Loyola University Chicago Loyola eCommons Master's Theses Theses and Dissertations 1940 A Study of the Equilibrium Diagrams of the Systems, Benzene- Toluene and Benzene-Ethylbenzene John B. Mullen Loyola University Chicago Follow this and additional works at: https://ecommons.luc.edu/luc_theses Part of the Chemistry Commons Recommended Citation Mullen, John B., "A Study of the Equilibrium Diagrams of the Systems, Benzene-Toluene and Benzene- Ethylbenzene" (1940). Master's Theses. 299. https://ecommons.luc.edu/luc_theses/299 This Thesis is brought to you for free and open access by the Theses and Dissertations at Loyola eCommons. It has been accepted for inclusion in Master's Theses by an authorized administrator of Loyola eCommons. For more information, please contact [email protected]. This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 3.0 License. Copyright © 1940 John B. Mullen A S'l'IJDY OF THE EQUTI.IBRIUM DIAGRAMS OF THE SYSTEMS, BENZENE-TOLUENE AND BENZENE-~ENZENE By John B. Mullen Presented in partial :f'u.J.tilment at the requirements :f'or the degree o:f' Master o:f' Science, Loyola University, 1940. T.ABLE OF CONTENTS Page Acknowledgment 1i Vita iii Introduction 1 I. Review of Literature 2 II. Apparatus and its Calibration 3 III. Procedure am Technique 6 IV. Observations on the System Benzene-Toluene 9 V. Observations on the System Benzene-Ethylbenzene 19 VI. Equilibrium Diagrams of the Systems 30 Recommendations for Future Work 34 Bibliography 35 ACKNOWLEOOMENT The au1hor wishes to acknowledge with thanks the invaluable assistance, suggestions, and cooperation offered by Dr. J"oseph D. Parent throughout the course ot this work. He is also gratetul tor the cooperation and encourage­ ment given by Dr. G. M. Schmeing and Dr. A. P. Davis which was helptul in carrying this work to its conclusion. i1 --- VITA The author was born in Chicago September 22, 1916, and has lived in Chi­ ago throughout his life. He received his high sChool education at Loyola cademy, and his collegiate training at Loyola University of Chicago, from nich he received the degree or Bachelor of Science in 1937. Since that time e has been engaged as Research Chemist with the Technical Service Bureau, Inc. r Chicago, and has been pursuing graduate studies in Chemistry at Loyola Uni­ ersity. iii INTRODUCTION The purpose of this work is to study the equilibrium diagrams of the systems, benzene-toluene and benzene-ethylbenzene. The method employed is the investigation of cooling curves of binary mixtures of these sUbstances. The equilibrium diagrams are then constructed from the data determined from the cooling curves. -1- -- I. REVIEW OF LITERATURE A search of the literature reveals no information on the equilibrium diagrams of the systems benzene-toluene and benzene-ethylbenzene. Kramer (1) and Richiardi (2) have investigated the equilibrium diagrams of other binary systems of benzene and mono-substituted benzenes. The information contained in their papers is the only data available related to this problem. Methods available tor the investigation of equilibrium diagrams in general are given in standard works on the subject of the phase rule, such as those by Findlay (3) and Bowden (4). However, the published information on the technique required relates primarily to systems in which freezing points of the components and equilibium temperatures are not below room temperature, so that air can be used as cooling medium. Kramer and Richiardi, in the work previously cited, have developed methods for determining equilibrium. tempera­ tures in samples which solidify at low temperatures, using dry ice-acetone mixtures as coolant. In the present work, the same method was used in deter­ mining equilibrium tanperatures within the range of the dry ice-acetone bath (the minimum temperature obtained with dry ice-acetone baths is about -78°0.) • -2- II. APPARATOB AND ITS CALIBRATION The apparatus used consisted of a cooling bath for lowering the tempera­ ture of the sample, and a thermocouple pyrometer system for determining the temperature of the sample as it is cooled. For samples which begin to solidify above approximately -65°C., a cooling bath of acetone and dry ice was used. This cooling bath was contained in a beaker which was insulated with heavy layers of cotton to reduce rate of heat exchange w1 th surroundings to a minimum.. For samples which do not solidity within the range of dry ice-acetone mixtures, liquid air was used as coolant. Because of the necessity of protecting this substance from heat, it was con­ tained in a Dewar flask. To prevent excessively rapid cooling of the sample in the bath, the test i tube containing the sample was placed in a larger tube before insertion into the bath. In practice it was found desirable to use an outer tube or jacket considerably larger than the sample tube, and to use rings of cork to hold the sample tube approximately centered in the jacket. A spiral of Nichrome wire was inserted into the sample, and agitated up and down during the test to keep the sample well mixed. A copper-constantan thermocouple system was used, both thermocouple junctions being silver soldered. One thermocouple junction was placed in a reference constant-temperature bath, the other in the sample being cooled. -3- paz Pyrometer Cop1er Heference Thermocouple constantan wire Junction Glass tube J"acket tube ,/ ........· • 0 • '· ... :- .; 1 1---H--1----; .,. • o 4 I : : ~ ~ I I,'' I ,..,Sample 0 • • -~ ....... ' '.·· tube . 0. \.. '• .... '0 0 0 0. : .. · • 00 - ·... · (•, ..' '... •o -:.. ~:" .•. / Insulation Ice-wvater I"ixture ----------Thermocouple Junction ---Dewar flask Liquid :\ir DIAGR.AJI:' O.B' Arf'ARATUS .... -4- The electromotive force generated in the system was measured on a Brown Pyro- meter, essentially a millivoltmeter with a range of 3.8 millivolts and an arbitrary scale of 100 units. Boiling tetrachloride, under reflux, was used as reference constant temperature bath in conjunction with the dry ice cooli bath, and a freezing mixture of ice and water was used in conjunction with th liquid air cooling bath. The them.ocouple pyrometer was calibrated by determining the freezing points, as indicated on the pyrometer scale, of various pure substances. Plotting the known freezing points of these substances, as ordinates, against the observed freezing points in scale units, as abscissae, gives a calibra­ tion curve by means of which an::y reading on the pyrometer can be translated into degrees centigrade. The materials used as calibration standards were carefully purified by distillation. The substances used in calibrating the pyrometer are given in the following table: Substance Freezing Point (Degrees Centigrade) Benzene 5-5 Water o.o Carbon Tetrachloride -22.6 Chloroform -63.5 Toluene -92.0 Ethyl Bromide -117.8 In practice it was found that there were minor variations in the cali­ bration of the instrument during the period of work. (A possible explanatio -5- of this lies in the tact that the thermocouple junctions had to be re-solderEd at times, which both substituted a new junction and shortened the lead wires. 1 In addition, the temperature range of the instrument was intentionally shiftal on more than one occasion. For these reasons, it was found desirable to cali­ brate the instrument before use every working :period; and in the data :presenre in the following sections, calibration data and calibration curves will be found accompanying their respective cooling curve data and cooling curves. III. PROCEDURE AND TECBNIQ.UE To determine the solid-liquid equilibrium point of a mixture ar given composition, it is necessary to run a "cooling curve" on the sample. In this procedure, a tube containing the mixture is placed in the cooling bath, with a stirring device to insure uniform temperature throughout the mixture during the test, and a thermocouple junction to measure the temperature of the mix­ ture. The sample in the tube is then cooled and the temperature of the sam­ ple, as indicated on the thermocouple pyrometer, is recorded at intervals of 15 seconds. The sample is cooled until after the appearance of a solid phase. The temperature readings are then plotted, as ordinates, with time as abscissae, giving the cooling curve for the sample. The point at which the appearance of a solid phase began can be determined by inspection of the cool­ ing curve. In the case of a pure substance, the rate of cooling {that is, the slope of the cooling curve) varies continuously and uniformly until solidir­ fication begins, at which point the temperature will remain constant until the solidification is complete. In the case of mixtures, there is a decrease in the rate of cooling when the solid phase first appears, caused by the evolution of the latent heat of fusion as the phase forms. This point can be observed as a pronounced "break" in the cooling curve, and the ordinate of that point represents the temperature at which a liquid of that composition is in equilibrium with solid. This is loosely spoken of as the "freezing -6- -7- point" of such a mixture. If the components of the system are substantially immiscible in the solid state, and form no coapounds, the solid phase which first appears will be one of the pure components, and it will appear, generally, at a temperature below the freezing point of the pure component. At a certain composition, the solid phase which separates out is a mixture of the two pure components, and the temperature at which this solid mixture forms is a constant for a given system. It is known as the eutectic point of the system, and is the lowest freezing point for any mixture w1 thin the system. It is the tempera­ ture at which both solid phases are in equilibrium with liquid.