VAPOR-LIQUID E

RIA

Ethylene Oxide-Acetaldehyde and Ethylene Qxide-rater Systems

IC. F. COLES AND FELIX POPPERL
Petrocarbon Limited, Manchester 17, England
T h e vapor-liquid equilibria for the systems ethylene
oxide-acetaldehyde and ethylene oxide water were determined at atmospheric pressure and also at higher pressures for some compositions. The vapor pressures of
ethylene oxide and acetaldehyde were determined between 0" and 35" C. The system ethylene oxide-water is
discussed in terms of its activity coefficients.

I"

T H E manufacture of ethylene oxide from ethylene via

ethylene chlorohydrin, it is necessary to recover the product
from an aqueous solution and to separate it also from a small
amount of acetaldehyde which is produced a t the same time.
This separation is normally achieved by first distilling overhead a product containing about 70Yc water, the remainder
being ethylene oxide and acetaldehyde. This material is then
fed to a series of fractionation columns, either operating under
pressure, so that water condensers can be used, or operated
under atmospheric pressure with refrigeration. In making
the calculations for such columns it is necewiiy to know vaporliquid equilibria for the components of the system in certain concentration ranges. Since the ethylene oxide and acetaldehyde are
far more easily separated by distillation from water than from
one another the information required for practical purposes is
that for the three binary systems ethylene oxide-water, acetaldehyde-witer, and ethylene oxide--acetaldehyde. From the general considerations advanced by Hildebrand ( 6 ) it is to be expected that the ethylene oxide-acetaldehyde system ill not deviate widely from the ideal, whereas the ethylene oxide-water
system would deviate strongly. Published data are available
(16) for the system acetaldehyde-water and show clearly the deviation from ideal behavior.
As there vas no reported information on the system ethylene
oxide-acetaldehyde, the vapor-liquid equilibria for this system
was determined. Some information (7) is available on the
ethylene oxide-water system, but this is not of sufficient precision
in the range, where it is chiefly required-that is, for low concentration of a ater. In the work mentioned, the authors designate
as 1Wyo ethylene oxide the vapor composition in equilibrium
with liquid mixtures containing more than 20.27, ethylene oxide
by weight. This indicates an insufficiently precise method of
analysis
Vapor-liquid equilibria for acetaldehyde and water are available (16) for liquid compositions up to 38yo by weight of acetaldehyde. These data are given in Table I with the activity coefficients calculated so that they can be compared with those for
the system ethylene oxide-water

Acetaldehyde was fractionated on the same column in order

to separate it from polymers and acetic acid. The distillate was
either used immediately after fractionation or was stored a t
-10" C. in a closed bottle. Vapor pressure determinations indicated the high purity of the samples.
VAPOR P R E S S U R E DETERMILTATIONS

If the vapor-liquid equilibria are to be expressed in terms of

activity coefficients, the vapor pressures of ethylene oxide and
acetaldehyde are required over the temperature range of the
equilibrium experiments. The vapor pressure of ethylene oxide
has been determined by Maass and Boomer (11) from -57" t o
f12.8' C. and by Moor et al. (IS)from -5' to +40 C. The
following equations can be fitted to these two sets of data.
3laass and Boomer (11): log p =
Moor et az. (IS):log p =

- 1356 + 7.653
-

-1410
+ 7.839

where p is the pressure in millimeters of mercury and T is the

absolute temperature,
Since these equations differ appreciably, experimental determinations were made with an Loteniscope and the resuks are
shown in Table XI. The range over which vapor pressures were
determined was from 0" to 32' C. The data can be representcd
by the equation

+ 7.659

log p =

This is in close agreement with the equation fitted to the data

of Maass and Boomer (11) and as the temperature range in the

present experiment differs from that of Maass, it appears probable
that an equation of this type gives a good approximation over the
whole range.
Since the completion of the experimental part reported here,

TABLEI. VAPOR-LIQUIDEQLTLIBRIA FOR ACETALDCHYDBWATERAT 760 MM.

[Data from Pascal et al. (fs)]
Mole % Acetaldehyde
Liquid
Vapor
0.5
25
1
50
4
75
10
89
20
93

B.P.,
0

c.

93.5
82
63
43
33

PURIPICATION O F COMPONENTS

Activity Coefficients
CHsCHO
Ha 0
5.4
0.95
7.3
1 .oo
4.6
1.15
4.0
1.43
3.0
1.75

OF ETHYLEYE
OXIDE
TABLE
11. VAPORPRESSURE

The ethylene oxide used contained small amounts of acetaldehyde and water. It was purified by mixing with 5% triethanolamine and fractionating on a column, 2.5 cm. in diameter
and 60 cm. high, packed with glass Fenske helices. The column
was operated a t a 10 t o 1 reflux. The first 5% v a s rejected and
a residue corresponding to 20% of the charge was left in the reboiler. The remaining distillate vias used for the experimental
work.

(-273.2'

Temp.,
C.
0.3
0.4
1.1
1.2
10.5
10.7
11.1
12.55
15.7

1 Present address, Coal Tar Research Association, Oxford Road, Gomersal,Leeds, England.

1434

Mm. H g
506
508
522
526
700
766
775
823
928

C.

0' K.)
Temp., O C.
16.05
16.6
16.75
21.6
24.9
29.0
30.35
31.8

Mm. Hg
939
958
964
1156
1294
1518
1574
1654

INDUSTRIAL AND ENGINEERING CHEMISTRY

July 1950

Giauque and Gordon ( 4 ) have also reported data of ethylene

oxide vapor pressures. Over a range from -50' to +12' C. the
equation
log p =

- (2045.70/T) - 0.021507 T

2.3328 X 10-6 T a = 14.31363

is in excellent agreement with their experimental results.

Using these equations to find the boiling point at atmospheric
pressure (760 mm.) the following result:
Moor et al. ( I S ) : 11.2' C.
Maass and Boomer (11): 10.7 * 0.1' C.
Giauque et al. ( 4 ) : 10.50 * 0.05' C.
Present work: 10.4 * 0.2" C.
The boiling point of ethylene oxide has also been reported (19)

as 10.7"C. by Timmermans and Hennaut-Roland, but no further

vapor pressure data are recorded in that paper.
The freezing point of the ethylene oxide used for these experiments was -113 * 0.5' C. This may be compared with melting pointa in the literature of -111.4' C. (II), -111.7' C. (19),
and -112.51 * 0.05' C. (a).

1435

The Othmer still is normally operated with liquids boiling

above the ambient temperature. This results in a slight reflux
taking place initially in the outer jacketing space. Under these
conditions, and with liquids whose boiling points are not far
apart, the temperature recorded in the vapor stream will approach closely that recorded in the boiling liquid. With the
liquids under consideration here the two observed temperatures,
in the vapor and liquid, respectively, differed appreciably. When
ethylene oxide-acetaldehyde mixtures were being distilled at
atmospheric pressure the vapor stream was always slightly superheated unless the top of the still was cooled below the dew
point of the vapor. When this was done the same temperature
was observed in the liquid and in the vapor. During the experiments with ethylene oxide-acetaldehyde mixtures some observations were made with and without cooling the top of the still.
No significant difference in the vapor and liquid compositions
was found for this change in conditions.
With ethylene oxide-water mixtures of high water content in
the glass equilibrium still the observed temperature in the vapor
was found t o be lower than that in the boiling liquid, as a result
of the very large difference between the boiling point of the liquid
and the dew point of the vapor.

TABLE
111. VAPORPRESSURE
OF ACETALDEHYDE
(-273.2''

C.

Temp.,

-0.2
2.7
6.7
9.3
11.6

C.

Mm. Hg

0" K.)

Temp.,

332
375
443
494
531

.a

C.

13.3
17.6
20.7
30.8
34.4

Mm. H g

577
682
766
1120
1259

The vapor pressure of acetaldehyde has been determined by

Gilmour (6) from its atmospheric boiling point to 28' C. and by
Emeleus (3)from -97' t o 0" C. The determinations by Emeleus are in line with those of Gilmour over the temperature interval of 0" to -23' C., but below this temperature the points deviate so widely from the straight line, when plotted as log p
against 1/T, that they are assumed in error. Experimental data
by the present authors are recorded in Table 111. The following
equations are used to express the results:

- 1412 + 7.694
T
1413
= -+ 7.694

Gilmour (6): log p =

Present work: log p

From these equations the following boiling points a t 760 mm. can
be calculated:
Gilmour (6): 20.2' C.
Present work: 20.4 * 0.2"C.
The agreement in the case of acetaldehyde is excellent. Agreement on ethylene oxide is not so general. It should, however, be
noted that the present results are in good agreement with the results of Giauque and Gordon ( 4 ) of recent date. In any case, it
is considered that errors which might arise from the presence of
impurities of the order indicated by the boiling point differences
are small in relation t o those arising from the inaccuracy of the
analytical methods used in the vapor-liquid equilibrium determinations,
VAPOR- LI QUID E QUI LIBRIA

The vapor-liquid equilibria were determined in stills of the

Othmer type. T h e experiments a t atmospheric pressure were
done in a glass still of conventional design ( l a ) , and the experiments above atmospheric pressure were done in a pressure still
based on a design by Othmer (16). As ethylene oxide boils a t
10.4' C., it was necessary to circulate a cooling fluid in the condenser.

MCkEoh%HzfzO
Figure 1.

80

IN LIO.

Ethylene Oxide-Water System

Solid curves on activity coefficient plot represent the

van Laar equations; broken lines are drawn through
experimental points. triangles represent data in Table
I for Acetaldehyde-water

INDUSTRIAL AND ENGINEERING CHEMISTRY

1436

The pressure still ( 1 6 ) was designed to take a charge of 500

ml. of liquid. The pressure was measured vith a Bourdon gage
accurate to * 1 pound per square inch. Samples were withdrawn
undrr pressure With this metal still n o difference was observed
between the temperatures in the liquid and in the vapor stream.
The temperatures were above atmospheric and the larger size and
metal construction favored heating of the thermometer in the
vapor stream to the correct temperature.

TABLE

Is'.

VAPOR-LIQUID E Q C I L I B R I A FOR

b:THYLEKE

OXlDE-

ACETALDEHYDE
T

C.
10.4
10.4
10.6
10.6
10.6
10.6
10.6
10.7
10.7

11.6
13.5
14.6
16.0
17.3

...
...

33.5
33.5

...

34.7

~Mole
, ,% (CHzh0 in

Liquid
99.65
99.17
99.12
98.95
98.77
98,52
97.94
96.75
96.66
88.30
64.0
52.8
41 .0
29.5
19.4
17.2
98.68
98.66
97.50
81.4

Vapor

Activity Coefficients
~ _ _ _ _ ~
CIIICHO

(CHdzO

A t 760 Mm. Pressure

99.82
1.002 = 0.005
99.56
1.005 * 0,005
99.47
0.993 0.005
99.30
0.998 * 0.005
99.12
0.993 = 0.005
99.08
0.995 * 0 . 0 0 5
98.61
0.996 = 0.005
97.78
0.995 * 0.005
97.92
1.00 * 0.01
91.80
1 . 0 0 * 0.02
72.0
1.00 * 0.04
63.6
1.02 = 0.04
51.3
1.00 * 0.04
39.0
1.03
0.04
25.4
...
23.0
...
f

A t 34 Lb./Bq. Inch Pressure

98.99
1 . 0 3 * 0.03
99.04
1 . 0 3 * 0.03
98.20
86.2
1.06 i O . 0 5

0.76
0.12
0.78 = 0.08
0.88 * 0 . 0 8
0.98 1 0 . 0 8
1.05 * 0.08
0.92 + 0 08
0.99 * 0.08
0.99 * 0 . 0 8
0.91 t 0 . 0 8
0.99 * 0 . 0 8
1.01 1 0 . 0 4
0.96 i- 0.04
0.97 = 0 . 0 4
0.99 * 0.04

where yi
P
p,

Vol. 42, No. 7

activity coefficient for component 1

total vapor pressure of system
vapor pressure of pure component 1 a t the temperature of the system
21 = mole fraction of component' 1 in liquid
y1 = mole fraction of component 1 in vapor
=
=
=

This calculation assumes that the vapors approximate ideal

gases.
I n making this calculation it is clear that the effect of the
analytical accuracy can become very large, for example, where 211
is small and is found by determination of component 2. Thc
estimated accuracy of the activity coefficientshas been included,
therefore, in Tables I V and 17.

, .

1.09
1.03

* 0.1
* 0.1

1 , 0 3 ' i0 . 1

When the ethylene oxide-wat,er system was studied, the rate

of hydrolysis was known to be appreciable above 50" C., if more
than an hour was allowed for equilibrium to be reached. Below
this temperature the glycol formation is negligible provided t>hc
pH of t,he mixture is maintained in the range of 6 to 8. A s a precaution, each day's work was started with freshly prepared liquid
mixtures.
ANALYSES

Three methods of analysis were used in this work. For the

ethylene oxide-acetaldehyde system, amounts up to 10% acetaldehyde were determined by t'hr silver oxide met,hod ( 1 7 ) . For
the remainder of the range, ethylene oxide was determined by a
modified Lubatti method ( 1 0 ) in which the ethylene oxide reacts
with hydrochloric acid to give ethylene chlorohydrin. This
method is subject to certain errors which tend to give low results.
The reasons for this have been discussed hy Lichtenstein and
Twigg (9) and a more detailed study has been made in t,his laboratory and is being prepared for publication. In the ethylene
oxide-water system, the mixtures cont,aining less than 5% water
were analyzed by the Karl Fischer reagent.
The accuracy of the analyses is estimated to be 170for ethylcne
oxide, 2y0for acetaldehyde, and 2% for water, the percentage in
each case being on the result. The significance of the accuracy
of the analyses is discussed below.
RESULTS

While the curves relating liquid to vapor composition and to

boiling point are sufficient for distillation calculations, the expression of the results in terms of activity coefficients is much to
be preferred, as it admits an immediate appreciation of the deviation from the behavior of an ideal mixture. It also enables
some evaluation of the consistency of the data and, if necessary,
extrapolation from a few experimental results over the a-hole
range of compositions. The significance of the activity coefficient
and the application of vapor-liquid equilibrium data is discussed
by Carlson and Colburn ( 2 ) . The activity coefficients have been
calculated from

F7.

T'.~POR-IJIQCID EQUILIBRI.4
ATER

_X t . 70HzO in Mole_% (CHd20

11.5
11.7
11.8
11.9
12.0
18.2
13.7
14.3
15.0
15.1
16.4
31 .O
31.5
37.6
50.0

FOR E T H Y L E S E OXIDE-

IT'

Liquid

Vapor

2.05
2.85
4.2
4.95
5.85
20.1
24 5
35.5
52

0.80
0.27
0.41
0.39
0.46
0.61
0.64
0.61
0.64
0.65
0.75

57

60
79.5
82.2
85.4
90.7

1.14

1,66

2.58
6.3

Liquid

Vapor

~
.4ctivity Coefficient ~
~(CH2)rO
H20

At 760 M m . Pi' e w m
95.1
99,27
1 01 =0.005
93.3
99.34
1.02 * 0 . 0 1
91 . o
99.00
1.04 * 0.02
99.05
89.0
1.06 =t 0 . 0 2
98.88
87.5
1.06 * 0.02
98.53
61.5
1.44 * 0 . 0 5
98.45
1 . 5 6 =k 0.05
56.0
98.53
1.96 * 0.05
43.2
98.45
3 . 0 1 * 0.05
27.4
98.41
23.2
3.55 * 0 . 0 5
98.16
21 . 0
3 . 7 2 * 0.05
96. 48
4.85 * 0.08
9.5
95.95
8.2
5.54 + 0.1
6.5
93,i
5.55 * 0.1
86.0
5.5fi * 0 . 1
4.0

11.1

7.3
8.1
6.3
6.5
2.6
2.3
1.62
1.27
1.22
1.27

0.0

0.6

*o 6

*0.5
-0.5

=0.2
*lLl

* 0.1
* 0.08
0.08
* 0.08
* 0.06
* 0.06
=t

0.88
0.97
1.05 ;t 0 06
1.20 * 0.06

Pres-

~sure,
b . 1 ~T~~~~. ~ ~ Wi.
, , ,c/o M 2 0
Inch

C.

Liquid Vapor
Above 760

34
34
34
34
65

35.4
35,4

...

37.5
56.3

1.41
1.36
2.20
4.70
7.9

0.27

0.67

(CH2)zO

Pressure
96.56 99.34
9 6 . 6 8 99.27
9 4 . 8 5 98.90
8 9 . 3 98.36
8 2 . 7 97.58

0.97
0.97
0.96
0.99
1.13

11111.

0.30
0.45
0.99

1Iole % (CHd20
Liquid Vapor

Activity CoeFi,
120

8.4
9.3
9 3
5.6
a.7

Figure 1 shows the plot of activity coefficient on a logarithmic

scale against' the liquid mole composition of each component.
The activity coefficients for the ethylene oxide-acetaldehyde
can be seen from Table IV to be, within the limits of experimental
error, unity over the whole range except for a slight decrease in the
region of below 1% acetaldehyde. These data, therefore, have
not been represented graphically, and it is concluded that' tjhe
system obeys Raoult's lam with close approximation. This is not
surprising in view of the many similarit,ies to which reference has
already been made by Maass and Boomer ( 1 1 ) .
The system ethylene oxide-water is shown graphically iii
Figure 1. The equilibrium curve is shown only for the rango
95 to 100 mole % ethylene oxide in the vapor phase in order to
show this section clearly.
The Gibbs-Duhem equation may be expressed as

Assuming the vapors to behave as ideal gases this may bc rcwritten for a binary mixture as

This equation has been integrated in several ways, notably by

van Laar (8),
Margules (IS),and Scatchard ( I t ? ) , and it is of in-

INDUSTRIAL AND ENGINEERING CHEMISTRY

July 1950

1437

The change of activity coefficient with temperature is described

by

Figure 2. Change of Activity Coefficient

with Temperatule for Ethylene OxideWater System
Broken lines show the experimental results corrected for temperature variation; solid lines
show the van Laar equations

terest to apply the derived equations to the present data. In

integrating the Gibbs-Duhem equation it is necessary to assume constant temperature over the whole range of mixture compositions and for most systems of industrial interest this does not
prevent the possibility of fitting the derived equations closely
t o the experimental data, since the components normally boil
within 20" C. or less of one another and the temperature range
for constant pressure data is relatively small. With ethylene
oxide and water this is not the case. The derived equations
were first fitted t o the uncorrected experimental data. The van
Laar and Margules equations give essentially the same curves for
these data, whereas the Scatchard equation gives a curve that is
obviously not appropriate. The van Laar equation, therefore, is
used here in the form

111 y2

(1

z)2

where L1 is the heat absorbed when 1 mole of component 1 is

added to a n infinite amount of component 2. Bichowski and
Rossini (1) give LI for ethylene oxide and water as 1500 calories
per mole a t 18" C. Using this value for L1 it is possible to make
an approximate calculation of the effect on In y, for ethylene
oxide a t the terminal value, for a temperature drop from 100 ' to
20" C. Taking the terminal value of In y as 1.92 from the experimentally derived curves, this would become 2.40 for an 80' C.
temperature fall. Similar calculations can be made for the experimental values in the range where the temperature was above
20" C. I n Figure 2 the In y curves, corrected for temperature
in this manner, are shown and the "corrected" curves and those
for the corresponding van Laar equations may be compared.
Although the curve representing experimental results for water
now approximates very closely to the van Laar curve, the deviation of the ethylene oxide curve is about the same as that found
for the curve for water in the direct representation of the experimental results in Figure 1. Therefore, it appears t h a t the wide
temperature range for this system is not the cause of the failure of
the van Laar equations t o fit the experimental data very closely.
It is of interest t o compare the equilibrium data for acetaldehyde-water with those for ethylene oxide-water. The activity
coefficients have been calculated for the former system (16) and
are shown in Table I, and they are compared with the ethylene
oxide-water equilibria over the corresponding compositions range
in Figure 1. Agreement between the two sets of results is close.
This appears to be consistent with results showing t h a t the ethylene oxide-acetaldehyde system is ideal, although present theoretical treatments do not appear to permit a rigid comparison t o
be made. It is proposed to discuss this point further in a later
publication.
Carlson and Colburn ( 8 ) quote the acetaldehyde-water system
as one which cannot be fitted closely with derived equations.
VARIATION O F ACTIVITY COEFFICIENT WITH P R E S S U R E

The experimental determination of the vapor-liquid equilibria

a t elevated pressures was done only for compositions of immediate practical interest. Those for ethylene oxide-acetaldehyde
(Table I V ) confirm the ideality of the system. Those for ethylene oxide-water (Table V) show the expected decrease of activity coefficients from the values a t atmospheric pressure.
These data are not sufficiently complete for further consideration.

where A and B are the terminal values of the In y versus liquid

composition curves. From the experimental curves, taking
these constants to be A = 1.92 and B = 2.68, the van Laar
curves have been drawn in Figure 1. The agreement is rather
good and supports the view ( a ) that these equations form a useful method of smoothing or extrapolating data of this type, even
for such highly irregular liquids as those under discussion.
It has already been noted that the derived equations from the
Gibbs-Duhem relationship assume constant temperature and
pressure over the whole range of compositions. For the system
under discussion, the total variation of temperature is from 10"
to 100" C., although from 10 to 100 mole yoethylene oxide in the
liquid the variation in the boiling point is only 20" C. It is
therefore possible that the terminal value of the ethylene oxide
is lower than it would be for isothermal data, since increased temperature will cause the activity coefficients to approach unity for
any system.

CONCLUSIONS

Ethylene oxide and acetaldehyde behave as an "ideal" liquid

mixture in regard t o their vapor-liquid equilibria. Ethylene
oxide and water mixtures show high positive activity coefficients
for both components.
ACKNOWLEDGMENT

The authors wish t o thank H. Steiner for his assistance and

encouragement in preparing this paper and also R. K. Truelove
for carrying out the analytical work.
LITERATURE CITED

Bichowsky, F. R., and Rossini, F. D., "Thermochemistry of

Chemical Substances," p. 46, New York, Reinhold Publishing Corp., 1936.
Carlson, H. C., and Colburn, A. P., IND.
ENG.CHEM.,34, 581-9
(1942).

Emeleus, H. J., J . Chem. SOC.,1929, 1733-9.

Giauque, W. F., and Gordon, J., J . Am. Chem. SOC.,71, 217681 (1949).

INDUSTRIAL AND ENGINEERING CHEMISTRY

1438

Vol. 42, No. 7

(6) Gilmour, R., J . SOC.Chem. Ind., 41, 293-4T (1922).

(13) Moor, V. G., K a n e p , E. K., a n d D o b k i n , I. E., Trans. Ezptl.
(6) H i l d e b r a n d , J. H., Solubility of Konelectrolytes, 2nd cd.,
Research Lab. K h e m g a s , Materials o n Cracking and Chemical
chap. 111, 1936.
Treatment of Cracking Products U.S.S.R.,
3, 320-8 (1937).
(14) O t h m e r , D. F., J N D .EXG.CHEM.,35, 614-20 (1943).
(7) Kireev, V. A., a n d P o p o v , A. A . , J . Applied Chem. (U.S.S.E.),
7, 489-94 (1934).
(15) O t h m e r , D. F., a n d Morley, F. R., Ibid.,38,751-7 (1946).
(16) Pascal, P., D u p u y , Ero, a n d Garnier, Bull. soc. chim. France,
(8) Laar, J. J. v a n , 2 . phusik Chem., 72, 723-51 (1910); 83, 599608 11913).
29, 9-21 (1921).
.
,
(9) Lichtenstein, H.J., a n d Twigg, G . H., Trans. F a ~ a d a ySoc., 44,
(17) P o n n d o r f , W., Ber., 64, 1913-6 (1931).
905-9 (1948).
(18) Scatchard, G., a n d H a m e r , W.J., J . Am. Chem. Soc., 57, 1805(10) L u b a t t i , J., J . SOC.Chem. Ind., 51, 361-7T (1932).
9 (1935).
(11) Maass, 0.. a n d Boomer, E. H.. J . Am. Chem. Soc., 44, 1709-28
(19) T i m m e r m a n s , J., a n d Hennant,-Roland, -MMme., J . chim. phys.,
(1922).
34, 693-739 (1937).
(12) Margules, M., Sitzber. A k u d . Wiss Wien, itlath.-nutunu. K ~ S S E .
11, 104, 1243-78 (1895).
RECEIVED
December 28, 1949.

Solubility Diagrams for Ternary and Quaternary Li

Correction and Addendum
Since the article on Solubility Diagrams for Ternary and Quaternary Liquid Systems appeared [Smith, J. C., ISD. ENQ.
CHEM.,41, 2932 (1949)], several errors and omissions have been
called to the authors attention. On page 2932 in Table I

ADDITIONALSYSTEMS
Components of
Aqueous Ternary
Systems
Acetone
Chloroform
Glycerol
n-Heptane
n-Hexane
Polyvinylpyrrolidone
(Kollidon)
Allyl alcohol
Carbon tetrachloride
Trichloroethylene
Ethanol
Benzene
Ethyl acetate
Ethyl ether
Toluene
Trichloroethylene
Trichloroethylene
m-Xylene
~\Ha)zSOr
Etkyl ether
Ethanol
Vinyl pyrrolidone
&PO4
Glycerol
Acetone
tert-Amyl alcohol
Aniline
Benzyl alcohol
%-Butylalcohol
Cyclohexanol
Methyl ethyl ketone
Methanol
iMethylmethacrylate
Methyl ethyl ketone
Benzene
Butyl Cellosolve
Chlorobenzene
Glycerol
n-Heptane
n-Hexane
1,1,2-Triohloroethane
Trichloroethylene
Phenol
Benzine
Isopropyl alcohol
Diisopropyl ether
n-Propyl alcohol
n-Propyl acetate
Pvridine
Benzoic acid
Toluene
Diethylamine
Ethanol
Trichloroethylene
Allyl alcohol
Ethanol
Ethanol
Methyl ethyl ketone
Nicotine
Vinylpyrrolidone
Ethyl acetate
Ethyl ether
Methylene chloride

Temp.,

C.

25,60

the citation number for the system water-acetaldehyde-vinyl

acetate should be ( 112), not (102). On page 2933 the temperature
listed for the system water-ethanol-p-xylene should be 15 C.,
not 0 C.; the system water-ethanol-p-nitrotoluene should be
water-ethanol-0-nitrotoluene, although incorrectly listed in
several places in the original reference (21). The system benzenetoluene-n-heptane-methyl sulfate should be deleted from Table
IV on page 2935.
Additional ternary systems for which data are available are
listed, with literature citations.

25
25

LITERATURE CITED

25

25

25 and b.p.

25 and b.p.
25
70

20
25
25
20,67
25
33
20
25
0

25
7.6, 25,48.6

25.75

25,75
25
60
25
25

25, 50
25
25
25

25

25
25

25
80,90

25
20,35
50

25
25
25 and b.p.
25
20,67
25
17

25
25
2 :.

system-

(Al) B o n n e r , W. D., a n d Williams, R.I. B., J . Phga. Chem., 44, 404

(1940).
(A2) Colburn, A. P., a n d Phillips, J. C., Trans. Am. Inst. Cham.
Engrs., 40, 333 (1944).
(A3) C o p e n h a v e r , J. W.,a n d Bigelow, 1LI. H., Acetylene a n d
C a r b o n Monoxide C h e m i s t r y , pp. 76-9, New York,
Reinhold P u b l i s h i n e Corls.. 1049.
(A4) Elgin, J. C . ( t o ColGte-Palmolive-Peet Co.), U. S. P a t e n t
2,479,041 (Aug. 16, 1949).
(A5) Frere, F. J., IND.
ENGI.
CHEM., 41, 2366 (1949).
(A6) Griswold, J . , C h u , P. L., a n d Winsauer, W. O., Ibid., 41, 2352
(1949).
(A7) H a n d s , C . H. G., a n d N o r m a n , W. S., Trana. Inst. Chem.
Engirs. (London),23, 76 (1945).
(AS) Kooi, J., Rec. trav. chim., 68, 34 (1949).
(A9) Mertslin, P. B., J . Gen. Chem. (U.S.S.R.), 8, 1742 (1938).
(A10) M o n d a i n - l l o n v a l , P., a n d Quiquerez, J., Bull. 8oc. him,,
7, 240 (1940).
( A l l ) N e w m a n , hl., H a y w o r t h , C. B., a n d T r e y b a l , R. E., IND.
ENC.CHEV.,41, 2039 (1949).
(A12) Reilly, J., Kelly, D. F., a n d OConnor, M., J . Chem. SOC.
(London), 1941, 275.
(A13) Reinders, W., a n d Minjer, C. I-I. de, Rec. trav. c h i m . , 66, 552
(1947).
(A14) Ibid., p. 573.
(A15) R u d e r m a n , L. Ya., J. Applied Chem. (U.S.S.R.), 20, 908
(1947).
(816) Shell Chemical Co.. S a n Francisco, M e t h y l E t h y l Ketoiie,
pp. 33, 34, 1938.
(A17) S m i t h , T. E., a n d Bonner, R. F., IND.ENG.CHEM..42, 896
(1950).
(A18) T r a u b e , J., a n d N e u b e r g , O., 2. physik. Chent., 1, 509 (1887).
(819) T r e y b a l . R. E., a n d Vondrak, 0. J., IND.ENG.CHEnf., 41,
1761 (1949).
(A20) Ust-Kachkintsev, V. F., a n d Khlebnikov. P. A., J . Gen
Chem. (U.S.S.R.),9, 1742 (1939).
(A21) W e h n , W. E., a n d F r a n k e , N. W., IND.ENG.CHBM.,41,
2853 (1949).
(A22) Zhuravlev, E. F., Bull. inst. recherche8 bid. Perm., 11, 37
(1937).

. ,

J. C. S m m