Chemical Engineering Commons^™

Equilibrium And Reaction Rate Constants Of Esterification Of Nitrobenzoic Acids, John Nicholas Korzun

Theses

A determination of equilibrium constants and reaction kinetics for the esterification of ortho, meta, and para-nitrobenzoic acids with methanol and ethanol was performed. A search of past literature showed that the equilibrium constants for the above acids and alcohols had not been measured previously.

The equilibrium constants (Ke) obtained for ortho, meta, and para-nitrobenzoic acids using p-toluene sulfonic acid as catalyst and ethanol as the alcohol were 3.59, 4.56, and 2.91: respectively. Using methanol as the alcohol, the corresponding constants were 2.61: 2.65, and 1.92.

Hydrochloric acid was also studied as a reaction catalyst, but, a side reaction between catalyst …

The Electrochemical Product Of Sodium Meta Periodate, John Joseph Mooney

Theses

An investigation of an electrolytic cell utilizing a nickel anode in alkaline solution for the production of sodium meta periodate from sodium iodate was conducted. The problem was to find an improved method of producing the salts of periodic acid.

The test conditions of cell operation were varied, i. e., temperature, concentration, hydrogen ion concentration, current density and the physical dimensions of the electrolytic cell. The optimum conditions cell operation were found to be a temperature of 21°C, a concentration of 0.10 grams per milliliter of sodium iodate, a pH of 13, current density of between 32 and 42 milliamperes …

The Synthesis And Cyclization Of 5-Chloro-2, 3-Dichloroacetamidopyridine, Edward Aloysius Naiman

Theses

The acetylation of 5-chloropyridine-2,3-diamino with chloroacetyl-chloride to yield 5-chloropyridine-2,3-dichlo-roacetamide and the subsequent ring closure form 6-chloro-2-chloromethyl-3H-imidazo-(b)pyridine has been studied in detail. The method of experimentation utilized statistically designed mathematical experiments.

The yield of 5-chloropyridine-2,3-dichloroacetamido is dependent upon the excess of the reactants and temperature, while time is not a significant factor. An important contribution to the study was obtained by extracting the product with solvents and discovering that the ring closed material 6-chloro-2-chloromethyl-3H-imidazo-(b)pyridine yields in quantity during the diacetylation reaction.

The ring closure of 5-chloro-2,3-dichloroacetamidopyridine is markedly temperature dependent. Time has little effect on the reaction yield. The analysis of …

Enthalpies And Partial Molal Enthalpies For N-Butane-Nitrogen System, Charles Fisk Paddock

Theses

Enthalpies and partial molal enthalpies are presented for the nitrogen-n-butane system at 340°F. and at pressures from 200 to 10,000 psia. The enthalpies were calculated for the pure components and for five mixtures using a graphical residual method which is described by Van Ness.⁽¹⁾ This method makes use of the Redlich-Kwong equation of state⁽²⁾ to calculate approximate values which are then adjusted by graphical correction factors. This paper illustrates both the advantages and disadvantages of this method, the graphical residual method being advantageous only when the graphical contribution to the total result is relatively small. Calculated enthalpies of …

Fugacity Coefficients Of Gases In Binary Mixtures, David W. H. Roth

Theses

Fugacity coefficients of components in gaseous mixtures have been calculated by a method proposed by Joffe which is based on the use of generalized thermodynamic functions, and on Kay's rule for definition of the pseudocritical points of a gaseous mixture. The method should be applicable to compounds which can be correlated by the theory of corresponding states.

The method was tested by application to 255 experimental points comprised of four gaseous systems, and included Argon-Ethylene, Hydrogen - Nitrogen, Methane - Ethane, and Methane n Butane. Thermodynamic functions from two recent generalized correlations, that of Pitzer et al., and that of …

Power Requirements For Agitation In Fully Baffled Vertical Cylinders, Leo Francis Ryan

Theses

The decrease in power number with increasing Reynolds number sought in this thesis was observed. However, the majority of the data is not an indication of this phenomenon. Only with a relatively high ratio of turbine diameter to vessel diameter could a power number fall-off be obtained. The power number fall-off thus appears to be dependent upon this ratio of turbine diameter to vessel diameter. When the power number fall-off was evidenced, a deep vortex existed despite the presence of full baffling, and large quantities of air were entrained by the liquid.

Even after applying pseudo corrections for both entrained …

Esterification Of Technical Grade Lactic Acid, George John Swier

Theses

A step in the method for manufacturing a purified grade of lactic acid from the technical grade lactic acid (44%) was investigated. In this method, technical grade lactic acid was reacted with normal butyl alcohol, the water formed during esterification was azeotropically removed. The ester formed, was separated from the excess butanol by vacuum distillation. The final step, the hydrolysis of the distilled ester to a purified grade of lactic acid was not covered in this investigation.

In this study, several features are reported, which to the best of knowledge, appear in a publication for the first time. They are …

Thermodynamic Properties Of Methyl Isobutyl Ketone, Lionel James Sirois

Theses

The thermodynamic properties of methyl isobutyl ketone (4-methy1-2-pentanone, hexone) have been determined for the saturated region from 32°F to the critical temperature, 569°F. Properties in the superheated region were determined for temperatures from 200°F to 2000°F and over a pressure range from 5 psia to 1000 psia. Enthalpies, entropies, and specific volumes are reported for both phases where applicable. The datum point for all calculations was zero enthalpy and entropy for a unit mass of saturated liquid at 32°F and 0.083 psia.

Pressure-volume-temperature relations were predicted using the equation of state of Martin and Hou.⁽⁶⁾ This equation of state …

Absolute Viscosity Of The N-Paraffin Liquids, Gerald Permutt

Theses

The absolute viscosity of the normal paraffins C₅H₁₂ to C₂₀H₄₂ was studied to determine a relationship more useful in predicting liquid viscosities than existing correlations such as the methods of Andrade, Souders, Thomas, and Doolittle.

It was found that a function of corresponding liquid states could be designed which related viscosity to the number of carbon atoms. This function, here called liquidity, is defined as the extent to which a substance exists as a liquid with respect to temperature. This function can be expressed mathematically as:

L_c = (t - t_m)/(t …

Correlation Of Maximum Air Velocity With Angle Of Installation For Wire Mesh Mist Eliminators, John Lawrence Reid

Theses

Wire mesh entrainment separators were installed in a vertical cylindrical column at varying angles from the horizontal. With a fixed liquid loading, air flow rates were varied in order to determine the maximum capacity of the mist eliminator for any given angle of installation. Mist eliminators studied were 4" thick and constructed of 0. 011" diameter Type 304 stainless steel wire with a density of 12 lbs. per cubic foot and 5 lbs. per cubic foot.

For normal installations of mist eliminators in the horizontal plane, the following equation is used to determine maximum allowable design capacity:

V = K …

Single Particle Crushing Of Glass, John Boyd Painter

Theses

An investigation was made to determine the relationship between new surface formed and energy input in the slow compression crushing of single glass particles at levels of high energy input.

Particle geometry, as represented by various sized hollow and solid cylinders, showed no effect on the energy-area relationship obtained.

Using an average particle size relationship as a measure of surface area, a definite relationship was found to exist between the new surface formed and the energy input for the slow compression crushing of glass.

Surface area measurements were attempted by employing gas adsorption techniques using a continuous flow method. This …

The Electrolytic Reduction Of Ethyl Paranitrobenzoate, Matthew Felix Lipworth

Theses

The factors governing the electrolytic reduction of ethyl para-nitrobenzoate have been investigated, and conditions established for the optimum yield of the end-product benzocaine. The formation of intermediate compounds was studied, and a mechanism for the reduction favoring the mono-molecular route has been suggested. The material costs of the electrolytic reduction have been shown to compare favorably with the material costs of a chemical reduction, such as the Bechamp process.

Fugacity And Activity Coefficients For Methane-Carbon Dioxide System, Robert J. Capik

Theses

The Redlich and Kwong equation of state has been used along with the method derived by H. C. Van Ness (18) to calculate the fugacity and activity coefficients of the components of the methane-carbon dioxide system. Calculations have been carried out for the pure gases and four mixture compositions at 160°F. and 280°F. with pressures up to 600 atmospheres.

The method of Van Ness was used because it offered an accurate and simple way of calculating the fugacity and activity coefficients. This is accomplished by a combination of analytical and graphical procedures in which the graphical error is minimized by …

Reductive Dehalogenation Of Alkyl Iodides, Vsevolod Gruenman

Theses

The rates of reductive dehalogenation reactions of alkyl iodides with zinc and acetic acid relative to the rate of deiodination of methyl iodide were investigated.

The order of ease of replacement of the iodine for the various substituents on the carbon atom of methyl iodide was found to be;

Exploratory Study High Purity Colbalt Using An Anion Exchange Resin, Charles Edward Hoffman

Theses

This investigation accounts for the exploratory phase of a program to develop a commercial or semi-commercial process for producing high purity cobalt; in effect, a separation of cobalt and nickel.

An extensive review of all published literature, patents, etc. from 1900 to 1958 of all known commercial, semi-commercial and analytical methods of separating cobalt and nickel was completed. Qualitative evaluation of these methods to determine the possibility of one being practically extended and/or developed to produce high purity cobalt yielded one potential commercial method. Developed for analytical purposes by Moore and Kraus (1), use is made of the fact that …

Alkylation With Some Alkyl Borate By The Friedel-Crafts Methods, Richard Ernest Huber

Theses

Normal butyl, allyl, methylbutyne and 2-chloroethyl borates were synthesized in yields above 90.0% from their corresponding alcohols and boric acid. Using some of the above alkyl borates, and others commercially available, as alkylating agents, benzene was alkylated by the Friedel-Crafts method, using aluminum chloride as the catalyst. Yields were dependent on catalyst concentration. The alkyl benzenes were identified by means of: 1) physical constants, 2) infrared spectra, 3) melting points of derivatives, and 4) chemical analysis. Starting with normal alkyl borates, the formation of isomeric and dialkylated products was established through the analytical data.

Diffusion Coefficient From Hydrogen Ion Exchange Studies, Michael Maxwell Kahn, Norman A. Martin

Theses

The study of monovalent and bivalent ion diffusion coefficients was undertaken to determine the practicability of using the Reichen berg equation to calculate a film thickness from a single diffusion coefficient and through the use of this film thickness to predict the diffusion coefficient of any monovalent or bivalent ion.

Experimentation employed the use of a mixing vessel with a two bladed propellor into which a solution of known ion concentration was kept at a constant temperature and mixing speed. Dowex 50 x -8 hydrogen ion type resin was added to the solution and by means of a pH meter …

Collection Of Germanium From Acid Etch Waste By Ion Exchange, Robert Welsh Meyler

Theses

This report is an investigation of the use of ion exchange resins to recover germanium from acid etch wastes encountered in transistor manufacture.

Most of the experiments were performed with acid etch waste of unknown germanium content. The object was to determine if the ion exchange technique were applicable, and to select the most practical operating procedure.

When a satisfactory procedure had been established, later experimental runs were made with an acid etch solution of known germanium concentration to determine the yields of recovered germanium.

Yields of 60 per cent to 75 per cent recovery of germanium from the etch …

Vapor Liquid Equilibria Of Diacetone Alcohol In Various Solvents, John A. Mulligan

Theses

This paper presents the initial study of vapor-liquid equilibria data for the systems (a) diacetone alcohol-methanol (b) diacetone alcohol-ethanol and (c) diacetone alcohol-benzene at 100mm and 200mm and confirms the data reported by Hack and Van Winkle (6) on the system (d) diacetone alcohol-water at the same pressures. Margules and Redlich and Kister constants have been determined from the data, and are presented for use in future studies.

A comparison has been made between Redlich and Kister constants determined from laboratory data, and Redlich and Kister constants predicted from the physical properties of the components. Redlich and Kister constants predicted …

Enthalpies And Partial Molal Enthalpies For Methane-Carbon Dioxide System, Isaac Pass

Theses

Enthalpies and partial molal enthalpies have been calculated by a combination of analytical and graphical procedures for the methane carbon dioxide binary system at 160°F, and at pressures from 200 to 9000 psia.

Mixtures containing .0852, .19912, .3583 and .6685 weight fraction of methane in carbon dioxide, as well as the pure components were used. The method for calculation of the enthalpies was outlined by Van Ness (1) and involves the application of residuals to the Redlich-Kwong equation of state (2).

The results of this paper illustrate the value of the method as an accurate and reasonably convenient tool. Excellent …

Salt Effects On Distribution Of Fatty Acids, John Henry Sivori

Theses

Data are reported on the extraction of formic, acetic, propionic, and butyric acids from water with methyl isobutyl ketone. Prime consideration is given to the effect of an added inorganic salt, calcium chloride, and also to the effect of the presence of a common ion on the distribution of the acids in the solvent-water system. Extraction into the solvent phase is increased by the addition of calcium chloride, but only slightly affected by the addition of a common ion.

Batch Heating And Cooling Nomographs, Stephen Zakanycz

Theses

Heat transfer problems associated with batch heating and cooling processes are relatively complex since conditions of unsteady state prevail. Complex mathematical equations are available which relate the time required to heat or cool a quantity of material in a specific piece of equipment or to design heat exchangers to transfer the desired amount of heat in a specified time. By the use of alignment charts, these equations are solved graphically with speed and accuracy. Nomographs are presented for equations dealing with heating and cooling agitated batches, counterflow and nonisothermal medium for two cases: coil-in-tank or jacketed vessel and external heat …

The Volumetric Analysis Of Nitrocompounds Using Chromous Chloride, Charles Caslin Jamison

Theses

Chromous chloride has been shown to be more efficient than titanous chloride in the reduction of refractory nitro and nitramine groups in both aromatic and aliphatic compounds.

It was found that concentrated hydrochloric acid increases the efficiency of chromous chloride to a point where it would reduce the most difficult to deduce nitro-campounds.

The compounds studied were p-Nitromethylaniline, 2,4-Dinitrotoluene, 2,4-Dinitroaniline, 2,4,6-Trinitrotoluene, Nitroguanidine, I,9-Di4cetoxy-2,4,6,8-penta-methylenetetranitramine, Sym-Cyclotrimethylenetrinitrimine, and Sym-Cyclotetramethylenetetranitramine.

Heat Transfer By Natural Convection In Horizontal Fluid Layers : A Statistical Correlation Of Experimental Data, John Lawrence O'Toole

Theses

The rate of heat transfer due to natural convection in confined, horizontal, fluid layers can be expressed by equations involving the dimensionless parameters Nusselt No., Rayleigh No., and Prandtl No., where Rayleigh No. equals the product of Grashof and Prandtl Nos.

Statistical correlation by stepwise multiple regression of experimental data obtained from four different investigators, on both gases and liquids, yields three separate equations corresponding to three distinct regimes of convection. The total range spanned by the data is from the onset of convection to Rayleigh = 109.

The equations are Regime Ra Range Equation Std. Error of Estimate Initial …

The Effect Of Agitation On The Polymerization Of A Vinyl Chloride-Ethyl Acrylate Latex, Roger Wolf Rubens

Theses

The effect of agitation was studied on a 65-35 vinyl chloride-ethyl acrylate copolymer latex. Polymerizations were carried out in a 2 gallon stainless reactor with automatic control of jacket water temperature. Standard, "power calibrated" flat blade turbine impellers of 2 in., 3 in., and 4 in. diameter were used at speeds which provided an over-all range of impeller power from 0.00007 to 0.09 hp. Work on the technology of agitation, from the literature, used to characterize agitation with respect to the polymerization, was reviewed.

The investigation indicated that conversion, reaction rate, molecular weight and the stability of the emulsion were …

Fugacity And Activity Coefficients For Methane-Carbon Dioxide System, Philip John Sievering

Theses

Fugacity and activity coefficients have been calculated by a combination of analytical and graphical methods for the methane-carbon dioxide system at 100° F. for pressures up to 680 atmospheres.

Four mixtures of the two gases, methane and carbon dioxide, and the pure gases themselves were used in the calculations according to the adaptation and interpertation of the Redlich and Kwong equation of state as set forth by H.C. Van Ness (1).

The results of this thesis seem to substantiate H.C. Van Ness's paper as a convenient and accurate method of calculating thermodynamic properties of gases from experimental compressibility-factor data. Since …

Vapor Liquid Equilibria Studies For System 1: Cyclohexane, Neo-Hexane; System 2: Neo-Hexane, Iso-Octane; System 3: Cyclohexane, Iso-Octane; At Atmospheric Pressure, Robert Halper

Theses

Vapor liquid equilibria studies were conducted on three systems at atmospheric pressure. The systems represented were: -

System #1 - Neo-hexane, cyclohexane.

System #2 Neo-hexane, isooctane.

System #3 - Cyclohexane, isooctane.

The object of these studies was: -

1. To obtain reliable experimental data on the above systems that would enable the plot of a series of characteristic curves.

2. To test the experimental data for thermodynamic consistency.

3. To correlate the data with the best of several theoretical equations as represented by Van Lear, Margules, Scatchard-Hamer or Redlich-Kister.

Investigation Of Liquid Partition Chromatography Of Polyhydric Alcohols, Michael Homiak

Theses

Polyhydric alcohols have previously been separated by tedious chemical procedures and in microgram quantities on columns prepared from silica gel and silica gel - Celite combinations. This study was undertaken to determine whether separation of these alcohols was possible by chromatography on columns of Celite alone, and in quantities considerably greater than those formerly handled. In addition, as a preliminary step to the actual separation, the capacities of the columns for the two polyhydric alcohols were determined. The effect of several variables on the capacities of the columns were investigated. A calculation of the number of theoretical plates in a …

Kinetics Of Hydrolysis Of Some Halonitrobenzenesulfonates, Walter C. Kania

Theses

The object of this thesis was to determine the rela¬tive activity towards hydrolysis of several halogen deriv¬atives of nitrobenzenesulfonate. The halide is Para to a nitro group and ortho to the sulfonic acid group.

The compounds studied were:

(I) sodium 2-chloro-5-nitrobenzenesulfonate

(II) sodium 2-bromo-5-nitrobenzenesulfonate

The chlorine was found to be more reactive than the bromine.

A dichloride, (III), sodium 2,5-dichloro-3-nitroben-zenesulfonate was also studied. Here one chlorine is activated by both the nitro and sulfonic acid groups. The other chlorine being meta to the nitro and sulfonic acid groups would be adverse to hydrolysis.

Rates of hydrolysis of (I), (II), and …

Study Of The Solid-Liquid Quaternary Equilibria : The Manganous Sulfate, Ammonium Sulfate, Sodium Sulfate And Water Phase System, John Kalman Kaufman

Theses

This investigation details the Solid-Liquid Equilibria in the Quaternary phase system at 30° Centigrade of Manganous Sulfate - Ammonium Sulfate - Sodium Sulfate - Water. These three salts, with a common ion and water, are represented by the Janecke projection method and summarized in the tabulation of results.

Additional data were obtained on the applicable Ternary phase systems which were used in completing the Quaternary phase projection. The systems,

Manganous Sulfate - Ammonium Sulfate – Water

Manganous Sulfate - Sodium Sulfate – Water

Ammonium Sulfate - Sodium Sulfate – Water

are represented by the Roozeboom Equilateral Triangle mode.

This is …