Article

pubs.acs.org/jced

Reactive Extraction of (E)‑Butenedioic Acid (Fumaric Acid) by

Nontoxic Diluents
Hasan Uslu,*,‡ Ayşegül Gemici,† Aslı Gök,† and Ş. Iṡ mail Kırbaşlar†
†
Chemical Engineering Department, Engineering Faculty, Iṡ tanbul University, 34320 Avcılar, Iṡ tanbul, Turkey
‡
Chemical Engineering Department, Engineering & Architecture Faculty, Beykent University, Ayazağa, Iṡ tanbul, Turkey

ABSTRACT: In this work, the equilibrium distribution of (E)-

butenedioic acid (fumaric acid) between water and tridodecylamine
(TDDA) or tributylamine (TBA) was carried out at 298 K. The
organic phase was prepared using both TDDA and TBA in three
nontoxic diluents (canola oil, sesame oil, and almond oil). The batch
equilibrium experimental data are presented by calculation of the
loading factor (Z), extraction efficiency (E), and distribution
coefficient (KD). The highest extraction efficiencies of 92.59 % and
92.50 % with values of KD equal to 12.50 and 12.40 were obtained
with 0.789 mol·kg−1 TDDA in canola oil and 2.080 mol·kg−1 TBA in
canola oil. The extraction abilities of TDDA and TBA in different
nontoxic natural diluents in terms of KD and E were found to be in
the order of canola oil > almond oil > sesame oil. Partition
coefficients (P = 0.3819, 0.4739, and 0.7535) and dimerization
constants (D = 83.64, 50.28, and 43.51) were calculated according to physical extraction for sesame oil, almond oil, and canola
oil, respectively.

■ INTRODUCTION
(E)-Butenedioic acid, which is also called fumaric acid, is a four-
carbon dicarboxylic acid. It is a white crystalline compound.
Currently, fumaric acid is synthesized chemically from maleic
anhydride. However, as petroleum prices are increasing day by
day, maleic anhydride as a petroleum derivative has increased in
price as well. This situation has caused a search for new ways to
produce fumaric acid, such as fermentation.1 Recently, three
strains of the fungus Rhizopus oryzae were screened to produce
fumaric acid using untreated and treated corn distillers’ dried
grains.2 Microbial production has even been discussed using the
bacterial strain Lactobacillus.3 Fumaric acid has many uses in
industrial applications, such as the production of synthetic
resins, alkyd resins, paper resins, plasticizers, biodegradable
polymers, succinic acid, maleic acid, etc.4 Therefore, it is
important to purify fumaric acid for use in the above-mentioned
applications.
Liquid−liquid extraction is a prominent, energy efficient,
environmentally friendly, and economical process for the
separation of carboxylic acids from the downstream of chemical
industry (pharmaceutical, petroleum, food processing, tanning,
etc.) and fermentation broth.5−10 Organophosphorus-bonded
(tri-n-butyl phosphate) and long-chain aliphatic amine (tri-n-
octylamine) extractants are reactive extractants and more
effective than conventional extractants.11,12 The use of a
reactive extractant in a liquid−liquid extraction process is
termed reactive extraction. In reactive extraction, the extractant
and acid molecules form a complex in the organic phase,
thereby allowing more acid to be extracted from the aqueous
phase. In the reactive extraction process, a nonreactive
extractant is used as a diluent to decrease the viscosity and
enhance the surface properties of the reactive extractant.12
There are very limited studies about extraction of carboxylic
acids from aqueous solutions using nontoxic diluents such as
rice bran oil, sunflower oil, soybean oil, and sesame oil. Keshav
et al.13 studied the extraction of citric acid from aqueous media
using the reactive extractant tri-n-octylamine (TOA). The
nontoxic natural diluents rice bran oil, sunflower oil, soybean
oil, and sesame oil were used to dilute TOA. TOA was found to
be an effective extractant for the removal of acid, providing
distribution coefficients (KD) as high as 18.51 [extraction
efficiency (E) = 95 %], 16.28 (E = 94 %), 15.09 (E = 94 %),
and 12.82 (E = 93 %) when used with rice bran oil, sesame oil,
soybean oil, and sunflower oil, respectively. Overall extraction
constants for TOA + rice bran oil, or sunflower oil, or soybean
oil, or sesame oil were determined as (35.48, 29.79, 33.79, and
37.64) mol·kg−1, respectively. Harrington and Hossain14 used
sunflower oil as the solvent for recovery of lactic acid from
aqueous solution. Organic solutions consisting of Aliquat 336,
TOA, and tributyl phosphate (TBP) mixed with sunflower oil
(as the solvent) were prepared for equilibrium studies. The
optimum extraction parameters were determined as a function
pH (range 4.0 to 6.5). The highest extraction was reached with
an organic phase consisting of a mixture of 15 wt % TOA and
Received: July 8, 2014
Accepted: September 23, 2014
Published: October 3, 2014

© 2014 American Chemical Society 3767 dx.doi.org/10.1021/je500634s | J. Chem. Eng. Data 2014, 59, 3767−3772
Journal of Chemical & Engineering Data
Table 1. Physical Properties of the Chemicals Used in This Study
chemical IUPAC name
fumaric acid (E)-butenedioic acid
tridodecylamine (TDDA) N,N-didodecyldodecan-1-amine
tributylamine (TBA) N,N-dibutyl-1-butanamine
Figure 1. Plots of KD,diluent vs [H2A]aq for physical extraction of fumaric acid using natural diluents:▲, canola oil; ■, almond oil; ◆, sesame oil.
15 % Aliquat 336 dissolved in 35 wt % TBP and 35 % sunflower
oil. They reported that lactic acid was recovered from the
organic phase by using 0.5 M aqueous sodium carbonate, with
90 % of it being obtained within a time of 4 h. Waghmare et
al.15 used sunflower oil and castor oil as nontoxic solvents for
extraction of picolinic acid by TBP, and the distribution
coefficients and extraction efficiencies were compared. KD
changed from 0.0066 to 0.664 for sunflower oil and from
0.0099 to 0.94 for castor oil, while E was changed from 0.65 %
to 42.9 % for sunflower oil and from 0.9 % to 74.6 % for castor
oil. They reported that loading factors < 0.5 were found.
Athankar et al.16 focused on extraction of phenylacetic acid
from aqueous media because of its wide usage in the
production of β-lactam antibiotics. Rice bran oil was chosen
as well as benzene and hexan-1-ol for dilution of TBP. The
equilibrium of reactive extraction of phenylacetic acid was
presented in light of the mass action law model. Waghmare et
al.17 investigated the extractability of both picolinic acid and
nicotinic acid from fermentation broth. Soybean oil was
selected as the nontoxic solvent to dilute TBP, and comparative
results were presented in terms of distribution coefficients and
extraction efficiencies. KD increased from 0.01 to 0.374 for
picolinic acid and from 0.0073 to 0.0752 for nicotinic acid. E
increased from 0.9 % to 27.22 % for picolinic acid and from
0.72 % to 6.99 % for nicotinic acid.
The extraction of fumaric acid by amine-based extractants
such as tridodecylamine (TDDA) and tributylamine (TBA)
with nontoxic natural diluents was the aim of the present work.
To date, no previous work on the reactive extraction of fumaric
acid using natural nontoxic diluents such as sesame oil, almond
oil, and canola oil is available.
Article
MW density purity
kg·kmol−1 kg·m−3 supplier (wt %) pKa
116.07 1635 Sigma-Aldrich > 99 3.03, 4.44
521.99 823 Sigma-Aldrich > 97 −
185.36 778 Sigma-Aldrich > 98.5 −
■ MATERIALS AND METHODS
Materials. The properties of the chemicals used in this
study are presented in Table 1. The nontoxic natural solvents
sesame oil, almond oil, and canola oil are commercial. All of the
chemicals were used without any pretreatment. Ultrahigh-
purity water from a Millipore Milli-Q3 water system was used
for the experiments.
Experiments. Five different organic phase concentrations
were prepared by adding diluents to TBA or TDDA in ratios of
(50, 60, 70, 80, and 90) vol %. The concentrations were (0.157,
0.315, 0.473, 0.631, and 0.789) mol·kg−1 for TDDA and (0.418,
0.851, 1.255, 1.674, and 2.080) mol·kg−1 for TBA. The aqueous
phase was prepared as 0.054 mol·kg−1 fumaric acid because of
its highest solubility in water at 298 K. To perform the
equilibrium experiments, mixtures of equal volumes (15 mL) of
the aqueous and organic phases were shaken for 12 h at 298 K
in a constant-temperature shaking bath and then allowed to
settle for 2 h. Preliminary studies showed that this was a
sufficient time to reach the equilibrium. Experiments were
performed in duplicate. Final concentrations of fumaric acid in
the aqueous phase were determined by acid−base titration
using sodium hydroxide (0.1 N), which was standardized with
0.1 N HCl as the titrant and 3,3-bis(4-hydroxyphenyl)-
isobenzofuran-1(3H)-one (phenolphthalein) as the indicator.
The relative uncertainty in the titration method was found not
to exceed ± 3 %. The extracted acid concentration in the
organic phase was calculated by considering complete mass
balance.
■ RESULTS AND DISCUSSION
Physical Extraction. In this section, the results obtained for
the extraction equilibrium of fumaric acid from aqueous
solutions with a single nontoxic natural diluent (sesame oil,
3768 dx.doi.org/10.1021/je500634s | J. Chem. Eng. Data 2014, 59, 3767−3772
Journal of Chemical & Engineering Data Article

almond oil, or canola oil) are presented. Two factors were 0.3819 and 83.64, 0.4739 and 5028, and 0.7535 and 43.51,
taken into account to show the influence of the pure diluents respectively.
on the extraction of acid: (1) partial dissociation of the acid in Chemical Extraction. Reactive extraction is described as a
the aqueous phase and (2) dimerization in the organic phase. reaction between undissociated acid molecules R′(COOH)n (n
The physical extraction of carboxylic acids with pure diluents is = 1 for monoprotic acids, n = 2 for diprotic acids, etc.) in the
described using the distribution coefficient (KD,diluent). For low aqueous phase and amine molecules (R3N) in the organic
concentrations of acids (as used in the study), Kertes and King7 phase, which in general form can be written as follows:
presented a correlation of KD,diluent in terms of the dimerization
constant (D = [(H2A)2]/[H2A]2) and the partition coefficient m[R′(COOH)n ]aq + p(R3N)org
(P = [H2A]org/[H2A]aq), as shown in eq 1:
⇄ {[R′(COOH)n ]m · (R3N)p }org (2)
KD,diluent = P + 2DP 2[H 2A]aq (1)
Here the extractability of fumaric acid (a dicarboxylic acid,
Plots of KD,diluent versus [H2A]aq were drawn using linear fitting H2A) from aqueous solution was studied. Replacing the symbol
in Excel 2010 (Figure 1), and the values of P and 2DP2 were R′(COOH)2 with H2A allows eq 2 to be written more
obtained from the intercepts and slopes, respectively. To compactly as follows:
estimate the parameters, the χ2 minimization or “weighted
(H 2A)aq + p(R3N)org ⇄ [H 2A·(R3N)p ]org (3)
least-squares” method was used, in which the goal is to
minimize the sum of the squares of the deviations between the In eq 3, the value of m from eq 2 has been set equal to 1, so p
theoretical curve and the experimental points for a range of denotes the number of amine molecules that react per molecule
independent variables. The values of P and D obtained for of acid.
extraction of fumaric acid using the natural diluents are The reactive extraction of fumaric acid can be explained with
presented in Table 2 and shown in Figure 1. two different mechanisms depending on the pH because
fumaric acid is a dicarboxylic acid, as explained by Kloetzer et
Table 2. Results for Physical Extaction of Fumaric Acid by al.18 At low pH values, one must consider the first dissociation
Single Diluents at T = 298.15 Ka constant of fumaric acid (Ka1) and the corresponding
[H2A]init [H2A]aq [H2A]org E D dissociation reaction:
diluent mol·kg −1
mol·kg −1
mol·kg −1
% P kg·mol−1 (H 2A)aq ⇄ (HA−)aq + H+ (4)
sesame oil 0.01 0.0064 0.0036 36.00 0.3819 83.64
0.02 0.0120 0.0080 40.00 [HA−]aq ·[H+]
0.03 0.0171 0.0129 43.00 K a1 =
0.04 0.0211 0.0189 47.25
[H 2A]aq (5)
0.05 0.0248 0.0252 50.40 − +
where [H2A]aq, [HA ]aq, and [H ] are the concentrations of
almond oil 0.01 0.0061 0.0039 39.00 0.4739 50.28
undissociated fumaric acid, singly dissociated fumaric acid, and
0.02 0.0116 0.0084 42.00
hydrogen ion in the aqueous phase. [H2A]aq can be found as
0.03 0.0166 0.0134 44.67
0.04 0.0207 0.0193 48.25 [H 2A]aq = [H 2A]tot,aq − [HA−]aq (6)
0.05 0.0243 0.0257 51.40
canola oil 0.01 0.0049 0.0051 51.00 0.7535 43.51 where [H2A]tot,aq is the total concentration of all forms of the
0.02 0.0092 0.0108 54.00 acid in the aqueous phase. Combining eqs 5 and eq 6 gives
0.03 0.0128 0.0172 57.33
[H 2A]tot,aq
0.04 0.0159 0.0241 60.25 [H 2A]aq = K a1
0.05 0.0184 0.0316 63.20 1+ [H+] (7)
a
[H2A]init is the initial acid concentration in the aqueous phase,
[H2A]aq is the concentration of acid in the aqueous phase after The extraction equilibrium constant (KE) can be written
extraction, [H2A]org is the concentration of acid in the organic phase according to eq 3 as follows:
after extraction, D is the dimerization constant, and P is the partition
coefficient. [H 2A·(R3N)p ]org
KE = p
[H 2A]aq · [R3N]org (8)
The distribution coefficient (KD) is defined as the ratio of the
The physical extraction experiments of fumaric acid were concentration of the acid in the organic phase to that in the
studied using three different nontoxic natural diluents: sesame aqueous phase (i.e. KD = [H2A·(R3N)p]org/[H2A]tot,aq).
oil, almond oil, and canola oil. Figure 2 shows equilibrium Combining eqs 7 and 8 gives the following expression for KD:
isotherms for physical extraction of fumaric acid. At the p
beginning, a linear relationship for the equilibrium of fumaric KE·[R3N]org
KD =
acid between the organic and aqueous phases was determined
until an initial acid concentration of 0.02 mol·kg−1. Above this (1 + K a1
[H+] ) (9)
concentration, a parabolic relationship was observed for the
three diluents. At higher concentrations, some deviation from Equation 9 can be converted to logarithmic form:
Henry’s law (nonideal behavior) was observed. The partition ⎛ K a1 ⎞
coefficients (P) and dimerization constants (D) for fumaric acid ln KD + ln⎜1 + ⎟ = ln KE + p ·ln[R3N]org
in sesame oil, almond oil, and canola oil were determined as ⎝ [H+] ⎠ (10)

3769 dx.doi.org/10.1021/je500634s | J. Chem. Eng. Data 2014, 59, 3767−3772

Journal of Chemical & Engineering Data Article

Figure 2. Equilibrium isotherms for physical extraction fumaric acid. Symbols: ▲ for canola oil; ■ for almond oil; ◆ for sesame oil.

Table 3. Experimental Results for the Extraction of Fumaric Acid by TDDA in Nontoxic Natural Diluents at T = 298.15 Ka
[R3N] [H2A]org E
−1 −1
diluent mol·kg mol·kg pH(aq) KD Z % KE p
canola oil 0.157 0.037 3.776 2.47 0.236 71.15 6.73·102 0.98
0.315 0.040 3.843 3.08 0.127 75.47
0.473 0.044 3.907 4.89 0.093 83.02
0.631 0.047 3.955 6.71 0.074 87.03
0.789 0.050 3.972 12.50 0.063 92.59
almond oil 0.157 0.038 3.721 2.37 0.242 70.37 4.80·102 0.89
0.315 0.040 3.786 2.86 0.127 74.07
0.473 0.045 3.896 5.00 0.095 83.33
0.631 0.048 4.045 8.00 0.076 88.89
0.789 0.050 4.110 10.00 0.063 90.91
sesame oil 0.157 0.039 3.787 2.60 0.248 72.22 4.58·102 0.86
0.315 0.041 3.810 3.15 0.130 75.92
0.473 0.043 3.980 4.30 0.091 81.13
0.631 0.046 3.985 6.57 0.073 86.79
0.789 0.049 4.110 9.80 0.062 90.74
a
[R3N] is the initial amine concentration in the organic phase, [H2A]org is the concentration of acid in the organic phase after extraction, KE is the
thermodynamic extraction equilibrium constant, and p is the number of amine molecules per acid molecule.
p
If the reactive extraction is carried out at pH > pKa2, the KE·[R3N]org
second dissociation constant of fumaric acid must be taken into KD =
account: (1 + K a2
[H+]2 ) (15)
2− +
(H 2A)aq ⇄ (A )aq + 2H (11) Similarly, eq 15 can be represented in logarithmic form:

[A2 −]aq ·[H+]2 ⎛ K a2 ⎞

K a2 = ln KD + ln⎜1 + ⎟ = ln KE + p ·ln[R3N]org
[H 2A]aq ⎝ [H+]2 ⎠ (16)
(12)
Under these conditions, the concentration of undissociated acid At both low pH and high pH, the values of the extraction
in the aqueous phase is given by equilibrium constant (KE) and the number of aminic extractant
molecules per acid molecule (p) can be calculated from the
[H 2A]aq = [H 2A]tot,aq − [A2 −]aq (13) intercepts and slopes, respectively, of plots of {ln KD + ln(1 +
Ka1/[H+])} versus ln[R3N]org (at low pH) and {ln KD + ln(1 +
Combining eqs 12 and 13 gives Ka2/[H+]2)} versus ln[R3N]org (at high pH). Tables 3 and 4
[H 2A]tot,aq present KE and p values for extraction of fumaric acid by both
[H 2A]aq = TDDA and TBA in natural diluents. As shown in Tables 3 and
K a2
1+ 4, the KE values changed from (4.58·102 to 6.73·102) kg·mol−1
[H+]2 (14)
for TDDA and from (2.03·102 to 4.48·102) kg·mol−1 for TBA.
In the same way as for the low-pH conditions, the following The values of p in canola oil, almond oil, and sesame oil were
expression for the distribution coefficient (KD) is obtained: calculated as 0.98, 0.89, and 0.86, respectively, for TDDA and
3770 dx.doi.org/10.1021/je500634s | J. Chem. Eng. Data 2014, 59, 3767−3772
Journal of Chemical & Engineering Data Article

Table 4. Experimental Results for the Extraction of Fumaric Acid by TBA in Nontoxic Natural Diluents at T = 298.15 Ka
[R3N] [H2A]org
diluent mol·kg−1 mol·kg−1 pH(aq) KD Z E/% KE p
2
canola oil 0.418 0.039 6.742 2.60 0.248 72.22 4.48·10 0.93
0.851 0.042 6.858 3.50 0.133 77.77
1.255 0.045 6.969 5.00 0.095 83.33
1.674 0.046 6.987 5.75 0.073 85.18
2.080 0.050 6.994 12.40 0.063 92.50
almond oil 0.418 0.038 6.796 2.37 0.242 70.37 2.11·102 0.84
0.851 0.041 6.850 3.15 0.130 75.92
1.255 0.044 6.871 4.40 0.093 81.48
1.674 0.046 6.903 5.75 0.073 85.18
2.080 0.049 6.932 9.80 0.062 90.74
sesame oil 0.418 0.033 6.472 1.57 0.210 61.11 2.03·102 0.81
0.851 0.039 6.782 2.60 0.124 72.22
1.255 0.042 6.877 3.82 0.088 79.24
1.674 0.045 6.922 5.62 0.071 84.90
2.080 0.048 6.984 8.00 0.061 88.88
a
[R3N] is the initial amine concentration in the organic phase, [H2A]org is the concentration of acid in the organic phase after extraction, KE is the
thermodynamic extraction equilibrium constant, and p is the number of amine molecules per acid molecule.

Figure 3. Reaction between fumaric acid and TDDA or TBA to form the 1:1 acid·amine complex.

0.93, 0.84, and 0.81, respectively, for TBA. These values show
that one amine molecule reacts with each acid molecule to form
the complex. This situation also can be explained by the loading
factor (Z), which expresses the extent to which the organic
phase (extractant and diluents) may be loaded with acid. Z is
defined as the ratio of the total acid concentration in the
organic phase at equilibrium to the total initial extractant
concentration in the extract phase:
[H 2A]org
Z=
[R3N]
It can clearly be observed from Tables 3 and 4 that the
loading factor values for all of the natural diluents were lower
obtained: canola oil (12.50) > almond oil (10.00) > sesame
oil (9.80) in TDDA and canola oil (12.40) > almond oil (9.80)
> sesame oil (8.00) in TBA. The maximum extraction
efficiencies of fumaric acid were 92.59 % and 92.50 % using
canola oil at 0.759 mol·kg−1 TDDA and 2.080 mol·kg−1 TBA,
respectively. Increasing in the amine concentration results in a
regular increase in the extraction efficiency. When the
extraction efficiencies of physical extraction and chemical
extraction were compared, the extraction efficiency increased
approximately from 63 % to 93 % for canola oil, from 51 % to
(17) % 91 for almond oil, and from 50 % to 90 % for sesame oil.
These efficiencies may be raised by using reactive extractants.
Further extra benefits of natural nontoxic diluents may be
gained by using canola oil, almond oil, and sesame oil.

than 0.5. The Z values were in the range from 0.062 to 0.248
for TDDA and 0.061 to 0.248 for TBA. Overloading (Z > 1)
was not observed. This suggests that the complex form contains
one amine molecule and one acid molecule (1:1) for both
extractants. Figure 3 presents the reaction between fumaric acid
and TDDA or TBA to give the complex. Barrow and Yerger19
presented an acid·amine complex structure. They proposed that
the proton (H+) in the −COOH group of the carboxylic acid
molecule interacts directly with the amine to form an ion pair
and hence the 1:1 acid·amine complex.
The results of extraction of fumaric acid by TDDA and TBA
■
CONCLUSION
The extractability of fumaric acid by amine extractants (TDDA
and TBA) dissolved in natural nontoxic diluents (canola oil,
almond oil, and sesame oil) were investigated. Physical and
chemical extraction were compared in terms of extraction
efficiency. The extraction equilibrium was taken to be a result of
the formation of 1:1 acid·amine complexes. The thermody-
namic extraction constants KE were obtained from a graphical
method. The maximum synergistic extraction efficiency (E) was
determined as 92.59 % with TDDA in canola oil.

■
dissolved in the natural nontoxic diluents canola oil, almond oil,
and sesame oil in terms of distribution coefficient and
AUTHOR INFORMATION
extraction efficiency are tabulated in Tables 3 and 4. The
extraction power of (TDDA + diluent) and (TBA + diluent) Corresponding Author
mixtures changes with increasing initial concentration of amine *E-mail: hasanuslu@gmail.com.
in the organic phase. When the distribution coefficients (KD) of Notes
the diluents were compared, the following orders were The authors declare no competing financial interest.
3771 dx.doi.org/10.1021/je500634s | J. Chem. Eng. Data 2014, 59, 3767−3772
Journal of Chemical & Engineering Data

■
Article

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