Sulfur Dioxide In A Regenerative Reactor, Raymond Henry Edgecomb

Theses

A novel dual-unit sulfuric acid converter is depicted that performs in cyclic operation in unsteady state. A mathematical model and IBM 1130 Computer program were developed to show the temperature and conversion profiles in commercial-sized vanadium oxide catalyst beds. In the catalytic oxidation of sulfur dioxide conversions of 95-97% were attained without benefit of conventional heat exchangers. A single exchanger operating in conjunction with the dual-unit system might attain conversions as high as 99%.

Batch Heat Transfer To Suspensions In An Agitated Vessel, John Philip Horzepa

Theses

Batch heat transfer data was experimentally determined for two phase (solid?liquid) systems in a baffled agitated vessel. Three iron oxide and water and two kaolin and water suspensions were evaluated and were found to be pseudoplastic. A total of 231 heating and cooling data points were examined. Each suspension was evaluated using anchor, paddle, propeller and turbine impellers. Various sizes of the latter three impellers were used.

The experimental heat transfer results for suspensions were compared with the Hagedorn and Salamone correlation for pseudoplastic liquids. Only partial agreement with the more dilute suspensions was obtained. Overall, the data for suspensions …

Determination Of The Electronic State Of Aryl Nitrenes In An Intramolecular C-H Insertion Reaction, Ali Mohammad Khonsari

Theses

β,γ-Dideuteriopropylbenzene was obtained in 84% yield from deuteration of allylbenzene. Nitration of this compound resulted in o-nitro (β,γ-dideuteriopropyl)-benzene. Reduction of this compound gave o-(β,γ-aideuterio-propyl)aniline. o-(β,γ-Dideuteriopropyl)phenyl azide was prepared by dizotization of the aniline compound, followed by treatment with sodium azide.

Decomposition of the azide in isooctane solution by photolysis at room temperature gave no trace of deuterio-2-methylindoline (intramolecular insertion product).

Photolysis of the azide at the reflux temperature of the solvent (99?C) resulted in the formation of deuterated-2-methylindoline as the major product (40%) yield. The reaction is presumed to proceed through an aryl nitrene intermediate. Analysis of the nuclear magnetic …

A Comparative Analysis Of Multicomponent Distillation Minimum Reflux Methods, Joesph H. F. Loozen

Theses

One of the most important factors to know in the design of distillation columns is the minimum reflux ratio. Numerous procedures have been developed for the determination of the value of the minimum reflux ratio for multicomponent mixtures requiring various degrees of computational effort. Shortcut techniques are obviously advantageous with respect to computation time. After reviewing the available methods, those by Underwood, Colburn, Scheibel and Montross, Murdoch and Holland, and Shiras et al. were selected for further evaluation, mainly on the basis of practical potential.

Comparison of these procedures was accomplished by calculating the minimum reflux ratio for a large …

The Optimization Of A Catalytic Methanol Reactor Using Quench Feed, John Paul Mcburney

Theses

The production of methanol in a catalytic quench feed reactor is studied by means of a computerized model and optimized in terms of total reactor length necessary to achieve a given production rate. The methanol reaction rate can be maximized in a quench reactor through the use of cold stream feeds along the length of reactor.

Since the methanol reaction temperature is restricted to an upper limit of 405°C, the addition of cold stream feed along the adiabatic reactor enables the desired conversion to be reached. For two given levels of conversion, 12% and 15%, an optimum inlet temperature, quench …

A Computer Program For The Optimization Of Binary Distillation In A Dual-Column System, Richard Vincent O'Lenick

Theses

A computer program is presented for the optimization of a two-column distillation system involving a two-component mixture. The economic reflux ratios in each column are determined using the McCabe-Thiele Method. Activity coefficients are computed by either the Wilson equation, the Margules equation, or both. The program is general and may be used for any binary system where the assumption of constant molal overflow is valid.

Options in the program permit use of either column in separate calculation schemes.

While the optimization effort was prepared in general terms, the initial work was directed toward the acetone-water system. Full data for this …

Effect Of Column Diameter On Mixing In Water Fluidized Beds, Donald P. Schiesl

Theses

In this investigation, the effect of column diameter and flow rate on the mixing characteristics of fluidized beds were studied.

Tests were made on columns of 4, 6, 8 and 10 inches in diameter using water to fluidize glass beads of 0.0185 inches in diameter. The tests were run both at minimum and three times minimum fluidization. Step, impulse, and sinusoidal forcing signals were fed to the columns, using a sodium chloride solution as a tracer with the inlet and outlet concentrations being monitored continuously by a conductivity recorder.

The result of this study showed increased fluid dispersion with increasing …

The Effect Of Polymerization Variables On Reaction Rate And Intrinsic Viscosity, David H. Smith

Theses

The free radical solution polymerization of vinyl acetate in benzene was studied under simulated commercial conditions. The effects of monomer, initiator, inhibitor, and chain transfer agent concentration on the reaction rate and intrinsic viscosity were examined. The initial reaction rates with monomer concentrations from 40% to 70% and AIBN concentrations from 0.2% to 0.5% were in agreement with the kinetic equation, - d[M]/dT = K[M]² [I]^1/2. After the initial reaction there was an increase in the reaction rate apparently associated with high viscosities, which is consistent with the Trommsdorff effect. The addition of hundredths of a percent …

Fluid Friction Reduction By Water Soluble Linear High Polymers, Arthur Edward Davis

Theses

The effects of various dilute aqueous linear high polymer solutions on turbulent pipe flow were studied to determine the polymer most suitable for testing as the drag reducing component in the proposed coating. Results of this study are presented for commercial schedule 40 1/4 inch NPS black iron pipe. Tests were conducted at Reynolds numbers of 6.2x10⁴,8.3x10⁴ and 9.8x10⁴.

Attempts were made to prepare a coating containing a friction drag reducing polymer - Polyhall 295 polyacrylamide - utilizing various techniques of polymer incorporation into the paint including several grinding and dispersion methods, adding the polymer …

The Effect Of Organic And Inorganic Salt On The Relative Volatility Of Non-Aqueous Systems, Glenn W. Lindberg

Theses

The effects of dissolved salts on the vapor-liquid equilibrium of two non-aqueous binary systems have been studied. Vapor-liquid equilibrium data were taken for the binary systems ethanol - n-hexane and ethanol - hexene-1. Then potassium acetate was dissolved in each of the binary systems at a level of 1.5 mole per cent and equilibrium data were collected. The effect of the dissolved potassium acetate at this low concentration was found to be minimal.

Greater levels of salt solubility could be achieved only in the binary systems containing high ethanol concentrations. Consequently, the 15 mole per cent n-hexane in ethanol binary …

P-V-T Properties Of Hydrogen And Mixtures Containing Hydrogen (With A Generalized B-W-R Equation Of State), Arnold Brief

Theses

A Generalized B-W-R Equation of State is tested for hydrogen which is a quantum gas and for systems containing hydrogen.

The gases and systems studied are: hydrogen, nitrogen-hydrogen methane-hydrogen and ethane-hydrogen.

The pressure is calculated using observed P-V-T data and the deviation is computed therefrom. For the pure gas, hydrogen, the generalized equation is compared against the original B-Vi-R equation. For mixtures, the Gunn-Chueh-Prausnitz method which is used to calculate the pseudo-critical conditions of the mixture is compared against the Prausnitz-Gunn method.

The ranges studied in this paper are as follows:pure hydrogen 30-773°K and 1 to 1200 atm., n itrogen-hydrogen …

A Computer Program For Determining Hinshelwood Rate Mechanisims From Nonisothermal Pellet Data, Joseph J. Atkins

Theses

Methods of determining Hinshelwood rate correlations from non isothermal catalyst data was studied. It was determined for any chemical system involving a reacting gas mixture over a porous catalyst a node analysis could be used to determine chemical concentration and temperature variation through the pellet. Calculation performed with a spectra 360/Fortran 4 program defined the Hinshelwood equation from estimated surface rates. Then utilising nods analysis to determine concentration and temperature variance, transport and rate equations were integrated through the pellet to obtain a total pellet rate of reaction. For acceptance of Hinshelwood equations the calculated total rate must equal the …

Hypothetical Liquid Fugacity Coefficients, Douglas F. Patterson

Theses

The object of this thesis was to derive values of the hypothetical liquid fugacity coefficient of carbon dioxide for various temperatures and pressures. Most of the temperatures studied were above the critical temperature of carbon dioxide and thus carbon dioxide could not truly exist as a pure liquid. Hence the prefix "hypothetical" was used to acknowledge this apparent discrepancy. Carbon dioxide was purposely chosen for this reason. Also,the necessary data for carbon dioxide were generally more available than for any other normally gaseous solute.

The hypothetical liquid fugacity coefficients were derived from the published binary vapor-liquid equilibrium data of carbon …