Fluid Phase Equilibria 363 (2014) 117–120

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Measurement and correlation of the mutual solubility of

diisopropylamine + water and triethylamine + water systems at high
pressure
Yiling Tian, Pingfang Yuan, Liqian Cao, Rongjiao Zhu ∗
Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin
300072, China

a r t i c l e i n f o a b s t r a c t

Article history: The mutual solubility data of diisopropylamine + water and triethylamine + water systems were mea-
Received 15 July 2013 sured at the pressure up to 100 MPa and the temperature range was 293.2–316.2 K. Experiments were
Received in revised form performed in a high-pressure autoclave with a moveable piston. The experimental data were correlated
11 November 2013
satisfactorily with NRTL activity coefficient model and the binary parameters were obtained.
Accepted 17 November 2013
Available online 23 November 2013
© 2013 Elsevier B.V. All rights reserved.

Keywords:
Mutual solubility
Diisopropylamine
Triethylamine
High pressure
NRTL model

1. Introduction method of standard additions was used to analyze samples of each

The chief use of aliphatic amines is as intermediates of the pro-
duction of surfactants, rubber accelerators, insecticides, dyes and
medicines. Considerable quantity of industrial manufactures for the
above products use water, which is very cheap, as solvents. Thus,
the mutual solubility of water and aliphatic amines is important for
industrial design. Some experimental work on mutual solubility of
amines and water has been reported in very little literature [1–3].
The summaries of the little earlier work are given by Sorensen and
Arlt [4] and the Solubility Data Series of the International Union Pure
and applied Chemistry [5]. The worthful work on above object has
been given by Stephenson. He and his co-workers measured mutual
solubility of more than 300 binary and ternary systems contain-
ing organic-water pairs [1]. It was found that all organic amines
up to C4 are miscible with water in arbitrary proportions up to
the boiling points of the amines. The amines with high molecu-
lar weight such as C6 to C10 show lower mutual solubility with
water. For a given molecular weight, there is no extreme differ-
ence in the solubility of primary, secondary and tertiary amines at
normal pressure. Very little experimental work on the mutual sol-
ubility of the above systems at high pressure has been reported.
For mutual solubility determination at atmospherical pressure, the
layer. In present work, the experimental mutual solubility data of
diisopropylamine + water and triethylamine + water systems were
given. The pressure was up to 100 MPa and the temperature range
of 293.2–316.2 K. The results show that the liquid–liquid two-phase
region decreased with increasing pressures at constant tempera-
ture or with decreasing temperature at constant pressure. The data
have also been correlated with NRTL activity coefficient model. The
parameters of the model were obtained as well as the deviation
between the calculated data and the experimental data.
2. Experiment
2.1. Materials
Three-time distilled water was produced in our laboratory and
it has a conductivity of 0.06 ␮S cm−1 at 25 ◦ C. The suppliers, the
purities and the refractive index of the organics used in this work
are summarized in Table 1. The purities of all organics were estab-
lished by gas chromatography. And the refractive index of the
materials were measured using Abbe refractometer at temperature
20 ◦ C.
2.2. Apparatus and accuracy

∗ Corresponding author. Tel.: +86 2227406140. Experiments were performed in a high-pressure autoclave with
E-mail addresses: zhurongjiao@tju.edu.cn, yltian@tju.edu.cn (R. Zhu). a moveable piston which has been described previously [6]. A

0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2013.11.027
118 Y. Tian et al. / Fluid Phase Equilibria 363 (2014) 117–120

Table 1
Supplier, purity and refractive index of samples used in this worka .

Amine Supplier Purity (w %) n20

D

Diisopropyl amine J&K Chem Ltd. >99.0 1.3922

Triethyl amine Tianjin Special Agent Ltd. >99.5 1.3966
Water Homemade Three-time distilled 1.3330
2-Butanol Guangfu Fine Chemical Research Institute >99.5 1.3962
a
u(n20
D
) = ±0.0001.

0.1 MPa min−1 so the cloud pressure in the increasing or decreasing

branches agreed within 0.1 MPa. For improving the sensitivity and
stability of the detection, the laser light detector which was made
of Selenium cell was placed in a isothermal box by water cooling.
The translucent Ag-plating mirror was installed at angle of 45◦ with
the straight laser beam. The laser light passed through the mirror
was reflected back to the mirror and then it was reflected to the
laser light detector.

2.3. Experimental procedure

Fig. 1. Schematic diagram of the high-pressure apparatus. (1) autoclave body, (2)
screw-driven pump for generating pressure, (3) pressure meter, (4) Hall probe, (5)
heat jacket, (6) piston, (7) O-ring, (8) stirrer, (9) magnet, (10) screw-driven pump
for adding water, (11) thermocouple and display,(12) sample valve for liquid, (13)
digital multimeter and computer, (14) mirror, (15) quartz window, (16) laser light,
(17) hold down gag, (18) sample valve for vapor, (19) pressure sensor and display,
(20) vacuum pump.
schematic is shown in Fig. 1. The tube-like autoclave (o.d 50 mm, i.d
20 mm, maximum internal 100 cm3 ) was made of austenitic man-
ganese steel. The moveable piston separated the contents in the
autoclave from the pressure-transmit medium oil which drove the
piston to generate high pressure inside the autoclave. A sapphire
window enabled the visual observation of phase transition. The sur-
face of the piston facing the window was silvered for reflexing light
from the semitransparent mirror in front of the window.
To provide rapid mixing and the homogenization of tempera-
ture, an egg-shaped magnetic stirrer was used. The pressure was
generated with a manually operated screw-driven pump and was
measured by a strain gauge precision transducer. The output, I(p),
from gauge for either rising or falling pressure showed a reproduc-
ibility of 0.2% of full scale. The estimated maximum uncertainty
for high pressure was about ±0.1 MPa. The temperature of the ves-
sel was measured by a platinum resistance thermometer with an
estimated maximum uncertainty of ±0.2 K.
In order to determine more accurate phase transition, a newly
developed laser light scattering technique was used in this work.
Since the turbidity of the system sharply increased in the vicinity of
the cloud point and this can be reflected by the lowing of the inten-
sity of light reflecting, the electrical current intensity produced by
light detector would turn to zero in the vicinity of the cloud point. A
He–Ne laser (made in Tianjin University) source and a digital multi-
meter were incorporated in present determining system replacing
the visual observation in our previous work. The change rate of the
pressure in the vicinity of cloud point was controlled within about
The synthetic method was used to determine the phase bound-
aries. The procedure was similar to the literature [7]. First, amine
and water were weighted using an electronic balance precise to
0.0001 g. And then they were introduced into the evacuated and
dried cell. The mass of amine or water injected into the cell was
determined by difference method, so the standard uncertainty for
mass was 0.0002 g. When the temperature reached the desired
value, the pressure of the system was gradually increased or
decreased while the mixture was stirred continuously. The mixture
would eventually reach a fairly sharply defined pressure at which
the laser light beam passing through the mixture would become
fairly diffuse and the light spot on the screen would disappear. This
was because that the intensity of reflected light from mirror nearly
turned to zero when the clear uniphase mixture began to separate
into two phase consisted of microemulsion. Record the pressure
for each of the different mixture composition. To obtain an accu-
rate pressure, the same experiment was repeated for three times
at least. The agreement of the cloud point determined from the
appearance of the second phase agreed within ±0.1 MPa and about
±0.3% of the total pressure. Each cloud point noted a point on the
isothermal p–w phase boundary.
To test the reproducibility and accuracy of the apparatus used in
this work and the operating procedure adopted, the mutual solubil-
ity of 2-butanol and water have been measured in the rich-water
and rich-butanol regions respectively and compared with litera-
ture data reported by Moriyoshi [8]. The test results are presented
in Table 2. The comparison results demonstrate that the agree-
ment between the measured data using our apparatus and the data
reported in literature [8] is fairly good.
3. Results and discussion
The experimental data of the cloud points for the two systems
are presented in Figs. 2 and 3. The data at atmosphere in Figs. 2 and 3

Table 2
The comparison between experimental data of cloud point and literature values for water +2-butanol system.

Rich-2-butanol phase Rich-water phase

T (K) w (H2 O) p (MPa) RD%a T (K) w (H2 O) p (MPa) RD%

Present Literature Present Literature

334.3 17.43 32.12 32.0 0.38 356.1 52.58 54.16 54.0 0.30
313.4 29.38 54.26 54.0 0.48 333.7 59.26 47.84 47.45 0.82
334.2 41.68 84.34 84.0 0.40 324.2 59.61 35.33 35.0 0.94
 pexp −p 
a
RD% =  p
lit 
× 100, u(T) = ± 0.2 K, u(p) = ± 0.1 MPa.
lit
 Y. Tian et al. / Fluid Phase Equilibria 363 (2014) 117–120 119

110 318

100

90

80

70 312

60
p/MPa

T/K
50

40
306
30

20

10

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
A B A B
w w

Fig. 2. The experimental isothermal p–w data of diisopropylamine (A) + water Fig. 4. The experimental and calculated isobaric T–w curve of diisopropy-
(B) binary system at different temperature: ()303.2 K; ()305.2 K; ()308.2 K; lamine (A) + water (B) binary system: () 80.1 MPa; ()74.8 MPa; ()49.9 MPa;
()310.2 K; (䊉)313.2 K; ()316.2 K. Solid lines are the trends of the experimental ()40.1 MPa; (♦)20.0 MPa. Solid lines have been calculated using NRTL equation.
data.

are from literature [1]. It can be found that the liquid-liquid
two-phase region decreases with increasing pressures at a constant
temperature. From thermodynamics the influence of pressure on
the mutual solubility can be connected to the pressure dependence
of the excess Gibbs energy (gE ), thus to the sign of the excess vol-
ume (vE = ∂gE /∂p). If the excess volume vE < 0, pressurization helps
miscibility, while the opposite happens in the case of vE > 0 [9].
The triethylamine + water system shows negative excess volumes
[10,11] as well as the aqueous solutions of butylamine isomers
[12]. As an isomer of triethylamine, diisopropylamine should have
the similar property (vE < 0). Hence, there is a positive correlation
between the mutual solubility and pressure at constant temper-
ature for the two systems. The upper critical solution pressure
(UCSP) at different temperature and corresponding mass percent
of the two systems are listed in Table 6. The UCSP increases in
accordance with the temperature for the two systems.
In Figs. 2 and 3, some horizontal lines were drawn when
the paper was being prepared. The horizontal lines would
intersect the isothermal lines when the pressure was proper. The
points of intersection in the rising period of the isothermal lines
correspond with the composition of the rich-water phase and the
points of intersection in the falling period correspond with the rich-
amine phase. So the isobaric T–w (T–x) data at certain pressures
were obtained and the isobaric T–w curves for the two systems were
then drawn using the pressure, temperature and corresponding
composition data. And they are shown in Figs. 4 and 5, respectively.
The lower critical solution temperature (LCST) of each pressure is
listed in Table 7. The LCST increases as the pressure rises. Obviously,
the liquid-liquid two-phase region increases as the temperature
rises at a constant pressure. Every physical system tends to evolve
spontaneously to a situation that minimizes its Gibbs free energy. In
other words, one system minimizes energy and maximizes entropy
in the most favorable case. For these two systems, Stephenson
measured their mutual solubility of different temperature at atmo-
sphere [1]. The results showed that the mutual solubility of the
two systems decreased as the temperature increased. This indi-
cates that it will release heat while amine dissolves in water in

90
306
80

70

60
300
50
p/MPa

T/K

40

30

294
20

10

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
A B A B
w w

Fig. 3. The experimental isothermal p–w data of triethylamine (A) + water (B) binary Fig. 5. The experimental and calculated isobaric T–w curve for triethylamine
system at different temperature: () 293.2 K; (䊉) 295.2 K; () 299.2 K; () 301.2 K; (A) + water (B) binary system: ()57.1 MPa; ()33.5 MPa; ()22.2 MPa; ()12.6 MPa.
() 303.2 K; ()306.2 K. Solid lines are the trends of the experimental data. Solid lines have been calculated using NRTL equation.
120 Y. Tian et al. / Fluid Phase Equilibria 363 (2014) 117–120

Table 3
The NRTL parameters and mean relative deviations of [diisopropylamine (1) + water (2) system] and [triethylamine (1) + water (2) system] at different pressure.

p (MPa) NRTL parametersa MRD%b

−1 −1
(g12 –g22 ) (J mol ) (g21 –g11 ) (J mol )

a12 b12 a21 b21

Diisopropylamine (1) + water (2)

100.0 −17.1 4722.6 −23.5 10,000.0 0
80.1 100.0 9982.4 −77.0 −10,000.0 1.701
74.8 −1.7 9219.8 15.7 −4968.9 0
65.0 3.7 −4163.5 3.7 4083.5 0
49.9 5.1 −4284.4 5.4 3782.3 0
40.1 −4.4 −9975.3 43.6 −10,000.0 0
31.0 3.0 −4872.9 4.4 2671.4 0
20.0 4.0 −4164.2 3.8 2252.3 0
Triethylamine (1) + water (2)
57.1 100.0 5465.9 −93.1 −10,000.0 0.755
45.8 100.0 5465.9 45.9 4330.9 0.436
33.5 −12.7 10,000.0 42.0 10,000.0 0.054
22.2 −19.8 710.4 −46.5 10,000.0 1.966
12.6 −16.4 569.6 −43.3 10,000.0 2.613
4.9 1.8 −2583.1 −1.0 10,000.0 2.244
−1 −1
a
˛ = 0.2, (g12 − g22 ) (J mol ) = (a12 T + b12 )R, (g21 − g11 ) (J mol ) = (a21 T + b21 )R.
The parameter uncertainty is less than 0.2%.

n
 
b
MRD% = 1
n
xcal,i − xexp,i /xexp,i  × 100.
i=1

rich-water phase or water dissolves in amine in rich-amine phase, (˛12 = ˛21 = 0.2) and was taken into account by choosing the value
that is sol H < 0. Therefore, low temperature is beneficial to the that has given the lowest deviation. The NRTL parameters and the
miscibility of the two systems. At a molecular level, the attrac- mean relative deviations (MRD %) are shown in Table 3. The results
tive interaction between unlike molecules (amine and water) is of the correlation are also presented in Figs. 4 and 5. The calculated
stronger than that between like molecules (amine and amine or data and experimental data show a good agreement.
water and water) due to the generation of hydrogen bonds. Hydro-
gen bonds can lower the energy of the system, so the energy of 5. Conclusion
the miscible phase is lower than that of the immiscible one. The
number of hydrogen bonds increases as temperature is lowered. The mutual solubility data of diisopropylamine + water and tri-
ethylamine + water systems were measured at the pressure up to
4. Correlation calculation 100 MPa and the temperature range was 293.2–316.2 K. The results
show that the liquid–liquid two-phase region decreased with
The isobaric T–x data was correlated with NRTL activity coef- increasing pressures at constant temperature or with decreasing
ficient model using ASPEN PLUS software. The concept of local temperature at constant pressure. The upper critical solution pres-
composition was used in Renown’s derivation of the NRTL (non- sure at different temperature of the two systems was obtained as
random, two liquid) equation [13] and this equation is applicable to well as the lower critical solution temperature at different pres-
partially miscible as well as completely miscible systems. The NRTL sure. The isobaric T–x data were also correlated satisfactorily with
equation can provide a good representation of experimental data the NRTL activity coefficient model. The binary parameters were
for strongly no ideal mixture and especially for partially immiscible obtained for the two systems.
systems. The NRTL equation for the excess Gibbs energy of a binary
solution is Appendix A. Supplementary data
gE
  G 12 G12

21 21
= x1 x2 + (1)
RT x1 + x2 G21 x2 + x1 G12 Supplementary material related to this article can be found, in
where the online version, at http://dx.doi.org/10.1016/j.fluid.2013.11.027.
g12 − g22 g21 − g11
12 = 21 = (2)
RT RT References

G12 = exp(−˛12 12 ) G21 = exp(−˛12 21 ) (3) [1] R.M. Stephenson, J. Chem. Eng. Data 38 (1993) 625–629.
[2] R.M. Stephenson, J. Stuart, J. Chem. Eng. Data 31 (1986) 56–70.
The parameter gij is an energy parameter characteristic of the i–j [3] R.M. Stephenson, J. Chem. Eng. Data 38 (1993) 634–637.
interaction and the parameter ˛12 is related to the no randomness [4] J.M. Sorensen, W. Arlt, Liquid–liquid Equilibrium Data Collection, vol. 5,
in the mixture. From Eq. (1), the activity coefficients are DECHEMA, Frankfurt/Main Germany, 1979, Part 1.
  2  [5] International Union Pure and Applied Chemistry, Solubility Data Series,
Macmillan Publishing Co., Inc., Riverside, NJ, 2013.
G21 12 G12
ln 1 = x22 21 + (4) [6] R.J. Zhu, J.G. Zhou, S.C. Liu, J. Ji, Y.L. Tian, Fluid Phase Equilibria. 291 (2010) 1–7.
x1 + x2 G21 (x2 + x1 G12 )2 [7] K. Ochi, M. Momose, K. Kojima, et al., Can. J. Chem. Eng. 71 (1993)
982–985.
  2  [8] T. Moriyoshi, S. Kaneshina, K. Aihara, K. Yabumoto, J. Chem. Thermodyn. 7
G12 21 G21 (1975) 537–545.
ln 2 = x12 12 + (5) [9] Rebelo, P.N. Luis, Phys. Chem. Chem. Phys. 1 (1999) 4277–4286.
x2 + x1 G12 (x1 + x2 G21 )2 [10] T.M. Letcher, W. Spiteri, J. Chem. Thermodyn. 11 (1979) 905–906.
[11] T.M. Letcher, W. Spiteri, J. Chem. Thermodyn. 15 (1983) 965–970.
In this calculation, the parameter ˛12 is a constant of proportion- [12] M.A. Saleh, S. Akhtar, A.R. Khan, Phys. Chem. Liq. 38 (2000) 137–149.
ality similar to the no randomness constant of the NRTL equation [13] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135–144.