Advanced Materials Research Online: 2012-07-26

ISSN: 1662-8985, Vols. 550-553, pp 2616-2620

doi:10.4028/www.scientific.net/AMR.550-553.2616
© 2012 Trans Tech Publications, Switzerland

Vapor-liquid equilibrium for binary systems of methyl ethyl ketone and

methyl isobutyl ketone

Xiao Li a, Yunren Qiu b

School of Chemistry and Chemical Engineering, Central South University, Changsha, 410083,
China; Key Laboratory of Resources Chemistry of Nonferrous, Ministry of education, China
a
[email protected], [email protected]

Keywords: Methyl Isobutyl Ketone, Methyl Ethyl Ketone, Vapor-Liquid Equilibrium, Distillation

Abstract. Atmospheric vapor-liquid equilibrium data of methyl ethyl ketone (MEK) - methyl isobutyl
ketone (MIBK) were measured using an improved Rose still and were used to recover the parameters
of NRTL and UNIQUAC models. The results show that the simulated results agree well with the
experimental data. The mean temperature variation is 0.14 °C and the mean mole fraction variation is
0.0023 using UNIQUAC model while the mean temperature variation is 0.17 °C and the mean mole
fraction variation is 0.0025 using NRTL model. Both models can be used to calculate the atmospheric
vapor-liquid equilibrium data of MEK - MIBK.

Introduction
The organic solvents removal liquid of cathodic electrophoretic emulsion consists of methyl ethyl
ketone (MEK) and methyl isobutyl ketone (MIBK), as good middle boiling point organic solvents [1,
2], both MIBK and MEK take significant part in chemical industry. The vapor-liquid equilibrium
(VLE) data of binary MEK-MIBK system are necessary in the separation of the binary system by
distillation. Yuzhi Xue, et al. [3, 4] used vapor-liquid equilibrium components analysis method in
solvents experimental screening and research to obtain best solvent in acetic acid-water extractive
distiilation. Dimethly carbonate-methyl hydrate atmospheric vapor-liquid equilibrium data was
measured and correlated using UNIFAC and NRTL model [5, 6]. The results indicated that the
models were suitable for the binary system and the data were reliable. Zhongbo Li [7] measured
maleic anhydride-Di-n-butyl phthalate isothermal vapor-liquid equilibrium data to obtain the
parameters of NRTL model so as to provide the important foundation data of new maleic anhydride
recovery and production process. However, so far, no study has been reported on measurement of
MEK-MIBK atmospheric vapor-liquid equilibrium data. In the present work, the MEK-MIBK
atmospheric vapor-liquid equilibrium data were determined and correlated using UNIQUAC and
NRTL model by Aspen Plus simulation software.

Experimental
Chemicals. Methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) were high-purity grade,
no detectable impurities were found by gas chromatography (GC) analyses.
Apparatus. An improved Rose still was used as shown in Fig.1. The boiling point temperatures
were measured using a precise thermometer with an accuracy of 0.1 °C after exposed stem correction
[8]. An electro-thermal wire with adjustable heating voltage was inserted at the serpentine glass tube
to heat the mixture. The experimental temperatures were taken at this constant pressure 101.3 kPa.
The accuracy of the pressure control was within 0.05%.
Concentration Determination. The MIBK and MEK concentrations were determined by a gas
chromatograph (GC) (Shimadzu 2010) connected with GC-solution working station using the
normalization method. The GC column was packed with RTX-1 with 30 m in length and 0.25 mm in
diameter. The temperature of the injection port of the GC was maintained at 180 °C and the column
temperature was 100 °C. Nitrogen gas with a purity of 99.9% was used and the carrier gas flow rate

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications, www.ttp.net. (#69780304, Pennsylvania State University, University Park, USA-16/09/16,02:53:15)
 Advanced Materials Research Vols. 550-553 2617

was 1.55 ml/min. The split flow ratio was 10. The added quantity was 0.5 µl. The GC was calibrated
using mixtures of known compositions. The MIBK and MEK concentration of each sample was
measured at least three times, the accuracy of the equilibrium composition measurements was within
±0.001 mole fraction.

1: Discharging port, 2: Boiling device, 3: Inner heater, 4: Liquid sample outlet, 5: Vapor room, 6:
Vapor-liquid riser, 7: Vapor-liquid separator, 8: Thermometer casing, 9: Vapor condensing tube, 10:
Vapor sample outlet, 11: Mixer
Fig.1 The structure of improved Rose still

The relative correction factors were calculated using Eq. (1) by the analysis of samples with known
concentrations of analyte.

M i % = f i Ai / ∑ f i Ai (1)

where M i % is the mass fraction of component i ， f i is the relative correction factor of component
i ， Ai is the peak area of component i . Selecting one of substance k as standard and f k equal to 1,
the value of each rest f i can be obtained.
Since MEK and MIBK can form a homogeneous solution at atmosphere pressure and room
temperature, MEK was chose as standard to calculate relative correction factor through four group of
different concentrations homogeneous solution concentration determination. The correction factors
are shown in Table 1.

Table 1 Correction Factor

Component 1 2 3 4 Average
MIBK 1.265 1.260 1.255 1.257 1.259
MEK 1.000 1.000 1.000 1.000 1.000

Operation. The measurement of MEK-MIBK vapor-liquid equilibrium data was conducted at

atmosphere pressure. MEK-MIBK binary mixture with known concentration of analyte was added to
Rose still. The voltage of electro-thermal wire was adjusted after boiling tends towards stability to
maintain a speed around 80 drop/min. Equilibrium was usually reached after 0.5 h, when the
temperatures of the liquid and vapor phases were constant and their difference was within ±0.2°C.
The temperature was regarded as atmospheric equilibrium temperature. Vapor sample and liquid
sample were taken simultaneously for analyzing. Significantly, small quantities of liquid remaining in
the sample switch were removed before sampling for avoiding determination errors. When done,
repeat this step for another MEK-MIBK mixture of different concentrations.
2618 Advances in Chemical Engineering II

Results and discussion

The measured MEK-MIBK atmospheric vapor-liquid equilibrium data were shown in Table 2.
When vapor-liquid equilibrium was obtained, not only pressure and temperature, but also chemical
potential of each component becomes equal. The basic thermodynamic relations of mixture were
indicated as Eqs. (2) and (3).

V L
fi = fi (2)
0
ϕ i pyi = γ i f i xi (3)
V V
where f i is the fugacity of component i in vapor phase, f i is the fugacity of component i in liquid
phase, ϕ i is the fugacity coefficients of component i in vapor phase, p is the system pressure, kPa,
0
yi is the mole fraction of component i in vapor phase, f i is fugacity of component i in pure state,
xi is the mole fraction of component i in liquid phase, γ i is the activity coefficient of component i in
liquid phase.
0
At the low pressure condition, the fugacity coefficients in Eq. (3) equal to 1 and f i equal to
0
saturated vapor pressure of component i ( pi ) by neglecting the effects of pressure on fugacity of
liquid phase. Then the Eq. (3) can be modified as Eq. (4).

0
pyi = γ i pi xi . (4)

With fugacity coefficient and other parameters, the vapor-liquid equilibrium data could be obtained
by simulating calculation [9].

Table 2 Atmospheric vapor-liquid equilibrium data of binary system MEK(1)-MIBK(2)

(mole fraction)
T [°C] 115.92 114.79 112.02 108.72 104.21 102.42 100.54 99.92
x1 0 0.0213 0.0645 0.1246 0.2136 0.2546 0.2987 0.3125
y1 0 0.0584 0.1627 0.2935 0.4451 0.5138 0.5606 0.5771

T [°C] 96.44 94.62 93.33 92.20 90.77 88.70 86.84 86.41

x1 0.3985 0.4512 0.4878 0.5213 0.5648 0.6326 0.6969 0.7124
y1 0.6685 0.7160 0.7451 0.7785 0.8020 0.8444 0.8796 0.8885

T [°C] 84.45 84.04 82.65 81.70 81.11 80.10 79.54 79.64

x1 0.7854 0.8012 0.8569 0.8965 0.9213 0.9658 0.9912 1
y1 0.9217 0.9285 0.9511 0.9658 0.9746 0.9893 0.9974 1

Numerous models have been put forward for fugacity coefficient and activity coefficient, two of
the foremost are the NRTL equation and UNIQUAC equation. The chief distinguishing features of the
two models are that they were both developed from thermo-dynamical considerations, and that both
essentially involve only binary interaction parameters, even when applied to multi-component
mixtures.
The accuracy and stability of the calculation rely heavily on the care taken in the parameter
estimation stage. The parameters of each model calculated by Aspen Plus software using MEK-MIBK
atmospheric vapor-liquid equilibrium experimental data were shown in Table 3.
According to the calculated model parameters, simulative atmospheric vapor-liquid equilibrium
data of MEK-MIBK can be obtained. Table 4 shows the comparison of experimental data and
calculated results.
 Advanced Materials Research Vols. 550-553 2619

Table 3 NRTL and UNIQUAC model parameters

1.0

NRTL UNIQUAC
0.8
aij 0 0
0.6
aji 25.40948 0
yMEK

0.4
bij -17.92732 -154.3149
0.2
bji 242.2431 125.1522
0.0
0.0 0.2 0.4 0.6 0.8 1.0 cij 0.3 0
xMEK
Note：i: MIBK, j: MEK
Fig.2 Atmospheric VLE of MEK-MIBK
(mole fraction)

Table 4 Vapor-liquid equilibrium experimental data and calculated results of binary systems of MEK
and MIBK
NRTL UNIQUAC
T [°C] DT [°C] yMEK DyMEK T [°C] DT [°C] yMEK DyMEK
1 115.93 0.01 0 0 115.92 0.02 0 0
2 114.85 0.06 0.0569 -0.0015 114.78 -0.01 0.0587 0.0004
3 112.18 0.16 0.1653 0.0026 112.05 0.03 0.1683 0.0056
4 109.05 0.33 0.2884 -0.0051 108.84 0.12 0.2920 -0.0015
5 102.72 0.30 0.5013 -0.0125 102.59 0.17 0.5012 -0.0126
6 104.36 0.15 0.4450 -0.0001 104.24 0.03 0.4457 0.0006
7 100.78 0.24 0.5588 -0.0018 100.71 0.17 0.5576 -0.0030
8 100.19 0.27 0.5756 -0.0015 100.13 0.21 0.5740 -0.0031
9 96.72 0.28 0.6688 0.0003 96.77 0.33 0.6655 -0.0030
10 94.74 0.12 0.7173 0.0013 94.86 0.24 0.7135 -0.0026
11 93.42 0.09 0.7478 0.0027 93.58 0.25 0.7438 -0.0013
12 92.26 0.06 0.7736 -0.0049 92.45 0.25 0.7696 -0.0089
13 90.80 0.03 0.8045 0.0025 91.04 0.27 0.8006 -0.0014
14 88.65 -0.04 0.8472 0.0028 88.93 0.24 0.8439 -0.0005
15 86.73 -0.10 0.8825 0.0029 87.04 0.21 0.8799 0.0003
16 86.29 -0.12 0.8904 0.0019 86.60 0.20 0.8879 -0.0006
17 84.27 -0.18 0.9242 0.0025 84.60 0.15 0.9227 0.0010
18 83.85 -0.20 0.9309 0.0024 84.18 0.14 0.9296 0.0010
19 82.41 -0.24 0.9530 0.0019 82.74 0.09 0.9522 0.0013
20 81.43 -0.27 0.9673 0.0015 81.76 0.06 0.9668 0.0010
21 80.83 -0.28 0.9757 0.0012 81.16 0.05 0.9754 0.0009
22 79.80 -0.30 0.9899 0.0005 80.12 0.02 0.9898 0.0005
23 79.24 -0.30 0.9973 -0.0001 79.54 0.00 0.9975 0.0000
24 79.62 -0.02 1 0 79.65 0.01 1 0
Mean
0.17 0.7526 0.0025 0.14 0.7511 0.0023
variation
Note：DT=Tcal-Texp，Dy=ycal-yexp
As Table 4 indicated, the deviations in vapor phase compositions and equilibrium temperatures are
reasonably small, indicating that two activity coefficient models are suitable to represent the binary
experimental data. UNIQUAC model has a little higher accuracy than NRTL equation in calculating
MEK-MIBK atmospheric vapor-liquid equilibrium experimental data. The mean temperature
variation is 0.14 °C and the mean mole fraction variation is 0.0023 under the UNIQUAC model while
2620 Advances in Chemical Engineering II

the mean temperature variation is 0.17 °C and the mean mole fraction variation is 0.0025 under the
NRTL model. Fig. 2 shows the atmospheric MEK-MIBK binary mixture vapor-liquid equilibrium
diagram.
As illustrated in Fig.2, the atmospheric MEK-MIBK vapor-liquid equilibrium curve is far away
from diagonal line (y=x). No azeotrope is encountered for this atmospheric binary system. This
indicates that the mixture can be separated effectively by atmospheric distillation method. The results
can be used in the optimal design of MEK-MIBK distillation process.

Conclusions
The atmospheric MEK-MIBK binary mixture vapor-liquid equilibrium data was measured by using
an improved Rose still, the data were correlated by Aspen Plus software, and the NRTL and
UNIQUAC equation parameters were obtained. The simulated results of both activity coefficient
models agree well with the experimental data
The mean temperature variation is 0.14 °C and the mean mole fraction variation is 0.0023 under
UNIQUAC model while the mean temperature variation is 0.17 °C and the mean mole fraction
variation is 0.0025 under NRTL model. Both the NRTL and UNIQUAC model have high accuracy in
calculating MEK-MIBK atmospheric vapor-liquid equilibrium experimental data. The results can be
used in the optimal design of MEK-MIBK distillation process.

Acknowledgements
This work was financially supported by Hunan Provincial Natural Science Foundation of China
(Project 11JJ2010) and Undergraduate Free Exploration Research and Innovation Foundation of
Central South University (ZL110414).

References
[1] Y. Wang: Chemical Industry Vol. 27 (2009), p. 12 (In Chinese)
[2] C.M. Yu and Y. Zhao: Chemical Industry Vol. 25 (2007), p. 51 (In Chinese)
[3] Y.Z. Xue, L. Zhang and J.N. Lin: Journal of Dalian Railway Institute Vol. 24 (2003), p. 71
[4] I.C. Santos, A.P. Goncalves and C.S. Santo: Hydrometallurgy Vol. 23 (1990), p. 237
[5] H.P. Luo, W.D. Xiao and K.H. Zhu: Fluid Phase Equilibria Vol. 175 (2000), p. 91
[6] H.P. Luo, J.H. Zhu and W.D. Xiao: J. Chem. Eng. Data Vol. 46 (2001), p. 842
[7] Z.B. Li, X. Qi and L.Y. Xu: Chemical Industry and Engineering Vol. 21 (2004), p. 471 (In
Chinese)
[8] W.J. Zou and D.Y. Chen: Experiment of Physical Chemistry and Technology (East China
University of Science and Technology Press, China 1990).
[9] Z.X. Chen, Z.Y. Cai and W.Y. Hu: Chemical Engineering Thermodynamics (Chemical Industry
Press, China 2001).