T H E SYSTEM WATER-ACETIC ACID-TOLUENE: TRIANGULAR

DIAGRAM AT 25C., WITH DEXSITIES AND VISCOSITIES O F

THE LAYERS

B Y ROWLAND MARCUS WOODMAN

During work on the distribution of a consolute liquid between two im-

miscible solvents, it was found necessary to have an accurately-determined
diagram for a system containing a pair of partly miscible liquids, The present
paper deals with the distribution of acetic acid, an easily-estimated liquid
between water and toluene.

Fro. I

The glacial acetic acid used (D 2 5 0 = 1.045)was labelled B. D. H., A. R.,

4 O

and, by titrating a weighed port,ion, previously diluted, against n-NaOH in

the presence of phenolphthalein,*the sample was found to contain 98.96 per

Waddell (J. Phys. Chem., 2 , 233 (1898)) hae investigated the system water-acetic
acid-benzene by a method similar to that used here. The syptem water-acetic acid-
toluene has been partially investigated by Herz and Fischer (Bcr.,37,4746; 1904~38,I 138
go$ with the view of determining the distribution of the acid between the two im-
miscible solvents.
* Krauch: Chemical Reagents, 3 (1919).
 WATER, ACETIC ACID, TOLUENE

TABLE
I1
a = ratio of gram-moles acetic acid in I litre of aqueous phase to gram-moles
in I litre of toluene phase
Aqueous Layer: Toluene Layer:
Wt. percent. Drnsity Viscosity Wt. percent. Dcnsity Viscosity 1
of Ac-tic of Layrr of Layer of dcstic of Liver of Liver
Acid iD$ q 2 e Arid (D$ 7250

0 0.9971 0.008928 0 0.8600 0.004967 -

21.38 1.025 0.01116 1.374 0.8614 - 18.51
30.87 1.035 0.01337 2.797 0.8630 0.005202 I3 ' 23
37.69 1.042 0.01470 4.072 0 . 8 6 5 0 0.005201 (?) 11.I j
4 7 . 50 1.050 0.01642 6.363 0.8676 0,005309 9.035
58.05 1.oj4 0.01875 10.35 0.8730 0.005298(?) 6.774
62 53' 12.98
64.86 1.052 1980
0 .o 14.98 0.8796 O.OOj441 5,178
67.70 1,049 0.01974 18.55 0.8847 0.OOjjjI 4.337
69.71 1.044 0,01940 2 1 .jo 0.8896 0.005615 3,805
70.jj 1,039 0.01904 24.88 0.8952 0.005761 3.291
69.8; 1.024 0.01677 32.96 0.9099 0.006362 2.384
69.40 36.I3
66.68 1.006 0.01469 40.64 0.9276 0.007263 1.779
65.31 44.41
58.46 0.9757 0.01272 53.07 0.9588 0.01025 I. I20

S . R. The corrc5ponding weight percents. of water and toluene can tie read off from
Ill? curve.

The diagram clearly shows that the critical point lies well over on the
toluene side of the curve (between the points marked a and b ) , and thus, as
the percentage of acetic acid in the aqueous layer passes through a maximum
on approaching this point, some diffidence might be shown as t o which side
of the maximum to place several of the points corresponding to the aqueous
phase, were it not for the fact that the percentage of acetic acid in the toluene
layer must increase continuously in approaching the critical point.
The tie-lines on being produced converge to a point; this is quite different
from the systems fvater-pyridine-benzene' and lead-tin-zinc,* where there are
changes in the direction of slope of the ties. The critical point should ob-
viously be the point of contact of the tangent to the curve drawn from this
point of convergence.
The densities-measured by a small pyknometer-and the viscosities of
the aqueous layers also pass through maxima, the values being much higher
than for pure acetic acid at the same temperature; in the case of the toluene
layers the densities and viscosities increase continuously as the layer ap-
1 Koodman and Cor) e t ' J. Chem. Yoc., 127, 2461 (1925).
Wright: Proc. Foy Poc , 5 0 , 372 ( I f 9 2 ' .