VAPOR-LIQUID EQUILIBRIA OF TERNARY NON-IDEAL SOLUTIONS. SYSTEM: ACETONE - CHLOROFORM - METHANOL

185 Pages·08.132 MB·English

by  SESONSKE, ALEXANDER

69-7921
SESONSKE, Alexander, 1921-
V AP OR - LIQUID EQUILIBRIA OF TERNARY NON­
IDEAL SOLUTIONS. SYSTEM: ACETONE-
CHLOROFORM-METHANOL.
University of Delaware, Ph.D., 1950
Engineering, chemical
University Microfilms, Inc., Ann Arbor, Michigan
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I
VAPOR-LIQUID EQUILIBRIA
OF
TERNARY NON-IDEAL SOLUTIONS
Sys tem: A cetone-C hlorof orm-Me th ano l
by
A lexander Sesonske
A d is s e rta tio n subm itted to the F acu lty of the
U n iv ersity of Delaware in p a rtia l fu lfillm e n t of the
requirem ents fo r th e degree of Doctor of Philosophy.
Septem ber, 1950
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(1) Approved CPrtLA-~+sf-o / . u--
P ro fesso r £n Charge*'of T hesis
(2) Approved
Head of Departmeri
(3) Approved ^
Dean of School 6f EEnnggiinneering
(4) Approved
Dean of School of Graduate S tudies
■ . ^1 *7 O I /
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ACKNOWLEDGEMENT
The author is p a rtic u la rly indebted to Dr. Robert L.
Pigford fo r h is advice and many h elp fu l suggestions given
in the course of th is in v estig atio n .
The aid of M essrs. J . C, Reynolds and W. H. Severns,
J r . , in c e rta in phases of the experim ental work is g ra te ­
fu lly acknowledged.
The author would also lik e to express h is ap p reciatio n
to Mr. H arrison C. C arlson and Dr. Kurt Wohl fo r a ssista n ce
in th e c o rre la tio n work. The advice of Mr, John M itch ell,
J r . , was extrem ely h e lp fu l in the development of the chem ical
methods of a n aly sis.
This in v e stig a tio n was made p o ssib le by the fin a n c ia l
assistan ce of the Engineering Departm ent, E. I. duPont de
Nemours and Company.
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TABLE OF CONTENTS
Page No,
SUMMARY........................................................... .................................................. 1
INTRODUCTION. . . . ................................................................................... 3
EXPERIMENTAL METHODS. ......................................................................... 7
A. V apor-Liquid E quilibrium Work..................................... 7
B. A n a ly tica l Work. .....................................................................14
C. P rep aratio n of M aterials • « • • . • • . . . 20
D. Planning of E quilibrium Experim ents...........................22
E. Heat of S o lu tio n M easurements. . . . . . . . 23
EXPERIMENTAL RESULTS. ...............................................................................30
THEORETICAL BACKGROUND.................................... 46
A. L iquid S tru c tu re .................................... 46
* .
B. C o rrelatio n M ethods. . . . . . . . . . . . . o2.
CORRELATION OF RESULTS. ..........................................................................80 -
GENERAL DISCUSSION.............................................. 110
CONCLUSIONS AND RECOMMENDATIONS....................................................1 2 3
NOMENCLATURE........................................................... . 124
LITERATURE CITED.................................................................................................127
VITA...................................................................................................................... . 131
APPENDIX A. • . • .................................... 132
E ffe c t of A ssociation in th e L iquid Phase on
Duhem- Mar gules E quation
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TABLE OF CONTENTS f Continued*)
Page No.
APPENDIX B ....................................................................................................... 13 5
Least Squares Method fo r the D eterm ination of
M argules Binary Constants
APPENDIX C ........................................................................................................ 137
A d ditional Tables and Figures
APPENDIX D .................................................................. 14-9
Sample C alcu latio n s
LIST OF TABLES
TABLE 1. Isotherm al V apor-Liquid E quilibrium Data *
System: A cetone-C hloroform ............................. .3 2
TABLE 2. Isotherm al V apor-Liquid E quilibrium Data
System: Acetone-M ethanol . . . . . . . . 34-
TABLE 3* Isotherm al V apor-Liquid E quilibrium Data
System: Chloroform -M ethanol. . . . . . . 36
TABLE 4-. Isotherm al V apor-Liquid E quilibrium Data
System: Acetone-Chloroform -M ethanol. . . 38
TABLE 5. Heat of Mixing Experim ents at 50°C.
System: Acetone-Chloroform -M ethanol. . . 39
TABLE 6. V isco sity Measurements
System: Acetone-Chloroform -M ethanol. . . 138
TABLE 7. R efractiv e Index D eviations
System: Acetone-Chloroform . • -'^ v . . . 141
TABLE 8. R efractiv e Index D eviations
System: H ethanol-Chloroform . . . . . . 142
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TABLE OF CONTENTS (Continued)
LIST OF FIGURES
%
Page Ho.
Figure 1.. E quilibrium S t i l l . ................. 8
F igure 2. E quilibrium S t i l l P h o to g rap h ......... 9
Figure 3. E quilibrium A pparatus. • • • • • • . • . 10
Figure 4. Pycnometer. .......... 16
F igure 5. P u rific a tio n Column Photograph. . . . . 21
F igure 6. Ternary Network Showing L ocation of
Acetone-Chloroform -M ethanol Experim ents 24
Figure 7. C alorim eter Photograph..................... 25
Figure 8. C alorim eter.................................... . . . • • • • 26
Figure 9* C alorim eter Measuring C irc u it......... 27
Figure 10. x-y Diagram fo r Acetone-Chloroform System 41
Figure 11. x-y Diagram fo r Acetone-M ethanol System 42
Figure 12. x-y Diagram fo r Chlorof orm-Methanol
System. .................................... 43
Figure 13* x-y Diagram fo r A cetone-Chloroform -
M ethanol S y stem ............................................... 44
Figure 14. Vapor Pressure-C om position P ro file
Diagram5 Acetone-Chloroform -M ethanol
S y s te m ............................................................................. 45
F igure 15. A c tiv ity C o e ffic ie n ts fo r A cetone-
Chloroform System . • • • • • • . . . . 81
Figure 16. A c tiv ity C o efficien ts fo r Acetone-
Methanol System • • . • • • • • • • • . 82
Figure 17. A c tiv ity C o efficien ts fo r Chloroform -
Methanol System ................................... 83
Figure 18. "J" vs. x,A cetone-C hloroform System. . . 85
Figure 19. "J" vs. x,A cetone-M ethanol System. . . . 85 ,
Figure 20. uJ n vs. x, Chloroform-M ethanol System. • 86
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TABLE OF CONTENTS (Continued)
• - LIST OF FIGURES :
(Continued) pgge N
Figure 21. Comparison of Acetone A ctiv ity
C oefficients w ith Ternary T hree-S uffix
Margules E quation.................................................... 91
Figure 22. Comparison of Chloroform A c tiv ity
C o efficien ts w ith Ternary T hree-S uffix
Margules E quation. • • • « . • • • . . 92
F igure 23. Comparison of M ethanol A ctiv ity
C o efficien ts w ith Ternary T hree-S uffix
Margules Equation. ............................................... 93
Figure 24. "JM v s. x fo r Acetone. Comparison w ith
T hree-S uffix M argules E quation • • • • 95
F igure 25. ”J n vs. x fo r Chloroform . Comparison
w ith T hree-S uffix M argules E quation. . 95a
Figure 26. "J*1 v s. x fo r M ethanol. Comparison w ith
T hree-S uffix M argules Equation. . . . 9%
Figure 27. "J" vs. x fo r Acetone. Comparison of
T hree- and F our-S uffix M argules Equation 96
F igure 28. "J" vs. x fo r Chloroform . Comparison of
Three- and F ou r-S u ffix M argules E quation 96a
Figure 29. "J“ vs, x fo r M ethanol. Comparison of
Three- and F our-S uffix M argules Equation 97
Figure 30. R edlich and K ister P lo t fo r Acetone-
Chloroform S y s te m ..................................................... 98
Figure 31. R edlich and K iste r P lo t fo r Acetone-
Methanol System. ............................................... 99
Figure 32. R edlich and K ister P lo t fo r Chloroform-
M ethanol System. . . . . . .......................... . 100
Figure 33. Comparison of R edlich and K iste r and
M argules Ternary E quations, Yj/Yg • • • 102
/
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TABLE OF CONTENTS (Continued)
LIST OF FIGURES (Continued)
Page No.
Figure 34. Comparison of R edlich and K ister and
M argules Ternary E quations, Y^/Y^ . . 103
Figure 35. Comparison of R edlich and K iste r and
Margules Ternary E quations, Y2/Y^ • . 104
Figure 36. Excess Thermodynamic Functions fo r
A cetone-Chloroform System . . . . . . 107
Figure 37. Excess Thermodynamic Functions fo r
Acetone-M ethanol S y ste m .............................. 108
Figure 38. Excess Thermodynamic Functions fo r
Chloroform-M ethanol System. ...................... 109
Figure 39. Some Previous Data fo r Acetone-M ethanol
System, R edlich and K iste r P lo t . . . I l l
Figure 40. Chloroform -M ethanol Data of K iriev and
S itnikov at 49.3°C ............................................... 112
Figure 41. S p ecific Heat - C oncentration Curves
at 50°C......................................................................... 143
Figure 42. E nthalpy of Mixing in Acetone-Chloroform -
M ethanol Ternary System at 50°C. . . 144
Figure 43. D eviation from Id ea l D ensity a t 2 5°C. 145
Figure 44. R efractiv e Index D eviations from Id ea l
M ixture Law fo r Acetone-Chloroform
System. .................................................................... 146
Figure 45. R efractiv e Index D eviations from Id eal
M ixture Law fo r A.cetone-Methanol System 147
Figure 46. V isco sity Measurements a t 25°C.................... 148
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SUMMRY
V apor-liquid equilibrium measurements were carried out
on th e acetone-chloroform -m ethanol system a t 50°C, using an
improved v a p o r-re circu la tio n -ty p e s t i l l . The com plete range
of concentrations was in v e stig a te d , including th e c o n stitu e n t
binary system s. Chemical methods were used fo r a n aly sis, sup­
plemented by d en sity and re fra c tiv e index measurements.
R esults are presented in the form of a c tiv ity c o e ffic ie n ts,
Y, as a fu n ctio n of various co n cen tratio n s. Binary and tern ary
constants fo r the th re c -su ffix M argules eq u atio n sw ere d eter-
mined by p lo ts of log y/( 1 - x) as a fu n ctio n of the mole
fra c tio n , x. The th re e -s u ffix M argules equations have been
found to rep resen t both the b in ary and the te rn a ry data ade­
q u ately . Using a new form of the th re e -su ffix M argules equa­
tio n , i t was p o ssib le to p red ict tern a ry conditions approxim ately
from binary data alone. The agreement w ith tern ary data was
improved, however, by using a co n stan t in the equation^ which
is c h a ra c te ris tic of the te rn a ry so lu tio n s and cannot be
evaluated from bin ary data alone.
The usefu ln ess of other q u a n tita tiv e re la tio n s was con­
sid ered . Although the data were s a tis fa c to r ily represented
by th e R edlich and K ister re la tio n s , these equations were
considered le ss u se fu l than th e th re e -su ffix M argules expres­
sions as w ritte n by 7fohl, As y e t, equations based on s t a ti s ­
tic a l mechanics have not been developed which can adequately
d escrib e the larg e d ev iatio ns present in th is system . F u rth er­
more, s t a ti s t i c a l expressions adequate fo r the d e sc rip tio n of
sim pler system s are as yet too com plicated fo r g en eral engin­
eerin g use.
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