1428 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 44, No.

6
second-order transition point. Another item of general theoretical
interest is the fact t h a t interpretation of some of the data seems
t o require that segments of the polymer chains be in motion more
than 100' below the second-order transition point.
Polybutadiene, prepared with sodium as the catalyst, changes
in physical properties with baking a t a rate about four times as
fast as does the emulsion polymer. Furthermore, the ratio of
cross linking to cyclization is higher in the sodium polymer.
These differences are believed t o be due t o the higher content of
(2) Blokh, G. A., and Zaionchkovakli, A . D., Legkaya Prom., 11-12,
43 (1946); Rubber Chem. and Technol., 21, 727 (1948).
(3) Bolland, J. L., and Orr, W. J. C., Trans. Inst. Rubber Id.,21, 133
(1945); Rubber Chem. and Technol., 19, 277 (1946).
(4)Boyer, R. F., and Spencer, R. S., "Advances in Colloid Science,"
Vol. 11, p. 26, Mark, H., and Whitby, G. S., editors, Kew
York, Interscience Publishers, 1946.
( 5 ) Marvel, C. S.,Bailey, %', J., and I n s k e e p , 0 . E., J . Polymer Sci..
1, 275 (1946).
(6) Morton, A. A., Patterson, G. H., Donovan, J. J., and Little, E. L.,
J . Am. Chem. SOC..68. 93 11946).
-,-
~ ~

dangling vinyl groups in the sodium polymer (7) Schmidt, O., Schnell,B., and Rleyer, E. (to I. G. Farbenindustrie),
U. S.Patent 1,901,044(1933).
( 8 ) Spencer, R. S., and Boyer, K. F., J . Applied Phys., 17, 398
LITERATURE CITED (1946).
(1) Alfrey, T.,Goldfinger, G., and M a r k , H., ,J. A p p l t e d Phz/s, 14,
700 (1943). RXCI:IY?.D
for review M a y 23, 1951. ACCEPTED
January 19, 1952.

System yl Acetate-Ac
c.
J J

SOLVENT EXTRACTION EQUILIBRIUM DATA

V. R. SOHONI AND U. E. WARHADPANDE
Lamrninarayan Institute of Technology, Nagpur, M . P . , India

E T H Y L acetate is used as a solvent for the extraction of acetic

acid from dilute aqueous solutions. Knowledge of the ter-
nary mutual solubility and distribution of acetic acid between
GRADES OF MATERIALS USED
A laboratory source of distilled water and analytical reagent
grade chemicals were used. The solvent and the acid were tested
water and solvent is essential for the design of extraction equip- for purity by density as well as refractive index determination.
The acid was purified by fractional crystallization and its purity
ment and evaluation of solvent merits. Complete published data was also ascertained by titration. Ethyl acetate required no
of such nature are, however, lacking. The niutual solubility curve purification. The properties of the purified chemicals a t 30" C.
was determined by Mion (4)at 30" C., but the tie line data have are giwn below.
not been given. Therefore, the complete data nere obtained by Refractive Density, Yo Purity by
the present authors. Substance Index G./MI. Titration
Water 1.3320 0.9957
Acetic acid 1.3680 1,0392 99 FO
Ethyl acetate 1.3700 0.8939 . .

EXPERI-MEYTA L

The data for the binodal curve were obtained by the synthet,ic
method ( 8 ) a t 30" C. using a constant temperature bath. The
end point was ascertained by the disappearance of turbidity on
addition of increasing amounts of acid to water-solvent mixture8
of known composition. The composition of phases in equilibrium
for the heterogeneous region was established by analytical estima-
tion of acetic acid in each phase. Hydrolysis during titration
was avoided by addition of ice during titration. This furnished
the tie line data.

I.
TABLE SOLUBILITY D.4T.i FOR BINODAL
CUR\-t.:
(Composition by weight)
Yo Acetic
c/o Ethyl Acetate
A Fter C
Acid

5.30 3.9
9.60 13.0
17.90 17.4
24,60 20.1
33.10 22.1
41.00 22.0
48.90 21.8
Figure 1. Phase Diagram for S y s t e m A c e t i c Acid-Water- 41.25 21.75
Ethyl Acetate 57.00 21.00
67,50 17.25
X. Experimental t i e lines 80.30 11.70
0. .Extrapolated t i e lines 92.90 0 0
Solubility data 3.50 0 0
0. Mion (4)
A. Present Authors
June 1952 INDUSTRIAL AND ENGINEERING CHEMISTRY 1429

19
TABLE
11. EXPERIMENTAL
TIELINE DATA
Ethyl Acetate Layer Water Layer
18 Ethyl Acetio Ethyl Acetic
acetate, Water, acid, acetate, Water, acid,
% % % % % %
17 93.0 4.5 2.5 7.95 89.3 2.75
89.3 5.7 5.0 8.75 86.0 5.25
85.3 7.2 7.5 10.00 82.3 ' 7.70
76 81.0 9.0 10.0 11.20 79.0 9.80
77.5 10.26 12.24 11.7 76.5 11.80
75

i 4

13

12

ii

is il i3 75 17 T9

Figure 2. Tie Line Correlation

Othmer (5) and Hand (2)

Experimental data are given in Tables I and I1 and are repro-

duced in Figure 1. The tie lines are not shown in this figure, but
the conjugate line has been drawn on which experimental and
extrapolated points are differentiated.

C; z/ ( b2 + c2)-
Figure 4. Selectivity Curves (6)

equation discussed by Smith (8) for calculation of partition coef-

ficients in solutropic systems is, however, inapplicable in this case.

SOLVENT PROPERTIES

Certain conclusions of importance in commercial extraction op-

dl 0.2 0.3 0.4 0.5
Figure 3. Equilibrium Distribution Curves
TIE LINE CORRELATION
Many equations have been proposed for tie line correlation,
two of which have been plotted in Figure 2. The tie lines corre-
late best by the O t h e r plot (6),and, hence, the O t h e r plot was
used for the extrapolation of tie lines.
PLAIT POINT
Determination of the plait point presented experimental dif-
ficulties and therefore it was located by plotting the conjugate
line on either side of the binodal curve and interpolating the point
of intersection of the conjugate and binodal curve. The equilib-
rium values at the plait point are found t o be 32.7% solvent,
45.3% water, and 22% acid by weight in each layer. These val-
ues fit the Othmer plot correctly.
SOLUTROPY
From the values of equilibrium distribution of acetic acid it
will be seen t h a t the system is a solutrope-Le., the selectivity of
the acid for the solvent reverses at a certain stage and then be-
comes selective towards water. Figure 3 shows this more
clearly. Below 9.570 acid in the water layer the acid is present in
higher concentration in the solvent than in the water layer. For
higher concentrations the reverse is the case. The distribution
erations can be drawn from the data obtained in these experi-
ments. A plot of the selectivity curve (6) and equilibrium distri-
bution curve is necessary for this purpose. These are, therefore,
plotted in Figures 3 and 4 along with those for some other possible
solvents (1, 8,7').
The equilibrium curve gives a rough idea of the quantity of the
solvent required for extraction. It will be seen from Figure 3
that ethyl acetate has a high dissolving power for acetic acid in
comparison with other solvents and, hence, will be required in
less amounts than all other solvents for extracting the same
amount of acid.
NOMENCLATURE
a = weight fraction of solvent
b = weight fraction of water
c = weight fraction of acid
Subscript 1 = compositions in extract layer
2 = compositions in raffinate layer
LITERATURE CITED
(1) Campbell, H., Trans. Am. Inst. Chem. Engrs., 36,593 (1940).
(2) Hand, D.B., J . Phg8. Chem., 34, 1961 (1930).
(3) Major, C. J., and Swenson, 0. J., IND. ENG.CHEM.,38, 834
(1946).
(4) Mion, Compt. rend., 193, 1330 (1931).
(5) Othmer, D. F., and Tobias, P. E., IND. ENG.CWEM., 34, 693
(1942).
(6) Othmer, D.F.,et al., Ibid., 37,890 (1945).
(7) Saletore, 8. A., Mene, P. S.,and Warhadpande, U. R., Trans.
I n d i a n Inst. Chem. Engrs.,2, 16 (194849).
( 8 ) Smith, A. S., IND.ENG.CHEM.,42,1206 (1950).
(9) Taylor, 9.F., J. Phys. Chem., 1,461 (1897).
R E C E I V ~for
D review August 17, 1951. January 21, 1952.
ACCEPTED