Liquid-Liquid Equilibria of the System

Water + Acetic Acid Methyl Propyl Ketone +

A . B U N C O , J . M. CORREA, A. ARCE and A. CORREA
Chemical Engineering Department, University of Santiago de Compostela (Spain)
+
This article reports equilibrium data for the binary liquid-liquid system water methyl propyl ketone at temperatures
in the range 20-55”C, together with solubilities and equilibrium compositions of the ternary system water + acetic
+
acid methyl - _ .ketone at 25,35,45 and 55°C. NRTL and UNIQUAC equations have been fitted to the experimental
- propyl
data for the ternary system, which are likewise compared with the values predicted by the group contribution method
UNIFAC.

+
Dans cet article on prksente des donn6es d’bquilibre pour le systbme binaire liquide-liquide eau methyl propyle
&one B des temptratures comprises entre 20 et 55”C, ainsi que les solubilitks et les compositions h 1’6quilibre du
+
systbme ternaire eau + acide acktique methyl propyle &tone B 25, 35, 45 et 55°C. On a ajuste les equations NRTL
et UNIQUAC les donn6es exptrimentales du systbme ternaire; ces donnkes sont Bgalement comparees semblables aux
valeurs prkdites par la mtthode de contribution de groupe UNIFAC.

Keywords: liquid-liquid equilibria, ternary liquid-liquid equilibria, binary liquid-liquid equilibria.

L iquid-liquid extraction has several advantages over

rectificationas a method for separating the components
of a mixture, especially when the aim is to concentrate dilute
solutions. In the work described in this article, experimental
solubility and equilibrium data were determined for the
+ +
ternary system water acetic acid methyl propyl ketone
(MPK) at 25, 35, 45 and 55°C so as to allow evaluation of
methyl propyl ketone as an agent for the extraction of acetic
acid from dilute aqueous solutions.
Experimental
MATERIALS
Acetic acid and methyl propyl ketone supplied by Carlo
Erba were both >99.8% pure as determined chromato-
graphically. Water was triple-distilled.
injector and detector temperatures of 240°C. Calibration was
carried out using internal standards. The maximum error in
composition measurements was determined as a mole fraction
of 0.002.
Results
Figure 1 shows the equilibrium data obtained for the system
+
water MPK together with those published by Gross et al.
(1939) and Ginnings et al. (1940). The solubility of MPK
in water is practically independent of temperature in the range
considered (20-55”C), whereas the solubility of water in
MPK increases considerably as temperature rises. The new
data agree quite well with those of Gross et al. and Ginnings
et al. as regards the aqueous phase, but there are small dis-

PROCEDURE

Solubility curves were determined by the cloud point

I I
method (Othmer et al., 1941) in a magnetically stirred cell 60 -
(Correa, 1985) whose temperature was both thermostatted u 0 0
and measured with a precision of f0.05”C. Compositions ol
0
defining the ends of tie-lines were determined in a similar 0 0
cell with a lateral orifice closed by a septum, through which f
samples of the separated phases in equilibrium were with- 40
L 0
0
drawn using hypodermic needles. In each experiment the aJ
ternary mixture to be separated was stirred vigorously for F
aJ
A B1
1 hour and then left to settle for 4 hours, which preliminary oA A
experiments had shown to be long enough for the two phases
I-
20 - A Q
to reach equilibrium. Quantitative analysis of the conjugate
phases was performed using a Perkin-Elmer Sigma 3 gas 0
chromatograph equipped with a thermal conductivity detector
and a Perkin-Elmer-Sigma 15 integrator. 6’ x 1 / 8 ” (outer 0 I 1
diameter) stainless-steel columns packed with Chromosorb
0.10 0.15 0.20 0.95 1.00
102 80/100 were used with a nitrogen carrier gas (N48) flow
rate of 25 mL/min, an oven temperature of 190°C and Mole fraction o f water
+
Figure 1 - Solubility data for the mixture water methyl propyl
ketone. , Gross et al. (1939); A , Ginnings et al. (1940); 0 ,
Correspondence: Dr. A. Arce. this work.
136 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66, FEBRUARY, 1988
 TABLE1 TABLE4
+
Binodal Compositionsof the System Water Acetic Acid + Methyl +
Binodal Compositions of the System Water Acetic Acid + Methyl
Propyl Ketone at 25°C Propyl Ketone at 55°C

Mole fraction Mole fraction Mole fraction Mole fraction

Water Acetic acid MPK Water Acetic acid MPK Water Acetic acid MPK Water Acetic acid MPK

0.988 0.OOO 0.012 0.735 0.134 0.131 0.990 O.OO0 0.010 0.767 0.121 0.112
0.977 0.009 0.014 0.707 0.141 0.152 0.980 0.009 0.011 0.755 0.124 0.121
0.970 0.015 0.015 0.672 0.149 0.179 0.970 0.018 0.012 0.730 0.130 0.140
0.962 0.021 0.017 0.634 0.156 0.210 0.959 0.027 0.014 0.701 0.136 0.163
0.952 0.030 0.018 0.590 0.162 0.248 0.948 0.036 0.016 0.671 0.141 0.188
0.93 1 0.047 0.022 0.545 0.163 0.292 0.936 0.044 0.020 0.633 0.146 0.221
0.916 0.058 0.026 0.495 0.161 0.344 0.917 0.058 0.025 0.583 0.149 0.268
0.897 0.071 0.032 0.443 0.151 0.406 0.897 0.071 0.032 0.539 0.147 0.314
0.876 0.083 0.041 0.381 0.135 0.484 0.875 0.083 0.042 0.486 0.139 0.375
0.853 0.094 0.053 0.316 0.107 0.577 0.851 0.094 0.055 0.435 0.123 0.442
0.840 0.100 0.060 0.245 0.069 0.686 0.825 0.104 0.071 0.312 0.069 0.619
0.829 0.105 0.066 0.165 0.015 0.820 0.796 0.113 0.091 0.211 O.OO0 0.789
0.777 0.122 0.101 0.140 O.OO0 0.860

TABLE5
Liquid-Liquid Equilibria of the System Water + Acetic Acid +
Methyl Propyl Ketone at 25, 35, 45 and 55°C
TABLE2
+
Binodal Compositionsof the System Water Acetic Acid + Methyl Aqueous phase (m.f.) Organic phase (m.f.)
Propyl Ketone at 35°C Acetic Acetic
Mole fraction Mole fraction Temperature Water acid MPK Water acid MPK

Water Acetic acid MPK Water Acetic acid MPK 25°C 0.979 0.007 0.014 0.179 0.029 0.792
0.969 0.016 0.015 0.226 0.059 0.715
0.989 0.OOO 0.011 0.762 0.125 0.113 0.953 0.029 0.018 0.293 0.097 0.610
0.978 0.009 0.013 0.712 0.139 0.149 0.926 0.051 0.023 0.37 1 0.129 0.500
0.971 0.015 0.014 0.642 0.153 0.205 0.905 0.065 0.030 0.452 0.155 0.393
0.960 0.024 0.016 0.600 0.158 0.242 0.881 0.080 0.039 0.540 0.164 0.296
0.953 0.030 0.017 0.556 0.159 0.285
35°C 0.978 0.010 0.012 0.23 1 0.042 0.727
0.936 0.044 0.020 0.510 0.155 0.335 0.970 0.016 0.014 0.251 0.057 0.692
0.917 0.058 0.025 0.455 0.148 0.397 0.950 0.032 0.018 0.296 0.094 0.610
0.898 0.071 0.031 0.400 0.131 0.469
0.877 0.083 0.040 0.338 0.104 0.558 0.919 0.057 0.024 0.400 0.134 0.466
0.854 0.094 0.052 0.270 0.074 0.900 0.070 0.030 0.488 0.155 0.357
0.656
0.885 0.078 0.037 0.564 0.160 0.276
0.829 0.105 0.066 0.218 0.041 0.741
0.801 0.114 0.085 0.152 O.OO0 0.848 45°C 0.980 0.W 0.01 1 0.246 0.040 0.714
0.970 0.017 0.013 0.293 0.069 0.638
0.963 0.023 0.014 0.310 0.081 0.609
0.932 0.047 0.021 0.404 0.129 0.467
0.909 0.064 0.027 0.475 0.147 0.378
0.885 0.079 0.036 0.577 0.156 0.267
TABLE3
+
B i n d Compositions of the System Water Acetic Acid + Methyl 55°C 0.982 0.008 0.010 0.253 0.032 0.715
Propyl Ketone at 45°C 0.971 0.017 0.012 0.309 0.069 0.622
~~~ ~ -
0.959 0.027 0.014 0.347 0.090 0.563
Mole fraction Mole fraction
0.929 0.050 0.021 0.461 0.134 0.405
Water Acetic acid MPK Water Acetic acid MPK 0.914 0.060 0.026 0.522 0.146 0.332
0.888 0.076 0.036 0.631 0.146 0.223
0.990 O.OO0 0.010 0.691 0.142 0.167
0.979 0.009 0.012 0.651 0.149 0.200
0.968 0.018 0.014 0.611 0.153 0.236 crepancies for the organic phase, though the earlier data, in
0.957 0.027 0.016 0.570 0.154 0.276 spite of their scantiness, appear to exhibit the same tendency
0.947 0.036 0.017 0.524 0.151 0.325 for the solubility of water in the ketone to rise with increasing
0.918 0.058 0.024 0.468 0.145 0.387 temperature.
0.898 0.071 0.031 0.409 0.129 0.462 Tables 1-4 list the compositions determining the solubi-
0.877 0,083 0.040 0.377 0.114 0.509 +
lity curves of the ternary system water acetic acid + MPK
0.853 0.094 0.053 0.330 0.096 0.574 at 25, 35, 45 and 55"C, and Table 5 lists the compositions
0.827 0.104 0.069 0.285 0.072 0.643 corresponding to the ends of tie-lines. Figure 2, in which
0.784 0.118 0.098 0.234 0.040 0.726
these experimental data are illustrated (unbroken lines),
0.748 0.128 0.124 0.170 O.OO0 0.830 shows that the immiscibility region shrinks slightly as
temperature rises.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66, FEBRUARY 1988 137
 TABLE6
Residuals F and AP of NRTL and UNIQUAC Equations Fitted to Liquid-Liquid Equilibrium Data for
the System Water + Acetic Acid +
Methyl Propyl Ketone at 25, 35, 45 and 55°C
Model 25°C 35°C 45°C 55°C

NRTL Pm - 3.8 - 3.7 - 4.5 - 3.3

(av = 0.1) F (%) 0.36 0.37 0.57 0.59 0.43 0.44 0.59 0.58
AP (%) 8.3 4.1 13.8 8.8 4.7 3.6 7.3 4.9
NRTL Pm - 3.9 - 3.7 - 4.7 - 4.3
(av = 0.2) F (%) 0.28 0.31 0.21 0.23 0.34 0.36 0.18 0.23
A0 (%) 11.6 4.0 9.6 9.4 7.3 3.3 3.7 3.2
NRTL P, - 4.0 - 4.0 - 4.8 - 4.0
(a,, = 0.3) F (%) 0.19 0.24 0.36 0.44 0.28 0.32 0.32 0.33
AP (%) 10.3 4.1 17.7 9.0 10.1 3.6 7.8 3.6
UNIQUAC - 3.9 - 3.8 - 4.6 - 3.7
F (%) 0.22 0.25 0.37 0.44 0.28 0.34 0.30 0.32
A@ (%) 10.5 4.4 17.3 10.2 14.2 4.2 9.6 4.8

Figure 2 - Binodal curves and tie-lines for the system water
+
acetic acid methyl propyl ketone at 25, 35,45 and 55°C. -,
Experimental results; - - - , UNIFAC predictions.
+ Figure 4 - Binodal curves and tie-lines calculated for the system
+
water + acetic acid methyl propyl ketone at 25, 35, 45 and 55°C
using the equation NRTL (- - -) and UNIQUAC (- - . -), +

together with the corresponding experimental tie-lines ends ( o ).

Correlation by the NRTL and UNIQUAC equations

0 The NRTL equation (Renon and Prausnitz, 1968) and the

UNIQUAC equation (Abrams and Prausnitz, 1975) were
both fitted to the experimental data for the ternary system
using the computer program developed by Ssrensen (1980),
the NRTL non-randomness parameter c y i j being successively
assigned the values 0.1, 0.2 and 0.3. For each set of data
for a given temperature, the system-specific parameters of
both equations are estimated by this program by minimizing
L
v. l
c 2 the objective function.

is 0 yy
0
cc 0.02 0.04 0.06
0.08
F, =
k
min
i j
(nijk - 2ijk)2
Mole fraction o f acetic acid (aqueous phase)

Figure 3 - Influence of the value of fi, on the accuracy of NRTL

and UNIQUAC curves in the low-concentration region. 0 ,
Experimental values (25°C); -, NRTL equation (aii = 0.2); The second term of the right-hand side of (1) is a penalty
_ _ _ , UNIQUAC equation. term designed to avoid multiple solutions by reducing the

I38 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66, FEBRUARY 1988
 TABLE7 TABLE9
Optimized System-SpecificParameters of the NRTL Equation with Goodness of Fit (F,,, Equation (4)) of
a,, = 0.2 for the System Water (1) + Acetic Acid (2) Methyl + UNIFAC Predictions for the Liquid-Liquid
Propyl Ketone (3) at 25, 35, 45 and 55°C +
Equilibria of the System Water Acetic Acid
+ Methyl Propyl Ketone at Several
Temperature @, i-j a, Temperatures
25°C 3.9 1-2 30.57 - 126.63 Temperature ("C) Resjdual, Fp (mol %)
1-3 1268.30 160.72
2-3 -740.43 926.71 25 3.03
35 4.79
35°C 3.7 1-2 1731.80 -779.58
45 6.40
1-3 1351.00 88.03
55 8.82
2-3 32.96 193.96
45°C 4.7 1-2 147.98 - 228.05
1-3 1481S O 65.13
2-3 -745.95 842.86 Parameter optimization was performed both with and
55°C 4.3 1-2 1809.80 -866.42
without the value of 0, being fixed beforehand. Approxi-
1-3 1537.20 25.79 mation to the optimal fixed value was initiated using the value
2-3 424.99 -224.46 obtained by graphical extrapolation of the experimental data,
and terminated when AP attained a minimum. Table 6 lists
the values of F and A@ both for 0, unfixed and for the
value of 0, minimizing AO. In the latter case F is slightly
larger than in the former, i.e. the overall goodness of fit is
TABLE8 slightly poorer, but the improvement in accuracy for low con-
Optimized System-SpecificParameters of the UNIQUAC Equation centrations of acetic acid is considerable, as can be seen in
for the System Water (1) +Acetic Acid (2) +
Methyl Propyl Figure 3, which shows the experimental values of the distri-
Ketone (3) at 25, 35, 45 and 55°C bution ratio at 25°C together with those calculated using the
Temperature 0, i-j IJ bJ1
NRTL equation (ail = 0.2) and the UNIQUAC equation
with and without 0, being fixed at its optimal value. In
25°C 3.9 1-2 128.18 - 286.80 spite of the improvement, however, the tendency of the ex-
1-3 64.10 41 1.53 perimental distribution ratio data is still not accurately
2-3 -83.73 -2 15.88 modelled for the lowest concentrations of solute. Similar
35°C 3.8 1-2 131.12 - 267.92 results are obtained for the. other temperatures considered
1-3 90.35 355.04 (Correa, 1985).
2-3 62.71 -3 18.48 The values listed in Table 6 also show that the NRTL equa-
45°C 4.6 1-2 87.18 -356.64 tion can be fitted rather more closely than the UNIQUAC
1-3 108.28 339.04 equation, and that the best NRTL results are achieved with
2-3 - 184.76 -287.24 aii = 0.2. Both sets of theoretical curves are compared with
55°C 3.7 1-2 - 124.71 -380.24 the experimental results in Figure 4. The system-specific
1-3 169.50 270.41 parameters obtained for the two equations using fixed optimal
2-3 -79.65 -689.19 values of 0, for the various temperatures considered are
presented in Tables 7 and 8.
The values of F and A0 listed in Table 6 are smaller than
those reported by Ssrensen (1980) and Magnussen et al.
Component rl 41 (1980) for a set of representative systems.
Water 0,9200 1.4000 Prediction of equilibria by the UNIFAC method
Acetic acid 2.2024 2.0720
MPK 3.9223 3.4160
The liquid-liquid equilibria of the ternary system were
also predicted using the UNIFAC method (Fredenslund
et al., 1975) to calculate the coefficients of activity of the
numerical value of the parameters. and deviations from ex- components of each phase. The computer program used
perimental results in the low solute-concentration region are (Fredenslund et al., 1977) was fed group interaction parani-
accentuated by the last term, in which P, is the solute eters obtained by Magnussen et al. (1981) from experimental
distribution ratio at infinite dilution, (Ssrensen, 1980). liquid-liquid equilibrium data for temperatures between 10
Goodness of fit was measured by the residual function and 40°C. Equilibrium compositions were calculated starting
from that of a hypothetical two-phase mixture corresponding
to the midpoint of the experimental tie-line. The goodness
of fit of the predictions was quantified by the residual
function.
......................................... (2)
and by the mean error of the solute distribution ratio

whose values for the various temperatures considered are

listed in Table 9. The dashed lines in Figure 2 show that the
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66, FEBRUARY 1988 I39
predicted immiscibility region is larger than that observed
experimentally.
Conclusions
The experimental liquid-liquid equilibrium data obtained
+
in this work for the system water methyl propyl ketone
in the range 20-55°C confirm those published by Gross
et al. (1939) and Ginnings et al. (1940) as regards the aqueous
phase, and provide new information concerning the organic
phase, for which they differ quantitatively from those of
Ginnings et al. The solubility of methyl propyl ketone in
water is practically independent of temperature, whereas the
solubility of water in the ketone increases with temperature.
The solubilities and liquid-liquid equilibrium data at 25,
+
35,45 and 55°C for the system water acetic acid methyl +
propyl ketone, for which no such data have previously been
published, show the area of the immiscibility region to
decrease slightly as temperature rises. NRTL and UNIQUAC
equations fitted by minimizing an objective function designed
to favour accuracy at low solute concentrations proved gen-
erally satisfactory as regards both the overall goodness
of fit and the mean error in the solute distribution ratio
(Table 6), the results obtained using the NRTL equation with
a value of 0.2 for the non-randomness parameter adbeing
slightly better than the others. However, even fixing the
optimal value of P,, the solute distribution ratio at infinite
solution, failed to bring the theoretical curves quite into line
with the experimental data for the lowest concentrations of
acetic acid, especially at the temperature of 35”C, for which
all the equations considered presented their greatest devia-
tions from the experimental values. The specific NRTL and
UNIQUAC parameters listed in Tables 7 and 8 appear to
exhibit tendencies to increase or decrease with rising
temperature, but with anomalous behaviour at 35 “C.
The predictions of the ternary equilibria obtained using
the UNIFAC method differ considerably from the experi-
mental values (Figure 2 and Table 9). Similar findings have
+
been obtained for the system water acetic acid methyl +
ethyl ketone (Correa et al., 1987), for which the residual
Fp is about 5 % . This poor performance by UNIFAC may
be due in part to the interaction parameters employed having
been obtained from experimental data that were not always
reliable (either because of analytical difficulties or because
of the lack of any test of thermodynamic consistency). It is
also true that acetic acid is a weak acid, whereas the UNIFAC
method strictly applies only to non-electrolytes. It may be
noted that owing to the interaction parameters’ having been
obtained for a wide range of temperatures (10-40°C), the
UNIFAC predictions are very insensitive to this variable,
whose only effect derives from its appearance (in Kelvins)
in the denominator of an exponential term. The experi-
mental data, on the other hand, exhibit evident temperature
dependence.
Acknowledgement
The authors are grateful to Prof. Aage Fredenslund for making
available to them the computer program used to fit the NRTL and
UNIQUAC equations to the experimental data.
Nomenclature
a,, = NKTL binary interaction parameter, (K)
b,, = UNIQUAC binary interaction parameter, (K)
F = residual defined by Equation (2), (mol %)
F, = objective function, Equation (1)
F, = residual defined by Equation (4), (mol %)
g;, = energy of interaction between an i-j pair of molecules,
(Jlmol)
140 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 66, FEBRUARY 1988
M = number of tie-lines
P, = parameter values (NRTL or UNIQUAC) in the penalty term
of Equation (1)
qi = com onent i UNIQUAC surface area parameter
Q = lo-’, constant in the penalty term of Equation (1)
ri = component i UNIQUAC volume parameter
R = universal gas constant, (J/mol . k)
u ij = UNIQUAC binary interaction parameter, (J/mol)
x = liquid phase mole fraction
Greek letters
a i j = NRTL non-randomness parameter
fi = solute distribution ratio
A @ = average error in solute distribution ratio
y = activity coefficient
Subscripts
i , j = components i and j
J = phase;, Equations (l), (2) and (4)
k = tie-line k
n = 1, 2 , . . . , NP (parameters, Equation (1))
s = solute
03 = infinite dilution
Superscripts
,I,.I1 = calculated values
= phases I and 11, Equation (1)
References
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of liquid mixtures: A new expression for the excess Gibbs energy
ofpartly or completely miscible systems”, AIChE J. 21, 116-128
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Correa, J. M., “Determinacidn, correlacidn y prediccidn del
equilibrio lfquido-liquido. Sistemas Agua +
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+ Cetonas”, Tesis Doctoral, Universidad de Santiago de
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Acetic acid +
Methyl ethyl
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(1940).
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Manuscript received October 17, 1986; revised manuscript
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