Journal of Solution Chemistry

https://doi.org/10.1007/s10953-020-00946-8

Using Diaminomethanal as an Entrainer for the Separation

of Isopropanol + Water Mixture

Rajat Kataria1 · Tarun Jain1 · Neetu Singh1   · Jai Prakash Kushwaha1 ·

Bandhana Sharma1

Received: 5 December 2018 / Accepted: 24 May 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
Diaminomethanal (an organic compound), was examined as entrainer for dehydration of
isopropanol−water system by extractive distillation. Isobaric vapor−liquid equilibrium
(VLE) data were studied for isopropanol−water−diaminomethanal system at 101.3  kPa,
employing modified Othmer type still. The VLE data studied for the system comprising
diaminomethanal were quite different from that of diaminomethanal-free system. The
diaminomethanal represented a significant increase in the relative volatility of the isopro-
panol−water solution and led to termination of the azeotrope at a specific concentration. It
was observed that the relative volatility for isopropanol−water mixture increases continu-
ously with the increase in diaminomethanal concentration till 15.7 mol%. Results demon-
strate that diaminomethanal is a functional entrainer for the separation of isopropanol−
water mixture and 13 mol% of diaminomethanal concentration is enough to terminate the
azeotrope. Furthermore, the experimental VLE data for ternary system were correlated by
nonrandom two-liquid (NRTL) model and predicted values correlated with the experimen-
tal data very well. Further, the experimental data was verified for thermodynamic consist-
ency by Wisniak–Tamir’s modification of McDermott-Ellis and Wisniak’s L-W thermody-
namic consistency test.

Keywords  IPA–water · VLE · Azeotrope · Extractive distillation

1 Introduction

Isopropanol (IPA), also known as 2-propanol, is a bulk chemical product and raw mate-
rial. Due to its physico-chemical properties, IPA is useful in diverse areas like; a solvent
in the pharmaceutical industry, an intermediate for producing mono-isopropyl amine
and isopropyl acetate. IPA is useful for many engineering applications and biofuels [1].
Generally, it’s mass production in done using propylene as raw material by different
routes: direct and indirect hydration technique [2]. Several industries like semiconductor

* Neetu Singh
neetu.singh1479@gmail.com
1
Department of Chemical Engineering, Thapar Institute of Engineering & Technology, Patiala,
Punjab, India

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 Journal of Solution Chemistry

and electronics industries require very pure IPA as a cleansing agent [3]. Therefore,
it is necessary to separate water from IPA. This separation is challenging due to the
well-known fact that they form a minimum-boiling azeotrope at 0.675 mol fraction IPA,
353.45 K temperature and standard atmospheric pressure. This represents the separation
limitation by conventional distillation [4].
For the separation of such mixtures various processes are available including those
tested on industrial scale like azeotropic distillation, extractive distillation and distilla-
tion with salt addition. Some other recent development in this area such as, pervapora-
tion [5], adsorptive distillation [6], membrane distillation [7] and diffusion distillation
[8, 9], showed promising results at the laboratory scale. Hybrid methods combining
these options are also used and are well described in the literature [10]. Out of all pre-
sent methods, extractive distillation is an encouraging technology, mainly for mass
production. Extractive distillation includes the addition of a third compound which
interacts with the constituents of the mixture to be separated. Entrainers increase the
relative volatility of the binary mixture above unity and do not encourage phase separa-
tion or azeotrope formation. Extractive distillation is an energy-efficient technique and
is appropriate for systems which do not show any pressure sensitivity.
As entrainer is the key to extractive distillation, so a careful choice is very essen-
tial. A good entrainer must have following characteristics: high boiling point, low toxic-
ity, thermal stability, selectivity and easy recovery. Different salts like lithium chloride,
lithium bromide, sodium chloride, sodium bromide [11], magnesium chloride, magne-
sium bromide [12], potassium carbonate [13], 2,2′,2″-nitrilotrisethanol [14] and ionic
liquids [15] are reported to be suitable extracting agents for the dehydration of IPA.
However, they have many disadvantages like; corrosion, environmental pollution and
challenges in reuse/recycling. Further, 1,2-ethanediol, dimethyl sulfoxide (DMSO),
N-methyl-2-pyrrolidone (NMP), N-methyl-2-piperidone and N-methyl-6-caprolactam
were also examined as entrainers for IPA–water separation by Gmehling and Mӧllmann
[16]. Out of these four entrainers, DMSO performed best by giving maximum relative
volatility value. Moreover, Arifin and Chien [17] presented the design and control of an
IPA–water separation by employing DMSO as entrainer via extractive distillation.
The objective of this study is to examine diaminomethanal (commonly known as
urea) as extracting agent for dehydration of IPA–water binary system. Diaminomethanal
is presented as entrainer because of many advantages over traditional entrainers.

(1) Diaminomethanal is nontoxic and cheap.

(2) Its availability is widely available due to its voluminous production.
(3) Good solubility in IPA and water both.
(4) Due to non-volatile nature of diaminomethanal, the product will be free of entrainer.

Other than these advantages, it is always possible to recover the large amount of
diaminomethanal present in the bottom product and this can be reused in many indus-
trial applications.
Isobaric vapor−liquid equilibrium (VLE) data for isopropanol (1)−water (2)−
diaminomethanal (3) were examined using modified Othmer type recirculation still at
101.3  kPa. The experimental findings were well fitted with the nonrandom two-liquid
(NRTL) model. Further, experimental results were verified for thermodynamic consist-
ency using modified McDermott-Ellis consistency test [18] and Wisniak’s L-W consist-
ency test [19].

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2 Experimental Section

2.1 Materials

IPA of purity (> 0.99 mass fraction) was procured from Sigma–Aldrich and used with-
out further purification. Diaminomethanal of purity (> 0.995 mass fraction) was pur-
chased from the Merck chemicals. Due to the hygroscopic nature of diaminomethanal,
it was vacuum dried for 24 h before use. To prepare IPA–water mixture, double distilled
water was used in all experiments. Hydrogen gas with the purity of > 99.98% was used
for GC analysis.

2.2 Apparatus and Procedure

A modified Othmer type recirculation still was used for generating the isobaric VLE
data. The complete detail of the equilibrium still, experimental methodology and
authentication of the experimental setup is described in our previous publications
[20, 21]. The apparatus mainly contains a still, a glass-sealed heater and a magnetic
stirrer for stirring the contents of the still. The apparatus is operated at atmospheric
pressure during the experimentation. Air-cooled and water-cooled condensers are con-
nected to the still in sequence. Calibrated mercury thermometers were used to meas-
ure the equilibrium temperatures with an uncertainty of 0.1  K. 100  ml of IPA–water
mixtures of known composition were taken in the still and a predetermined amount of
diaminomethanal was introduced to the mixture. The mixture undergoes rigorous boil-
ing with stirring. Vapors generated in the still were condensed and circulated back in
order to achieve the equilibrium. 45 min was provided for the evaporation and conden-
sation cycle to establish the equilibrium. Further, the heating was switched off, and the
samples were drawn for analysis. Condensed vapor phase sample was drawn from the
condensate sampling bulb, which is attached beneath the condenser. Liquid sample was
drawn from the still.

2.3 Analysis

Gas chromatograph (GC) (AIMIL-NUCON: 5765 GC with the data station “DASTA”)
with a thermal conductivity detector (TCD) was used for the analysis of condensed
vapor phase and bottom samples. Hydrogen gas (purity > 99.9% v/v) was employed as
carrier gas with 4.7 × 10–7 m3·s−1 flow rate and 240 kPa inlet pressure. The GC column
(2  m × 0.032  m) was packed with Porapak QS. Temperatures of the injector, detector
and oven were set at 375, 375 and 433  K, respectively, with the uncertainty of ± 1  K.
For the GC analysis and equilibrium composition measurements in the samples, a cal-
ibration curve was previously prepared with gravimetrically measured standard solu-
tions. Liquid samples were analyzed using a glass liner before the column. After each
gas chromatogram, a clean glass liner was used which could successfully prevent the
diaminomethanal from entering in the column. The vapor and liquid phase compositions
were calculated in mole fraction with an uncertainty of 0.003. The uncertainty in mole
fraction were calculated using the triplicate measurement data.

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Table 1  Effect of Mol% of diami- T (K) x1′ y1 Relative

diaminomethanal concentration nomethanal volatility
on the relative volatility (x1′ (α12)
≈ 0.675) of IPA (1) + water
(2) system at atmospheric
0.0 353.5 0.667 0.681 1.07
pressure (101.3 kPa):
diaminomethanal = (0 to 15.7) 5.6 354.8 0.664 0.705 1.21
mol% 13.0 358.4 0.665 0.751 1.52
15.7 359.6 0.675 0.778 1.69

Standard uncertainty u(x1′) = u(y1) = u(mole fraction of diaminometh-

anol) = 0.003, u(α) = 0.02

Fig. 1  Effect of diaminometha- 1.8

nal concentration on relative
volatility α12 (x1′ ≈ 0.675) of the
of IPA (1) + water (2) system
at 101.3 kPa. Error bars are 1.6
presented for the relative volatil-
ity only

1.4

1.2

1.0
0.0 5.0 10.0 15.0 20.0

Diaminomethanal concentration (mol%)

3 Results and Discussion

3.1 Effectiveness of Diaminomethanal as Extracting Agent

Since, it is essential to evaluate the effectiveness of diaminomethanal for breaking the

IPA−water azeotrope, therefore VLE experiments were performed for azeotropic mix-
ture of IPA−water in the presence of diaminomethanal. The influence of entrainer con-
centration on relative volatility (α12) of azeotropic mixture of IPA−water was studied by
varying the diaminomethanal concentration in the range of 0−15.7 mol% at 101.3 kPa.
The maximum of diaminomethanal concentration (15.7 mol%) was selected on the basis
of the solubility limit of diaminomethanal in IPA at its boiling point. Table 1 and Fig. 1
represents the influence of diaminomethanal amount on α12 of azeotropic composition
of IPA−water mixture (67.5 mol % IPA). It can be observed from Fig. 1 that with the
addition of diaminomethanal, the relative volatility of IPA to water increases and this is
more evident with increasing diaminomethanal concentration. The normal boiling point
of IPA−water mixture increases the system equilibrium temperature by addition of the
non-volatile component diaminomethanal up to 15.7  mol% concentration. The more
diaminomethanal, added to the system, the higher the equilibrium temperature.

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Journal of Solution Chemistry

3.2 Experimental VLE Data

The VLE of IPA−water−diaminomethanal ternary system at two different diaminometh-

anal concentrations (13  mol% and 15.7  mol%) have been determined experimentally at
101.3 kPa and are given in Table 2. The VLE data comprise the equilibrium temperature
(T), equilibrium mole fractions of IPA (x1) and water (x2) in liquid phase, equilibrium mole
fractions of IPA in vapor phase (y1) and liquid phase on entrainer-free basis (x1′). Due to
the nonvolatilite nature of diaminomethanal, the vapor phase composition can be repre-
sented in terms of IPA mole fraction. Figures 2 and 3 present the equilibrium temperature
(T)−composition diagram in the presence of diaminomethanal at 13 mol% and 15.7 mol%
concentrations, respectively. Bubble point and dew point curves without entrainer are also
plotted for comparison. Figures  2 and 3 show that introducing diaminomethanal to the
azeotropic system caused the elevation of bubble point. With increasing amount of diami-
nomethanal in the azeotropic mixtures, the equilibrium temperature also increases. It can
be seen in Figures that with the introduction of diaminomethanal, azeotropic point switches
toward x1 = 0.1 . For both studied diaminomethanal concentrations T − y1 curve remains
�

over the T − x1 curve for the complete concentration range, which shows that the azeotrope
�

could be completely terminated at these diaminomethanal concentrations.

To make it easier to explicate the effect of diaminomethanal on IPA−water system,
the x1 − y1 diagram for IPA−water−diaminomethanal ternary system were plotted in the
�

absence and presence of diaminomethanal (13 mol% and 15.7 mol%) at 101.3 kPa (Fig. 4).

It can be observed that the addition of diaminomethanal increases the concentration of IPA
in the vapor phase, and this outcome is more apparent with increasing diaminomethanal
amount. The distribution diagram of IPA−water system (without entrainer) crosses the
diagonal line at 67.5 mol% IPA, however, for diaminomethanal concentrations of 13 and
15.7 mol%, it remains over the diagonal line for complete concentration range. Therefore,
diaminomethanal concentration of about 13 mol% is sufficient enough to break the IPA−
water azeotrope.

3.3 Correlation of VLE Data

VLE is calculated from the fugacity equality in vapor and liquid phases, as given in Eq. 1.

f̂ V = f̂ L (1)
Using the γ–φ approach, the equilibrium Eq. 2 is obtained.

yi 𝜙̂ V p = xi 𝛾i psi 𝜙si PEi (2)

where f̂ V and f̂ L are fugacities of ith component in the vapor and liquid phases respec-
tively, ­yi and xi are the mole fraction of ith component in vapor phase and liquid phase
respectively, P the total system pressure, 𝜙Vi the fugacity coefficient of ith component in
vapor phase, γi the activity coefficient of ith component in the liquid phase, 𝜙Si the fugac-
ity coefficient at saturation condition and system temperature and psi is vapor pressure of
ith component at saturation condition and system temperature. psi was evaluated using
Antoine equation and equation parameters were taken from the literature [22].
Fugacity coefficients were evaluated by employing virial equation of state reduced at the
second coefficient with Tsonopoulo correlations [23]. Saturated liquid molar volumes and

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Table 2  Experimental iso- No T (K) x1′ x1 x2 y1 γ1exp γ2exp α12

baric VLE data for the
IPA(1) + water(2) + diami- Diaminomethanal = 13 mol%
nomethanal (3) system at atmos-
pheric pressure (101.3 kPa) 1 372.9 0.000 0.000 1.009
2 369.6 0.029 0.025 0.845 0.178 3.543 0.963 7.25
3 366.4 0.099 0.087 0.784 0.338 2.228 0.940 4.65
4 365.2 0.158 0.138 0.733 0.409 1.770 0.940 3.69
5 364.3 0.248 0.216 0.654 0.496 1.416 0.928 2.98
6 362.7 0.350 0.305 0.566 0.582 1.254 0.947 2.59
7 361.4 0.460 0.401 0.470 0.625 1.079 1.074 1.96
8 359.1 0.629 0.548 0.323 0.721 0.998 1.272 1.52
9 358.2 0.687 0.598 0.272 0.763 1.003 1.327 1.47
10 358.0 0.749 0.652 0.218 0.807 0.981 1.358 1.40
11 357.9 0.823 0.717 0.154 0.840 0.933 1.603 1.13
12 357.3 0.827 0.720 0.151 0.858 0.972 1.490 1.26
13 357.2 0.856 0.745 0.125 0.874 0.960 1.595 1.17
14 357.2 0.896 0.780 0.090 0.900 0.945 1.753 1.04
15 357.2 0.921 0.801 0.069 0.934 0.954 1.523 1.21
16 357.2 0.952 0.829 0.042 0.961 0.950 1.481 1.24
17 357.1 0.961 0.837 0.034 0.962 0.945 1.783 1.03
18 357.1 0.972 0.846 0.024 0.976 0.948 1.569 1.17
19 357.1 1.000 1.000 0.945
Diaminomethanal = 15.7 mol%
1 373.5 0.000 0.000 0.987
2 368.5 0.045 0.038 0.805 0.179 2.394 1.018 4.63
3 365.4 0.092 0.078 0.765 0.299 2.205 1.026 4.21
4 363.9 0.144 0.122 0.722 0.355 1.773 1.060 3.27
5 361.3 0.198 0.167 0.676 0.435 1.752 1.094 3.12
6 360.5 0.265 0.224 0.620 0.499 1.550 1.092 2.76
7 359.4 0.340 0.288 0.556 0.547 1.383 1.148 2.34
8 358.9 0.365 0.308 0.535 0.569 1.369 1.157 2.30
9 358.5 0.420 0.355 0.489 0.603 1.281 1.185 2.10
10 358.4 0.473 0.399 0.444 0.651 1.233 1.151 2.08
11 358.2 0.561 0.473 0.370 0.705 1.135 1.177 1.87
12 357.7 0.660 0.557 0.287 0.778 1.086 1.167 1.81
13 357.7 0.741 0.625 0.218 0.832 1.035 1.159 1.73
14 357.6 0.826 0.697 0.147 0.871 0.976 1.330 1.42
15 357.6 0.894 0.754 0.089 0.918 0.950 1.388 1.33
16 357.6 0.913 0.770 0.073 0.944 0.957 1.155 1.61
17 357.6 0.937 0.790 0.053 0.962 0.950 1.082 1.70
18 357.6 0.951 0.802 0.041 0.969 0.943 1.135 1.61
19 357.6 0.960 0.809 0.034 0.972 0.937 1.256 1.45
20 357.6 1.000 1.000 0.925

Standard uncertainty u(x1) = u(x1′) = u(y1) = u(mole fraction of

diaminomethanol) = 0.003 u(T) = 0.1 K, u(P) = 0.1 kPa

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Journal of Solution Chemistry

Fig. 2  Experimental T−x′,y 380

diagram for IPA (1)–water, (2)–
diaminomethanal, (3) system at
atmospheric pressure: diami- 375
nomethanal = 13 mol%; open tri-
angle, T−y1; open square, T − x1 ;
�

dotted lines for diaminomethanal 370

free system

T (K)
365

360

355

350
0.0 0.2 0.4 0.6 0.8 1.0

Fig. 3  Experimental T−x′,y 380

diagram for IPA (1)–water (2)–
diaminomethanal (3) system at
atmospheric pressure: diami- 375
nomethanal = 15.7 mol%; filled
triangle, T−y1; filled square,
T − x1 ; dotted lines for diami-
�
370
nomethanal free system
T (K)

365

360

355

350
0.0 0.2 0.4 0.6 0.8 1.0

vapor pressures essential for calculation of Poynting effect (PE) were estimated with the help
of DIPPR equations [24].
[ L( )]
vi p − psi
PEi = exp (3)
RT

So, the activity coefficients can be expressed as following:

yi 𝜙̂ V p
𝛾i = (4)
xi psi 𝜙si PEi

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 Journal of Solution Chemistry

Fig. 4  Isobaric vapor−liquid 1.0

equilibrium diagram for the IPA
(1)−water (2)−diaminomethanal
(3) ternary system at 101.3 kPa:
dotted line, diaminomethanal- 0.8
free system; filled circle,
13 mol% diaminomethanal;
filled triangle, 15.7 mol%
0.6
diaminomethanal; solid lines,
correlated using NRTL model

y1
0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0

The value of PE ≈ 1 at low/moderate pressure. Thus above equation should be writ-

ten simply as:

yi 𝜙̂ Vi p = xi 𝛾i psi 𝜙si (5)

Diaminomethanal is a nonvolatile substance and will not appear in the vapor phase.
However in the liquid phase, diaminomethanal mole fraction was considered for calcu-
lating the activity coefficients of both the compounds. Experimental activity coefficients
were determined using above equation and were correlated with the values obtained
from the NRTL model.
The model parameters were regressed by minimizing the following objective func-
tion [25].
n
[ exp ]2
∑ 𝛾i − 𝛾icalc
OF = exp (6)
i=1 𝛾i

where i and n defines to the component and experimental data point respectively.
The relative volatility (α12) were evaluated by
�
y1 ∕x1
𝛼12 = � (7)
y2 ∕x2

where x1 and x2 are IPA and water mole fractions in the liquid phase represented on diami-
′ ′

nomethanal-free basis, respectively, and y1, y2 are the mole fractions of IPA and water in
the vapor phase, respectively.
It can be seen from the results that, predicted values from NRTL model provided
good correlation with the experimental VLE data as shown in Fig. 4. The results of cor-
relation for the average difference in T and vapor mole fraction in ternary system are

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Journal of Solution Chemistry

reported in Table 3. The average and maximum difference in T and IPA mole fraction in
the vapor phase are defined as following:
n
∑ | exp |
DT = (1∕n) |T − T calc |
| |k (8)
k=1

( )
| |
dT = max |T exp − T calc |
| | (9)

n
∑ | exp |
Dy1 = (1∕n) |y1 − ycalc
| 1 ||k (10)
k=1

( )
| exp |
dy1 = max |y1 − ycalc
| 1 |
| (11)

where “n” represents the number of data points and “exp” and “cal” represents to the exper-
imental and calculated values respectively. The average absolute difference for the tem-
perature and IPA mole fraction in the vapor phase are 0.172 K and 0.0017 K respectively.

3.4 Thermodynamic Consistency Test of VLE Data

In order to ensure the reliability of the measured data, thermodynamic consistency of the
experimental data were examined applying Wisniak’s L-W test and modified McDermott-
Ellis test. According to McDermott-Ellis test [18] for ternary systems two experimental
points, a and b, are thermodynamically consistent if local deviation (D) < local value of the
maximum deviation (Dmax) [19]. The local deviation (D) and local value of the maximum
deviation (Dmax) are defined as following:
n
∑ ( )( )
D= xib + xia ln 𝛾ib − ln 𝛾ia (12)
i=1

Dmax = D1max + D2max + D3max + D4max (13)

where
1−n ( )
∑ ( ) 1 1 1 1
D1max = xib + xia + + + Δx (14)
i=1
xia yia xib yib

Table 3  The NRTL parameters obtained from correlations of experimental VLE data, and correlation devi-
ations for the systems {IPA (1) + water (2) + diaminomethanal (3)} at 101.3 kPa
Systems Δg12 Δg21 α DT (K) dT (K) Dy1 dy1

IPA(1) + water (2) + diaminomethanal (3) − 2564.4 7766.9 0.3 0.172 0.947 0.0017 0.033

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n
∑
D2max = 2 |ln 𝛾ib − ln 𝛾ia | Δx
| | (15)
i=1

n
∑ ( ) Δp
D3max = xib + xia (16)
i=1
p

n
[ ]
∑ ( ) 1 1
D4max = xib + xia Bi ( )2 + ( )2 ΔT (17)
i=1 Ta + Ci Tb + Ci

where n is the number of components and ∆x, ∆T, ∆P are the errors in the measurement of
the mole fraction, temperature and pressure respectively. The values of D, Dmax and
|D|−|Dmax| are presented in Table 4 and Table 5 for 13 mol% and 15.7 mol% diaminometh-
anal concentrations respectively. The findings of thermodynamic consistency test show
that, D < Dmax for all the experimental VLE data. Therefore, according to modified McDer-
mott–Ellis test all the experimental data are thermodynamically consistent. In addition to
this, experimental data also pass the Wisniak’s L-W point-to-point test as the values of Wi
L
i
lies between 0.92 and 1.08.

Table 4  Results obtained in application of Wisniak–Tamir’s modification of McDermott-Ellis to the ternary

system {IPA (1) + water (2) + diaminomethanal (3)} for diaminomethanal = 13 mol%
T (K) x1 D D1max D2max D3max D4max Dmax |D| − ||Dmax ||

372.9 0.000 – – – 0.0020 0.0019 – –

369.6 0.029 − 0.1030 0.0477 0.0015 0.0020 0.0019 0.0531 − 0.1561
366.4 0.099 − 0.0605 0.0456 0.0007 0.0020 0.0020 0.0502 − 0.1107
365.2 0.158 − 0.1100 0.0477 0.0007 0.0020 0.0020 0.0523 − 0.1623
364.3 0.248 − 0.0454 0.0495 0.0004 0.0020 0.0020 0.0539 − 0.0993
362.7 0.35 0.0289 0.0505 0.0008 0.0020 0.0020 0.0553 − 0.0263
361.4 0.46 0.0691 0.0516 0.0007 0.0020 0.0021 0.0563 0.0128
359.1 0.629 0.0352 0.0508 0.0001 0.0020 0.0021 0.0550 − 0.0198
358.2 0.687 − 0.0188 0.0511 0.0001 0.0020 0.0021 0.0553 − 0.0741
358.0 0.749 − 0.0078 0.0505 0.0006 0.0020 0.0021 0.0553 − 0.0631
357.9 0.823 0.0418 0.0496 0.0003 0.0020 0.0021 0.0541 − 0.0122
357.3 0.827 0.0015 0.0500 0.0002 0.0020 0.0021 0.0544 − 0.0529
357.2 0.856 − 0.0053 0.0495 0.0003 0.0020 0.0021 0.0540 − 0.0592
357.2 0.896 − 0.0084 0.0499 0.0005 0.0020 0.0021 0.0545 − 0.0629
357.1 0.921 − 0.0122 0.0522 0.0001 0.0020 0.0022 0.0564 − 0.0686
357.2 0.952 0.0080 0.0496 0.0006 0.0020 0.0022 0.0543 − 0.0464
357.1 0.961 − 0.0027 0.0500 0.0004 0.0020 0.0022 0.0545 − 0.0572
357.1 0.972 – – – 0.0020 0.0022 – –
357.1 1 – – – 0.0010 – – –

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Table 5  Results obtained in application of Wisniak–Tamir’s modification of McDermott-Ellis test to the

ternary system {IPA (1) + water (2) + diaminomethanal (3)} for diaminomethanal = 15.7 mol%
T (K) x1 D D1max D2max D3max D4max Dmax |D| − ||Dmax ||

373.5 0.000 – – – 0.0020 0.0019 – –

368.5 0.045 0.0033 0.0441 0.0003 0.0020 0.0019 0.0482 − 0.0450
365.4 0.092 0.0057 0.0447 0.0008 0.0020 0.0020 0.0494 − 0.0438
363.9 0.144 0.0490 0.0461 0.0001 0.0020 0.0020 0.0502 − 0.0011
361.3 0.198 − 0.0598 0.0476 0.0004 0.0020 0.0020 0.0520 − 0.1118
360.5 0.265 0.0014 0.0488 0.0005 0.0020 0.0020 0.0533 − 0.0519
359.4 0.340 0.0024 0.0492 0.0001 0.0020 0.0021 0.0533 − 0.0509
358.9 0.365 − 0.0226 0.0498 0.0003 0.0020 0.0021 0.0541 − 0.0767
358.5 0.420 − 0.0663 0.0505 0.0002 0.0020 0.0021 0.0547 − 0.1211
358.4 0.437 − 0.0639 0.0515 0.0003 0.0020 0.0021 0.0558 − 0.1198
358.2 0.561 − 0.0604 0.0526 0.0002 0.0020 0.0021 0.0569 − 0.1172
357.7 0.660 − 0.0721 0.0535 0.0002 0.0020 0.0021 0.0578 − 0.1299
357.7 0.741 − 0.0324 0.0534 0.0006 0.0020 0.0021 0.0581 − 0.0905
357.6 0.826 − 0.0338 0.0531 0.0002 0.0020 0.0021 0.0574 − 0.0912
357.6 0.894 − 0.0230 0.0532 0.0006 0.0020 0.0022 0.0579 − 0.0809
357.6 0.913 − 0.0228 0.0558 0.0002 0.0020 0.0022 0.0602 − 0.0830
357.6 0.937 − 0.0090 0.0556 0.0002 0.0020 0.0022 0.0599 − 0.0689
357.6 0.951 − 0.0031 0.0541 0.0003 0.0020 0.0022 0.0585 − 0.0616
357.6 0.960 – – – 0.0020 0.0022 – –
357.6 1.000 – – – 0.0010 – – –

4 Conclusions

This work indicates that diaminomethanal is a potential entrainer for separation of IPA‒
water azeotropic mixture in the concentration range of 13‒15.7 mol%. The isobaric VLE
for the ternary system IPA‒water‒diaminomethanal were studied at atmospheric pres-
sure using Othmer type recirculation still. The VLE results exhibited that the inclusion
of diaminomethanal enlarges the relative volatility of IPA to water, which led to the ter-
mination of azeotrope. Results indicate that 13 mol% of diaminomethanal concentration
is sufficient enough to eliminate the azeotrope of IPA‒water system completely. NRTL
model was used to correlate the experimental VLE data of the ternary systems, good
correlations were obtained. An average absolute difference for the temperature and IPA
mole fraction in the vapor phase are 0.172 K and 0.0017 K respectively. The measured
experimental results were also examined for its thermodynamic consistency with the
help of modified McDermott–Ellis and Wisniak’s L-W tests and found to be consistent.

Acknowledgements The authors acknowledge Thapar Institute of Engineering & Technology, Patiala,

India, for the financial support to conduct this research under the Grant TU/SEED/2014/CHE/NS.

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 Journal of Solution Chemistry

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