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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 Acetaldehyde was fractionated on the same column in order
oxide-acetaldehyde and ethylene oxide water were deter- to separate it from polymers and acetic acid. The distillate was
either used immediately after fractionation or was stored a t
mined at atmospheric pressure and also at higher pres- -10" C. in a closed bottle. Vapor pressure determinations in-
sures for some compositions. The vapor pressures of dicated the high purity of the samples.
ethylene oxide and acetaldehyde were determined be-
tween 0" and 35" C. The system ethylene oxide-water is VAPOR P R E S S U R E DETERMILTATIONS
discussed in terms of its activity coefficients.
If the vapor-liquid equilibria are to be expressed in terms of
activity coefficients, the vapor pressures of ethylene oxide and

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
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
amount of acetaldehyde which is produced a t the same time. f12.8' C. and by Moor et al. (IS)from -5' to +40° C. The
This separation is normally achieved by first distilling over- following equations can be fitted to these two sets of data.
head a product containing about 70Yc water, the remainder
being ethylene oxide and acetaldehyde. This material is then 3laass and Boomer (11): log p =
- 1356 + 7.653
-
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 Moor et az. (IS):log p =
-1410
- + 7.839
the calculations for such columns it is necewiiy to know vapor-
liquid equilibria for the components of the system in certain con- where p is the pressure in millimeters of mercury and T is the
centration ranges. Since the ethylene oxide and acetaldehyde are absolute temperature,
far more easily separated by distillation from water than from Since these equations differ appreciably, experimental deter-
one another the information required for practical purposes is minations were made with an Loteniscope and the resuks are
that for the three binary systems ethylene oxide-water, acetalde- shown in Table XI. The range over which vapor pressures were
hyde-witer, and ethylene oxide--acetaldehyde. From the gen- determined was from 0" to 32' C. The data can be representcd
eral considerations advanced by Hildebrand ( 6 ) it is to be ex- by the equation
pected that the ethylene oxide-acetaldehyde system ill not de-
viate widely from the ideal, whereas the ethylene oxide-water log p = + 7.659
system would deviate strongly. Published data are available
(16) for the system acetaldehyde-water and show clearly the de- This is in close agreement with the equation fitted to the data
viation from ideal behavior. of Maass and Boomer (11) and as the temperature range in the
As there vas no reported information on the system ethylene present experiment differs from that of Maass, it appears probable
oxide-acetaldehyde, the vapor-liquid equilibria for this system that an equation of this type gives a good approximation over the
was determined. Some information (7) is available on the whole range.
ethylene oxide-water system, but this is not of sufficient precision Since the completion of the experimental part reported here,
in the range, where it is chiefly required-that is, for low concen-
tration 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 TABLEI. VAPOR-LIQUIDEQLTLIBRIA FOR ACETALDCHYDB-
by weight. This indicates an insufficiently precise method of WATERAT 760 MM.
analysis [Data from Pascal et al. (fs)]
Vapor-liquid equilibria for acetaldehyde and water are avail- B.P., Mole % Acetaldehyde Activity Coefficients
able (16) for liquid compositions up to 38yo by weight of acetal- 0 c. Liquid Vapor CHsCHO Ha 0
93.5 0.5 25 5.4 0.95
dehyde. These data are given in Table I with the activity co- 82 1 50 7.3 1 .oo
efficients calculated so that they can be compared with those for 63 4 75 4.6 1.15
43 10 89 4.0 1.43
the system ethylene oxide-water 33 20 93 3.0 1.75

PURIPICATION O F COMPONENTS
TABLE OF ETHYLEYE
11. VAPORPRESSURE OXIDE
The ethylene oxide used contained small amounts of acetal- (-273.2' C. 0' K.)
dehyde and water. It was purified by mixing with 5% tri- Temp., C. Mm. H g Temp., O C. Mm. Hg
ethanolamine and fractionating on a column, 2.5 cm. in diameter
and 60 cm. high, packed with glass Fenske helices. The column 0.3 506 16.05 939
0.4 508 16.6 958
was operated a t a 10 t o 1 reflux. The first 5% v a s rejected and 1.1 522 16.75 964
a residue corresponding to 20% of the charge was left in the re- 1.2 526 21.6 1156
boiler. The remaining distillate vias used for the experimental 10.5 700 24.9 1294
10.7 766 29.0 1518
work. 11.1 775 30.35 1574
12.55 823 31.8 1654
1 Present address, Coal Tar Research Association, Oxford Road, Gomer-
15.7 928
sal,Leeds, England.
1434
July 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 1435

Giauque and Gordon ( 4 ) have also reported data of ethylene The Othmer still is normally operated with liquids boiling
oxide vapor pressures. Over a range from -50' to +12' C. the above the ambient temperature. This results in a slight reflux
equation taking place initially in the outer jacketing space. Under these
log p = - (2045.70/T) - 0.021507 T +
2.3328 X 10-6 T a = 14.31363
conditions, and with liquids whose boiling points are not far
apart, the temperature recorded in the vapor stream will ap-
proach closely that recorded in the boiling liquid. With the
is in excellent agreement with their experimental results. liquids under consideration here the two observed temperatures,
Using these equations to find the boiling point at atmospheric in the vapor and liquid, respectively, differed appreciably. When
pressure (760 mm.) the following result: ethylene oxide-acetaldehyde mixtures were being distilled at
Moor et al. ( I S ) : 11.2' C. atmospheric pressure the vapor stream was always slightly su-
Maass and Boomer (11): 10.7 * 0.1' C. perheated unless the top of the still was cooled below the dew
Giauque et al. ( 4 ) : 10.50 * 0.05' C. point of the vapor. When this was done the same temperature
Present work: 10.4 * 0.2" C. was observed in the liquid and in the vapor. During the experi-
The boiling point of ethylene oxide has also been reported (19) ments with ethylene oxide-acetaldehyde mixtures some observa-
as 10.7"C. by Timmermans and Hennaut-Roland, but no further tions were made with and without cooling the top of the still.
vapor pressure data are recorded in that paper. No significant difference in the vapor and liquid compositions
The freezing point of the ethylene oxide used for these experi- was found for this change in conditions.
ments was -113 * 0.5' C. This may be compared with melt- With ethylene oxide-water mixtures of high water content in
ing pointa in the literature of -111.4' C. (II), -111.7' C. (19), the glass equilibrium still the observed temperature in the vapor
and -112.51 * 0.05' C. (a). 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.
111. VAPORPRESSURE
TABLE OF ACETALDEHYDE
(-273.2'' C. 0" K.)
Temp., C. Mm. Hg Temp., .a C. Mm. H g
-0.2 332 13.3 577
2.7 375 17.6 682
6.7 443 20.7 766
9.3 494 30.8 1120
11.6 531 34.4 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 Eme-
leus are in line with those of Gilmour over the temperature inter-
val of 0" to -23' C., but below this temperature the points de-
viate 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:

Gilmour (6): log p = -- 1412 + 7.694


T

Present work: log p


-
= -+ 7.694
1413

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. Agree-
ment on ethylene oxide is not so general. It should, however, be
noted that the present results are in good agreement with the re-
sults 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 deter-
minations,

VAPOR- LI QUID E QUI LIBRIA


The vapor-liquid equilibria were determined in stills of the a I I I I I
Othmer type. T h e experiments a t atmospheric pressure were 0 0 80
done in a glass still of conventional design ( l a ) , and the experi- MCkEoh%HzfzO IN LIO.
ments above atmospheric pressure were done in a pressure still Figure 1. Ethylene Oxide-Water System
based on a design by Othmer (16). As ethylene oxide boils a t Solid curves on activity coefficient plot represent the
10.4' C., it was necessary to circulate a cooling fluid in the con- van Laar equations; broken lines are drawn through
experimental points. triangles represent data in Table
denser. I for Acetaldehyde-water
1436 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 7

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
where yi activity coefficient for component 1
=
undrr pressure With this metal still n o difference was observed P total vapor pressure of system
=
between the temperatures in the liquid and in the vapor stream. p, vapor pressure of pure component 1 a t the tempera-
=
The temperatures were above atmospheric and the larger size and ture of the system
21 = mole fraction of component' 1 in liquid
metal construction favored heating of the thermometer in the
y1 = mole fraction of component 1 in vapor
vapor stream to the correct temperature.
This calculation assumes that the vapors approximate ideal
gases.
TABLE Is'. VAPOR-LIQUID E Q C I L I B R I A FOR b:THYLEKE OXlDE- I n making this calculation it is clear that the effect of the
ACETALDEHYDE
analytical accuracy can become very large, for example, where 211
T ~ ~ , ,% (CHzh0 in
~Mole Activity Coefficients
C. Liquid Vapor (CHdzO
~ _ _ _ _ ~
CIIICHO
is small and is found by determination of component 2. Thc
estimated accuracy of the activity coefficientshas been included,
A t 760 Mm. Pressure
10.4 99.65 99.82 1.002 = 0.005 0.76 f0.12
therefore, in Tables I V and 17.
10.4 99.17 99.56 1.005 * 0,005 0.78 = 0.08
10.6 99.12 99.47 0.993 0.005
f 0.88 * 0 . 0 8
10.6 98.95 99.30 0.998 * 0.005 0.98 1 0 . 0 8
10.6 98.77 99.12 0.993 = 0.005 1.05 * 0.08
10.6 98,52 99.08 0.995 * 0 . 0 0 5 0.92 + 0 08 F7. T'.~POR-IJIQCID EQUILIBRI.4 FOR E T H Y L E S E OXIDE-
10.6 97.94 98.61 0.996 = 0.005 0.99 * 0.08 ATER IT'
10.7 96.75 97.78 0.995 * 0.005 0.99 * 0 . 0 8
10.7 96.66 97.92 1.00 * 0.01 0.91 t 0 . 0 8
11.6 88.30 91.80 1 . 0 0 * 0.02 0.99 * 0 . 0 8 _X t . 70HzO in Mole_% (CHd20 ~.4ctivity Coefficient ~
~-
13.5 64.0 72.0 1.00 * 0.04 1.01 1 0 . 0 4 Liquid Vapor Liquid Vapor (CH2)rO H20
14.6 52.8 63.6 1.02 = 0.04 0.96 i- 0.04
16.0 41 .0 51.3 1.00 * 0.04 0.97 = 0 . 0 4 At 760 M m . Pi' e w m
17.3 29.5 39.0 1.03 0.04 0.99 * 0.04 11.5 2.05 0.80 95.1 99,27 1 01 =0.005 11.1 * 0.0
... 19.4 25.4 ... , . 11.7 2.85 0.27 93.3 99.34 1.02 * 0 . 0 1 7.3 *o 6
... 17.2 23.0 ... 11.8 4.2 0.41 91 . o 99.00 1.04 * 0.02 8.1 * 0.6
11.9 4.95 0.39 89.0 99.05 1.06 =t 0 . 0 2 6.3 *0.5
A t 34 Lb./Bq. Inch Pressure 12.0 5.85 0.46 87.5 98.88 1.06 * 0.02 6.5 -0.5
33.5 98.68 98.99 1 . 0 3 * 0.03 1.09 * 0.1 18.2 20.1 0.61 61.5 98.53 1.44 * 0 . 0 5 2.6 =0.2
33.5 98.66 99.04 1 . 0 3 * 0.03 1.03 * 0.1 13.7 24 5 0.64 56.0 98.45 1 . 5 6 =k 0.05 2.3 *lLl
... 97.50 98.20 14.3 35.5 0.61 43.2 98.53 1.96 * 0.05 1.62 * 0.1
34.7 81.4 86.2 1.06 i O . 0 5 1 , 0 3 ' i0 . 1 15.0 52 0.64 27.4 98.45 3 . 0 1 * 0.05 1.27 * 0.08
15.1 57 0.65 23.2 98.41 3.55 * 0 . 0 5 1.22 =t0.08
16.4 60 0.75 21 . 0 98.16 3 . 7 2 * 0.05 1.27 * 0.08
31 .O 79.5 1.14 9.5 96. 48 4.85 * 0.08 0.88 * 0.06
31.5 82.2 1,66 8.2 95.95 5.54 + 0.1 0.97 * 0.06
When the ethylene oxide-wat,er system was studied, the rate 37.6 85.4 2.58 6.5 93,i 5.55 * 0.1 1.05 ;t 0 06
50.0 90.7 6.3 4.0 86.0 5.5fi * 0 . 1 1.20 * 0.06
of hydrolysis was known to be appreciable above 50" C., if more
than an hour was allowed for equilibrium to be reached. Below Pres-
this temperature the glycol formation is negligible provided t>hc ~sure,
b . 1 ~T~~~~. ~ ~ Wi.
, , ,c/o M 2 0 1Iole % (CHd20 Activity CoeFi,
pH of t,he mixture is maintained in the range of 6 to 8. A s a pre- Inch C. Liquid Vapor Liquid Vapor (CH2)zO €120

caution, each day's work was started with freshly prepared liquid Above 760 11111. Pressure
mixtures. 34 35.4 1.41 0.27 96.56 99.34 0.97 8.4
34 35,4 1.36 0.30 9 6 . 6 8 99.27 0.97 9.3
34 ... 2.20 0.45 9 4 . 8 5 98.90 0.96 9 3
ANALYSES 34 37.5 4.70 0.67 8 9 . 3 98.36 0.99 5.6
65 56.3 7.9 0.99 8 2 . 7 97.58 1.13 a.7
Three methods of analysis were used in this work. For the
ethylene oxide-acetaldehyde system, amounts up to 10% acet-
aldehyde were determined by t'hr silver oxide met,hod ( 1 7 ) . For
the remainder of the range, ethylene oxide was determined by a Figure 1 shows the plot of activity coefficient on a logarithmic
modified Lubatti method ( 1 0 ) in which the ethylene oxide reacts scale against' the liquid mole composition of each component.
with hydrochloric acid to give ethylene chlorohydrin. This The activity coefficients for the ethylene oxide-acetaldehyde
method is subject to certain errors which tend to give low results. can be seen from Table IV to be, within the limits of experimental
The reasons for this have been discussed hy Lichtenstein and error, unity over the whole range except for a slight decrease in the
Twigg (9) and a more detailed study has been made in t,his labora- region of below 1% acetaldehyde. These data, therefore, have
tory and is being prepared for publication. In the ethylene not been represented graphically, and it is concluded that' tjhe
oxide-water system, the mixtures cont,aining less than 5% water system obeys Raoult's lam with close approximation. This is not
were analyzed by the Karl Fischer reagent. surprising in view of the many similarit,ies to which reference has
The accuracy of the analyses is estimated to be 170for ethylcne already been made by Maass and Boomer ( 1 1 ) .
oxide, 2y0for acetaldehyde, and 2% for water, the percentage in The system ethylene oxide-water is shown graphically iii
each case being on the result. The significance of the accuracy Figure 1. The equilibrium curve is shown only for the rango
of the analyses is discussed below. 95 to 100 mole % ethylene oxide in the vapor phase in order to
show this section clearly.
RESULTS The Gibbs-Duhem equation may be expressed as
While the curves relating liquid to vapor composition and to
boiling point are sufficient for distillation calculations, the ex-
pression of the results in terms of activity coefficients is much to
be preferred, as it admits an immediate appreciation of the de- Assuming the vapors to behave as ideal gases this may bc rc-
viation from the behavior of an ideal mixture. It also enables written for a binary mixture as
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 This equation has been integrated in several ways, notably by
calculated from van Laar (8),Margules (IS),and Scatchard ( I t ? ) , and it is of in-
July 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 1437

The change of activity coefficient with temperature is described


by

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 ex-
perimentally derived curves, this would become 2.40 for an 80' C.
temperature fall. Similar calculations can be made for the ex-
perimental 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 devia-
tion of the ethylene oxide curve is about the same as that found
for the curve for water in the direct representation of the experi-
Figure 2. Change of Activity Coefficient mental results in Figure 1. Therefore, it appears t h a t the wide
with Temperatule for Ethylene Oxide- temperature range for this system is not the cause of the failure of
Water System
the van Laar equations t o fit the experimental data very closely.
Broken lines show the experimental results cor- It is of interest t o compare the equilibrium data for acetalde-
rected for temperature variation; solid lines
show the van Laar equations hyde-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
terest to apply the derived equations to the present data. In oxide-water equilibria over the corresponding compositions range
integrating the Gibbs-Duhem equation it is necessary to as- in Figure 1. Agreement between the two sets of results is close.
sume constant temperature over the whole range of mixture com- This appears to be consistent with results showing t h a t the ethyl-
positions and for most systems of industrial interest this does not ene oxide-acetaldehyde system is ideal, although present theo-
prevent the possibility of fitting the derived equations closely retical treatments do not appear to permit a rigid comparison t o
t o the experimental data, since the components normally boil be made. It is proposed to discuss this point further in a later
within 20" C. or less of one another and the temperature range publication.
for constant pressure data is relatively small. With ethylene Carlson and Colburn ( 8 ) quote the acetaldehyde-water system
oxide and water this is not the case. The derived equations as one which cannot be fitted closely with derived equations.
were first fitted t o the uncorrected experimental data. The van
Laar and Margules equations give essentially the same curves for VARIATION O F ACTIVITY COEFFICIENT WITH P R E S S U R E
these data, whereas the Scatchard equation gives a curve that is
The experimental determination of the vapor-liquid equilibria
obviously not appropriate. The van Laar equation, therefore, is
a t elevated pressures was done only for compositions of immedi-
used here in the form
ate practical interest. Those for ethylene oxide-acetaldehyde
(Table I V ) confirm the ideality of the system. Those for ethyl-
ene oxide-water (Table V) show the expected decrease of ac-
tivity coefficients from the values a t atmospheric pressure.
These data are not sufficiently complete for further consideration.
111 y2 = -
(1
R
+ z)2 CONCLUSIONS

Ethylene oxide and acetaldehyde behave as an "ideal" liquid


where A and B are the terminal values of the In y versus liquid mixture in regard t o their vapor-liquid equilibria. Ethylene
composition curves. From the experimental curves, taking oxide and water mixtures show high positive activity coefficients
these constants to be A = 1.92 and B = 2.68, the van Laar for both components.
curves have been drawn in Figure 1. The agreement is rather
ACKNOWLEDGMENT
good and supports the view ( a ) that these equations form a use-
ful method of smoothing or extrapolating data of this type, even The authors wish t o thank H. Steiner for his assistance and
for such highly irregular liquids as those under discussion. encouragement in preparing this paper and also R. K. Truelove
It has already been noted that the derived equations from the for carrying out the analytical work.
Gibbs-Duhem relationship assume constant temperature and
pressure over the whole range of compositions. For the system LITERATURE CITED
under discussion, the total variation of temperature is from 10"
Bichowsky, F. R., and Rossini, F. D., "Thermochemistry of
to 100" C., although from 10 to 100 mole yoethylene oxide in the Chemical Substances," p. 46, New York, Reinhold Pub-
liquid the variation in the boiling point is only 20" C. It is lishing Corp., 1936.
therefore possible that the terminal value of the ethylene oxide Carlson, H. C., and Colburn, A. P., IND.
ENG.CHEM.,34, 581-9
is lower than it would be for isothermal data, since increased tem- (1942).
Emeleus, H. J., J . Chem. SOC.,1929, 1733-9.
perature will cause the activity coefficients to approach unity for Giauque, W. F., and Gordon, J., J . Am. Chem. SOC.,71, 2176-
any system. 81 (1949).
1438 INDUSTRIAL AND ENGINEERING CHEMISTRY 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).
(7) Kireev, V. A., a n d P o p o v , A. A . , J . Applied Chem. (U.S.S.E.), (14) O t h m e r , D. F., J N D .EXG.CHEM.,35, 614-20 (1943).
7, 489-94 (1934). (15) O t h m e r , D. F., a n d Morley, F. R., Ibid.,38,751-7 (1946).
(8) Laar, J. J. v a n , 2 . phusik Chem., 72, 723-51 (1910); 83, 599- (16) Pascal, P., D u p u y , Ero, a n d Garnier, Bull. soc. chim. France,
.
608 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 system-


Correction and Addendum
Since the article on “Solubility Diagrams for Ternary and Quat- the citation number for the system water-acetaldehyde-vinyl
ernary Liquid Systems” appeared [Smith, J. C., ISD. ENQ. acetate should be ( 112), not (102). On page 2933 the temperature
CHEM.,41, 2932 (1949)], several errors and omissions have been listed for the system water-ethanol-p-xylene should be 15” C.,
called to the author’s attention. On page 2932 in Table I 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 benzene-
ADDITIONALSYSTEMS toluene-n-heptane-methyl sulfate should be deleted from Table
Components of IV on page 2935.
Aqueous Ternary
Systems Temp., C. Additional ternary systems for which data are available are
Acetone listed, with literature citations.
Chloroform 25,60
Glycerol 25
n-Heptane 25 LITERATURE CITED
n-Hexane 25
Polyvinylpyrrolidone 25 (Al) B o n n e r , W. D., a n d Williams, R.I. B., J . Phga. Chem., 44, 404
(Kollidon)
Allyl alcohol (1940).
Carbon tetrachloride 25 and b.p. (A2) Colburn, A. P., a n d Phillips, J. C., Trans. Am. Inst. Cham.
Trichloroethylene 25 and b.p. Engrs., 40, 333 (1944).
Ethanol
Benzene 25 (A3) C o p e n h a v e r , J. W.,a n d Bigelow, 1LI. H., “Acetylene a n d
Ethyl acetate 70 C a r b o n Monoxide C h e m i s t r y , ” pp. 76-9, New York,
Ethyl ether 20 Reinhold P u b l i s h i n e Corls.. 1049.
Toluene 25
Trichloroethylene 25 (A4) Elgin, J. C . ( t o ColGte-Palmolive-Peet Co.), U. S. P a t e n t
Trichloroethylene 20,67 2,479,041 (Aug. 16, 1949).
m-Xylene 25
~\‘Ha)zSOr 33 (A5) Frere, F. J., IND. ENGI. CHEM., 41, 2366 (1949).
Etkyl ether (A6) Griswold, J . , C h u , P. L., a n d Winsauer, W. O., Ibid., 41, 2352
Ethanol 20 (1949).
Vinyl pyrrolidone 25 (A7) H a n d s , C . H. G., a n d N o r m a n , W. S., Trana. Inst. Chem.
&PO4 0
Glycerol Engirs. (London),23, 76 (1945).
Acetone 25 (AS) Kooi, J., Rec. trav. chim., 68, 34 (1949).
tert-Amyl alcohol 7.6, 25,48.6
Aniline 25.75 (A9) Mertslin, P. B., J . Gen. Chem. (U.S.S.R.), 8, 1742 (1938).
Benzyl alcohol 25,75 (A10) M o n d a i n - l l o n v a l , P., a n d Quiquerez, J., Bull. 8oc. him,,
%-Butylalcohol 25 7, 240 (1940).
Cyclohexanol 60
Methyl ethyl ketone 25 ( 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.
Methanol ENC.CHEV.,41, 2039 (1949).
iMethylmethacrylate 25 (A12) Reilly, J., Kelly, D. F., a n d O’Connor, M., J . Chem. SOC.
Methyl ethyl ketone
Benzene 25, 50 (London), 1941, 275.
Butyl Cellosolve 25 (A13) Reinders, W., a n d Minjer, C. I-I. de, Rec. trav. c h i m . , 66, 552
Chlorobenzene 25
Glycerol 25 (1947).
n-Heptane 25 (A14) Ibid., p. 573.
n-Hexane 25
1,1,2-Triohloroethane 25 (A15) R u d e r m a n , L. Ya., J. Applied Chem. (U.S.S.R.), 20, 908
Trichloroethylene 25 (1947).
Phenol
Benzine 80,90 . ,
(816) Shell Chemical Co.. S a n Francisco, “ M e t h y l E t h y l Ketoiie,”
pp. 33, 34, 1938.
Isopropyl alcohol
Diisopropyl ether 25 (A17) S m i t h , T. E., a n d Bonner, R. F., IND.ENG.CHEM..42, 896
n-Propyl alcohol
n-Propyl acetate 20,35 (1950).
Pvridine (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).
Benzoic acid 50 (819) T r e y b a l . R. E., a n d Vondrak, 0. J., IND.ENG.CHEnf., 41,
Toluene
Diethylamine 25 1761 (1949).
Ethanol 25 (A20) Ust-Kachkintsev, V. F., a n d Khlebnikov. P. A., J . Gen
Trichloroethylene
Allyl alcohol 25 and b.p. Chem. (U.S.S.R.),9, 1742 (1939).
Ethanol 25 (A21) W e h n , W. E., a n d F r a n k e , N. W., IND.ENG.CHBM.,41,
Ethanol 20,67
Methyl ethyl ketone 25 2853 (1949).
Nicotine 17 (A22) Zhuravlev, E. F., Bull. inst. recherche8 bid. Perm., 11, 37
Vinylpyrrolidone (1937).
Ethyl acetate 25
Ethyl ether 25
Methylene chloride 2 :. J. C. S m m