VAPOR-LIQUID EQUILIBRIUM DATA FOR THE SYSTEM

ACETONE-METHANOL SATURATED WITH SALTS"

SHUZO OHE, KIMIHIKO YOKOYAMA, AND SHOICHI NAKAMURA
Ishikazvajima-Harima Heavy Industries Co., Ltd.
Research Institute, Yokohama
Vapor-liquid equilibrium data at atmospheric pressure of the system : acetone-methanol-salt are
studied. The Salts, Kl, NaCI, MgCI2, CaCI2/ LiCI, and CaBr2 are examined to observe the salt effect
on the acetone-methanol system.
Effective salts are CaQ2, LiC! and CaBr2, which are more soluble in methanol than Kl, NaCI and
MgCh. CaCI2, LiCI and CaBr2 are observed to shift the azeotropic composition from 8O.I to 88.6,
9I-O and 94.O mole /# of acetone, respectively. The salt effect at each infinite dilute concentration
of acetone and methanol increases with the increasing solubility of each salt in the rich concentration
component.

In general, salts shift azeotropic compositions or 2) Experimental method

eliminate azeotropes. For example, sodium chloride The salt, being completely non-volatile, appears only
saturated in ethanol-water system shifts the azeotropic in the liquid, hence yielding a system consisting of
composition from 87 to over 90 mole %ethanol45 and a two-component vapor phase and a three-component
calcium chloride saturated in the ethanol-water system liquid phase. The concentrations of acetone and
eliminates the azeotrope25. This salt effect may be
used for the separation of azeotropic mixtures.
Systems which contain water as one component have
been well studied5>9>10), but studies on non-aqueous
systems are scarce from the point of salt effect. L.
Belcku studied the effect of calcium chloride on the
acetone-methanol system and reported on a constant
concentration of 2.3 moles of salt/mole of solution.
J. Proszt and G. Kollar6) also studied the effect of
calcium-chloride and lithium-chloride and reported on
a constant concentration of 1 mole of salt/liter of
solution.
In this study, isobaric vapor liquid equilibrium data
at atmospheric pressure are reported for the six systems ;
acetone-methanol-KI, NaCl, MgCl2 CaCl2, LiCl and
CaBr2. L. Belckl:> suggested the possibility of the
elimination of the azeotrope, if the data observed from
0 to 95 mole % acetone were extrapolated to 100 mole
%acetone. But, the authors' data show the fact that
azeotropic composition is only shifted from 80.1 to

Apparatus and Method

1) Equilibrium still
The authors modified further the improved Othmer
recirculation still presented by Johnson and Furter4)
for salt effect studies. Fig. 1 shows the equilibrium
still employed.
Heating is done by a wall electric heater adjusted
by a transformer. Two high quality standard thermo-
meters are used for measurement of the boiling-liquid
and vapor-phase temperatures.
Fig.
Received on December 2, 1967 Equilibrium still
1
VOL.2 NO.1 1969
 methanol in the equilibrium liquid phase were cal-
culated by mass balance, using the concentration of
acetone and methanol in the original charge, and the
analyzed concentrations of acetone and methanol in
the equilibrium vapor condensate samples. The hold-
up in the vapor phase chamber and condenser was
neglected. Only the equilibrium vapor condensate
samples were analyzed. Salt concentrations were cal-
culated by the original charge of each component,
which had been weighed. The saturation with salt
was attained with slight excess of solid salt persisting
in the still. The excess solid of salt in the liquid
phase was observed from the windowof the still.
Twelve runs of measurement were made using the
binary system acetone-methanol at atmospheric pres-
sure, in order to check the accuracy of data obtained
from the still. The results without salt were compared
with the literature data8) and found to be consistent
with the data, within the maximumerror of 1%.
Fig. 2 x-ycurvesofacetone (I)-methanol (2)-
CaCh system at I atm.
Thermodynamic consistency of the data was tested by
Herington's3) method, and the data of the system with-
out salt were shown to be consistent thermodynami-
cally. The method, however, cannot be applied to the
system containing salt, thus the consistency was not
tested. To avoid change of salt concentration in the
boiling chamber owing to the deposit of salt on the
inner wall of the still, the revolution rate of the
magnetic stirrer and the distillation rate were adjusted
carefully by continuous observation from the window
of the still.
3) Materials
Acetone, methanol and salts used for experiments
were guaranteed reagents.
4) Analysis
Analysis of the vapor condensate samples was made
Fig. 3 x-y curves of acetone (l)-methanol (2) by refractive indices. The refractive indices of acetone
saturated with LiCI, CaBr2 and CaCh at I atm. and methanol at 20°C are, respectively, 1.3587 and
1.3920. The difference in value of these components
is 0.0333, which is sufficient to determine the concent-
rations. Compositions were calculated from the tables
of refractive index for the acetone-methanol system
published in Timmermans8) data-book, with the tabu-
lated data plotted on a large scale. The refractometer
employed was an Abbe type.
Results
All data are reported on a salt-free basis. Vapor
liquid equilibrium data at atmospheric pressure are
shown in Figs.2, 3, 4, and Tables1,2,3. The salt
effect of six salts on the azeotropic composition are
listed in Table 15).
The data for acetone-methanol-calcium-chloride are
plotted in Fig. 2 and listed as smoothed values in Table
2. Relative volatility of acetone to methanol increases
with increasing CaCL concentrations at liquid phase
concentrations from 0 to 90.0 mole % acetone, but
decreases from 90.0 to 100 mole %acetone. (Fig. 4)
Fig. 4 Relation of relative volatility of acetone CaCl2, LiCl and CaBr2 are observed to shift the azeo-
(I)-methanol (2)-salts system at I atm. tropic composition from 80.1 to 88.6, 91.0 and 94.0
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 Table I Salt effect of six saturated salts on acetone (l)-methanol (2) system and solubilities" (l atm)
Salt effect* Solubility at 55°C** in
Salts Solubility ratio -
Acetone (A) Methanol (B) D
KI 0.809 0.811
NaCl 0. 809 0.818 3.00X10"
55.6
MgCl2 0. 802 0.839
56.2 0.0005 0.0027
CaCl2 0. 802 0. 840
57.0 0.0083 0.0328
LiCl 0. 806 0. 908
57.1 0.0098 0.0775
CaBr2 0. 800 0. 938
* Salt saturated
** Mole fraction

Table 2 The smoothed data of vopor-Iiquid equilibrium in acetone (l)-methanol (2j-CaC!2 (l atm)

Concentrations of calcium chloride

Xi
5 wt.: 10 wt. % 15 wt. % 20 wt. % Saturated
*_rc] t[°C] t[°C]
y\

t[°C]

yi
yi t[°C] ^i

0.050 0.133 63.6 64.4 64.9 0.148 64.8 0.175 70.6

0.100 0.227 61.9 62.8 63.0 0.251 63.0 0.312 65.8
0.150 0.302 60.8 61.3 61.7 0.373 61.6 0.422 63.4
0.200 0.365 59.9 60.1 60.5 0.459 60.5 0.501 61.7
0.300 0.467 58.6 58.6 58.7 0.580 58.8 0.600 59.4
0.400 ' 0.550 57.6 57.6 57.6 - - 0.659 57.9
0.500 0.628 56.7 56.6 __ __ _ 0. 704 56.9
0.600 0.694 56.0 0.745 56.2
0.700 0.765 55.6 0.790 55.8
0.800 0.835 55.9 0.834 55.9
0.850 - 0.860 55.9
0.900 - 0.883 56.1
0.950 - 0.921 56.2

Table 3 Vapor-Liquid equilibrium data for Acetone (l)-Methanol (2) with saturated LiCI and CaBr2 (l atm)
X\ yi
tC°c] yi t [°C] yi

t re]
LiCl LiCl CaBr2
0.025 0.117 95.2 0.494 0.868 63.1 0.050 0.164 82.8
0.050 0.232 92.1 0.600 0.883 60.5 0.096 0.274 86.2
0.075 0.321 89.2 0.703 0.890 57.8 0.245 0.596 77.9
0.096 0.433 0.805 0.899 57.4 0.351 0.718 69.0
85.1
0.129 0.515 0.890 0.907 57.8 0.486 0.852 62.8
84.0
0.179 0.610 0.940 0.931 56.5 0.800 0.930 57.1
78.5
0.245 0.718 73.1 0.950 0.932 56.6 0.902 0.938 56.6
0.359 0.818 67.8 0.982 0.958 56.5 0.950 0.948 56.4

mole % acetone, respectively. (Figs. 2, 3) CaCL, LiCl concentrations, the effect is LiCl>CaCl2>CaBr2. At
and CaBnare the most effective at about 20, 50, and acetone-rich concentrations, the effect is CaBr2>LiCl
60 mole % acetone, respectively, when the salts are >CaCl2. Saturated salt concentrations were not deter-
saturated. (Fig. 4) mined directly. Approximate solubilities, however, are
available from x-y curves of each concentration of
Discussion of Results salt. In Fig. 2, the x-y curves of constant salt con-
centrations: 5, 10, 15wt. % intersect the x-y curve of
Generally, the salt effect may be predicted by the salt saturated. The salt concentration at each inter-
solubility of salt in each component. If the salt is sected point must be the same as that of the respective
more soluble in a less volatile component, then the constant salt concentration x-y curve. Therefore,
relative volatility will be raised, because of the lowered solubilities are able to be determined, graphically at
vapor pressure of the less volatile component. In this each intersected liquid concentration. Solubilities thus
case, the salts are more soluble in methanol, the less obtained are as follows :
volatile component, thus increasing relative volatility. mole % acetone solubility
(Table 1) (salt free 45.8basis) (weight
15.0
%)
On the other hand, the salt effect increases with 63.3 10.0
increasing solubility ratio of salt in acetone to methanol 78.3 5.0

at the concentration from 60 to 100 mole %acetone.

The effect is CaBr2>LiCl>CaCl2. In addition to this,
the salt effect at each infinite dilute concentration of
acetone and methanol increases with increasing solu-
bility of salt in the rich component. At methanol-rich
VOL.2 NO.1
Acknowledgment
The authors acknowledge the continuing guidance of Professor
Mitsuho Hirata (Tokyo Metropolitan University) and the sugges-
1969
tions on experiments of Mr. Motoyoshi Hashitani (Tokyo Met- Literature cited
ropolitan University, Dr. Course) 1) Belck, L.: Chem. Ingr. Techn., 23, 90 (1951)

Nomenclature 2) {Chem.
Hashitani,Eng. M.,
Japan),
M. Hirata, & Y. Hirose: Kagaku Kogaku
32, 182 (1968)
3) Hala, E., et al. : "Vapour Liquid Equilibrium", Pergamon
D = percentage deviation Press (1958)

:
= the value of log (71/V2) dxi 4) Johnson, A. L, & W. F. Furter: Can. J. Technol., 34, 413
(1957)
where?i and j2 are activity coeff.
J a function of boiling points
5) Landolt-Bornstein Zahlenwerte und Funktionen aus Physik.
Chemie. Astronomic Geophysik und Technik 2. Teil b (1962)
Tnim = the lowest measured temperature [°K] 6) (1966)
Meranda, D. & W. F. Furter: Can. J. Technol., 44, 298
x\, xi = mole fractions of acetone & methanol in liquid phase,
respectively (salt free basis) 7) Proszt, J. & G. Kollar: Roczen. Chem., 32, 611 (1958)
yi, j/2 = mole fractions of acetone & methanol in vapor phase, 8) Timmermans, J. : "The Physico-Chemical Constants of Binary
respectively (salt free basis) Systems in Concentrated Solutions" Interscience Pub. (1959)
9) Eng.
Uchida, S., S. Ogawa, & M. Yamaguchi: Jap. Set. Rev.
a = relative volatility of acetone to methanol Sci.y 1, 41 (1950)
as = relative volatility salt free basis including salt 10)16, Yamamoto, Y. et al. : Kagaku Kikai {Chem. Eng. Japan),
0 = a function of boiling points 166 (1952)

= a function of log (7-1/7*2) <fc ll) 28, Yoshida,

133 (1964)
F. et al. : Kagaku Kogaku {Chem. Eng. Japan),

VAPOR-LIQUID EQUILIBRIA OF BINARY SYSTEMS

CONTAINING ALCOHOLS : ETHANOL WITH
NITROMETHANE AND DIETHYLAMINE*
KOICHIRO NAKANISHl*2 RITSUJI TOBA*3 AND HIDEKO SHIRAl*4
Department of Industrial Chemistry, Shinshu University,
Wakasato, Nagano-shi
Vapor-liquid equilibrium data are reported for the binary systems ethanol-nitromethane (MeNO2)
and ethanol-diethylamine (Et2NH) at 73OmmHg.As expected from a strong hydrogen-bond interaction
between hydroxyl group and amino base, the ethanol-Et2NH system shows negative deviation from
the idea! solution law and no azeotrope can be found. The ethano!-MeNO2 system shows a positive
deviation. MeNO2forms an azeotrope at 76.4°C and 75.0 mole % of ethanol. Based on these
results and other activity coefficient data available, the prediction of azeotrope3 formation in binary
ethanol solutions by the previously presented correlation and azeotrope diagram is discussed.

In a series of studies on the vapor-liquid equilibria direction of the deviation from the ideal solution law,
of binary solutions,^12'1" we have obtained the equi- is primarily dependent on the proton accepting ability
librium data for ten binary methanol solutions. We of the molecule in alcohol solution. However, the
have also proposed a correlation between the limiting value of the activity coefficient is also affected by the
value of the activity coefficient of various liquids in difference in size and shape of component molecules.
a large excess of methanol, log?"0, and the "hydrogen- It is thus necessary to obtain detailed information on
bond shift" of the stretching vibration of the O-H
bond of methanol in these liquids, Jvs.12^ It was
such size effect for the purpose of establishing a gene-
ralized activity coefficient correlation in alcoholic and
demonstrated in these studies that the sign and magni- other associated solutions. Although a survey of the
tude of the activity coefficient, i. e., the degree and literature indicates that, in contrast with binary metha-
nol systems, both isobaric and isothermal vapor-liquid
Received on April 30, 1968 equilibrium data are widely available for binary ethanol
Presented in partEngineers,
of Chemical
at the 1stJapan,autumn meeting, Osaka,
Toyonaka,
the Society
Nov. solutions, some important information as to the activity
1967 coefficient behavior in the ethanol systems is still
To whomcorrespondence should be addressed to Depart- missing.
ment of Industrial Chemistry, Kyoto University, Kyoto
Present address : Hitachi Seisakusho Co. Ltd.,of Tokyo. In this paper, wewill report the barometric vapor-
Present address: The Tokyo College Pharmacy, liquid equilibrium data of ethanol (EtOH) with nitro-
Shinjuku, Tokyo methane (MeNCh) and with diethylamine (Et2NH).
4
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