Volumetric Behavior and Thermodynamics Properties of Ethylene Oxide

178 Pages·7.327 MB·English

by  Walters, Charles Joseph

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
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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.