PURDUE UNIVERSITY THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Charles Joseph Walters Volumetric Behavior___________________ en titled _______________ and Thermodynamic Properties of Ethylene Oxide COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF Doctor of Philosophy ’ROFESSQR IN CHARGE OF THESIS Head of School or Department TO THE LIBRARIAN:---- THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL. KBGISTKAH FORM 10—7.4 7—IM VOLUMETRIC BEHAVIOR AND THERMODYNAMIC PROPERTIES OP ETHYLENE OXIDE A Thesis Submitted to the Faculty of Purdue University by Charles Joseph Walters In P artial Fulfillm ent of the Requirements for the Degree of Doctor of Philosophy June, 1951 ProQuest Number: 27714263 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 27714263 Published by ProQuest LLC (2019). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 ACKNOWLEDGMENTS ïhë author expresses his sincere appreciation of the constant interest and helpful guidance of Professor J. M, Smith who suggested the problem studied and under whose direction the investigation was conducted. Thanks are due L. Petty and G. Thompson for th eir help with the experimental work and to Mr. E. Boohultz fo r constructing parts of the equipment. Grateful acknowledgment is made for the financial assistance from the Purdue University Engineering Experimental Station, Lafayette, Indiana, and the American Cyanamid Company, New York, New York. TABLE OF CONTENTS Page ABSTRACT....................................................... i INTRODUCTION........................................................................................................ 1 SURVEY OF THE LITERATURE..................................................... 3 The Extent of P-v-T Data in the L iterature.................. 3 Calorimetrie Data................................. 5 Spectroscopic Data.............................................................. 8 General Survey of P-v-T Equipment.............................................. 9 SCOPE OF EXPERIMENTAL WORK.................................................................... 13 Pressure and Temperature R a n g e # .................... 13 Apparatus.............. 13 Purity of Ethylene Oxide...................................... 14 DESCRIPTION OF EQUIPMENT......................................................................... 17 Compressibility U nit .............. 19 Temperature Control and Measurement. .............21 Pressure Control and Measurement .................................24 Volume Me a sûrement ........................................... 26 Sample Transfer Apparatus............................... 29 CALIBRATION OF EQUIPMENT................................................................... 32 Calibration of Thermocouples. ............ 32 C alibration of Pressure Gauge ............................. 33 Calibration of Volume Device ................... 37 PROCEDURE............................ 40 Compressibility Runs ........................ 40 Test Runs ....................................................... 49 Page RESULTS................................................................................................................. 56 Vapor Phase Data ....................................................... 56 Vapor Pressure Data ........................................... 68 Liquid Phase Data................ 74 Extrapolations ..................... 76 Best C ritical C onstants. .................................................. 79 CALCULATIONS......................................................................................... 82 Properties.invthe Ideal Gas S ta te .................... 82 Application of the Beattie-Bridgeman Equation.. . . . . . 86 Graphical Methods • • • • ....................................... 88 DISCUSSION OP RESULTS AND CONCLUSIONS....................................... 112 LITERATURE CITED.................................... 119 NOTATIONS.................................... 124 APPENDIX A. ILLUSTRATION OF DATA AND CALCULATIONS FOR VOLUME CALIBRATION................................. 125 APPENDIX B. ILLUSTRATION OF DATA AND CALCULATIONS FOR MERCURY-LEVEL CALIBRATION........................... 126 APPENDIX C. CONVERSION OF LABORATORY MEASUREMENTS TO P-V-T DATA............................................................... 128 APPENDIX D. TABLES OF ORIGINAL P-V-T DATA....................... 129 APPENDIX E. SAMPLE CALCULATIONS INVOLVED IN DETERMIN­ ING THERMODYNAMIC PROPERTIES................ 135 V IT A .............................................................................................. 138 LIST OF FIGURES Figure Page 1. Schematic Diagram of Equipment.................... 18 2. Compressibility Cylinder......................... 20 3. Thermostatic Control C ircu it. ........................ 23 4* Weighing Bomb..................................... 31 5. Pressure Gauge Calibration C u rv es......................................35 6. Change of Residual Volume with Time at 280°F.. . . . . . 47 7. Apparent Polymerization Rate vs l/T . ...................... 48 8. Test Runs with Nitrogen at 160°F.. . . . . . . . . . . . . . . . . . 51 9. Test Runs with n-Butane at 190°F...................... 52 10. Pres sure-Volume-Tempera ture Data.................... 57 11. Residual Volume versus Temperature............. 58 12. Residual Volumes from Data of Maass and Boomer 61 13. P-v-T Data in the C ritical Region. ...................... 67 14. Vapor Pressure of Ethylene O x id e..................................... 69 15. Pressure versus Volume 70°F. ...................... 71 16. Specific Volume of Liquid Ethylene Oxide.. . . . . . . . . . 75 17. Law of R ectilinear Diameters ............... 78 18. (dcc/jT)p versus Pressure. .................... 90 19. Pressure-Enthalpy Diagram for Ethylene Oxide 105 20. Temperature-Entropy Diagram for Ethylene O xide.... 106 21. Fugacity Coefficient for Ethylene Oxide....................... 109 22. Compressibility Factor for Ethylene Oxide.................. 110 LIST OF TABLES Table Page 1. Thermodynamic Properties of Ethylene Oxide for the Ideal Gas State at One Atmosphere......................85 2. Properties of Saturated Ethylene Oxide............ 97 3. Properties of Saturated and Superheated Ethylene Oxide.......................................................................................... 98 4. Original P-V-T Data......................................................................129 i VOLUMETRIC BEHAVIOR AND THERMODYNAMIC PROPERTIES OP ETHYLENE OXIDE C. J, Walters and J. M. Smith Purdue University Lafayette, Indiana ABSTRACT The volume of ethylene oxide in the vapor and saturated liquid regions has been measured in a com pressibility bomb from 14.7 to 600 lb s./sq . in. abs. over a temperature range of 70 to 310°F. Additional data were taken in the c ritic a l region (tc e 584.40F, pe = 1043 lb s./sq . in. abs., ve = 0.051 eu. f t ./ l b .). Polymerization at temperatures above 220°F was rapid enough to require measurements as a function of time. At 310°F the volume decrease was 0.4% per hour. Testing of the apparatus with nitrogen and n-butane gave results within 0.2% of the accepted volumes for these sub­ stances. The inaccuracy of the ethylene oxide volumetric date is believed to be less than 0.3% below 310°F and less than 1% above 310°F. The available spectroscopic information was combined With the volume data to determine enthalpy and entropy values in the two-phase and gaseous regions. The results are shown in graphical and tabular form.