Fluid Phase Equilibria 482 (2019) 48e63

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Liquid-liquid equilibrium data and thermophysical properties for

ternary systems composed of water, acetic acid and different solvents
Leonardo Hadlich de Oliveira a, *, Grazielle Patrícia Morgado b, Rafael Boni b,
Laerti Reis Roque b, Rafaela Rocha Pinto c, Sarita Ca^ndida Rabelo b, d
a
Laboratory of Adsorption and Ion Exchange (LATI), Chemical Engineering Department (DEQ), State University of Maringa  (UEM), Maringa, PR, Brazil
b
Brazilian Bioethanol Science and Technology Laboratory (CTBE), Brazilian Center for Research in Energy and Materials (CNPEM), Campinas, SP, Brazil
c
School of Chemical Engineering (FEQ), State University of Campinas (UNICAMP), Campinas, SP, Brazil
d ~o Paulo State University (UNESP), Campus of Botucatu, Botucatu, SP,
Department of Bioprocess and Biotechnology, College of Agricultural Sciences, Sa
Brazil

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

Article history: Liquid-liquid equilibrium (LLE) data for water þ acetic acid þ {1-butanol or isopentanol or methyl-terc-
Received 22 April 2018 butyl ether (MTBE) or methyl isobutyl ketone (MIBK) or diisobutyl ketone (DIBK) or isoamyl propionate}
Received in revised form systems at T ¼ {293.2 and 313.2} K and P z 95 kPa were determined. Immiscibility region (LLE envelope)
12 October 2018
were determined experimentally through binodal curves (cloud point data). Thermophysical properties,
Accepted 23 October 2018
i.e., density, refractive index, speed of sound, isentropic compressibility and molar refractivity were
Available online 28 October 2018
obtained for each cloud point. Tie lines were attained using indirect method utilizing equations obtained
through cloud point data fit and partition coefficients, selectivities and percent of extraction were
Keywords:
Acetic acid
calculated in order to evaluate the effects of solvent type and temperature on acetic acid removal from
Liquid-liquid equilibrium water. Besides, thermophysical properties for all systems were compared. LLE data were correlated with
NRTL NRTL model, presenting root mean square deviation equal to 1.2366% for 66 tie lines. NRTL modelling
Thermophysical properties also estimated plait points for all systems.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction acid þ {1-butanol or isopentanol or methyl-tert-butyl ether

Acetic acid is a fermentation inhibitor for second generation
(2G) ethanol production from lignocellulosic materials [1,2]. Pro-
cesses investigated to remove acetic acid from fermentation broth
included electro-membrane separation [3], vacuum membrane
distillation [4], adsorptive membranes [5], electrodialysis [6] and
liquid-liquid extraction [1,7], which was demonstrated to have no
negative impact on fermentable sugars, providing an enhanced
bioethanol fermentation performance [1].
Liquid-liquid equilibrium (LLE) data and thermophysical prop-
erties are important information utilized to design, scaling up and
automation of liquid-liquid extraction processes [8,9], e.g., the hold
up in extraction columns is function of equilibrium phase's den-
sities [10] and interface between phases can be detected through
refractive index measurements [11].
In this work, binodal curves and LLE data for water þ acetic
(MTBE) or methyl isobutyl ketone (MIBK) or diisobutyl ketone
(DIBK) or isoamyl propionate} systems at T ¼ {293.2 and 313.2} K
and P z 95 kPa were determined experimentally and correlated
with NRTL model. Density, refractive index, speed of sound, isen-
tropic compressibility and molar refractivity were obtained
together with plait points, acetic acid partition coefficients, solvent
selectivities and percent of extraction.
Some systems studied here were already reported in literature,
using the following solvents and temperatures: 1-butanol at
298.15 K [12]; MTBE at 293.15, 298.15, 303.15, 308.15, 313.15, and
318.15 K [13]; MIBK at 294.15, 308.15 K [14,15]. However, none of
these works have detailed information about thermophysical
properties such as those investigated in this manuscript.
2. Experimental procedure

2.1. Chemicals utilized

* Corresponding author.
E-mail address: leonardoh.deoliveira@gmail.com (L. Hadlich de Oliveira). All chemicals utilized in this work and their characteristics are

https://doi.org/10.1016/j.fluid.2018.10.021
0378-3812/© 2018 Elsevier B.V. All rights reserved.
 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63 49

shown in Table 1. Density, refractive index and speed of sound for acetic acid to water molar fractions at binodal curve, as presented
each compound at T ¼ {293.2 and 313.2} K are shown in Table 2. by Equations (2) and (3):

x2 ¼ A2 þ B2 x1 þ C2 x21 þ D2 x31 þ E2 x41 (2)

2.2. Equipment

Schematic diagram of equipment utilized to obtain cloud point, x2 ¼ A3 þ B3 x1 þ C3 x21 þ D3 x31 (3)
liquid-liquid equilibrium and thermophysical properties measure-
ment is presented in Fig. 1. where: x2 is acetic acid molar fraction; A2, B2, C2, D2, E2 are adjusted
parameters of Equation (2); and A3, B3, C3, D3 are adjusted param-
eters of Equation (3).
2.3. Binodal curves

Binodal curves were obtained through cloud point data deter-
mination by titration method [27].
Solvent-rich (organic phase) branch of binodal curve was
determined inserting known masses of acetic acid and solvent in-
side glass equilibrium cells and, after temperature reached 293.2 or
313.2 K, adding water drop-by-drop to the homogeneous binary
mixture until it became turbid. Equilibrium cells utilized have
23  106 m3 internal volume and were manufactured equipped
with a jacket where water from a thermostatic bath (Tecnal TE-184,
precise to 0.1 K) can circulate to guarantee constant temperature
inside the cell. Water-rich (aqueous phase) branch of binodal curve
was determined in a similar way for solvent-rich branch, but
initially mixing known masses of acetic acid and water and finally
adding solvent drop-by-drop until turbidity occurs. In cloud point
method utilized in this work, turbidity was verified by naked eye.
After turbidity was attained, samples were collected for mea-
surement of density, refractive index and speed of sound. Density
and speed of sound were measured in an Antor-Paar DSA 5000 M
analyzer, precise to 0.005 kg m3 and 0.01 m s1, respectively.
Refractive index was measured in an Anton Paar Abbemat 550
refractometer, precise to 2  105.
Cloud points compositions and together with thermophysical
properties were correlated to provide equations to be used in tie
line determination (subsection 2.4). Two different type of equations
were used here. The first type corresponds to equations where
water molar fractions in binodal curve are related to density,
refractive index and speed of sound determinations, as shown by
Equation (1):
x1 ¼ A1 r þ B1 r2 þ C1 n þ D1 n2 þ E1 c þ F1 c2
where: x1 is water molar fraction; r is density (kg m3); n is
refractive index; c is the speed of sound (m s1); and A1, B1, C1, D1, E1,
F1 are fitting parameters.
The second type of equations are polynomial relations between
2.4. Tie lines
According to Nova k et al. [27], tie lines can be determined using
binodal curve if its shape and additional properties along this curve
are known.
Tie lines or LLE data were determined in this work inserting
known masses of water, acetic acid and solvent inside
equilibrium cell. The composition of this mixture must be
graphically inside the region previously determined with binodal
curve data, i.e., the mixture is in the heterogeneous region. This
ternary mixture was then agitated for 4 h and left settle for at
least 12 h. Such times were previously tested to guarantee that
phase equilibrium is established for systems studied here [28].
Samples of each phase were collected and their density,
refractive index and speed of sound were determined. Water molar
fraction was then obtained utilizing these properties values in
Equation (1) and acetic acid molar fraction, using them in Equation
(2) or (3). Solvent molar fraction was determined by mass balance,
as shown by Equation (4):
x3 ¼ 1  x1  x2 (4)
where: x3 is solvent molar fraction.
LLE data were used to calculated acetic acid partition coefficient
(K), solvent selectivity (S) and percent of extraction (E). Mass bal-
ance for each biphasic system was determined as the perpendicular
distance h between feed composition and tie line using ternary
diagram coordinates. These calculations and procedure are shown
in a previous publication [28].
(1)
2.5. Thermophysical properties
Density and speed of sound measurements were utilized to
calculate isentropic compressibility through Newton-Laplace's
equation, as shown by Equation (5) [29]:

Table 1
Sample provenance table.

Chemical CAS Molar mass (kg kmol1) Purity (mass fraction)a Supplier Purification method

Water 7732-18-5 18.015 Sabesp Distillation

Acetic acid 64-19-7 60.052 0.997 Sigma-Aldrich None
1-butanolb 71-36-3 74.123 0.995 Merck None
Isopentanolc 123-51-3 88.15 0.985 Vetec None
MTBEd 1634-04-4 88.15 0.998 Sigma-Aldrich None
MIBKe 108-10-1 100.16 0.985 Vetec None
DIBKf 108-83-8 142.239 0.95 Rhodia/Solvay None
Isoamyl propionate 105-68-0 144.214 0.98 Sigma-aldrich None
a
Informed by supplier.
b
Butan-1-ol.
c
3-Methylbutan-1-ol.
d
2-Methoxy-2-methylpropane.
e
4-Methylpentan-2-one.
f
2,6-Dimethyl-4-heptanone.
50 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63

Table 2
Properties of chemicals at T ¼ {293.2 and 313.2} K and P z 95 kPa.a

Chemical r/(kg m3) n c/(m s1)

T ¼ 293.2 K T ¼ 313.2 K T ¼ 293.2 K T ¼ 313.2 K T ¼ 293.2 K T ¼ 313.2 K

Exp. Lit. Exp. Lit. Exp. Lit. Exp. Lit. Exp. Lit. Exp. Lit.

Water 998.397 998.768b 992.201 992.744b 1.3330 1.3330b 1.3306 1.3307b 1482.79 1482.6c 1529.34 1529.0c
Acetic acid 1049.799 1048.9d 1028.134 1030.3d 1.3724 1.3730d 1.3644 1.3644d 1161.15 1149e 1093.09 1155.8f
1-butanol 809.375 809.8g 793.785 794.9g 1.3991 1.397g 1.3910 1.389g 1260.17 1258g 1192.99 1193g
Isopentanol 804.433 808.3h 794.426 793.2h 1.4074 1.3991 1253.18 1185.89
MTBE 739.453 740.65i 718.083 719.42i 1.3690 1.36597j 1.3579 1063.40 1035j 968.17
MIBK 799.608 801.18k 781.114 782.6l 1.3960 1.3976k 1.3863 1211.34 1131.01 1138l
DIBK 809.037 792.503 1.4140 1.4051 1246.91 1170.53
Isoamyl propionate 868.555 848.984 1.4061 1.3968 1244.89 1146.23
a
Maximum standard uncertainties, u, are u(T) ¼ 0.1 K, u(r) ¼ 0.45 kg m3, u(n) ¼ 0.0005, u(c) ¼ 1.97 m s1.
b
Ref. [16].
c
Ref. [17].
d
Ref. [18].
e
Ref. [19].
f
Ref. [20].
g
Ref. [21].
h
Ref. [22].
i
Ref. [23].
j
Ref. [24].
k
Ref. [25].
l
Ref. [26].

Fig. 1. Schematic diagram of equipment utilized to determine binodal curves, liquid-liquid equilibrium and thermophysical properties data.

2.6. Uncertainty measurements

1
bS ¼ (5) Uncertainties estimated for variables studied experimentally are
rc2
shown in the respective table footnote they were used and were
where: bS is the isentropic compressibility (Pa1). determined according to GUM [31] and Eurachem [32].
Besides, density, refractive index and cloud points molar frac-
tions were used to calculate another thermophysical property, i.e.,
2.6.1. Uncertainty for cloud point data
the molar refractivity (or molar refraction), given by Equation (6)
Uncertainty for could point data determined for water, acetic
[30]:
acid and solvent molar fractions were calculated using Equations

 (7)e(9):
n 2  1 x1 M 1 þ x2 M 2 þ x3 M 3 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Rm ¼ (6)    
n2 þ 2 r vx1 2 vx1 2
uc ðx1 Þ ¼ ½uc ðw1 Þ2 þ ½uc ðw2 Þ2 (7)
vw1 vw2
where: Rm is the molar refractivity; M 1 , M 2 , and M 3 are molar
masses of water, acetic acid and solvent (kg kmol1), respectively.
 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63 51

sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi and six ternary systems were studied in this work, 26 parameters
   
vx2 2 vx2 2 were fitted to LLE data. Besides, correlations were made consid-
uc ðx2 Þ ¼ ½uc ðw1 Þ2 þ ½uc ðw2 Þ2 (8) ering aij ¼ aji. This modelling was realized in Fortran program TML-
vw1 vw2
LLE 2.0 [35] The procedure is based on the modified Simplex
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi method [36] and consists in the minimization of a concentration-
   
vx3 2 vx3 2 based objective function F [37] shown in Equation (15):
uc ðx3 Þ ¼ ½uc ðx1 Þ2 þ ½uc ðx2 Þ2 (9)
vx1 vx2
X
T X
D X X
M N1 
exp
2

F¼ Wnmdt xnmdt  xcalc

nmdt (15)
where: uc(xi) is the combined uncertainty for molar fraction of
t d m n
component i; wi is the mass fraction of component i. Similar cal-
culations were detailed in a supplementary file previously pub- where: Wnmdt is the weight associated with component n in phase
lished [33]. m in tie line d at temperature t; xexp and xcalc represent experi-
nmdt nmdt
mental and calculated molar fraction of component n in phase m
2.6.2. Uncertainty for LLE data and tie line d at temperature t, respectively; N, M, D, and T are the
Combined uncertainties for water and acetic acid molar frac- total number of components, phases, tie lines and temperatures,
tions in LLE data were calculated utilizing Equations (10) and (11): respectively.
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Calculated and experimental molar fractions were compared
     
vx1 2 vx1 2 vx1 2 using percent root-mean-square deviation (dx), given by Equation
uc ðx1 Þ ¼ ½uðrÞ2 þ ½uðnÞ2 þ ½uðcÞ2
vr vn vc (16):
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
(10) uP P P  2
u D M N exp
t d m n xnmd  xcalc
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi dx ¼ 100
nmd
(16)
 
vx2 2 2MN
uc ðx2 Þ ¼ ½uc ðx1 Þ2 (11)
vx1
where: xexp
nmd
and xcalc
nmd
represent experimental and calculated molar
fraction of component n in phase m and tie line d, respectively.
where: u(r), u(n) and u(c) are the uncertainty of density, refractive
The thermodynamic consistency of parameters obtained was
index and speed of sound measurements; the derivatives were
checked utilizing the software available elsewhere [38].
applied in Equations (1)e(3).

2.6.3. Uncertainty for thermophysical properties 4. Results and discussion

Uncertainty for temperature measurements, u(T), was consid-
ered equal to the precision of thermostatic bath utilized. Besides, Cloud points molar fractions, densities, refractive indices,
combined uncertainty for density, refractive index, speed of sound, speeds of sound, isentropic compressibilities and molar re-
isentropic compressibility and molar refractivity determinations fractivities for water (1) þ acetic acid (2) þ solvent (3) at T ¼ {293.2
were calculated considering their standard deviations for triplicate and 313.2} K and P z 95 kPa, determined experimentally and
measurements and equipment error. For isentropic compressibility, through Equations (5) and (6) are shown in Table A1.
error propagation considering density and speed of sound mea- Binodal curves for each system are shown in Fig. 1 and the effect
surements were considered. Moreover, for molar refractivity, of solvent type and temperature can be shown in Figs. 2 and 3,
combined uncertainty regarding all variables in Equation (6) were respectively. It is verified that immiscibility region (two-phase en-
considered. velope) is increased in the order 1-butanol < isopentanol < MTBE z
MIBK < DIBK z isoamyl propionate for both temperatures studied.
3. Thermodynamic modelling Besides, considering the effect of temperature, it was expected that for
such ternary systems immiscibility region was smaller for greater
Experimental phase equilibrium data for water þ acetic temperatures. However, increasing temperature shows little effect on
acid þ solvent systems studied in this work were correlated using solubility of systems studied here, as shown in Fig. B.1.
non-random two-liquid (NRTL) model for activity coefficients Three notifications arise from LLE data obtained here: a)
calculation [34]. NRTL equations are given by Equations (12)e(14): although MTBE and isopentanol have similar molar masses, MTBE
P " P # systems present immiscibility regions greater than those for iso-
j tji Gji xj X G x k tkj Gki xk pentanol. It can be explained by a steric hindrance to oxygen
lngi ¼ P þ P ij j tij  P (12)
k Gki xk k Gki xk k Gkj xk
electrons by methyl group in MTBE molecule, which can diminishes
j
its polar character and interaction with acetic acid and water
molecules through hydrogen bonds; b) although MIBK molar mass
Dgij Aij
 is greater than MTBE, theirs systems have similar immiscibility
tij ¼ ¼ tij stji (13)
RT T regions. It can be possibly explained by a possibility of MIBK to


 make hydrogen bonds with acetic acid and water through a “more
Gij ¼ exp  aij tij aij ¼ aji (14) available” oxygen atom in its molecule; c) DIBK and isoamyl pro-
pionate have similar masses and similar regions. This can be due to
where: gi is the activity coefficient of component i; tij is the binary a similar nonpolar character of both molecules, effect of isoamyl
interaction characteristic energy parameter; Gij is a Boltzmann- group in the ester and two isobutyl groups in ketone. So, although
type local composition energy interaction between i and j com- they have non bonding electrons in oxygen atoms, such non polar
ponents; R is the ideal gas constant; aij non-randomness parameter effect predominates. An FTIR study on these molecules could
for i-j pair. indicate how such interactions truly occur [39].
NRTL model calculations employed here utilized two adjustable Densities, refractive index, speeds of sound, isentropic com-
parameters, Aij and Aji (K), for each binary. Since eight compounds pressibilities and molar refractivities determined along each
52 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63

Fig. 2. Ternary diagrams for water þ acetic acid þ solvents: a) 1-butanol, T ¼ 293.2 K; b) 1-butanol, T ¼ 313.2 K; c) isopentanol, T ¼ 293.2 K; d) isopentanol, T ¼ 313.2 K; e) MTBE,
T ¼ 293.2 K; f) MTBE, T ¼ 313.2 K; g) MIBK, T ¼ 293.2 K; h) MIBK, T ¼ 313.2 K; i) DIBK, T ¼ 293.2 K; j) DIBK, T ¼ 313.2 K; k) isoamyl propionate, T ¼ 293.2 K; l) isoamyl propionate,
T ¼ 313.2 K;B, feed points; -, cloud points; , experimental tie lines; , NRTL tie lines.
 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63 53

Fig. 2. (continued).

binodal curve for each system are shown in Fig. B.2. It can be propionate, but for x1 greater than 0.6, DIBK z isoamyl propionate.
verified that binodal curve's density increased in the order 1- Moreover, MTBE presents a maximum, indicating intermolecular
butanol < isopentanol z MTBE < MIBK < DIBK < isoamyl forces between components are higher than pure components and
54 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63

Fig. 3. Binodal curves for water þ acetic acid þ solvent compared for each solvent at a) 293.2 K and b) 313.2 K: -, 1-butanol; , isopentanol; , MTBE; , MIBK; , DIBK; , isoamyl
propionate; open symbols: NRTL plait points; lines: NRTL binodal curves.

that such mixtures does not behave ideally.

Refractive indices values variation with water molar fraction in
binodal curves are higher for 1-butanol, isopentanol and MIBK,
followed by DIBK z isoamyl propionate, and the MTBE presented
the smallest values determined. Speeds of sound are greater for
DIBK and isoamyl propionate probably because these systems are
denser than others studied. Isentropic compressibilites for MTBE at
313.2 K, in general, are higher than other solvents in range studied
and those of DIBK and isoamyl propionate are the smallest. Molar
refractivities presented an exponential decay with water molar
fractions and for x1 values greater than 0.3 and it seems to be in-
dependent of solvent used.
In Table A2, the equations obtained through fitting of binodal
curve data are shown for each system and temperature studied.
These equations were applied to determine unknown molar frac-
tions of LLE phases, presented in Table A3. Tie line data for each
system are shown in Fig. 2
It is verified that tie lines obtained agree with binodal curve and
with their respective feed composition, indicating small discrep-
ancies in mass balance. Besides, this could be quantified by small h
values show in Table A3.
Considering experimental partition coefficients shown in Fig. 4,
for acetic acid molar fractions in aqueous phase smaller than 0.02,
isopentanol is the solvent with higher K values. For xaq 2 between
0.02 and 0.05, isopentanol and MIBK present higher partitions than
other solvents. For xaq2 between 0.05 and 0.13, MTBE and MIBK are
the solvents with greater K's. Higher acetic acid molar fraction in
aqueous phase are possible only for DIBK and isoamyl propionate,
which have similar partition coefficients.
Selectivity values are shown in Fig. 5. It can be verified that S
values increased in the same order as immiscibility region. This is
explained by the relation selectivity has with tie line length, and for
greater immiscibility regions, greater are the S values. So, selectivity
values are higher for DIBK and isoamyl propionate, which indicates
water contents in the organic phase is smaller than other solvents
studied. Besides, this effect is more pronounced for small acetic acid
concentrations.
Percents of extraction determined for each system are shown in
Fig. 6. It can be verified, as C0 (acetic acid feed molar fraction in
Fig. 4. Acetic acid partition coefficients between organic and aqueous phases for
solvent free basis) increases, different solvents present higher E
water þ acetic acid þ solvent: -, ,; 1-butanol; , ; isopentanol; , MTBE; , MIBK;
, DIBK; , isoamyl propionate; lines, NRTL; solid lines, 293.2 K; dash dot lines, 313.2 K.
 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63 55

Fig. 5. Solvent selectivities for water þ acetic acid þ solvent: -, ,; 1-butanol; , ; isopentanol; , MTBE; , MIBK; , DIBK; , isoamyl propionate; lines, NRTL; full
symbols and solid lines, 293.2 K; open symbols and dash dot lines, 313.2 K.

Fig. 6. Percent of extraction of each solvent studied in water þ acetic acid þ solvent: -, ,; 1-butanol; , ; isopentanol; , MTBE; , MIBK; , DIBK; , isoamyl
propionate; full symbols, 293.2 K; open symbols, 313.2 K.

values. The following sequence can be stated: 0.02 < C0 < 0.07, 1-
butanol is the solvent that extracts more acid to solvent phase;
for 0.07 < C0 < 0.11, isopentanol present greater E values; for
0.11 < C0 < 0.2, MTBE is more recommended to capture more acetic
acid from solvents studied; for C0 > 0.2, DIBK and isoamyl propio-
nate are suitable solvents between those investigated here, but
percent of extraction values are smaller than 25%.
NRTL estimated parameters are shown in Table 3 together with
rmsd obtained for each system. NRTL tie line modelling results are
shown in Fig. 2, where can be verified that calculated tie lines agree
with experimental data, presenting similar length and slope.
Binodal curves calculated with NRTL also represent the region of
experimentally determined cloud points, as shown in Fig. 3 and
Fig. B.1. Plait points were obtained though modelling and show
greater water content than solvent, which can be another indica-
tion acetic acid solubilizes preferably in solvent-rich phase.
56 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63

Table 3
Estimated NRTL binary parameters and rmsd values for the ternary systems water (1) þ acetic acid (2) þ solvents (3e8) at T ¼ {293.2 and 313.2} K.

i j Aij (K) Aji (K) aij ¼ aji

1 2 290.85 174.43 0.3
1 3 1143.0 3.2132 0.3
1 4 1569.7 138.62 0.2
1 5 1324.0 560.59 0.3
1 6 1468.7 444.99 0.3
1 7 1563.1 273.34 0.2
1 8 1464.7 255.37 0.2
2 3 490.35 1355.4 0.4
2 4 253.64 638.69 0.3
2 5 262.43 678.55 0.3
2 6 197.85 473.17 0.3
2 7 162.45 341.94 0.4
2 8 135.27 331.79 0.4

System rmsd/(%)

water (1) þ acetic acid (2) þ 1-butanol (3) at T ¼ 293.2 K 1.1497

water (1) þ acetic acid (2) þ 1-butanol (3) at T ¼ 313.2 K 1.0862
water (1) þ acetic acid (2) þ isopentanol (4) at T ¼ 293.2 K 0.9219
water (1) þ acetic acid (2) þ isopentanol (4) at T ¼ 313.2 K 0.9029
water (1) þ acetic acid (2) þ MTBE at (5) T ¼ 293.2 K 0.5167
water (1) þ acetic acid (2) þ MTBE at (5) T ¼ 313.2 K 0.8638
water (1) þ acetic acid (2) þ MIBK at (6) T ¼ 293.2 K 0.8325
water (1) þ acetic acid (2) þ MIBK at (6) T ¼ 313.2 K 0.8354
water (1) þ acetic acid (2) þ DIBK at (7) T ¼ 293.2 K 1.6863
water (1) þ acetic acid (2) þ DIBK at (7) T ¼ 313.2 K 1.6442
water (1) þ acetic acid (2) þ isoamyl propionate (8) at T ¼ 293.2 K 1.8897
water (1) þ acetic acid (2) þ isoamyl propionate (8) at T ¼ 313.2 K 1.5205
1.2366

Partition coefficients calculated with NRTL model, Fig. 4, indicate
that for diluted acetic acid solutions, the following sequence are
obtained: 1-
butanol > isopentanol > MIBK > MTBE > DIBK z isoamyl propio-
nate. NRTL also described selectivity behavior for 1-butanol, iso-
pentanol, MIBK and MTBE systems studied, as shown in Fig. 5, but
exception was observed for DIBK and isoamyl propionate, where for
aqueous acetic acid molar fraction smaller than 0.15, NRTL under-
estimated selectivity values.
increased in the same order as immiscibility region, being higher
for DIBK and isoamyl propionate, which indicates these solvents
solubilize less water than the others studied. Percents of extraction
data indicate that for 0.02 < C0 < 0.07, 0.07 < C0 < 0.11,
0.11 < C0 < 0.2, and C0 > 0.2 regions, 1-butanol, isopentanol, MTBE,
and DIBK or isoamyl propionate extract more solute than other
solvents, respectively, with E z 5% minimum and E z 60%
maximum. NRTL calculated tie lines, binodal curves, plait points, K
and S were reported for each system with total root mean square
deviation equal to 1.2366%.

5. Conclusions

Experimental and calculated binodal curves and tie lines were

properly determined for water þ acetic acid þ {1-butanol or iso-
pentanol or methyl-terc-butyl ether (MTBE) or methyl-iso-butyl
ketone (MIBK) or di-iso-butyl ketone (DIBK) of isoamyl proprio-
nate} at T ¼ {293.2 and 313.2} K and P z 95 kPa. Mass balance and
uncertainty calculations indicate binodal and LLE data determined
in this work were adequate. Besides, each system had density,
refractive index, speed of sound, isentropic compressibility and
molar refractivity measured or calculated along cloud point data
and for each equilibrium phase. Also, plait points were determined
for each system. Binodal curves increased in the order 1-
butanol < isopentanol < MTBE z MIBK < DIBK z isoamyl propio-
nate for both temperatures studied, which could be explained by a
steric effect of alkyl groups on non bonding electrons of oxygen
atoms. Acetic acid partition coefficients and tie lines' inclination
indicate that solute preferably distributes to solvent-rich phase.
Moreover, it changes as aqueous phase acetic acid molar fraction
aq
changes: for low concentrations (x2 <0.02), isopentanol presents
higher K values; for medium, isopentanol, MIBK and MTBE are the
solvents with greater solute distributions; for high concentrations
only (xaq
2 > 0.13) DIBK and isoamyl propionate systems presented K
values due to their larger immiscibility region. Selectivity values
Acknowledgements
The authors would like to acknowledge financial support from
Coordination for the Improvement of Higher Education Personnel
(CAPES), process number: 23038.007211/2012e93. Also, we would
like to thank in the memory of Prof. Dr. Martin Aznar for laboratory
support to this project.
Appendix A. Tables: Binodal curve and liquid-liquid
equilibrium data
In Table A1, experimental binodal curves data for water
(1) þ acetic acid (2) þ solvent (3) at T ¼ {293.2 and 313.2} K and
P z 95 kPa are presented. In Table A2, the equations obtained
through nonlinear regression of cloud point data are shown.
In Table A3., liquid-liquid equilibrium data for water (1) þ acetic
acid (2) þ solvent (3) at T ¼ {293.2 and 313.2} K and P z 95 kPa are
presented.
 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63 57

Table A.1 Table A.1 (continued )

Experimental cloud points compositions (molar fractions), densities, refractive
indices and speeds of sound for water (1) þ acetic acid (2) þ solvent (3) at T ¼ {293.2 x1 x2 r (kg m3) n c (m s1) kS (  1010 Pa1) Rm
and 313.2} K and P z 95 kPa.a 0.2279 0.1526 774.614 1.3644 1042.09 11.89 19.55
0.2862 0.1930 797.528 1.3657 1066.93 11.02 17.58
x1 x2 r (kg m3) n c (m s1) kS (  1010 Pa1) Rm
0.3397 0.2169 817.484 1.3670 1092.32 10.25 15.99
1-butanol, T ¼ 293.2 K 0.3835 0.2289 832.240 1.3674 1111.01 9.73 14.81
0.5064 0.0000 846.409 1.3907 1314.68 6.84 12.82 0.4790 0.2381 864.500 1.3676 1153.56 8.69 12.45
0.5362 0.0278 857.712 1.3889 1320.64 6.68 12.03 0.5664 0.2301 893.840 1.3667 1195.78 7.82 10.53
0.5603 0.0497 862.217 1.3907 1323.52 6.62 11.56 0.7008 0.1910 942.466 1.3631 1312.53 6.16 7.94
0.6285 0.0739 892.724 1.3833 1343.30 6.21 9.89 0.7396 0.1775 955.997 1.3618 1322.31 5.98 7.26
0.7013 0.0823 916.132 1.3784 1367.28 5.84 8.47 0.8093 0.1453 981.000 1.3563 1417.86 5.07 6.09
0.7896 0.0748 943.915 1.3637 1406.91 5.35 6.79 0.8471 0.1254 999.000 1.3532 1474.61 4.60 5.48
0.8379 0.0661 960.824 1.3654 1438.88 5.03 6.09 0.8717 0.1049 1001.166 1.3500 1498.31 4.45 5.17
0.8954 0.0528 984.207 1.3575 1494.77 4.55 5.16 0.8995 0.0814 1002.524 1.3469 1525.44 4.29 4.85
0.9280 0.0396 993.680 1.3515 1528.52 4.31 4.67 0.9294 0.0561 1001.597 1.3425 1544.65 4.18 4.51
0.9547 0.0218 994.076 1.3462 1547.22 4.20 4.34 0.9579 0.0295 995.130 1.3379 1553.36 4.16 4.22
0.9798 0.0000 987.014 1.3413 1549.53 4.22 4.08 0.9863 0.0000 986.179 1.3315 1546.83 4.24 3.94
1-butanol, T ¼ 313.2 K MIBK, T ¼ 293.2 K
0.5304 0.0000 833.784 1.3824 1259.34 7.56 12.39 0.0915 0.0000 808.399 1.3956 1224.89 8.24 27.51
0.5697 0.0307 848.984 1.3805 1269.46 7.31 11.40 0.2122 0.1178 832.035 1.3945 1242.56 7.78 22.45
0.5925 0.0463 858.013 1.3792 1274.68 7.17 10.84 0.2992 0.1789 853.444 1.3931 1255.14 7.44 19.13
0.6593 0.0692 882.340 1.3756 1298.19 6.73 9.39 0.4324 0.2302 890.678 1.3887 1284.04 6.81 14.70
0.7296 0.0745 904.503 1.3492 1323.76 6.31 7.63 0.5270 0.2387 918.929 1.3865 1309.87 6.34 12.10
0.7663 0.0720 917.440 1.3539 1340.98 6.06 7.13 0.5911 0.2316 938.611 1.3833 1331.49 6.01 10.52
0.8009 0.0668 917.315 1.3513 1341.48 6.06 6.65 0.6642 0.2112 958.952 1.3795 1358.99 5.65 8.96
0.8741 0.0538 954.638 1.3525 1462.55 4.90 5.52 0.7532 0.1807 990.225 1.3725 1415.74 5.04 7.13
0.9267 0.0387 980.205 1.3471 1516.10 4.44 4.70 0.8231 0.1463 1014.251 1.3649 1481.70 4.49 5.88
0.9478 0.0273 984.892 1.3435 1540.35 4.28 4.42 0.8789 0.1067 1021.948 1.3573 1524.69 4.21 5.08
0.9648 0.0154 984.937 1.3396 1555.50 4.20 4.20 0.9094 0.0811 1020.597 1.3525 1536.86 4.15 4.71
0.9829 0.0000 981.412 1.3366 1562.51 4.17 4.02 0.9378 0.0554 1015.390 1.3475 1538.23 4.16 4.40
Isopentanol, T ¼ 293.2 K 0.9661 0.0285 1007.193 1.3416 1527.15 4.26 4.11
0.3283 0.0000 825.920 1.4030 1277.60 7.42 19.24 0.9953 0.0000 995.765 1.3349 1497.87 4.48 3.82
0.3926 0.0842 849.002 1.3992 1283.00 7.16 16.60 MIBK, T ¼ 313.2 K
0.4452 0.1334 868.893 1.3960 1291.05 6.90 14.71 0.1380 0.0000 786.441 1.3860 1145.28 9.69 26.53
0.5232 0.1745 897.466 1.3911 1307.85 6.51 12.33 0.2532 0.1111 813.319 1.3852 1164.77 9.06 21.59
0.5806 0.1814 915.183 1.3878 1323.10 6.24 10.91 0.3154 0.1731 834.830 1.3840 1181.57 8.58 18.85
0.6818 0.1730 947.585 1.3807 1359.33 5.71 8.68 0.4462 0.2227 871.287 1.3812 1213.57 7.79 14.55
0.7282 0.1608 962.304 1.3766 1381.71 5.44 7.78 0.5409 0.2304 899.323 1.3781 1241.98 7.21 11.92
0.7931 0.1410 986.083 1.3699 1427.27 4.98 6.55 0.6053 0.2221 902.002 1.3755 1266.18 6.92 10.55
0.8341 0.1259 1003.098 1.3644 1468.18 4.62 5.81 0.6839 0.2011 939.531 1.3696 1293.50 6.36 8.64
0.8734 0.1059 1016.044 1.3585 1509.78 4.32 5.18 0.7505 0.1786 968.171 1.3650 1386.37 5.37 7.23
0.9062 0.0817 1018.588 1.3532 1533.05 4.18 4.75 0.8202 0.1481 998.005 1.3589 1444.96 4.80 5.92
0.9349 0.0563 1014.340 1.3482 1540.21 4.16 4.43 0.8812 0.1044 1008.666 1.3514 1507.27 4.36 5.05
0.9651 0.0283 1006.018 1.3424 1533.04 4.23 4.12 0.9080 0.0819 1008.605 1.3477 1527.39 4.25 4.73
0.9941 0.0000 994.103 1.3360 1509.69 4.41 3.85 0.9385 0.0545 1005.071 1.3425 1541.78 4.19 4.38
Isopentanol, T ¼ 313.2 K 0.9641 0.0307 999.868 1.3378 1545.75 4.19 4.11
0.3461 0.0000 811.658 1.3946 1214.61 8.35 18.85 0.9966 0.0000 990.249 1.3312 1535.80 4.28 3.78
0.4191 0.0767 833.527 1.3916 1222.28 8.03 16.15 DIBK, T ¼ 293.2 K
0.4639 0.1219 852.411 1.3880 1233.19 7.71 14.45 0.0148 0.0000 809.017 1.4139 1245.51 7.97 43.36
0.5624 0.1628 886.125 1.3825 1257.07 7.14 11.60 0.1494 0.2782 846.156 1.4080 1245.19 7.62 29.40
0.6527 0.1661 915.978 1.3662 1287.48 6.57 9.22 0.2434 0.3855 878.416 1.3721 1250.23 7.28 20.79
0.7031 0.1575 931.753 1.3565 1294.90 6.38 8.08 0.2937 0.4204 898.501 1.3765 1256.44 7.05 18.21
0.7586 0.1430 953.008 1.3616 1323.88 5.99 7.14 0.3416 0.4367 918.124 1.3753 1264.98 6.81 15.94
0.8231 0.1226 972.947 1.3587 1441.26 4.95 6.10 0.3894 0.4339 933.500 1.3813 1272.81 6.61 14.49
0.8839 0.0954 1000.572 1.3522 1496.75 4.46 5.08 0.4563 0.4210 938.985 1.3816 1299.19 6.32 12.62
0.9218 0.0676 1004.613 1.3462 1533.70 4.23 4.58 0.4848 0.4209 978.641 1.3815 1320.74 5.86 11.26
0.9576 0.0350 999.072 1.3400 1548.47 4.17 4.20 0.5085 0.4147 990.430 1.3809 1331.47 5.70 10.54
0.9950 0.0000 988.406 1.3325 1543.86 4.24 3.82 0.5334 0.4035 997.474 1.3830 1336.02 5.62 10.01
MTBE, T ¼ 293.2 K 0.6115 0.3638 1033.458 1.3761 1394.52 4.98 8.08
0.0636 0.0000 744.180 1.3695 1071.03 11.71 25.41 0.6726 0.3153 1046.645 1.3730 1435.60 4.64 7.13
0.1476 0.0889 770.966 1.3718 1099.05 10.74 22.19 0.7343 0.2593 1050.619 1.3691 1471.26 4.40 6.38
0.2126 0.1550 797.838 1.3744 1128.98 9.83 19.74 0.7611 0.2343 1050.853 1.3676 1485.80 4.31 6.08
0.3536 0.2123 838.873 1.3760 1178.14 8.59 15.70 0.8041 0.1937 1049.334 1.3632 1507.54 4.19 5.60
0.3979 0.2230 853.511 1.3764 1196.08 8.19 14.52 0.8414 0.1573 1045.099 1.3594 1523.00 4.13 5.23
0.4834 0.2305 883.867 1.3754 1233.56 7.44 12.38 0.8907 0.1086 1036.182 1.3533 1535.93 4.09 4.75
0.6018 0.2152 918.706 1.3693 1279.75 6.65 9.81 0.9163 0.0832 1029.672 1.3495 1536.86 4.11 4.50
0.6617 0.1990 932.865 1.3703 1299.22 6.35 8.77 0.9438 0.0559 1021.215 1.3449 1530.79 4.18 4.24
0.7273 0.1748 938.548 1.3655 1307.15 6.26 7.68 0.9700 0.0297 1011.317 1.3397 1515.37 4.31 4.00
0.7982 0.1456 986.646 1.3629 1445.86 4.85 6.33 0.9998 0.0000 998.196 1.3331 1483.20 3.98 3.72
0.8676 0.1052 1008.861 1.3560 1512.33 4.33 5.27 DIBK, T ¼ 313.2 K
0.8975 0.0808 1011.146 1.3523 1535.26 4.20 4.91 0.0277 0.0000 792.715 1.4050 1169.52 9.22 42.92
0.9293 0.0557 1008.252 1.3467 1547.13 4.14 4.53 0.1022 0.1667 811.055 1.4021 1169.92 9.01 34.79
0.9591 0.0286 998.832 1.3420 1545.71 4.19 4.24 0.1794 0.2718 829.654 1.3992 1172.04 8.77 28.47
0.9879 0.0000 989.183 1.3350 1529.25 4.32 3.94 0.2169 0.3391 845.900 1.3961 1174.97 8.56 24.84
MTBE, T ¼ 313.2 K 0.2475 0.3739 858.180 1.3851 1178.05 8.40 22.06
0.0654 0.0000 722.924 1.3585 980.44 14.39 25.41 0.3105 0.4128 882.060 1.3839 1187.70 8.04 18.48
0.1435 0.0886 749.473 1.3616 1010.21 13.07 22.35 (continued on next page)
58 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63

Table A.1 (continued )

x1 x2 r (kg m3) n c (m s1) kS (  1010 Pa1) Rm

0.3570 0.4254 898.919 1.3787 1195.83 7.78 16.17

0.3938 0.4308 912.394 1.3746 1199.79 7.61 14.52
0.4635 0.4159 922.804 1.3775 1213.07 7.36 12.60
0.5252 0.4010 966.450 1.3774 1282.00 6.30 10.49
0.6102 0.3606 1009.449 1.3711 1335.80 5.55 8.27
0.6669 0.3184 1024.844 1.3673 1379.35 5.13 7.29
0.7355 0.2579 1032.761 1.3628 1429.40 4.74 6.38
0.8049 0.1925 1033.020 1.3574 1476.76 4.44 5.61
0.8468 0.1519 1029.583 1.3534 1503.01 4.30 5.18
0.8926 0.1065 1022.973 1.3483 1526.86 4.19 4.73
0.9167 0.0828 1018.104 1.3452 1535.85 4.16 4.50
0.9426 0.0571 1011.468 1.3413 1541.50 4.16 4.25
0.9706 0.0291 1003.207 1.3366 1540.69 4.20 3.99
0.9997 0.0000 992.231 1.3306 1529.23 4.31 3.72
Isoamyl propionate, T ¼ 293.2 K
0.0142 0.0000 868.09 1.4060 1225.60 7.67 40.30
0.1616 0.2785 898.06 1.4003 1226.24 7.41 27.11
0.2528 0.3717 921.25 1.3962 1232.97 7.14 21.14
0.3047 0.4131 939.32 1.3933 1241.76 6.90 18.06

x1 ¼ 15:18702r  7:61613r2  9:08027n þ 2:76190n2 þ 0:15187  103 c þ 0:15236  106 c2 x2 ¼  5:1737 þ 26:1547x1  49:2436x21 þ 41:6401x31  13:3914x41
x1 ¼ 25:3065r  14:2787r2  37:5879n þ 13:6399n2 þ 19:2856  103 c  5:8695  106 c2 x2 ¼  5:4633 þ 28:5630x1  55:3607x21 þ 47:9661x31 þ 47:9661x41
0.3577 0.4249 954.35 1.3910 1253.46 6.67 15.76
0.4027 0.4239 967.08 1.3889 1262.83 6.48 14.11
0.4384 0.4188 978.10 1.3877 1277.39 6.26 12.93

Equations obtained through cloud point data nonlinear regression for water (1) þ acetic acid (2) þ solvent (3) at T ¼ {293.2 and 313.2} K and P z 95 kPa.
0.4840 0.4086 995.81 1.3822 1284.73 6.08 11.40
0.5202 0.3979 1012.53 1.3807 1332.85 5.56 10.33

x1 ¼ 9:76701r  3:6785r2 þ 0:91632n  3:46568n2 þ 0:41217  103 c  0:31891  106 c2 x2 ¼  0:07433 þ 1:35297x1  1:66620x21 þ 0:38556x31

x1 ¼ 22:9731r  12:4081r2  36:3155n þ 14:4973n2 þ 21:1299  103 c  6:6967  103 c2 x2 ¼  0:03066 þ 2:61741x1  4:26941x21 þ 1:68781x31
x1 ¼ 20:4269r  11:1733r2  26:9810n þ 8:7732n2 þ 15:1960  103 c  4:7491  106 c2 x2 ¼  0:76990 þ 3:52437x1  3:91375x21 þ 1:16198x31

x1 ¼ 10:0116r  4:2997r2  0:27817n þ 2:9104n2 þ 1:3556  103 c  0:53582  106 c2 x2 ¼  0:07895 þ 1:37268x1  1:62071x21 þ 0:32196x31
0.5707 0.3791 1023.95 1.3793 1353.14 5.33 9.10

x1 ¼ 20:5747r  10:9753r2  23:6622n þ 7:2286n2 þ 12:6649  103 c  3:9561  106 c2 x2 ¼  0:11428 þ 1:39813x1  1:48742x21 þ 0:202x31

x1 ¼ 17:1387r  8:62322r2  8:9190n þ 1:1437n2 þ 2:9481  103 c  0:9307  106 c2 x2 ¼  0:20015 þ 1:70685x1  1:88057x21 þ 0:37425x31
x1 ¼ 16:9894r  8:9492r2  9:9116n þ 2:5406n2 þ 1:2447  103 c  0:1196  106 c2 x2 ¼  0:75547 þ 3:27967x1  3:47487x21 þ 0:95303x31

x1 ¼ 19:5830r  10:3466r2  16:5274n þ 5:1146n2 þ 5:1013  103 c  1:3346  106 c2 x2 ¼  0:0747 þ 2:7168x1  4:32607x21 þ 1:68314x31

x1 ¼ 13:2559r  6:1112r2  1:3573n  2:1439n2  1:4443  103 c þ 0:7129  106 c2 x2 ¼  0:11845 þ 2:80927x1  4:37781x21 þ 1:69202x31
0.6050 0.3606 1033.85 1.3772 1378.58 5.09 8.35

x1 ¼ 16:8917r  7:9737r2  3:2849n  1:7004n2  1:3721  103 c þ 0:6863  106 c2 x2 ¼  0:0309 þ 2:49407x1  3:97515x21 þ 1:51502x31
0.6332 0.3420 1040.80 1.3753 1401.96 4.89 7.82
0.6881 0.2992 1049.22 1.3718 1438.20 4.61 6.97
0.7305 0.2618 1051.64 1.3693 1465.08 4.43 6.44
0.7674 0.2281 1051.71 1.3661 1486.78 4.30 6.00
0.8039 0.1935 1049.56 1.3629 1505.75 4.20 5.61
0.8464 0.1522 1044.49 1.3585 1523.97 4.12 5.18
0.8931 0.1062 1035.56 1.3528 1535.60 4.10 4.72
0.9165 0.0831 1029.51 1.3494 1536.32 4.12 4.50
0.9415 0.0580 1021.90 1.3452 1531.35 4.17 4.27
0.9607 0.0390 1014.93 1.3416 1521.80 4.25 4.08
0.9998 0.0000 998.14 1.3330 1484.03 4.55 3.72
Isoamyl propionate, T ¼ 313.2 K
0.0490 0.0000 849.614 1.3966 1148.57 8.92 8.92
0.1870 0.2730 879.428 1.3910 1152.26 8.56 8.56
0.2636 0.3666 904.457 1.3873 1161.70 8.19 8.19
0.3308 0.3990 921.136 1.3843 1173.24 7.89 7.89
0.3857 0.4065 935.961 1.3805 1179.79 7.68 7.68
0.4265 0.4071 948.689 1.3743 1192.44 7.41 7.41
0.4599 0.4017 949.838 1.3724 1199.72 7.31 7.31
0.5061 0.3904 955.634 1.3727 1202.63 7.24 7.24
0.5389 0.3825 982.837 1.3726 1285.05 6.16 6.16
0.6008 0.3573 1010.803 1.3705 1320.78 5.66 5.66
0.6352 0.3366 1018.365 1.3686 1342.92 5.44 5.44
0.6725 0.3093 1026.344 1.3664 1374.74 5.16 5.16
0.7374 0.2545 1033.394 1.3622 1426.50 4.76 4.76
0.7663 0.2281 1034.077 1.3602 1448.36 4.61 4.61
0.8020 0.1947 1033.252 1.3574 1473.13 4.46 4.46
0.8462 0.1522 1029.810 1.3534 1501.51 4.31 4.31
0.8984 0.1008 1021.865 1.3475 1528.71 4.19 4.19
0.9165 0.0829 1018.097 1.3451 1535.46 4.17 4.17
0.9409 0.0586 1012.002 1.3415 1540.98 4.16 4.16
0.9696 0.0299 1003.247 1.3365 1540.39 4.20 4.20
0.9997 0.0000 992.093 1.3305 1529.34 4.31 4.31
a
Maximum standard and combined standard uncertainties, u and uc, are:
u(T) ¼ 0.1 K; uc(x1) ¼ 0.0035; uc(x2) ¼ 0.0032; u(r) ¼ 13.7 kg m 3; u(n) ¼ 0.0161;
u(c) ¼ 15.8 m s 1; uc(kS) ¼ 0.16  10-10 Pa-1; uc(Rm) ¼ 1.36.
Isoamyl propionate, T ¼ 293.2 K

Isoamyl propionate, T ¼ 313.2 K

Isopentanol, T ¼ 293.2 K

Isopentanol, T ¼ 313.2 K
1-butanol, T ¼ 293.2 K

1-butanol, T ¼ 313.2 K

MTBE, T ¼ 293.2 K

MTBE, T ¼ 313.2 K

MIBK, T ¼ 293.2 K

MIBK, T ¼ 313.2 K

DIBK, T ¼ 293.2 K

DIBK, T ¼ 313.2 K
Table A.2
Table A.3
Liquid-liquid equilibrium data for water (1) þ acetic acid (2) þ solvent (3) at T ¼ {293.2 and 313.2} K and P z 95 kPa.a

Feed Organic phase Aqueous phase K S E 104 h

x1 x2 x1 x2 r n c kS Rm x1 x2 r n c kS Rm

1-butanol, T ¼ 293.2 K
0.8006 0.0289 0.5705 0.0542 869.833 1.3872 1326.44 6.53 11.20 0.9625 0.0158 992.709 1.3449 1549.23 4.20 4.26 3.43 5.79 54.6 36
0.7991 0.0431 0.6076 0.0698 883.627 1.3849 1335.71 6.34 10.35 0.9485 0.0259 994.732 1.3473 1544.26 4.22 4.41 2.69 4.20 49.3 27
0.7951 0.0568 0.6519 0.0786 899.498 1.3820 1349.08 6.11 9.43 0.9337 0.0351 994.738 1.3502 1534.02 4.27 4.60 2.24 3.20 47.3 4
1-butanol, T ¼ 313.2 K
0.8024 0.0150 0.5572 0.0236 844.584 1.3808 1263.86 7.41 11.68 0.9701 0.0115 982.487 1.3387 1558.46 4.19 4.15 2.06 3.58 37.6 17
0.8012 0.0286 0.5921 0.0463 856.962 1.3793 1273.46 7.20 10.86 0.9650 0.0151 984.773 1.3404 1554.23 4.20 4.21 3.07 5.01 56.2 3
0.7996 0.0436 0.6855 0.0715 872.064 1.3434 1286.22 6.93 8.41 0.9551 0.0216 985.513 1.3427 1544.16 4.26 4.33 3.30 4.60 58.1 91
0.7981 0.0572 0.7199 0.0731 890.500 1.3467 1299.55 6.65 7.83 0.9395 0.0306 983.895 1.3456 1527.23 4.36 4.54 2.39 3.11 54.2 10
Isopentanol, T ¼ 293.2 K
0.8036 0.0224 0.3634 0.0495 838.254 1.4009 1280.58 7.27 17.75 0.9866 0.0129 997.895 1.3394 1523.62 4.32 3.90 3.84 10.42 52.4 16
0.7975 0.0443 0.3991 0.0868 850.093 1.3990 1284.75 7.13 16.43 0.9695 0.0265 1004.844 1.3423 1533.13 4.23 4.07 3.27 7.95 49.5 6
0.7917 0.0664 0.4322 0.1158 863.492 1.3970 1288.48 6.98 15.22 0.9508 0.0410 1010.112 1.3456 1539.03 4.18 4.28 2.82 6.21 46.9 32
0.7851 0.0876 0.4709 0.1429 877.657 1.3947 1295.03 6.79 13.95 0.9294 0.0572 1014.402 1.3494 1540.15 4.16 4.52 2.50 4.93 43.0 45

L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63

0.7842 0.1090 0.5221 0.1683 896.025 1.3916 1306.34 6.54 12.43 0.9019 0.0770 1017.738 1.3544 1534.20 4.17 4.86 2.19 3.78 36.9 50
0.7748 0.1283 0.5751 0.1832 914.665 1.3881 1321.18 6.26 11.01 0.8849 0.0887 1017.432 1.3570 1520.43 4.25 5.08 2.06 3.18 37.5 83
Isopentanol, T ¼ 313.2 K
0.8033 0.0201 0.3856 0.0477 823.590 1.3928 1219.55 8.16 17.31 0.9815 0.0178 992.089 1.3353 1547.97 4.21 3.93 2.68 6.82 27.1 83
0.7991 0.0386 0.4146 0.0755 833.545 1.3912 1222.69 8.02 16.24 0.9733 0.0242 995.620 1.3375 1549.67 4.18 4.02 3.12 7.32 47.4 21
0.7951 0.0574 0.4482 0.1028 845.077 1.3890 1227.57 7.85 15.06 0.9616 0.0332 998.950 1.3401 1548.84 4.17 4.15 3.10 6.65 50.8 22
0.7895 0.0769 0.4816 0.1251 857.780 1.3875 1234.82 7.65 13.98 0.9469 0.0442 1002.116 1.3428 1544.89 4.18 4.32 2.83 5.57 50.2 71
0.7829 0.0962 0.5193 0.1446 872.312 1.3850 1243.95 7.41 12.81 0.9281 0.0578 1004.115 1.3458 1536.13 4.22 4.54 2.50 4.47 47.2 102
0.7813 0.1063 0.5418 0.1536 883.532 1.3840 1249.55 7.25 12.13 0.9140 0.0676 1004.333 1.3476 1526.63 4.27 4.72 2.27 3.83 43.6 109
MTBE, T ¼ 293.2 K
0.6988 0.0301 0.1087 0.0536 760.227 1.3714 1087.94 11.11 23.59 0.9645 0.0266 996.053 1.3396 1541.92 4.22 4.15 2.01 17.84 35.5 61
0.6931 0.0593 0.1575 0.0990 776.710 1.3729 1109.08 10.47 21.80 0.9442 0.0424 1002.045 1.3433 1548.57 4.16 4.38 2.34 14.00 46.3 14
0.6856 0.0885 0.2359 0.1572 801.643 1.3744 1133.70 9.71 19.16 0.9235 0.0578 1005.904 1.3468 1549.24 4.14 4.61 2.72 10.64 49.4 49
0.6871 0.1150 0.2934 0.1890 822.032 1.3757 1160.92 9.03 17.37 0.9050 0.0713 1008.526 1.3501 1543.90 4.16 4.84 2.65 8.17 50.2 24
0.6736 0.1448 0.3826 0.2210 851.464 1.3764 1193.47 8.25 14.86 0.8825 0.0871 1009.635 1.3540 1530.01 4.23 5.13 2.54 5.85 50.8 24
0.6681 0.1717 0.4754 0.2338 882.472 1.3762 1232.24 7.46 12.55 0.8541 0.1061 1005.865 1.3583 1499.31 4.42 5.52 2.20 3.96 48.1 41
MTBE, T ¼ 313.2 K
0.6982 0.0310 0.1265 0.0694 742.530 1.3609 1002.99 13.39 23.03 0.9622 0.0282 989.345 1.3357 1552.69 4.19 4.16 2.46 18.72 33.7 128
0.6832 0.0913 0.2259 0.1522 776.749 1.3647 1046.30 11.76 19.55 0.9216 0.0616 996.202 1.3423 1544.05 4.21 4.61 2.47 10.07 47.7 18
0.7547 0.1102 0.3601 0.2203 824.211 1.3679 1102.62 9.98 15.48 0.8820 0.0919 996.238 1.3484 1507.45 4.42 5.10 2.40 5.87 27.9 177
0.6803 0.1164 0.2791 0.1849 796.826 1.3668 1069.09 10.98 17.85 0.9082 0.0721 998.020 1.3447 1531.80 4.27 4.77 2.56 8.34 50.6 46
0.6652 0.1747 0.4443 0.2393 852.575 1.3681 1141.38 9.00 13.27 0.8534 0.1123 989.894 1.3519 1467.40 4.69 5.49 2.13 4.09 46 55
MIBK, T ¼ 293.2 K
0.7807 0.0296 0.1455 0.0586 819.306 1.3952 1231.33 8.05 25.14 0.9788 0.0192 1.004138 1.3400 1520.80 4.31 3.96 3.06 20.56 47.6 14
0.7709 0.0581 0.2092 0.1153 832.547 1.3945 1241.34 7.79 22.54 0.9580 0.0382 1.010792 1.3442 1533.34 4.21 4.18 3.02 13.82 45.5 9
0.7642 0.0862 0.2747 0.1620 846.568 1.3936 1252.85 7.53 20.07 0.9344 0.0588 1.016471 1.3482 1538.70 4.16 4.43 2.76 9.38 42.1 11
0.7520 0.1144 0.3423 0.1984 864.974 1.3922 1263.83 7.24 17.65 0.9083 0.0804 1.020453 1.3525 1536.20 4.15 4.74 2.47 6.55 39.1 19
0.7422 0.1407 0.4151 0.2245 884.698 1.3905 1279.07 6.91 15.30 0.8829 0.1002 1.021936 1.3566 1525.48 4.21 5.06 2.24 4.77 37.2 43
0.7369 0.1655 0.5039 0.2387 910.649 1.3875 1301.65 6.48 12.73 0.8528 0.1221 1.018685 1.3611 1499.69 4.36 5.48 1.96 3.31 33.4 65
MIBK, T ¼ 313.2 K
0.7804 0.0297 0.1852 0.0545 798.814 1.3857 1153.53 9.41 24.32 0.9763 0.0219 996.558 1.3359 1544.58 4.21 3.97 2.49 13.15 40.3 4
0.7468 0.0562 0.2334 0.1014 810.658 1.3853 1162.65 9.13 22.25 0.9566 0.0393 1001.128 1.3392 1545.89 4.18 4.18 2.58 10.58 43.8 15
0.7604 0.0876 0.3043 0.1567 828.829 1.3843 1176.14 8.72 19.44 0.9289 0.0628 1006.247 1.3437 1539.41 4.19 4.49 2.49 7.62 39.2 7
0.7544 0.1119 0.3623 0.1903 844.712 1.3834 1189.03 8.37 17.35 0.9034 0.0833 1008.114 1.3478 1527.74 4.25 4.80 2.28 5.70 35.5 12
0.7459 0.1390 0.4341 0.2183 865.308 1.3818 1207.27 7.93 14.99 0.8764 0.1037 1008.032 1.3519 1504.83 4.38 5.15 2.11 4.25 34.0 20
(continued on next page)

59
Table A.3 (continued )

60
Feed Organic phase Aqueous phase K S E 104 h

x1 x2 x1 x2 r n c kS Rm x1 x2 r n c kS Rm

0.7372 0.1650 0.5200 0.2329 891.792 1.3792 1233.89 7.37 12.47 0.8414 0.1283 1001.432 1.3568 1464.10 4.66 5.66 1.82 2.94 29.9 39
DIBK, T ¼ 293.2 K
0.7493 0.0642 0.0665 0.1247 819.522 1.4143 1247.56 7.84 37.76 0.9336 0.0650 1021.728 1.3453 1531.62 4.17 4.35 1.92 26.94 17.7 171
0.7228 0.1230 0.0806 0.1532 828.076 1.4109 1245.10 7.79 35.86 0.8763 0.1200 1036.563 1.3537 1535.87 4.09 4.93 1.28 13.87 17.5 43
0.6983 0.1764 0.1056 0.1998 838.445 1.4093 1244.98 7.69 33.26 0.8266 0.1687 1045.501 1.3599 1521.86 4.13 5.42 1.18 9.27 16.4 27
0.6717 0.2297 0.1468 0.2666 851.130 1.4071 1247.97 7.54 29.54 0.7770 0.2169 1050.348 1.3653 1497.00 4.25 5.94 1.23 6.50 14.9 57
0.6521 0.2754 0.1830 0.3153 864.145 1.3927 1246.85 7.44 25.83 0.7324 0.2589 1050.282 1.3698 1469.18 4.41 6.45 1.22 4.87 12.8 107
0.6293 0.3208 0.2426 0.3768 884.170 1.3829 1250.95 7.23 21.40 0.6866 0.2997 1045.752 1.3732 1437.51 4.63 7.04 1.26 3.56 11.2 147
DIBK, T ¼ 313.2 K
0.7439 0.0637 0.0710 0.1019 801.872 1.4036 1170.33 9.11 38.10 0.9477 0.0488 1011.493 1.3413 1541.74 4.16 4.26 2.09 27.88 38.2 33
0.7177 0.1219 0.1009 0.1621 811.259 1.4020 1169.94 9.01 34.94 0.8922 0.1031 1023.617 1.3489 1525.28 4.20 4.81 1.57 13.90 29.0 73
0.6935 0.1769 0.1308 0.2155 821.059 1.4003 1169.84 8.90 31.99 0.8347 0.1606 1030.623 1.3546 1496.72 4.33 5.36 1.34 8.56 21.0 67
0.6711 0.2273 0.1620 0.2642 831.447 1.3986 1170.67 8.78 29.18 0.7824 0.2122 1033.214 1.3590 1465.26 4.51 5.88 1.24 6.01 16.1 73
0.6489 0.2759 0.2045 0.3196 845.797 1.3962 1173.29 8.59 25.74 0.7265 0.2649 1030.038 1.3633 1424.78 4.78 6.53 1.21 4.28 11.2 37
0.6306 0.3191 0.2475 0.3634 861.594 1.3938 1176.99 8.38 22.65 0.6706 0.3134 1024.763 1.3670 1383.93 5.10 7.27 1.16 3.14 6.7 12

L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63

Isoamyl propionate, T ¼ 293.2 K
0.7481 0.0632 0.0565 0.0975 875.461 1.4047 1225.76 7.60 36.06 0.9488 0.0509 1021.362 1.3449 1530.69 4.18 4.20 1.92 32.16 34.6 23
0.7213 0.1202 0.0917 0.1654 883.251 1.4031 1225.44 7.54 32.81 0.8959 0.1023 1035.823 1.3530 1535.87 4.09 4.72 1.62 15.80 28.4 53
0.6974 0.1750 0.1288 0.2276 891.791 1.4014 1225.79 7.46 29.67 0.8388 0.1583 1045.417 1.3593 1521.88 4.13 5.28 1.44 9.36 21.1 37
0.6734 0.2257 0.1696 0.2850 901.748 1.3996 1227.17 7.36 26.54 0.7827 0.2123 1050.330 1.3644 1498.11 4.24 5.86 1.34 6.20 15.4 6
0.6551 0.2698 0.2143 0.3358 912.265 1.3973 1229.47 7.25 23.48 0.7327 0.2583 1051.970 1.3684 1470.29 4.40 6.43 1.30 4.44 11.5 1
0.6330 0.3153 0.2644 0.3786 926.917 1.3953 1234.05 7.08 20.44 0.6735 0.3084 1047.472 1.3729 1433.74 4.64 7.23 1.23 3.13 7.2 1
Isoamyl propionate, T ¼ 313.2 K
0.7607 0.0578 0.0829 0.0853 856.219 1.3954 1148.76 8.85 35.47 0.9499 0.0498 1008.859 1.3404 1541.62 4.17 4.19 1.71 19.64 29.5 3
0.7387 0.1117 0.1144 0.1482 863.655 1.3939 1149.25 8.77 32.49 0.9003 0.0967 1020.805 1.3475 1529.27 4.19 4.70 1.53 12.06 26.4 56
0.7127 0.1651 0.1483 0.2073 871.926 1.3923 1150.41 8.67 29.53 0.8470 0.1481 1029.592 1.3532 1502.92 4.30 5.24 1.40 8.00 21.3 71
0.6929 0.2098 0.1811 0.2567 880.328 1.3908 1152.31 8.55 26.91 0.7983 0.1947 1033.312 1.3575 1472.97 4.46 5.75 1.32 5.81 16.2 58
0.6727 0.2541 0.2191 0.3046 890.564 1.3891 1155.73 8.41 24.15 0.7505 0.2390 1033.786 1.3612 1438.93 4.67 6.29 1.27 4.37 12.8 71
0.6537 0.2960 0.2664 0.3512 903.642 1.3869 1161.89 8.20 21.11 0.6987 0.2840 1030.149 1.3647 1396.89 4.97 6.96 1.24 3.24 8.9 65
a
Maximum standard and combined standard uncertainties, u and uc, are: u(T) ¼ 0.1 K; u(r) ¼ 7.32 kg m3; u(n) ¼ 0.0012; u(c) ¼ 1.87 m s1; uc(kS) ¼ 0.03  1010 Pa1; uc(Rm) ¼ 1.65; uc(x1) ¼ 0.0323; uc(x2) ¼ 0.0395.
 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63 61

Appendix B. Figures: binodal curves for each temperature

and thermophysical properties

Binodal curves for water þ acetic acid þ solvent compared for

each temperature are shown in Fig. B.1. Thermophysical prop-
erties along binodal curve for the systems studied here are
shown Fig. B.2.

Fig. B.1. Binodal curves for water þ acetic acid þ solvent compared for each temperature: a) 1-butanol; b) isopentanol; c) MTBE; d) MIBK; e) DIBK; f) isoamyl propionate; , 293.2 K;
, 313.2 K; open symbols: NRTL plait points; lines: NRTL bimodal curves.
62 L. Hadlich de Oliveira et al. / Fluid Phase Equilibria 482 (2019) 48e63

Fig. B.2. Thermophysical properties along binodal curve for water þ acetic acid þ solvent: -,, 1-butanol; , isopentanol; , MTBE; , MIBK; , DIBK; , isoamyl
propionate; full symbols, 293.2 K; open symbols, 313.2 K.2

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