THE fiPSTEM BUTYL ALCOHOL-ETHYL ACETATE-TOLUENE
377
In conclusion, the data which are now available for the construction of the freezing-point, boiling-point, and pentahydrate solubility curves have been assembled in table 3. All compositions are in percentages by weight. REFERENCES (1) BR@NSTED: 2. physik. Chem. 82,621 (1913). (2) DE COPPET:Ann. chim. phys. [5130, 411 (1883). (3) ETARD: Ann. chim. phys. 171 2, 503 (1894). (4) HILL,WILSON, AND BISHOP:J. Am. Chem. SOC.66, 521 (1933). (5) JABLCZYNSKI AND KON: J. Chem. SOC.123, 2953 (1923). (6) JOHNSTOX: Trans. Roy. SOC. Edinburgh 46 (2),855 (1908). (7) JONES,GETMAN, BASSETT, MCMASTER, AND UHLER:Carnegie Inst. Wash. Pub. No. 60, p. 35 (1907). (8) KREMERS: Pogg. Ann. 97, 1 (1856). (9) MEYERHOFFER: Unpublished data given in Landolt-Bornstein Tabellen, 5th edition, p. 673. J. Springer, Berlin (1923). (10) PANFILOW: J. Russ. Phys. Chem. SOC.86, 264 (1893); cf. Chem. Zentr. [4]6, 11, 910 (1893);Z. anorg. Chem. 6, 490 (1894). (11) RICCI:J. Am. Chem. Soo. 66, 295 (1934). (12) R ~ D O R F Pogg. F: Ann. 116, 55 (1862). (13) SCHLAMP: 2. physik. Chem. 14, 272 (1894). (14) SCOTTAND DURHAM: J. Phys. Chem. 34, 1424 (1930). (15) SCOTTAND FRAZIER: J. Phys. Chem. 31, 459 (1927).
T H E PHYSICAL PROPERTIES O F T H E TERNARY SYSTEM BUTYL ALCOHOL-ETHYL ACETATE-TOLUENE E. E. LITKENHOUS, J. D . VAX ARSDALE,
AND
I. W. HUTCHISON, JR.
Chemical Engineering Laboratories, University of Louiaville, Louisville, Kentucky Received June 67, 1 1 0 INTRODUCTION
This and two previous investigations (5, 6) were carried out to obtain physical data for use in chemical engineering design studies. The densities, viscosities, surface tensions, refractive indices, and boiling points of the ternary system butyl alcohol-ethyl acetate-toluene were determined and are reported in this paper. EXPERIMENTAL
Materials Normal C.P. butyl alcohol was treated as described in the paper of Ernst, Litkenhous, and Spanyer (5). The C.P. ethyl acetate was repeatedly distilled in a specially constructed ilong glass rectifying column,
378
LITKENHOUf3, VAN ARSDALE AND HUTCHISON
refluxed with phosphorus pentoxide for several hours (13), and finally redistilled. The toluene was purified by continued fractionation. Tests were made for aldehydes and acids before the materials were finally redistilled. The physical properties of the purified materials were next determined as a check upon their purity before the preparation of both binary and ternary samples. These physical constants and a comparison with those of other investigators are listed in table 1. TABLE 1 Physical constants of purified materials BUBFACE TENBION
BEPBACTIVE INDEX
BOILINQ POINT
'C.
Butyl alcohol . . .
Ethyl metate...
i
1
0.8075 (A) 0.02463 (A) 24.189 0.8080 (5) 0.02465 (5) 24.204 0.8080 (1) 0.02801 (10) 24.25 24.16 0.8083 (2)
(A) (5) (15) (9)
1.3981 1.3981 1.3974 1.4OOo
(A) (5) (1) (3)
0.8933 (A) 0.00438 (A) 22.973 (A) 1.3715 (A) 0.8935 (7) 0.00416 (8) 23.15 (9) 1.3704 (12) o.ag852 (io) 0.8599 (A) 0.00551 (A) 0.8654 (10)
117.7 117.69 117.71 117.6
(A) (5) (1) (11)
77.1 (A) 77.15 (7) 77.1 (18)
27.541 (A) 1.4941 (A) 110.7 (A) 27.96 (9) 1.4936 (13) 110.7 (4) 28.58 (14) 1.4910 (12) 110.8 (17)
Preparation of samples Sixty-six samples were then prepared, using weight increments of 10 per cent. The weight per cent composition of these samples is listed in table 2. Apparatus Apparatus identical with that used in the previous investigations ( 5 , 6 ) was employed. A temperature of 25OC. f 0.05' was maintained in the determination of density, viscosity, surface tension, and refractive index. All samples were kept in glass-stoppered bottles in a constant-temperature bath for 24 hr. before using. DISCU8SION
The results of the experimental work are summarized in table 3. Both binoidal and triangular diagrams have been drawn for each property. The binoidal curves are plotted with the composition of the sample as
THE SYSTEM BUTYL ALCOHOL-ETHYL
ACETATE-TOLUENE
370
abscissa against the particular property under consideration as the ordinate. The constant property lines on the triangular diagrams were prepared from the binoidal curves. TABLE 2 Composition of samples SAMPLE
BUTYL
NUMBER
ALCOHOL
ETHYL ACETATE
BUTYL UOHOL
ETHYL ACETATE
TOLEENE
weight per
weight p e r
weight per
weight per
cent
cent
cent
cat
50
10
40 30 20 10 70 60
10 10 10 10 20 20
50 40
20 20 20
40 50 60 70 80 10 20 30 40 50 60 70 10 20 30 40
TOLUENE
SAMPLE NUMBER
-~
weight p a Cent
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
25 26 27 28 29 30 31 32 33
~
weight per cent
100 100 10 20 30 40 50 60
70 80 90 90 80 70 60 50
40 30 20 10 10 20 30 40 50 60 70 80
90 80
70 60
100 90 80 70 60 50 40 30 20 10 10 20 30 40 50 60 70 80
90 90 80
70 60 50
40 30 20 10 10 10 10
10 20
30
34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66
30 20 10 60 50 40 30 20 10 50
40 30 20 10 40 30 20 10 30 20 10 20 10 10
20 20 30 30 30 30 30 30 40 40 40 40 40 50
50 50 50 60 60 60 70 70 80
50 60
10 20 30 40 50 10
20 30 40
10 20
30 10 20 10
Relative density Figure 1 is a binoidal graph of the relative densities plotted against composition. The relative densities of all mixtures of ethyl acetate and toluene decrease as the per'cent of butyl alcohol is increased (figure 1).
380
LITKENHOUS, VAN ARBDALE AND HUTCHISON
TABLE 3 Phyaical BAXPLE KZTYBEI
BOILINQ POINT
eoperties
DENSITY
VIWOSITY
0.8075 0.8933 0.8599 0.8636 0.8666 0.8700 0.8727 0.8755 0.8786 0.8818 0.8851
0.02463 0.00438 0.00551 0.00534 0.00512 0.00506 0.00484 0.00482 0.00478 0.00455 0.00445 0.00428 0.02120 0.01730 0.01441 0.01199 0.00997 0.00840 0.00715 0.00635 0.00560 0.00480 0.00510 0.00578 0.00648 0.00790 0.00987 0.01165 0.01425 0,01815 0.01570 0.01350 0.01O97 O.Oo908 0.00792 0.00694 0.00620 0.00563 0,01222 0.01022 0.00875 0.00755 0.00659 0.00594 0.00547
-
BWRACTIVB
INDEX
BUBFACE mNBION
1.3981 1.3715 1.4941 1.4840 1.4709 1.4588 1.4463 1.4340 1.4211 1.4087 1.3968 1.3845 1.4072 1.4160 1.4248 1.4329 1.4428 1.4512 1.4611 1.4713 1.4829 1.3742 1.3770 1.3793 1.3823 1.3849 1.3875 1.3901 1.3930 1.3958 1.4050 1.4132 1.4222 1.4314 1.4408 1.4505 1.4603 1.4711 1.4021 1.4110 1.4199 1.4288 1.4391 1.4490 1.4600
24.189 22.973 27.541 27.049 26.530 25.974 25.424 24.966 24.512 24.121 23.762 23,421 24.376 24.662 24.983 25.288 25.588 25.925 26.336 26.684 27.095 23.066 23.126 23.224 23.305 23.458 23.528 23.691 23.865 23.976 24.296 24.555 24.842 25.152 25.467 25.800 26.238 26.659 24.121 24.393 24.673 25.005 25.328 25.672 26.089
‘C.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
117.7 77.1 110.7 104.6 99.4 94.6 91.1 87.8 85.2 82.8 84.7 78.8 112.6 109.2 106.5 104.4 103.3 103.0 103.6 104.8 107.3 79.2 81.4 83.9 86.9 90.4 94.6 98.5 103.9 110.0 106.3 104.0 102.2 100.8 100.5 100.6 101.1 102.3 101.4 99.7 98.6 97.8 97.3 97.3 98.1
0.8880
0.8112 0.8156 0.8211 0.8260 0.8307 0.8365 0.8421 0.8481 0.8537 0.8811 0.8714 0.8621 0.8531 0.8438 0.8348 0.8273 0.8199 0.8132 0.8188 0.8236 0.8293 0.8344 0.8399
0.8460 0.8518 0.8576 0.8260 0.8313 0.8368 0.8427 0.8482 0.8543 0.8601
THE SYSTEM BUTYL ALCOHOL-ETHYL
uumm NUYBEB
46 47 48 49 50
51 52 53 54 55 56
57 58
59 60 61 62 63
64 65 66
BOIL~NQPOINT
'C. 97.3 96.0 95.2 94.5 94.2 94.3 93.2 92.4 91.8 91.4 91.3 89.4 88.8 88.3 88.1 86.2 85.8 85.5 83.1 82.8 80.8
DBNBITY
0.8335 0.8395 0.8454 0.8512 0.8578 0.8839 0.8424
0.8490 0.8544 0.8809 0.8671 0.8511 0.8572 0.8831 0.8697 0.8600 0.8655 0.8723 0.8682 0.8755 0.8782
ACETATE-TOLUENE
vI~oIITT
0.01005
0.00838 0.00737 0.00842 0.00592 0.00546 0.00809 0.00710 0.00633 0.00557 0.00520 0.00661 0.00600 0.00541 0.00511 0.00600 0.00540 0.00493 0.00516 0.00475 0.00468
381
BmBACTIVB INDm
IIOBIACE TlNUlON
1.4006 1.4087 1.4176 1.4254 1,4372 1.4477 1.3989 1.4062 1.4152 1.4246 1,4357 1.3943 1.4039 1.4127 1.4226 1,3919 1.4015 1.4109 1.3892 1.3887 1.3867
24.026 24.278 24.608 24.907 25.262 25.553 23.886 24.153 24.467 24.775 25.110 23.731 24.022 24.310 24.637 23.604 23.888 24.168 23.572 23.834 23.412
""TTmL a s0
20
So
60
WElGHr & K E N T
/a
610
TOLUENZ
FIG.1. Binoidal curves showing relative densities at 25°C.
ETHE ACETATE
BUTWL
FIG.2. Triangular diagram showing relative densities a t 382
25OC.
0
20
40
6
0
8
0
m
WEIGHT PLXCCNT TaUCNC
FIG.3. Binoidal curves showing viscosities a t 25°C.
BUTANOL
ETHYL AC€TATE Fro. 4. Triangular diagram showing viscosities a t 25°C. 383
I
1
I
I
1
FIG.5. Binoidal curves showing refractive indices at 25".
FIQ.6. Triangular diagram showing refractive indices at 26°C. 384
FIQ.7. Binoidal curves showing boiling points of butyl alcohol-ethyl acetate toluene mixtures
A
FIQ.8. Triangular diagram showing boiling points of butyl alcohol-ethyl acetate-toluene mixtures 385
BUTANOL FIG.9. Binoidal curves showing surface tensions at 25°C. WCfGM PERCENT
4
FIG.10. Triangular diagram showing surface tensions at 25°C. 386
THE SYSTEM BUTYL ALCOHOL-ETHYL
ACETATE-TOLUENE
387
The effect of varying weights of butyl alcohol-ethyl acetate and toluene upon refractive indices is shown in figure 6. These lines are practically parallel, the increasing weight increments of all three components causing almost regular increases in refractive index values. Boiling points
The boiling points of mixtures of butyl alcohol and toluene pass through a minimum a t about 60 per cent toluene (figure 7). Increasing additions of ethyl acetate to this binary system cause the minimum to disappear when 40 per cent has been added. The curve for the toluene-ethyl acetate system shows neither maximum nor minimum as does the butyl alcohol-ethyl acetate system. The triangular diagram (figure 8) showing compositions of mixtures of constant boiling point indicates that the minimum of the butyl alcoholtoluene mixtures a t 60 per cent toluene has a boiling point of about 103OC. The effect of increasing additions of ethyl acetate to the butyl alcoholtoluene mixtures is to decrease continually the boiling points of the threecomponent system.
Surface tension The binoidal curves for surface tension (figure 9) show slight curvature corresponding to those for refractive index. Increasing percentages of ethyl acetate to toluene-butyl alcohol mixtures tend to straighten the constant per cent ethyl acetate curves. The triangular diagram for surface tension (figure 10) shows that this property is very regular, the addition of increasing weight increments of toluene effecting regular increases of surface tension values. CONCLUSIONS
Densities, viscosities, refractive indices, boiling points, and surface tensions for the ternary system butyl alcohol-ethyl acetate-toluene have been determined. Both binoidal and triangular diagrams have been prepared for each property and are included in this paper. REFERENCES (1) BRUNEL, CRENSHAW, AND TOBIN:J. Am. Chem. SOC.43,566 (1921). AND FURNAS:Ind. Eng. Chem. 27,396 (1935). (2) BRUNJES (3) BUSHMAKIN, BEGETOVA, AND KUCHINSKAYA: Sintet. Kauchuk 4, 8 (1936). (4) DAVIS:Ind. Eng. Chem. 22, 380 (1930). (5) ERNST,LITKENHOUS, AND SPANYER: J. Phys. Chem. 36, 842 (1932). (6) ERNST,WATKINS, AND RUWE:J. Phys. Chem. 40, 627 (1936). AND LEIGHTON: Ind. Eng. Chem. 29, 709 (1937). (7) FURNAS (8) GILLAND DEXTER:Ind. Eng. Chem. 26, 881 (1934). (9) HENNAULT-ROLAND AND LEK:Bull. SOC. chim. Belg. 40, 177 (1931). (IO) Internatzonal Critical Tables: Vola. 111, IV, V, VII. McGraw-Hill Book Co., New Y ork (1933).
388
H. T. BRISCOE AND THEDFORD P. DIRKSE
(11) KAHLBAUM: 2. physik. Chem. 26, 577 (1898). (12) LANQE:Handbook of Chemistry and Physics, 2nd edition, p. 735. Handbook . Publishers Inc., Sandusky, Ohio (1936). J. Phys. Chem. 40,481 (1936). (13) MASONAND WASHBURN: AND COOMBS: J. Am. Chem. SOC.97, 1656 (1915). (14) RICHARDS (16) RICHARDS AND MATHEWS: J. Am. Chem. SOC.3 0 , s (1908). (16) SMITHAND WOJCIECHOWSKI: Rooaniki Chem. 16, 104 (1937). AND MARTIN:J. chim. phys. 23, 733 (1926). (17) TIMMERMANS J. Chem. Soo. 101, 2438 (1912). (18) WADEAND MERRIMAN:
T H E CONDUCTANCE O F SALTS I N MONOETHANOLAMINE
H.T. BRISCOE
AND
THEDFORD P. DIRKSE
Department of Chemistry, Indiana University, Bloomington, Indiana Received July 94, 1030
Solutions in which monoethanolamine acts as the solvent have received very little theoretical consideration. Monoethanolamine is very viscous, it has a dielectric constant approximately half that of water, and it is a very good solvent for many salts. This study deals with the conductances of solutions of salts in this solvent. The equations to be tested include (a) the equation of Debye-Hiickel for calculating activity coefficients, and ( b ) Onsager's conductance equation. EXPERIMENTAL
The bridge used in this work was similar to the bridge recommended hy Jones and Joseph (8). Every precaution they suggested was taken. All the leads were shielded to reduce capacitance, and a condenser was used to balance out capacitance that could not be eliminated by mechanical means. The average amount of this capacitance was 0.000005 microfarad. The frequency of the alternating current was 1250 cycles per second. Transformer oil was used in the constant-temperature bath to reduce stray capacitance between the leads of the cell. The temperature of the bath was maintained a t 25°C. f 0.015", as measured by a Beckmann thermometer which was calibrated against a U. S.Bureau of Standards' thermometer. The cell was made of Pyrex glass and was fitted with platinum electrodes.. It was constructed according to the directions of Jones and Bollinger (6). The electrodes were not platinized, since the solutions used were dilute and alkaline (5). The cell constant was measured by using 0.01 demal potassium chloride which has a conductance of 0.00140877 mho, as determined by Jones and Bradshaw (7). The salts were prepared according to the directions given by Dasher (2). The ethanolamine was purified by distillation. In the first distillation the middle fraction was directed into another distilling flask. This frac-
