1872
INDUSTRIAL AND ENGINEERING CHEMISTRY LITERATURE CITED
(1) B e r g s t r o m , as q u o t e d by H a u s b r a n d , E., ”Principles and P r a c tice of I n d u s t r i a l Distillation,” 4th ed., p. 238, New I-ork, C h a p m a n a n d Hall, 1925. (2) Blacher, a s quoted by H a u s b r a r i d , E., I h i d . , p. 238-42. (3) Cornell, L. W., aiid M o n t a n n a , R. E., IND.E N G . CHEii., 25, 1331 (1933). (4) F e n t o n , T. M., a n d G a r n e r , W. E., J . Chem. SOC.,1930, 694. (5) Garwin, L., a n d H u t c h i s o n , K . E., IND.ENS. C H E M . ,42, 727 (1950). (6) Gilmont. R., IND. ENG.CHEM.,ANAL.E D . , 18, 633 (1946). ( 7 ) Gilmont, R . , P h . D . thesis, Polytechnic I n s t i t u t e of Brooklyn, J u n e 1947. (8) G i l m o n t , R., a n d O t h m e r , D. F., IND.EBG. CHEM.,3 6 , 1061 (1944). (9) Gilmont, R., W e i n m a n , E. A, K r a m e r , F., Miller, E., H a s h m a l l , F., a n d O t h m e r , D . F., I b i d . . 42, 120 (1950). (10) H e r m a n , R. C., aiid H o f s t a d t e r , R., J . Chem. Phys., 6 , 534 (1938). (11) .Johnson, E. IT.,arid N a s h , L. K . , J . Am. Chem. SOC.,72, 547 (1950). (12) K a h l b a u m and Konowalow, “ I n t e r n a t i o n a l Critical T a b l e s . ” Vol. 111, p , 306, S e w Tork, McGraw-Hill Book Co., 1928.
Vol. 44, No. 8
(13) R a r r , A. E.. Scheibel. E. G.. Rowes. W. 31,. a n d O t h m e r . D. 12.. IND.E m . CHEW,43, 961 (1951). (14) K e e n a n , J, M.. a n d Keyes, F. G.. “ T h e r m o d y n a m i c Propertlcs of S t e a m , ” New Tork, J o h n Wiley 8: Sons, 1936. (15) MacDougall, F. H., J . Am. Chem. Soc., 58, 2585 (1936). (16) O t h m e r , D . F., Anal. Cheiia., 20, 763 (1948). (17) O t h m e r , D . F., IND. ENG.C H E l x . , 20, 743 (1928). (18) Ibid., 35, 614 (1943). E X G . CHEM.,A N A L .ED.,4, 232 (1932). (19) O t h m e r , D. F., IND. (20) Obhmer, D . F., a n d Gilmont, R., 1x0. ENG.CHEM.,36, 858 f 1944). (21) Ibid., 40, 2118 (1948). (22) O t h m e r , D. F., a n d M o i i e y , F. R.. Ihid., 38, 751 (1946). (23) Pascal, P., D u p u y . E , a n d G a i n i e r , Bull. SOC. chim. France 29, 9 (1921). (24) P o v a r n i n , G., a n d Markoi-. V., J . Russ. Phys. Chein. Sac., 55, 381 (1924). (25) Rayleigh, Phil. MuO., 4, Yo. 6, 521 (1902). (26) R i t t e r , H . L., a n d Simons, J. H., J . Am. C h e m Soc., 6 7 , 757 (1945). (27) Sorel, E., C o m p t . r e n d . , 122, 046 (1896). (28) Y o r k , R., Jr., a n d Holmes, R. C . , IND.ENS. CHEar., 34, 346 (1942). R X E I V E Dfor review March 1, 19.51,
ACCEPTED February 2 1 , 19.52.
(COMPOSITIOS OF VAPORS FROM BOILI-NG BINARY SOLL-TIOll;S)
Binary and Ternary Systems of Acetone, Methyl Ethyl Ketone, and Water DOSALD F. QTHMER, MANU M.CHUDGAR, AND SHERSI.4N L. LEVY Polytechnic I n s t i t u t e of Brooklyn, Brooklyn,
I
Tu’ T H E commercial synthesis of methyl ethyl ketone, acetone
is produced as a concomitant product; water is also present. Vapor-liquid equilibrium data are necessary for the separation of this mixture by fractional distillation as a step toward manufacturing high purity ketones. Furthermore such data were desired because of the interesting thermodynamic properties of this system. APPARATUS AND OPERATIhG PROCEDURE
An equilibrium still of the recirculating type which has been developed during the past 20 years for studying phase relations was fabricated from Type 316 stainless steel to permit studies t o be made a t pressures up t o 500 pounds per square inch absolute. The design and operation of this equipment have been described in a previous paper (17‘). The operating procedure was similar to that for the standard glass equilibrium still ( l a ) and has been discussed (f7). Particular reference has been made (6) to the supplying of external heat t o eliminate radiation losses; this is particularly necessary under the high temperatures encountered here. Pressure was measured with a combination of a dead-weight tester in series with a differential mercury manometer, and LYas controlled by balancing the heat input and output ( 1 7 ) . Temperatures a t the v a r i o u s points of the system were measured with 20 B. &. S. gage ironconstantan thermocouoles which were accurate within h 0 . 3 ‘ C. Previous investigators ( 17‘) have used sample bombs to collect for analysis samples of the two phases in equilibrium. For the systems methyl ethyl ketone-water and acetone-methyl ethyl ketone-water, there is a range of compositions where either the or both is miscible at the equi]ibliquid or the vapor rium temperature but immiscible a t room temperature. I n this range, an error would be introduced by using sample bombs because of the separation of the mixture into two phases upon cooling and subsequent disproportionate adherence of droplets on the n.alls while emptying the bombs. To circumvent this difficulty, small coolers nere used to allow the sample to be taken directlv in
N. 1..
the glass vessel used for aiialysis. They were made of xat,erjacketed copper tubing, having an inside diameter of 4 mm., and Tyere connected directly to the out,lets for sampling boiling liquid and condensate. These were cooled with ice water. About 25 1111. of cold samples were collected for analysis in test tubes immersed in a mixture of ice and water. This met,hod of sampling was checked in the miscible region of the methyl et,hyl ketonewater system a t 100 pounds per square inch absolute by redetermining the vapor liquid equilibrium curve obtained with the use of sample bombs. An excellent check was obtained. PERFORMANCE OF THE EQUILIBRIUM STILL
Tests were run for possrblc entrainment a t each of the fivc pressures studied. The still was charged with a highly colored solution of methyl orange of a known concentration. The vapor condensate sample was collected as in an actual run and examined in a spectrophotometer. From a calibration curve of standard samples, the concentration of methyl orange in the distillate n-as determined. It was found t h a t the entrainmcnt was only 0.014% of the condensate, which is insignificant. The experimental data for the system methyl ethyl ketonewater a t atmospheric pressure n ere compared with those of the literature (13, 2 3 ) in Figure 10. The agreement is within the limits of analytical accuracy. MATERIALS U S E D
Commercial grade synthetic acetone was dried with anhydrous calcium chloride t o remove water or lower alcohols and distilled in a batch-rectifying column. .4 middle portion comprising 80% of the total mas collected a t a constant boiling temperature. hiethyl ketone was purified. The distilled as required, and the refractive index and density of each batch were checked before use. Distilled x-ater from the laboratory &’asused without further purification. The atmoepheric boiling points, refractive indices, and densities for t h r ketone used in this wOr]i arc givPn acetoneand Table I.
INDUSTRIAL AND ENGINEERING CHEMISTRY
August 1952
1873
nometers. The compositions were calculated using the published relations between composiBoiling Pt., C . a t tion and density (25). These equations are ac760 M m . Density, d i n Refractive Index, n"D" curate within their respective ranges to 0.05 Obsvd. Lit. Obsvd. Lit. Obsvd. Lit. weight % of methyl ethyl ketone. The density Acetone 56,18 5 6 . 5 0 (26) 0 , 7 8 4 8 0.7849 (6) 1.35636 1.3566 (86) 5 6 , l O ($7) measurements were precise to 0.0003 gram per ml., Metliylethylketone 79 62 7 9 . 5 7 (9) 0 . 7 9 9 8 0.7995 (25) 1.37653 1.37616 (6) which corresponds to a precision of f 0 . 2 weight yo. A known auantitv of water was added to the ,9400 samples in the range of to 27 weight % of methyl ethyl ketone to bring the composition within the range of the abovementioned equations. -$ 9000 Samples in the immisciblc region Bere received directly in burets with their ends sealed off a t the 50-ml. mark. The burets were stoppered and kept in a thermostatically controlled water 2 Y bath a t 20" C. From a knowledge of the solubilities and densities 0 8600 of each of the two phases, the over-all composition was calculated by reading off the volumes of the two settled phases in the burets. The solubility of methyl ethyl ketone in the water-rich phase was l200 26.5 weight % a t 20" C. and 87.5 wcight % in the methyl ethyl ketone-rich phase. These values are in excellent agreement with the previously published data (4 23). The densities of the two coexistent liquid phases at 20" C. were determined as ,7100 IS600 136000 138400 136800 131200 137600 138000 0.8360 for the methyl ethyl ketone-rich phase and 0.9630 for the REFRACTIVE INDEX SOLUBIL,Ty D A ~ A water-rich phase. ACETOKE-METHYL ETHYL KETONE-WATERThis system was Figure 1. Analytical Chart for System Acetone-Methyl analyzed by the determination of the refractive indices and the Ethyl Ketone-Water densities of the samples a t 25" C. Synthetic mixtures a t 10 weight yo intervals &-ere carefully weighed on an analytical ANALYTICAL RIETHODS balance. Their refractive indices and densities are given in Refractive index and density were the two physical properties Table 111. These data were plotted as a composition grid with used in the analysis of the systems studied. The temperatures refractive index and density as coordinates as shown in Figure 1. for all analytical determinations were controlled t o h0.05 C. Liquid-liquid equilibrium and tie line data for this system were ACETONE-METHYL ETHYL KETONE.This system was analyzed determined at 25' C. and are given in Tables IV and V and by the determination of refractive index a t 25 ' C. using a Bausch Figure 2. The tie-line data were correlated by the method of and Lomb dipping refractometer. The precision of the measureOthmer and Tobias (19) with good results. The plait point was ments was within f0.00004,which corresponds to an analytical precision of 5 0 . 2 mole %. Refractive index-composition data for binary mixtures of acetone and methyl ethyl ketone are given in Table 11.
TABLE I. PHYSICAL PROPERTIES OF MATERIALS USED O
i7
-
c
.
I
TABLE 11. REFRACTIVE INDICES OF ACETOSE-METHYL ETHYL KETOXE Acetone, Wt. 3.78 7.45 13.58 19,24 24.38 32.20 36.66 37.55 43.94 48.84 56.06 66.43 67,25 74.57 81.52 85.74 88.56
95.81
h/IIXTURES AT
25"
c.
Refractive Index, 1 ,37579 1 ,37509 1.37383 1 .37269 1.37158 1.37003 1 ,36907 1 ,36887 1 ,36759 1.36658 1 ,36497 1.36283 1.36272 1.36127 1,35989 1.36890 1.35843 1.38693
ng
ACETONE-WATER. This system was analyzed by the determination of density a t 25" C. using capillary-arm pycnometers (8). The precision of the density measurements was 10.0003 gram per ml., which corresponds to an analytical precision of f 0 . 2 weight %. Squibb's data on the densities of acetone-water mixtures ( 2 4 ) were checked and used in this investigation. 3fETHYL ETHYL KETONE--WbTER. In the ranges Of 0 to 17 weight % ' and 88 to 100 weight %, this system was analyzed by the determination of density a t 20' C. using capillary-arm pyc-
M EK
WT.% WATER
-
Figure 2. Mutual Solubility Curve for Acetone-Methyl Ethyl Ketone-Water i n Units a t 25" C.
WATER
System Weight
estimated by the method of Treybal et al. (28). The refractive index and density of each experimental point on the boundary curve in Figure 2 were also determined for use in constructing Figure I, which is a plot of liquid composition versus refractive index (ng)and density (d?f'). Figure 1 inset shows that beyond 50 weight % water the grids tend to pinch out, resulting in poor analytical accuracy. A known amount of acetone was added to those samples containing more than 50 weight % water in order to bring them into the region of satisfactory analytical accuracy. A plot of refractive index against weight yo methyl ethyl ketone with weight % water as the third parameter was constructed. A plot of density against weight yo water with weight '%methyl ethyl ketone as a third parameter was also constructed. By referring to these two plots, a grid work was ruled on a great enlargement of Figure 1 at intervals of 2 weight % for use in analysis. The accuracy of the ternary analysis was checked with synthetic mixtures and was found to be better than 1 weight yo for each component.
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
1874
TABLE 111. DENSITIES A S D REFRACTIVE I X D I C E S O F A4CETONEMETHYL ETHYL KETONE-WATER SOLCTIOXS AT 25' C. hlEK", Rt. %
Acetone,
Wt. %
..
100.0
90.0 80.0 80.0 70.0 69.9 70.0 60.0 60.0 60.0 60.0 50.0 49.9 50.0 50.0 50.0 40.0 40.1 40.0 40.0 40.0 29.9 29.9 30.0 30.0 30.0 30.0 30.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 11.0 10.1 10.0 10.0
10:o
20: 0 10.1 30:O 20.0 10.0 40:O 30.1 20.0 10.0 50:O 39.9 30.0 10.0
..
60.1 50.1 40.0 30.0 20.0 10.1 70:O 60.0 50.0 40.0 30.0 20.0 79:l 30 0 19.9 10.0
10.0
..
90: 0 20.0 .. 10.0 100 0 Methyl ethyl ketone 1 .
..
a
Water, Wt. % 10: 0 10.0 20.0 10.0 20.0 30.0 10.0 20.0 30.0 40.0 10.0 20.0 30.0 40.0 50.0 10.0 20.0 30.0 50.0 60.0 10.0 20.0 30.0 40.0 50.0 ;9,9 70.0 10.0
20.0 30.0 40.0 50.0 60.0 80.0 9.9 59.9 70.1 80.0 90.0 10.0 80.0 90.0
..
Density, di5 0.7848 0.8146 0.8161 0.8432 0.8169 0.8435 0.8695 0.8188 0.8440 0.8696 0 8942 0,8200 0.8454 0.8695 0.8939 0.9159 0.8209 0.8460 0.8693 0.9153 0.9361 0.8221 0.8468 0.8705 0.8938 0.9153 0.9355 0.9537 0.8234 0,8477 0.8697 0.8930 0.9150 0.9359 0.9700 0.8244 0,9347 0,9540 0.9700 0.9831 0.8260 0.9707 0.9840 0.7998
Refractive Index, n%
1.35636 1.36020 1.36218 1.36270 1.36421 1.36465 1.36348 1.36632 1.36627 1.36515 1,36283 1.36819 1.36813 1,36681 1,36444 1.36078 1 ,37020 1.37000 1.36842 1.36236 1 ,36745 1.37210 1.37179 1.37017 1.36755 1,36390 1.35902 1.35272 1.37399
1.33983 1 ,37779 1.36026 1,34169 1.37653
Vol. 44, No. 8
thei-modynamic consistency a t all the pressures investigated by the method of Redlich and Kister (98) with satisfactory results. A comparison of the authors' data with previous data a t 14.7, 50, 100, and 200 pounds per square inch absolute shows deviations larger than can be accounted for by analytical error. This is probably caused by some rectification of vapors in the previous work (16). The wide difference in volatilities between these two liquids accentuates the difficulties in preventing change in composition of the vapors after a steady state a t the liquid interface has been reached. METHYLETHYL KETONE-WATER.The experimental .vaporliquid equilibrium data for t,his system are presented at 14.7, 50, 100, 250, and 500 pounds per square inch absolute in Table VI11 and Figures 8 and 9. The data a t 14.7 pounds per square inch absolute agree within the analytical accuracy with those in t,he literature (13, 23), as sho~vnin Figure 10. The system methyl ethyl ketone-water is incompletely miscible over a part of the range of liquid compositions a t the boiling temperatures corresponding to 14.7, 50, and 100 pound8 per square inch absolute. Experimental data were taken in the heterogeneous region; the terminal liquid compositions for the hvophase regien were determined from published mutual solubility data for methyl ethyl ketone and water a t high temperatures (93). The solubility limit curve on Figure 8 was then drawn with the horizontal line of each vapor composition curve representing the corresponding parameter of temperature. A smooth, flat Ushaped curve results with the plait point at the temperature of complete solubility. There has already been discussed ( I S ) the interesting relation of the mutual solubility to the left of the 45' line, the horizontal line which does not cross the 45' line, and 100
90
~
80 VAPOR CORlPOSITION DATA
ACETONE-METHYL ETHYL KETONE. The experimental vaporliquid equilibrium data for this sytem a t pressures of 14.7, 50, 100, 250, and 500 pounds per square inch absolute are presented in Table VI and Figures 3 and 4. This system was found to be ideal within the experimental error a t all pressures up to 500 pounds per square inch absolute. ACETONE-WATER.The experimental vapor-liquid equilibrium data are presented for this system at 14.7, 50, 100, 200, 250, and 500 pounds per square inch absolute in Table VI1 and Figures 5 and 6. The data a t 14.7 pounds per square inch absolute are compared with those of other investigators ( g , 13, 16, SO) in Figure 7. There is good agreement between the authors' data and those of York and Holmes (SO). The authors' data have been tested for
a 0 70 a
a >
60
z zww 0
k
Q
14.? R S I h
y 40 a
8
j30
0
z
20 IO
0
TABLE Iv. LIQUID-LIQVID SOLUBILITIES O F TERKARY SYSTEM ACETONE-METHYL ETHYL KETONE-WATER .4T 25" c. ~
wt.
3:2
7.1 8.0 10.1 12.0 12.4 12.5 12.5 12.1 11.4 9.9 8.1 4.5
..
0
MEKO, ~ Wt. % 87.4 83.4 76.7 75.0 70.1 63.6 58.5 56.5 49.9 46.4 39.6 34.5 30.6 26.5 24.8 37.9 ethyl ketone. ~
%
11.1 Methyl
~t ~ ~ Density, t ~ ~ Refractive ~ , Index, , Wt. % dZ5 n"D" 12.6 0.8312 1 ,37742 13.4 0.8333 1.37702 16.2 0,8404 1.37620 17.0 0.8425 1.37600 19.8 0.8490 1.37531 24.4 0.8596 1.37410 29.1 0.8690 1 37292 31.0 0.8735 1.37266 37.6 0.8870 1.37100 41.5 0.8950 1.36982 49.0 0.9107 1.36713 1 ,36455 55.6 0.9233 61.3 0.9349 1.36190 69.0 0.9515 1.35800 75.2 0.9618 1.35461 51.0 Estimated plait point (88)
0
IO
20 30 40 50 MOL. % ACETONE
60
70
88
90
100
IN L I Q U I D
Figure 3. Vapor-Liquid Equilibria for System AcetoneMethyl Ethyl Ketone at Various Pressures
TABLE V. LIQCID-LIQCID SOLUBILITIES o r TERXARY SYSTEM ACETOXE-~IETHYL ETHYL KETOKE-\y7-4TER AT 25' c. (Tie-line comnositions) Solvent Layer Water Layer Acetone, MEKa, Water, Acetone, L'IEKQ wt. % Wt. % nt. % wt. % wt. % 2.0 85.0 25.2 13.0 1.7 12.8 1.2 1.4 85.8 25.1 13.7 3.7 25.8 3.3 82.6 15.2 6.1 78.7 26.6 4.7 1'7.3 8.2 74.5 6.0 28.1 10.7 21.0 7.8 68.3 30.5 Methyl ethyl ketone.
Water, wt. % 73.1 73.7 70.9 68.7 65.9 61.7
INDUSTRIAL AND ENGINEERING CHEMISTRY
August 1952
1875
TABLE VII. VAPOR COMPOSITION DATAFOR ACETONE-WATER AT VARIOUS PRESSURES (Experimental data) Mole % Acetone T ~ ~ ~ . , Liquid Vapor O C. 14.7 Lb./Sq. In. Abs. 85.0 79.3 66.1 60.9 53.8 50.6 44.4 30.0 26 4 12.0 4 1 2.3 1.0
91.8 90.0 86.0 84.7 84.0 83.7 83.2 80.9 80.2 75.6 58.5 46.2 33.5
50 Lb./Sq. 95.0 89.0 77.8 63.3 54.5 38.8 27.3 19.4 10.7 5.5 2.4 1.7
57.1 57.4 58.5 58.9 59.5 59.7 60.0 61.1 61.8 66.2 76.5 83.0
87.8
In. Abs.
95.1 90.3 83.0 76.8 74.7 71.8 69.5 67.0 60.8 51.8 39.8 34.9
98.2 98.4 98.6 98.8 99.0 99.9 101.3 102.8 106.0 112.0 120.0 122.5
100 Lb./Sa. . - In. Abs.
M O L . % ACETONE
92.5 84.2 75.4 55.9 44.4 34.1 22.9 14.4
Figure 4. Temperature-Composition Diagram for Syst e m A c e t o n e M e t h y l Ethyl Ketone at Various Pressures
7.8 3.6 1.4
Mole % Acetone T ~ ~ ~ . , Liquid Vapor C. 200 Lb./Sq. In. Abs. 86.3 75.2 64.1 59.0 48.9 38.2 37.2 24.4 17.5 13.6 10.8 6.2 2.0
85.0 75.8 69.9 66.9 63.2 59.5 59.3 56.1 52.6 49.5 47.7 39.7 28.9
250 Lb./Sq. 94.7 90.3 80.9 72.2 60.8 49.4 39.1 27.4 17.6 8.7 4.4 1.6
93.1 88.4 78.4 73.1 66.6 61.2 58.0 55.1 50.5 42.3 33.5 20.6
157.2 157.6 157.8 157.9 158.4 159.1 159.9 160.6 162.5 163.9 164.4 168.9 177.2
In. Abs. 170.4 169.7 168.6 168.4 168.8 170.3 170.6 172.2 174.0 178.6 185.1 193.4
500 Lb./Sa. . - In. Abs. 92.1 85.3 75.0 66.3 58.5 52.7 46.5 40.8 31.8 14.0
91.2 84.5 78.1 70.0 66.5 65.0 61.8 58.2 50.7 39.5 24.9
TABLE VI. VAPORCOMPOS~TION DATAFOR ACETONE-METHYL ETHYL KETONEAT VARIOUS PRESSURES (Experimental data) Mole % Acetone T ~ ~ C. Liquid Vapor O C. Liquid Vapor 250 Lb./Sq. In. Abs. 14.7 Lb./Sq. In. Abs.
Mole % Acetone Temp.,
'
95.0 89.1 81.7 73.8 72.7 68.6 67.6 62.0 54.4 51.0 45.0 37.3 24.5 15.3 8.1 2.6
97.2 94.2 90.3 85.7 84.0 81.7 81.7 77.5 71.5 65.7 64.0 57.1 43.7 29.0 15.3 5.0
56.9 57.9 58.9 60.0 60.3 61.0 61.1 62.1 64.1 65.1 67.0 69.0 71.4 74.2 76.6 78.5
50 Lb./Sq. In. Aba.
4
90.9 81.0 67.3 58.8 57.4 45.3 42.0 38.8 29.6 20.8 16.9 13.3 7.6 1.9
94.6 89.2 80.5 74.4 73.5 62.5 59.3 56.4 46.3 35.0 30.2 24.7 13.0 3.7
100 Lb./Sq. I n . 92.0 95.4 82.7 89.5 81.5 71.3 80.2 68.7 58.9 73.0 51.5 66.8 44.0 60.3 35.4 51.2 44.3 29.6 19.4 31.5 14.7 25.7 10.3 19.0 7.6 12.4 3.5 1.9
Abs. 127.5 129.2 131.7 132.8 134.7 137.3 139.3 141.7 143.1 147.1 148.9 150.6 152.0 153.3
-
92.9 84.3 72.6 69.1 61.8 54.3 44.6 36.4 33.1 29.2 19.8 13.2 1.9
95.1 87.7 78.8 75.7 70.4 63.0 54.5 45.9 41.8 38.5 27.5 19.4 2.9
~ . ,
175.1 175.0 178.9 180.0 W3.2 186.1 188.9 191.5 193.1 194.0 197.5 199.5 203.5
500 Lb./Sq. In. Abs. 97.1 214.5 93.3 215.6 88.1 218.0 83.0 220.1 76.1 222.6 70.1 75.7 223.2 65.0 69.1 225.0 57.0 62.2 227.4 45.0 233.5 39.7 38.3 235.6 33.5 25.2 29.5 238.9 19.0 22.3 241.4 15.1 18.6 243.0 6.2 8.6 247.8 248.4 5.0 7.8 95.5 91.3 85.5 79.5 71.3
MOL.% ACETONE
Figure 5.
IN LIQUID
Vapor-Liquid Equilibria for System AcetoneWater a t Various Pressures
the fact that the crossing of the 45" line-i.e., the azeotropic point-is not a t the steam distillation temperature or composition and the concomitant disappearance of the horizontal section of the curve. The azeotropio temperature, and not the steam distillation temperature, therefore, represents the minimum point on the phase diagram of Figure 9. This indicates an interesting minimum point below the usual line of the steam distillation range.
INDUSTRIAL AND ENGINEERING CHEMISTRY
1876
Vol. 44, No. 8
-
TABLE 'I-111. VAPORCO\.IPOSITION DATLFOR ?~LETHYI, KETOSC--\TATCR AT 'I'ARIOKs PRE55VRES
ETHYL
(Experimental data)
14.7 Lb./Sq. I n . 96.3 92.9 89.8 81.6 76.7 73.6 73.8 70.7 70.7 69.8 69.6 68.3 67.6 67.6 67.1 66.1 65.7 65.5 65.4 64.5 64.5 61.8 51.5 39.4 1.1 20.7 0.5 18.4 0.4 8,s 0.2
99.3 97.7 95.8 91.2 88.0 84.8 83.6 80.3 80.0 78.1 77.5 74.4 72.9 72.1 70.9 66.7 66.5 65 5 63.5 55.0 19.0 3.6 1.7
MOL.
98 S 96.0 90.0 83.5 82.6 72 2 60.0 63.i 46 5 38.3 33.1 22 0 12.0 4 6 3.0
78.3 i7.0 76.4 i5.3 i4.5 73.8 74.1
73.9 73.9 i3.5
74.0 i3.z
73.g 73.8 73.C) 73.5 73.6 73.3 73 8
1.1
0.6 0.1
2.50 L b
i4.4
74.$
98.9 95.3 89.8 84 8 76 8 72.9 59.9 58.3 48.6 37.3 31.8 18.9 11.2 3.6 2.9 2.3 1.2 0.4
7J.J s1.2 84.6 99.0 03.2 97.(3
50 Lb./Sq. 111. .?il)s. 91.4 121.0 96.9 86.5 1 1 R '2 94.9 79.7 117 0 91.9 77.5 116 J 90.1 77.3 116 6 89.9 72.8 116 2 86.6 67.9 114.9 81.3 6 6 . 4 114 6 78.9 63.6 113.0 74.9 59.6 112 3 67.6 59.2 112 3 67.0 60.7 57.8 112.2 112.2 ~ 1 . 4 56.2 56.1 112.3 45.0 55.6 112.3 30.0 50.8 113 1, 1.7 51.6 116.3 1.4 34.8 124 2 0.8 14.1 i33 1 0 2
% ACETONE
Figure 6. Temperature-Composition Diagram for System Acetone-Water at Various Pressures
ACETONE-~~~ETHYL 7 h x I Y L ILT.4
FOR ACETOSE--hIETHYL E T H Y L KE10\h-J174TER
iPOR COhiPOSITIO\
(.it 50 pounds p e l s q u a i e inch absolute) _ _ _ ~ Vapor Water, Acetone. MEKa, niole mole % mole 70 14.3 83 2 4.8 8 9 78 i 10.3 76 5 11.1 12 9 24.7 72 8 8.5 71.2 7.9 17.9 37.3 68 .5 8.1 10.0 55 9 28.6 39.3 GO 0 14.2 52.1 17.6 26.8 ,54.3 34.4 18.7 33 3 37 8 18.5 57 4 44.8 14.4 63 2 53.9 8.2 48.6 50 4 19.8 53.3 60.7 13.7 41 3 40.8 26.8 37 0 29.7 33.5 57 4 71.2 9.5 31.5 42.9 33.6 32.7 44 6 33.0 24 3 9.0 58.2 53.0 12.9 78.7 65.3 34.4 29.4 28 R 35.6 53.2 37.6 26.3 75.3 30.7 34.7 70.5 24.2 36.7 63.2 15.8 31.2 50.0 19.0 43.1 58.8 50 2 11.4 88.6 78 6 23 4 37.0 15.2 50.2 45.4 11.5 2.3 79.7 29.1 83 8 31.9 68 7 15.6 46.4 14.8 91.1 39.8 ~~
'z
Water, mole % 12.0 11.0
12.4 18.7 10.9 23.4 15.5 25.8 21.1 27 0 28 0 28 9 28 6 31 6 32 8 31 9 29 3 33 1 34 9 34 3 17.5 32.1 36.2 36.4 36.1 34.6 39.1 34.2 37 9 38.4 39.6 39.4 8.8 39.0 38.0 45.4
Temp., C. 99 1 101 4 100 7 101 2 103 9 101 9 107 2 103 3 106 1
The authors wish to thank the Vulcan Copper and Supply Co. for supplying the equilibrium still described. Thanks are also due to the Carbide and Carbon Chemicals Corp. for supplying the acetone used and to the Shell Chemical Corp. for furnishing the methyl ethyl ketone SOMENCLATURE =
=
104 1
=
105 103 103 105
0 3 3 0 104 4 107 1 108 2 104 1 108 6 108 3 115.2 104., 107.8 109.1 107 6 108.6 109.2 116.1 111.6 107.1 109.2 107.1 120.0 108.8 112.0 120.0
=
= =
= = = = =
= = =
=
act,ivity coefficient of component 1 fugacity of component 1 in solut,ion fugacity of pure component 1 a t the t p m perature and pressure of the solution mole fraction of component 1 in t,hc liquid phase partial pressure of component, 1 in the vapor vapor pressure of pure component 1 a t the temperature of the solution mole fract,ion of component 1 in the vapor phase total pressure absolute temperature molal gas constant molal volume of pure component 1 in the liquid state second virial coefficient in the equation of state of pure component 1 critical temperature in degrees absolute critical pressure relative volatility, light romponmi t,o heavy component LITERATURE CITED
(1) Benedict, AI., Johnsoil, C . -k., Solomon, E., and Rubin. L. C . . acetone-water, the previously published subatmospheric data Trans. A m . I n s t . Chem. Engrs., 41, 371 (1945). ( I S ) mere found t o lie on the same straight, lines as the data of this ( 2 ) Rrunjes, A. s., and Bogart, hI. ,I.P., IND.ESG. CHEM., 35, 2% investigation, indicat,ing good agreement between the two sets of 11943). data. (3) Camson, B.IT., and Watson, K. XI,,S o i l . P e t r o k w n S e w s 36, The binarv methyl ethyl ketone-w~ter Ivas found to be azeoR623 (1944). tropic at all pressures studied, while the system acetone-water exhibited azeotropism at 100 pounds per square inch absolute and higher pressures. TABLE XI. VAPOR C:03IPOSITIOS D A T A FOR A%CETOSE-hh?THYI, E T H Y L The azeotropic data for these systems have been KETOiYE--\\-ATER correlated in Figure 14 according to the met,hod (AI 100 pounds per square inch absolute) of Othmer and Ten Eyck (18). Liquid &-ate;, Acetone, hIEK", Acetone, T'apor-liquid equilibrium data for t,he ternary mole R mole 70 mole % mole % syst,em were also correlat,ed by means of loga5.0 , 13,9 127,z 81.1 12 3 78 6 15.6 128,3 11.6 72.8 12 4 1: 68.1 rithmic plots. Log mole 70methyl ethyl ketone 22.8 127.8 9.0 68.2 24 5 13.9 61.6 1 0 . 8 129,3 10.8 78.4 8.0 19.4 72.6 in vapor was plotted against log total pressure 29.0 130.0 13.9 57,l 28 2 21 1 50.7 a t constant mole yo water in liquid with mole 16 2 136.4 3 0 . 5 53.3 45 0 9 4 45.6 130.8 14.1 31 . ? 54.2 39 2 J 1 8 . 3 42. 70methyl ethyl ketone in liquid as a parameter. 2 3 . 9 134.9 2 8 . 4 47.7 42.7 17.0 40.3 3 2 . 2 131.4 1 8 . 6 4 9 . 2 2 4 . 0 36 9 4 0 . 1 i\lole % acetone in vapor was plott,ed similarly. 3 2 . 6 131.9 1 9 . 7 4 7 . 7 38 2 24.5 37.3 The data plotted linearly indicating the utilit,y 129.6 34 0 9.6 56.4 9.3 54 9, 35.8 132.2 36 5 20 6 51 , 42.9 20.5 27.8 of this type of plotting for correlating ternary 130 6 3G 8 12.5 61 7 50.7 10.7 27.6 134.2 37 1 vapor-liquid equilibrium data over a n-ide range 25 9 37.0 43 0 26.4 30.6 131.5 24 0 7.8 68.2 61 3 13.1 25.6 of pressure. 136.3 34 8 33.3 29 8 31 9 45.6 24.6
5
CONCLUSION s
Consistent vapor-liquid equilibrium dat,a have been presented for the systems acetone-methyl ethyl ketone, a c e t o n e - w a t e r , m e t h g l e t h y l ketone-water, and acetone-methyl et.hyl ketonen-ater a t pressures of 14.7, 50, 100, 250, and 500 pounds per square inch absolute. Those data lmve been correlated so as to permit rapid and accurate interpolation. Two of the binaries were found to exhibit azeotropisni; t,he azeotropic data were correlated on logarithmic plots.
9.4 21.5 35.2 20.4 38.1 19.0 5.4 16.8 16 3 73.0 19.9 14 6 11.3 12 1 17.8 11 1 24.8 10 6 63.0 9 9 8 5 43.3 13.3 7 3 8.9 6 9 2.4 6 8 6 4 90 9 31 5 6 3 4 4 84 3 a Methyl ethyl ketone.
69 1 44 1 42 9 77 8 10.7 65,5 76.6 71,1 63.6 27.1 48.2 79 4 84 2 90 8 2 7 62 2 11 3
48 9
30.0 26.5 50.2 22 6 29 9 32 8 25 5 21 5 13 5 14 8 21 5 25 1 40 0 9 0 13 1 5 9
14.8 30.7 33.1
36 39 40 38
58.6 27.3 24.9 30.2 34.4 48 7 42.2 33.8 28.9 11.5 82 4 40 9 70 6
18 8 42 8 32 3 41 3 44 1 37 8
11.8
3 3 4
1
43.2 44 , 46 0 48 5 8 G 46 0 23 6
131.7 134.4 135.6 132.5 143,6 135.0 134,3 138.3 136,l 143.2 141.3 136.7 136,6 136.4 150 9 139 4 146 6
August 1952
INDUSTRIAL AND ENGINEERING CHEMISTRY
TABLE XII.
ACETONE-METHYL ETHYL KETONE-WATER
VAPOR COMPOSITION DATA FOR
(At 250 pounds per square inch absolute) Vapor Water, Acetone, MEKa, Water, mole % mole % mole % mole % 6.8 14.5 11.3 78.7 74.3 14.3 11.4 7.7 16.6 11.3 69.4 14.0 65.2 26.0 8.8 23.9 67.1 11.2 21.7 7.3 26.3 9.9 63.8 23.7 35.1 56.4 8.5 37.7 35.1 18.9 46.0 34.6 18.8 43.5 37.6 37.2 8.9 47.1 44.0 56.5
Liquid MEKa, mole % 10.5 21.0 21.3 14.1 31.2 15.2 11.9 25.8 25.4 9.7
Acetone, mole % 78.2 71.3 67.4 62.0 61.5 61.1 50.4 39.6 37.4 33.8
Temp., O C. 171.2 175.7 175.3 171.4 178.7 171.7 171.9 175.0 174.9 172.8
44.5 41.0 29.1 37.4 26.1 24.1 21.1 42.0 19.2 43.2
13.3 12.2 34.0 14.9 29.5 31.2 34.2 7.5 67.6 33.9
42.2 46.8 36.9 47.7 44.4 44.7 44.7 50.5 13.2 22.9
173.9 174.0 177.6 175.1 176.9 177.6 178.0 174.5 193.4 180.6
0 8
7 3
75 1 90 4
14 o
87 8 37 5 26 2
4 9 56 2 59 2
201 7 186.5 185 8
32.0 26.9 25.5 20.7 20.3 19.0 17.9 17.3 15.3 14.1
14.7 10.9 46.4 11.5 35.8 38.6 42.7 3.9 79.1 46.3
53.3 62.2 28.1 67.8 43.9 42.4 39.4 78.8 5.6 39.6
5 9 3 3 3 3
93 3 21 5 6 3
fi?
Methyl ethyl ketone.
a
TABLEXIII.
Liquid MEK~, mole % 13.8 24.6 17.3 19.5 27.8 10.8 27.8 7.1 51.0 27.3
__-
Acetone,
mole % 78 69 62 60 48 48 40 39 38 37
3 2 1 0 4 3 0 8 5 4
7 2 6 7 3 2 5
18.4 9.6 36.6 22.2 50.7 10.9 39.7 6.9 83.1 34.1
12.6 12.5 10.8 8.8 5.3 5.1 4.7 4.0
19.2 13.1 24.0 9.3 18.9 6.0 94.1 37.3
36 6 27 9
25 8
25 24 23 20 16 14 13
a
VAPOR
COMPOSITION
D.4TA
FOR
ETHYL KETONE-WATER
ACETONE-METHYL
(At 500 pounds per square inch absolute) Vapor WZAcetone, M E K a , water,‘ yo mole yo mole mole % mole % 7.9 78.7 9.9 11.4 6.2 72.6 18.5 8,9 12.8 20.6 62.2 25.0 20.5 60.5 14.4 25.1 23.8 49.9 20.3 29.8 8.7 40.9 52.1 39.2 20.8 32.2 42.6 36.6 53.1 47.7 6.2 46.1 40.4 10.5 40.5 19.1 35.3 39.3 20.7 40.0 46.0 40.4 14.7 44.9 62.5 39.7 9.8 50.5 37.6 28.7 28.5 42.8 52.1 31.3 18.3 50.4 25.1 42.1 26.6 31.3 65.5 34.0 11.6 54.4 31.5 39.6 22.9 45.6 76.8 29.8 10.9 59.3 2.7 17.0 78.5 4.5 52.4 16.7 29.9 53.4 68.2 74.4 65.2 81.9 75.8 88.9 1.2 58.7
17.5 22.0 14.9 18.7 8.7 15.8 6.9 5.4
23.2 18.0 27.1 18.8 28.5 17.0 91.6 35.7
59.3 60.0 5.8 .0 62.5 37.2 67.2 1.5 58.9
Temp., C. 213.6 218.5 212.3 212.8 215.6 209.2 214.1 209.6 225.4 214.1 211.4 211.2 215.9 214.0 219.4 212.8 216.4 214.4 241.7 216.4 215.6 216.5 216.0 216.1 221.1 221.0 247.3 225.7
1881
Griswold, J., and Dinwiddie, J. A., IND.ENG. CHEM.,34, 1188 (1942). “International Critical Tables,” New York, McGraw-Hill Book Co., 1928. Karr, A. E., Scheibel, E. G., Bowes, W. M., ENQ.CHEM.,43,961 and Othmer, D. F., IND. (1951). Keenan, J. H.,and Keyes, F. G., “Thermodynamic Properties of Steam,” New York, John Wiley & Sons, 1936. Lipkin, M. R., et al., IND.ENG.CHEM.,ANAL. ED., 16, 55 (1944). Marshall, A.,J. Chem. Soc., 1906, 1350. Meissner, H.P.,Chem. Eng. Progress, 45, 149 (1949). Othmer, D. F., IND.ENQ. CHEM.,32, 841 (1940). Othmer, D. F.,IND.ENG.CHEM.,~ A L ED., . 20. 763 (1948). (13) Othmer, D. F.,‘and Benenati, R. F., IND.ENG. CHEM.,37,299 (1945). (14)Othmer, D. F.,and Gilmont, R., Ibid., 36, 858 (1944). (15)Ibid., 40, 2118 (1948). (16) Othmer, D. F.,and Morley, F. R., Ibid., 38, 751 (1946). (17) Othmer, D.F.,Silvis, S. J., and Spiel, A , , Ibid., 44, 1872 (1952). (18) Othmer, D.F.,and Ten Eyck, E., Ibid., 41,2897 (1949). (19)Othmer, D. F.,and Tobias, P., Ibid.. 34, 693 (1942). (20)Perry, J., ed., “Chemical Engineers’ Handbook,” 3rd ed., New York, McGraw-Hill Book Co., 1950. (21) Redlich, O., and Kister, A. T., IWD.ENG. CHEM., 40, 341 (1948). (22)Ibid., p. 345. (23) Shell Chemical Corp., “Methyl Ethyl Ketone” (1950). (24) Squibb, E. R.,J . Am. Chem. Soc., 17, 189 (1895). (25) Stull, D.R.,IND.ENG.CHEM.,39, 517 (1947). (26) Timmermans, J., and Martin, F., J . Chim. phys., 25,411 (1928). (27) Timmermans, J.. and Martin, F., PTOC.Roy. Irish Acad., 13,333 (1912). (28)Treybal. R. E., Weber, L. D., and Daley, J. F., IND.ENG. CHEM.,38, 817 (1946). (29) Watson, K. M.,Zbid., 35,398 (1943). (30) York, R.,Jr., and Holmes, R. C.,Ibid., 34,345 (1942). RECEIVED for review April 21, 1951. ACCEPTED Fehruary 21, 1952. Presented before the X I I t h International Congress of Pure and Applied Chemistry, September 1951, New York. Previous articles of this series have appeared in IND. ENO. CHEM,,1928, 1943, 1944, 1945, 1946, 1947, 1948, 1949, and 1951: in IND.ENQ.Cnnnf., ANAL. ED., 1932. and i n Anal. Chem. in 1948.
Methyl ethyl ketone.
TABLEXIV. VAPOR PRESSURES OF ACETONEAND METHYL ETHYL KETONE Temp.,
C.
Acetone ______ Vapor pressure lb./sq. in. abs.’
Methyl Ethyl Ketone Vapor pressure., C. Ib./sq. in. abs.
TABLE xv. VALUES O F THE CONSTANTS IN THE REDLICH AND KISTERCORRELATION FOR THE BINARIES AT VAR~OUS PRESSURES Pressure, Lb /Sq In. Abs. -~ 14 7
Temp.,
B
C
B C
D
E
50
100
250
SYSTEM:ACETONE-WATER 0 680 0 640 0 681 -0 200 -0 190 -0 180
0 715 -0 084
a 0 0
0 490 -0 220
SYSTEM:METHYLETHYLKETONE-WATFR 0.940 0.850 0.800 0.639 0.489 -0,182 -0,240 -0.280 -0,280 -0,356 0.0924 0.0572 0.0408 0,0210 0.0047 -0.129 -0.110 .... .... , , ..
