August 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY LITERATURE CITED
(1) Am. Soc. Testing Materials, ASTM Designation D 8 7 1 4 6 T ~
for testing cellulose acetate.
(2) Castillo, E. B., Anales fls. y qutm., 42, 1019-35 (1946). (3) Cox, L. A., and Battista, 0. A., IND.ENQ.CHEM.,44, 893-6 119521. --, \-
Genung, L. B., and Mallatt, R. C., IND.ENG.CHEM.,ANAL. ED.,13,369-74 (1941). ( 5 ) Gonsalves, V. E., Rec. traa. chim., 69, 873-903 (1950). (6) Grace, H. P., Chem. Eng. Progr., 47, 502-7 (1951). (7) Hermans. P. H., and BredBe, H. L., J. SOC.Chem. Ind., 55,
(4)
1T-4T (1936). (8) Hermans, P. H., Bredbe, H. L., and Booys, G. de, Rec. trav. chim.. 54. 680-700 (1935). (9) Herrent, P.; Lud6, A.,‘and ’Jnoff, G., Svensk Papperstidn., 54, 153-68 (1951). (10) Mulm, C. J., Genung, L. B., and Lapham, G. B., Anal. Chem., 22, 656-61 (1950). (11) Marschall, A., Kunstseide u. ZeZZwoZZe, 24, 188-99 (1942). (12) Matthes, A., Chem. Tech. (Berlin), 3, 13-22 (1951).
1803
(13) Nicolaysen, V. B., and Bergh, W., Norsk Skogsind., 4 , 219-25 (1950). (14) Pfeiffer, G. H., and Osborn, R. H., “Cellulose and Cellulose Derivatives,” E. Ott, editor, Chap. IX, part F, pp. 956-75, New York, Interscience Publishers, 1943. (15) Samuelson, D., Svensk Papperstidn., 51, 331-5 (1948). (16) Ibid., 52, 465-73 (1949). (17) Sieminski, M. S., and Hotte, G. H., Rayon Textile Monthlu, 25, 608-10 (1944). (18) Technical Association of the Pulp and Paper Industry, “Testing Methods,” Thickness, T411, m-44 (August 1944), Air Resistance, T460, m-49 (April 1949). (19) Vosters, H. L., Svensk Papperstidn., 53, 29-34, 613-21, 771-82 (1950). (20) Ibid., 54, 539-61 (1952). (21) Youden, W. J., “Statistical Methods for Chemists,” New York, John Wiley & Sons, 1951.
RECEIVED for review February 9, 1953. ACCEPTED May 7,1953. Presented before the Division of Cellulose Chemistry a t the 122nd Meeting of the .~MERIcAN CHEMICAL SOCIETY, Atlantic City, N. J.
vapor-Liquid Equilibria at 760-Mrn. Pressure 2-PROPANOL-METHYL PROPYL KETONE AND 2-PROPANOLMETHYL ISOBUTYL KETONE SYSTEMS LOUIS H. BALLARD’ AND MATTHEW VAN WINKLE The University of Texas, Austin, Ten.
T
HIS investigation is one of a series of vapor-liquid equilibrium studies of the oxidized hydrocarbons resulting from eatalytic oxidation processes. Design of separation equipment requires a knowledge of these characteristics. MATERIALS
.
The three compounds used in this study were purified in a 5foot glass distillation column 3 / 4 inch in diameter, packed with glass helices. I n each case, both ends of the original charge were discarded and the middle fraction was retained until the desired purity was obtained. Purity was determined by boiling point and refractive index. The refractive index was determined at 20’ C. with a Bausch and Lomb refractometer. The boiling points were determined in a Cottrell boiling point apparatus. The total pressure was maintained a t 760 mm. of mercury by the use of air pressure. The comparison of properties of the compounds is presented in Table I, together with values from the literature.
Neither of the systems formed azeotropes, although both systems showed azeotropic tendencies. The experimental activity coefficients were calculated for each system and are plotted against the mole per cent 2-propanol. These data are presented in tabular form in Tables I1 and I11 and graphically in Figure 3. Vapor pressure data from the literature (&, 9) were used in the calculations. Plots of the activity coefficients vs. mole 2-propanol indicate that both systems deviate from the ideal solution law. The deviations are positive
APPARATUS AND PROCEDURE
A modified Colburn still (6) was used for the vapor-liquid equilibrium determinations. The apparatus and procedures have been described (1,S, 4 ) . RESULTS AND CONCLUSIONS
Vapor-liquid equilibrium data are presented for the binary eystems 2-propanol (iaopropano1)-methyl propyl ketone and 2propanol-methyl isobutyl ketone. The experimental data are given in tabular form in Tables I1 and I11 and graphically in Figures 1 and 2. The equilibrium compositions are reported t o the nearest 0.05 mole % and the temperatures to the nearest 0.1” F. The estimated limit of error of the experimental determinations is about 1%. Both the experimental vapor-liquid curves and the experimental temperature-composition curves are given. 1
Present address, Monranto Chemical Co., Texas City, Tex.
Methyl isobutyl ketone-2-propanol and methyl n-propyl ketone2-propanol systems at 760 mm.
’
INDUSTRIAL AND ENGINEERING CHEMISTRY
1804
I
Vol. 45, No. 8
l
l
2 -PROPANOL METHYL ISO-BUTYL KETONE
I60
I
1 -
I40 I-
z
w
I20
ll. ll.
IO0
0
w
0 0
*
t >
F
1
P
METHYL
N-PROPYL
KETONE
I40 2 -pRoppsJ0L
MOLE
Figure 3.
PERCENT
2 -PROPANOL IN
LIQUID. X
Activity- Coefficient Diagrams
2-Propanol-ketone systems a t i 6 0 mm.
MOLE PERCENT
Figure 2.
2-PROPANOL
Equilibrium Boiling Point Diagrams
Methyl isobutyl ketone-%propanol and methyl n-propyl ketone-%propanol systems at 760 mm.
T A B L E III. EXPERIMENTAL VAPOR-LIQUID EQUILIBRIUX D 4TA FOR 2 - P R O P A S O L - h f E T H Y I / I S O B U T Y I . KETOXE SYSTEM
(At 760 m m IIg) hctivitv Cocffioients
and apparently increase with the molecular weight of the ketone present in the binary system. Experimental vapor-liquid equilibrium data are presented rather than the data smoothed by use of the conventional thermodynamic consistency equations. The Gibbs-Duhem equation, the basis for the various methods of testing thermodynamic consistency, inherently assumes isothermal as well as isobaric data. The isothermal requirement is not met with these data, as the boiling ranges are 36” and 61.6’ F. for the two binaries. Heat .of solution data are not available and no direct relationship has been established for variation of activity coefficient with temperature.
Run NO.
Temp., F.
*-% Vapor
2-P10pano1 Liquid
1
2-Propanol
Methyl
14obuty1
ketone 1.03
2 3 4 5 6 7 8 9 10
1.05 1,08 1.14 1.17 1 26 1.36 1,49
1,61 1.14 1.02
11
Random experimental errors are considered to be very small in these data because the experimental points fall upon smooth curves, in the case of both temperature-composition and vapor composition-liquid composition curves. Systematic errors are TABLEI. COMPARISON OF LITERATURE AKD EXPERIMENTAL also considered to be reduced to a minimum because occasional VALUES O F BOILIXG P O I X T S AXD R E F R l C T I V E I N D I C E S random checks produced experimental points falling upon the Boiling Point, Refractive Index ComF. a t 20’ C. smooth curves within the estimated limit of experimental error, pound
Methyl
propyl ketone Methyl isobutyl
ketone %Pro-
panoi
Source Matheson Co.
Lit. 2 1 5 . 1 (i) 2 1 5 . 6 (8)
Eastman 2 4 6 . 2 (5) Kodak Co. 2 4 5 . 3 ( 2 )
Exptl.
Lit.
Exptl.
216 1
1 . 3 9 0 1 8 (2)
1 39111
2 4 1 . 8 1 . 3 9 5 9 0 (7) 1.39562 (#)
1.39581
Eastman 1 8 0 . 1 (.?, 1 0 ) 180.2 1.37757 ( 6 ) 1 37716 Kodak C o . 1.37711 (f0)
VAPOR-LIQUID EQUILIBRIUM DATA TABLE11. EXPERIMENTAL F O R %PROPANOL--?rlETHYL P R O P Y L KETOKE SYSTEM ( 4 t 7G0 mm. H g )
R~~ NO. 1 2 3 4 5 6 7 8 9 10
T
~
F.
208.8 202.8 196.5 191.4 188.0 185.8 183.9 182.5 181.4 180.6
~
~ bIole . , % 2-Propanol
Activity Coefficients Methyl 2-
prowl
Vapor
Liquid
Propanol
ketone
20.30 32.95 46.10 58.00 66.40 72.00 78.00 84.15 89 75 96.70
7.55 14.55 24.60 37.20 48.40 58.45 68.50 78.15 86.65 95.85
1,49 1.41 1,33 1.23 1.17 1.10
1.05 1.08 1.15 1.18 1.24 1.35 1.47 1.58 1.69 1.72
1.06
1.04 1.02 1.01
LITER.ATURE CITED
(1) Ballard, L . H., a n d Van Winkle, M., IND.EZG. CHEM.,44, 2450 (1952). (2) Cowan, D. M., Jeffery, G . H., a n d T’ogel, -4.I.. J . Chem. Soc., 1940, 171-6. (3) Hellwig, L. R., a n d Van Winkle, AI., IND.ENG.CHEM.,45, 624 (1953). (4) Hill, 11’. D., a n d Van Winkle. M., Ibid., 44, 205 (1952). (5) Hodgman, J. H., editor-in-chief, “Handbook of Chemistry and Physics,” 31st ed., pp. 610-1 129, Cleveland, Ohio, Chemical Rubber Publishing Co., 1949. (6) Jones, C. A , , Schoenborn, E. M . , and Colburn, A. P., IND. ENG.CHEM.,35, 666-72 (1943). ( 7 ) Lange, S . A , , “Handbook of Chemistry,” 5 t h ed., pp. 314653, 934-1026, Sandusky, Ohio, Handbook Publishers, Inc., 1944. (8) Rintelen, J. C . , Saylor, J. €I., a n d Gross, P. M., J . Am. Chem. SOC.,59, 1129-30 (1937). (9) Stull, D. R., IND. ESG. CHEM.,39, 5 1 7 4 0 (1947). (10) Vogel, A. I., J . Chem. Soc., 1948, 1814-19. RECEIVED for review October 2, 1951. ACCEPTED March 16, 1953. From a thesis in partial fulfillment of the requirements for the degree of master of science in chemical engineering.
