Separation Science and Technology

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Modeling and optimization of reactive extraction

equilibria and kinetic study of gallic acid using
tributyl phosphate in isoamyl alcohol

Nishant Joshi, Amit Keshav & A.K. Poonia

To cite this article: Nishant Joshi, Amit Keshav & A.K. Poonia (2020): Modeling and optimization
of reactive extraction equilibria and kinetic study of gallic acid using tributyl phosphate in isoamyl
alcohol, Separation Science and Technology, DOI: 10.1080/01496395.2020.1751200

To link to this article: https://doi.org/10.1080/01496395.2020.1751200

Published online: 20 Apr 2020.

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SEPARATION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01496395.2020.1751200

Modeling and optimization of reactive extraction equilibria and kinetic study of

gallic acid using tributyl phosphate in isoamyl alcohol
Nishant Joshi , Amit Keshav , and A.K. Poonia
Department of Chemical Engineering, National Institute of Technology Raipur, Raipur, India

ABSTRACT ARTICLE HISTORY

Equilibrium and kinetic experiments were performed for gallic acid recovery using tributyl Received 14 January 2019
phosphate dissolved in isoamyl alcohol as a diluent. Employing an extractive-reaction system Accepted 30 March 2020
results in significantly higher acid recovery in comparison to physical extraction. Overall equili- KEYWORDS
brium extraction complexation constant KE was found to be in the range 4.325–6.896. 1:1 acid: Gallic acid; tributyl
extractant complexes are proposed from the results obtained from mass action law model. phosphate; isoamyl alcohol;
Adsorption isotherm models (Langmuir, Freundlich, Temkin) and Response Surface reactive extraction
Methodology was used, Mass transfer coefficient (kL) and diffusivity coefficient were also calcu-
lated. Extraction kinetics was observed to be very slow based on the Hatta number.

Introduction There are chemical interactions between extractant and

Gallic acid (3, 4, 5 tri hydroxy benzoic acid) is
a valuable chemical compound present in beverages
such as tea, wine and in various food items such as
gall nut, blueberries, apples. It possesses antimutagenic,
anticancer, antiviral and antifungal properties due to
which it is of considerable interest to researchers in
medical community.[1] It is commercially available is
anhydrous and monohydrate form. It is a type of phe-
nolic carboxylic acid produced from acid hydrolysis of
tannins. An alternative biotechnological route is desired
as the acid hydrolysis produces high amount of toxic
compounds. This is usually done by bioconversion of
tannin by the enzyme tannase produced by microbes.[2–
6]
Also gallic acid is present in olive mill wastewater
and can be recovered from there.[7] In fermentation
broth as well as the olive mill wastewater the concen-
tration of gallic acid is very less, and therefore, it poses
a great challenge for the recovery process.
Past studies have shown that reactive extraction is
effective in extracting acid from aqueous solutions and
can also be applied for recovery from fermentation
broth.[8,9] It is the extractant molecule that reacts reversi-
bly with solute (acid) molecule and forms solute-
extractant complex in the organic phase. Because the
extractants are viscous, their properties like surface ten-
sion and viscosity can be lowered by employing diluents.
Diluents also provide solvation to acid: extractant com-
plex. Polar diluents are preferred over non-polar diluents.
acid, acid and diluent, and extractant and diluent. The
dipole-dipole interaction governs solvation of acid–
extractant complex and it has been observed that higher
neutralization occurs by increasing the dipole moment of
the diluent. The selection of the suitable extractant is
important to attain higher distribution coefficient. The
extraction of carboxylic acid from aqueous solutions and
separation of other phenolic compounds by using tributyl
phosphate (TBP) has been carried out by some
authors.[10–15] There are equilibrium studies on the recov-
ery of gallic acid in the literature.[16–23] Authors have
considered the influence of various parameters, such as
difference in the type of diluents, type and amount of
extractants, and temperature, on the distribution coeffi-
cient or extraction efficiency. Though there is sufficient
work published on recovery of other carboxylic acids there
is insufficient information present about the equilibrium
and kinetic study of gallic acid. Therefore, in the present
work equilibrium studies and kinetics study for recovery
of gallic acid from dilute aqueous solutions using TBP
dissolved in isoamyl alcohol is carried out. In the kinetic
study, effect of various hydrodynamic and reaction para-
meters has been shown on the initial rate of reaction to
draw inference about the kinetics of the reaction.[24]
Different classes of models such as mass action law,
relative basicity, adsorption isotherm models
(Langmuir, Freundlich and Temkin) and Linear
Solvation Energy Relationship (LSER) have been

CONTACT Amit Keshav dr.amitkeshav@gmail.com Assistant Professor, Department of Chemical Engineering, National Institute of Technology
Raipur, GE Road, Chhattisgarh 492010, India
© 2020 Taylor & Francis
2 N. JOSHI ET AL.

applied to describe the phenomena of reactive where the subscript aq and org represents aqueous and
extraction.[25,26] Adsorption isotherm models presents organic phase, respectively. Overall distribution coeffi-
a different outlook of the reactive extraction process cient (KD) is expressed as the ratio of total acid con-
and was used in the present work. centration in organic phase and total acid
Optimization is the technique of getting an optimum concentration in aqueous phase. It can be expressed
value (which can be minimum or maximum) of the by Eq. (3) defined as:
objective function governing the relation between inde-
P þ 2P2 D½HAaq
pendent variables and output variable within the KD ¼ (3)
defined regions of input variables. Some optimization 1 þ KHA=½H þ 
techniques are Response Surface Methodology (RSM),
Genetic algorithm (GE), Artificial Neural Networking Rearranging the above Eq. (4) can be written as
(ANN) and Differential Evolution (DE).

KD 1 þ KHA=½H þ  ¼ P þ 2P2 D½HAaq (4)
Response surface methodology RSM is a technique, which


establishes the relation among the variable and describes it thus, the plot of KD 1 þ KHA=½H þ  against [HA]aq
through a polynomial equation. It is best suited and can be could yield the values of dimerization (D) and partition
aptly used in a situation where level of several variables influ- coefficients(P).
ences response variable. The polynomial equation describes the
behavior of dataset. The purpose of using RSM is to establish
the relationship between response variable and input variable
and also to optimize the output variable to achieve best system Theory of reactive extraction
performance. For the optimization of chemical extraction pro- Organophosphorus compounds like TBP is a strong
cess parameters such as extraction efficiency or distribution solvating extractant and offer more distribution ratio.
coefficient authors have used response surface Phosphoryl group in TBP make it a strong Lewis base
methodology.[27] RSM central composite design (CCD) was and because of which it can participate in the hydrogen
used in the present work to optimize the response parameter bonding with the acid molecule. Reactive extraction
(extraction efficiency) affected by the factors such initial acid complexation of gallic acid (HA) with the extractant
concentration and extractant concentration. (E) can be thought to be occurring as follows:
m½HAaq þ n½Eorg $ ½HAm En org (5)
Theory here, m and n are the stoichiometric coefficients of acid
and extractant, respectively. The overall equilibrium
Theory of physical extraction
constant, KE, may be defined as Eq. (6)
Physical extraction can be explained by the use of mass
action law as applied by Kertes and Kings.[28] ½HAm En org
KE ¼
Intermolecular hydrogen bond in the aqueous phase lead ½HAm n
aq ½Eorg
to acid in monomeric form (as ionized or un-ionized; ½HAm En org ð1 þ KHA =½H þ Þm
defined by ionization coefficient (KHA) which is the ratio ¼ (6)
½HAm n
T ½Eorg
of ionized to un ionized fraction), whereas depending on the
organic phase the partitioned acid form different levels of where, ½HAT represents total (ionized and unionized)
dimerization (defined in terms of dimerization coefficient concentration of acid in aqueous phase The distribu-
(D) and is the ratio of dimerized acid to molar acid to the tion coefficient KD may be defined by the ratio of acid
power 2). The existence of acid in either dissociated or in organic phase to acid in aqueous phase and can be
undissociated state in aqueous solution depends on the obtained as given in Eq. (7) assuming that all the acid
pKa values and the later prevails when pH<pKa. Under was in the complex form.
that condition the partition of acid is in undissociated
½HAm En org
form and is defined as partition coefficient as, KD ¼ m (7)
½HAT
½HAaq $ ½HAorg (1)
Eqs. (6) and (7) can be combined to give overall equili-
brium complexation constant as given in Eq. (8)
½HAorg KD ð1 þ KHA =½H þ Þm
P¼ (2) KE ¼ (8)
½HAaq m½HAT m1 ½Enorg

The equilibrium extractant concentration [E]org can be
found by means of Eq. (9).
½Eorg ¼ ½E0  KD n½HAT =m
where [E]0 is the initial extractant concentration in the
organic phase. Combining Eqs. (8) and (9), the distri-
bution coefficient, KD ; can be presented as,
 n ½HAT m1
KD ¼ mKE ½E0  KD n½HAT
ð1 þ KHA =½H þ Þm
For m = 1 and the extractant concentration at equili-
brium can be taken as the initial concentration of
extractant (as it is very large compared to complexed
extractant) and Eq. (11) can be expressed as,


logKD þ log 1 þ KHA=½H þ  ¼ logKE þ nlog ½Eo (11)


Plot of logKD þ log 1 þ KHA=½H þ  versus log
½Eo gives the values of KE and n.
The loading of the extractant, Z, is defined as the
ratio of total concentration of the acid in the organic
phase to the initial extractant concentration in the
organic phase, ½E0
½HAorg
Z¼
½E0
The extraction efficiency (Ee %) is the ratio of acid
concentration in the organic phase to total acid con-
centration (present in both aqueous as well as in
organic phase). In terms of distribution coefficient, it
can be stated as
Ee%¼ KD
100
ð1þKD Þ
Theory of adsorption isotherm modeling
The interaction between the extractant and acid mole-
cules can be described by the adsorption isotherms
where acid molecules represent the adsorbate and the
extractant molecules represent the adsorbent at equili-
brium. Certain parameters characterize the Langmuir,
Freundlich, and Temkin adsorption isotherms. Values
of such parameters describe the surface properties and
attraction of the adsorbent toward the adsorbate. When
there is a dynamic balance between the concentration
of acid in organic phase and aqueous phase, equili-
brium is supposed to exist. The adsorption isotherms
parameter values directly depend on the extractant
composition, basicity of the extractant and its specific
surface area, the type of acid and its effect on the
medium.[25]
SEPARATION SCIENCE AND TECHNOLOGY 3
As per the assumption of Langmuir isotherm, there
are definite active sites equally scattered over the adsor-
(9) bent surface. Quantity of the acid extracted in the
organic phase (in gram) per gram of extractant can be
defined by the Langmuir equation. at constant tem-
perature as
Qo KL Ce
qe ¼ (14)
1 þ KL C e
where Ce (kg.m−3) represents the aqueous phase acid
(10) concentration and qe (kg.kg−1) represents organic phase
concentrations of acid respectively. KL (m−3·kg) is the
Langmuir equilibrium constant and Q0 (kg.kg−1) is the
monolayer capacity.
The slope and intercept provide the value of Q0 and
KL respectively when a graph is plotted between Ce/qe
and Ce.
The Freundlich isotherm is an exponential represen-
tation of energies and count of heterogeneous nature of
sites. It is represented as
qe ¼ KF Ce1=n (15)
The logarithmic plot of qe versus Ce, results in determi-
nation of n (heterogeneity factor) and KF (Freundlich
constant; (kg.kg−1) (m−3·kg)1/n) from slope and
intercept.
(12) The Temkin isotherm,[16] which represents interac-
tion between adsorbent and adsorbate and their bind-
ing energies is given as:
qe ¼ BT logKT Ce (16)
Plot of qe versus logCe results in determination of BT
(kg.kg−1), from the slope, which is related to heat of
adsorption and KT (kg.m−3) from the intercept.
(13)
Theory of response surface methodology
Response Surface Methodology works by fitting the
experimental data to a suitable model equation, which
works well for the given range of operation. It can be
used to optimize the process parameters, which are set
as input parameter and their effect is observed in the
output parameter called as response parameter. The
design of experiments is based on either CCD or Box-
Behnken design (BBD). The output parameter is
entered at different values of input parameters accord-
ing to the design of experiment. The table is then
analyzed to achieve the model equation.
Theory of kinetic study
The studies by Doraiswamy and Sharma (1984) pre-
sents the in-depth mechanism of interphase acid
4 N. JOSHI ET AL.

transfer.[29] They studied the reaction effect on transfer
rate of acid in Lewis type stirred cell.
On the basis of interface mass transfer theories, they
have classified the reaction in four different regimes
depending on relative rate of diffusion to reaction rate
as: Very Slow, Slow, Fast and Instantaneous (Table 1).
To classify a reaction regime, one has to examine the
effect of agitation, volume ratio of phases, effect of
initial acid and extractant concentration on initial rate
of reaction.
Determination of Mass-Transfer Coefficient (kL) in
isoamyl alcohol.
The mass transfer coefficient (kL) for the acid mole-
cules transfer from the aqueous phase to the organic
phase in physical extraction by diluent only is given by
the relation
Vorg dHAorg

¼ kL HAeq org  HAorg
t
(17)
A dt
Where Vorg is the organic-phase volume (m ), A is the 3
eq
interfacial area (m2), HAorg denotes the equilibrium acid
concentration and HAtorg represents the organic phase
acid concentration of at particular time. Eq. (18) is an
integrated form of Eq. (17)
! organic and aqueous phases for 5 h at fixed tempera-
eq
HAorg kL At
ln eq ¼ (18)
HAorg  HAorg
t Vorg
Reaction Kinetics The basic nature of reaction between
gallic acid and TBP is reversible. To determine the
kinetics of reactive extraction, the method of initial
rates is considered in order to evade difficulties due to
reversibility. Using Eq. (19), the initial specific rate of
reaction, RHA,0 (kmol.m−2. s−1), was calculated.
 
Vorg dHAorg
RHA:0 ¼ (19)
A dt t¼0
Back extraction
The success of the reactive separation process lies in the
ease with which acid can be extracted back from the
loaded organic phase. Therefore, two different methods
were employed for the back extraction of gallic acid
from loaded organic phase of isoamyl alcohol and TBP:
a) temperature swing b) contact with NaOH.
Material and methods
All chemicals were used of analytical grade. Gallic acid
(purity 98%) and isoamyl alcohol (purity 99%) was
obtained from Molychem, India. TBP (purity 99%)
was obtained from LobaChemie, India. The aqueous
solutions were prepared using ultrapure (Millipore)
water. UV spectrophotometer (Shimadzu UV1800)
was utilized for determination of gallic acid concentra-
tion. For carrying out the optimization using RSM,
Minitab 17.1.0.0 was used.
Method for equilibrium studies
As the concentration of gallic acid is less than 0.06
kmol.m−3 in olive mill wastewater, the experiments
were done within the range 0.01–0.06 kmol.m−3. The
concentration of TBP was varied from 10 to 40% v/v
in isoamyl alcohol. The extraction equilibrium
experiments involve the shaking of equal volumes of
ture of 303 K water bath shaker (REMI) followed by
settling of the mixture for at least 2 hours. Aqueous
phase acid concentration was determined by UV
spectrophotometer where the gallic acid was detected
at the wavelength of 264 nm. The acid content in the
organic phase was determined by a mass balance.
Enough time for contacting and time for settling
were provided.
Method for kinetic studies
Lewis type cell was used for kinetic study (Fig. 1).
A flat bottom cell of inner diameter 6.5 cm was used.
The interfacial area was 33.18 cm2. Constant stirring
was provided in the cell by means of overhead agi-
tator containing four blades. The width of blade was
1 cm and length of blade was blade was
2.4 cm.100 ml aqueous solution of gallic acid of
different concentrations was first poured in the

Table 1. Classification of different regimes for simultaneous reaction(irreversible) and extraction in stirred cell.
Effect on the specific rate of extraction (RA) of
Aqueous phase acid Organic phase extractant
Hatta concentration concentration Speed of agitation Volume ratio of the phases
Regime Description Number (½HA) (½E) (N) (Vorg/Vaq)
1 Very slow ≪1 / ½HAm / ½En None / (Vorg/Vaq)
2 Slow / ½HAm None / (N) None
3 Fast ≫1 / ½HAðmþ1Þ=2 / ½En=2 None None
4 Instantaneous None / ½En / (N) None

Figure 1. Experimental setup of stirred cell used in the study.
vessel. The dual stirrer was lowered to 1 cm below
interphase. 100 ml of the organic mixture comprising
extractant TBP and isoamyl alcohol was then added
in the vessel, and extraction was carried out for
a definite period. A sample collection from bottom
of aqueous phase (as shown in Fig. 1) by a syringe
was done without stopping the stirring at different
time interval and then analyzed.
Experimental design
In face centered CCD the out of limit point can be
eliminated which are present in Rotatable CCD.
Therefore a 3-level 2-factor face centered CCD was
used to optimize the extraction of gallic acid. The con-
centration of extractant TBP and initial concentration
of gallic acid were considered as independent input
variables. The extraction efficiency (%) was selected as
a response variable.
There were total 13 runs of experiments out of
which 5 runs were for the central point for the cube,
4 points for the cube points and 4 axial points. For the
face-centered CCD the value of alpha is 1.
Experimental data were regressed and fitted to
a second order polynomial model Eq. as follows:
X
K X
K X
K
Y ¼ βo þ βi xi þ βij xi xj þ
i¼1 1ij j¼1
In Eq. (22) βo, βi, βii, βij are the regression coefficient
for constant, linear, quadratic and interactive term,
respectively. xi, and xj, are independent variables repre-
sented by initial acid concentration ([HA]0) and initial
extractant concentration ([E]0), K is the number of
variables.
SEPARATION SCIENCE AND TECHNOLOGY 5
Method of back extraction
In the temperature swing method, the loaded organic
phase of isoamyl alcohol with TBP (20 mL) was con-
tacted at aqueous stream (20 mL) at high temperature
of 333 K for 8 h in the water bath shaker and settled for
2 h at the same temperature. The amount of acid was
then determined in the aqueous phase by UV
spectrophotometer.
In another method, the loaded organic phase of
isoamyl alcohol and TBP (20 mL) was contacted with
20 mL NaOH solution (0.1 N) for 1 hour at tempera-
ture of 303 K, which was then titrated with oxalic acid
for the determination of remaining NaOH.
Results and discussions
Extraction equilibria
Both the physical as well as the chemical extraction
equilibrium experiments were done at six different
concentration of gallic acid and isotherms are shown
in Fig. 2. In the chemical extraction, the TBP concen-
tration was varied from 10 to 40% v/v.in isoamyl alco-
hol. For the physical extraction, the distribution
coefficient KD was obtained in the range of 1.08–2.15
as the concentration of gallic acid changed between
0.01 to 0.06 kmol.m−3. Isoamyl alcohol being an active
diluent and a protic solvent, comprise of hydrogen
atoms attached to a strong electronegative element
O (-O-H) and therefore is a hydrogen bond donor. It
has high relative permittivity (ε = 14.7) and a high
dipole moment (DM = 1.7 D) demonstrating it to be
strongly polar. Thus, it provides high KD values. It was
βii xi2 (20)
Figure 2. Physical and chemical extraction equilibria for the
gallic acid.
6 N. JOSHI ET AL.

observed that as initial acid concentration in increased The loading of TBP is shown in Fig. 4 in which the
the distribution coefficient increases, which can be due aqueous phase equilibrium acid concentration is
to reason that at high initial acid concentration there is plotted against the loading (Z). It can be observed
higher concentration gradient of acid between aqueous that as equilibrium acid concentration in aqueous
and organic phase. The partition and dimerization phase increases the loading ratio (Z) increases. King
coefficient were calculated as 1.096 and 28.144 m3. and others also report similar observations and also
kmol−1. Although good efficiency in the range of report the similar type of complex formation at various
52–68% was obtained, it is not sufficient for high concentrations of TBP.
recovery of gallic acid from the wastewater or biocon- It can be seen from Table 2 that the value of KE is higher
version broth. Therefore, to enhance the efficiency of at high concentration. Also, the values of solvation number
recovery, extractant such as TBP was used. Higher (n) is above 1 at initial concentrations less than 0.04 kmol.
distribution coefficient in the range of 1.21–8.52 was
obtained when TBP was used. The highest extraction
efficiency of 89.5% was obtained when 40% v/v TBP
was used with initial acid concentration of 0.06 kmol.
m−3. Therefore, a 3–4-fold increase was obtained in the
value of KD in the chemical extraction as compared to
physical extraction.
For the chemical extraction, the extraction equili-
brium constant KE was found in the range of 4.325–-
6.896 from the intercept of graph logKD þ


log 1 þ KHA=½H þ  vs log[E]0 for different extractant
and initial acid concentration. Very low loading ratios
(very less than 0.5) were calculated for all the cases
thus supporting the formation of 1:1 acid extractant
stoichiometry. Low loadings are expected as there is
quite low initial acid concentration as compared to
extractant TBP concentration. The same was con-
firmed by the solvation number, that was found to Figure 4. Plot of loading ratio(Z) against the equilibrium con-
centration of aqueous phase(HAaq) for different extractant
be near 1 as shown by the slope of graph plotted

 concentration.
between logKD þ log 1 þ KHA=½H þ  and log[E]0 as
shown in Fig. 3. Table 2. Evaluation of overall equilibrium extraction complexa-
tion constant(KE) and solvation number(n) for the chemical
extraction process.
[HA]0 Conc. TBP, [E]0 [HA]aq KD Z KE n R2
0.01 0.3652 0.0044 1.272 0.0153 4.325 1.065 0.998
0.7305 0.0028 2.496 0.0097
1.0957 0.0021 3.761 0.0072
1.4609 0.0016 5.250 0.0057
0.02 0.3652 0.0076 1.637 0.0339 5.223 1.056 0.994
0.7305 0.0050 3.000 0.0205
1.0957 0.0035 4.714 0.0150
1.4609 0.0026 6.692 0.0119
0.03 0.3652 0.0100 2.000 0.0547 6.226 1.036 0.996
0.7305 0.0064 3.687 0.0323
1.0957 0.0043 5.976 0.0234
1.4609 0.0034 7.823 0.0182
0.04 0.3652 0.0130 2.076 0.0739 6.324 1.004 0.993
0.7305 0.0081 3.938 0.0436
1.0957 0.0057 6.017 0.0313
1.4609 0.0045 7.888 0.0243
0.05 0.3652 0.0155 2.225 0.0944 6.426 0.967 0.998
0.7305 0.0099 4.050 0.0548
1.0957 0.0070 6.142 0.0392
1.4609 0.0055 8.090 0.0304
0.06 0.3652 0.0170 2.529 0.1177 6.896 0.906 0.998
0.7305 0.0110 4.454 0.0670
Figure 3. Evaluation of overall equilibrium complexation 1.0957 0.0080 6.500 0.0474
constant(KE) and stoichiometric coefficient(n). 1.4609 0.0063 8.523 0.0367
 SEPARATION SCIENCE AND TECHNOLOGY 7

m−3 implying that it is the extractant that reacts with acid parameters for obtaining maximum efficiency are high-
molecules whereas for initial concentration above than 0.04 est initial acid concentration and highest extractant
kmol.m−3 the physical extraction by diluent also plays role as concentration. The optimal extraction conditions of
the solvation number is less than 1. gallic acid were determined as: [HA]0 = 0.06 kmol.m−3,
[E]0 = 1.4609 kmol.m−3. At the optimum conditions,
the experimental yield of gallic acid was 89.5%, which is
Adsorption isotherm models very close to the predicted value of 89. %.
The assessed values of modified Langmuir, Temkin and
Freundlich, parameters are listed in Table 3. From the
Table 4. Experimental and RSM predicted values of extraction
observed regression coefficient values, it can be said that efficiency.
in comparison to Langmuir and Temkin, Freundlich Variables Response (Efficiency %)
adsorption isotherm fits well, and it describes the phe- Extractant
nomena of acid−extractant interaction. Initial Acid Concentration
Concentration [E]0, Experimentally RSM
Run [HA]0, kmol.m−3 kmol.m−3 obtained Predicted
1 0.02 0.7305 75.00 75.13
RSM results 2 0.06 0.7305 81.66 81.63
3 0.02 1.4609 87.00 87.07
Table 4 shows the face centered CCD matrix with experi- 4 0.06 1.4609 89.50 89.41
mental and predicted response. Regression analysis applied 5 0.02 1.0957 82.50 82.28
6 0.06 1.0957 86.60 86.70
to the design matrix yields the following Eq. (21) 7 0.04 0.7305 79.00 78.89
8 0.04 1.4609 88.75 88.75
Ee ð%Þ ¼ 46:90 þ 367:5½HA0 þ 38:59½E0 9 0.04 1.0957 85.00 85.00
 2  2 10 0.04 1.0957 85.10 85.00
 1262 ½HA0  8:846 ½E0 11 0.04 1.0957 84.90 85.00
12 0.04 1.0957 85.20 85.00
 142:4½HA0 ½E0 (21) 13 0.04 1.0957 84.70 85.00

Statistical analysis Table 5. Analysis of Variance(ANOVA) results for the RSM study.
The analysis of variance (ANOVA) was performed to Source Coefficient Sequential Sum of Squares F-value p-value
mark the distinct and the interactive effects of the Model 85.0014 186.346 1039.37 <0.005
[HA]0 2.2100 29.305 817.25 <0.005
input variables on the response variable (extraction [E]0 4.9317 145.928 4069.67 <0.005
efficiency of gallic acid) and the results are presented [HA]0 *[HA]0 −0.505 2.942 19.63 0.003
[E]0* [E]0 −1.180 3.845 107.22 <0.005
in Table 5.High F values and lower p values(<0.005) [HA]0 *[E]0 −1.0400 4.326 120.66 <0.005
Error 0.251
for all the terms reflects that all the terms were Lack of fit 0.103 0.93 0.505
significant.

Response surface analysis Results for kinetic study

The surface plot (Fig. 5) as well as contour plot (Fig. 6) The physical mass-transfer coefficient of gallic acid (kL)
describes the efficiency variation at different extractant in isoamyl alcohol can be evaluated by making a plot of
 eq

and initial acid concentration. It can be seen from both HAorg
ln HAeq HAt vs time (t) at a constant agitation speed
the plots that efficiency increases with initial acid con- org org

centration and extractant concentration. The optimum (80 rpm), at an acid concentration of 0.06 kmol.m−3,

Table 3. Evaluation of Langmuir, Freundlich and Temkin parameters for the adsorption isotherm modeling of the reactive extraction
process of gallic acid.
Langmuir Freundlich Temkin
TBP
Concentration Qo KL KF BT KT
(kmol.m−3) (kg.kg−1) (m−3·kg) R2 (kg.kg−1) (m−3·kg)1/n n R2 (kg.kg−1) (kg.m−3) R2
0.3652 0.063 0.192 0.894 0.0151 0.677 0.997 0.1057 1.422 0.914
0.7305 0.042 0.275 0.894 0.0173 0.701 0.997 0.0609 2.243 0.927
1.0957 0.034 0.362 0.751 0.0204 0.712 0.99 0.0438 3.162 0.956
1.4609 0.032 0.406 0.746 0.022 0.748 0.993 0.0323 4.246 0.959
8 N. JOSHI ET AL.

Figure 5. Surface plot of extraction efficiency against extractant concentration and initial acid concentration.

Figure 6. Contour plot of extraction efficiency against extractant concentration and initial acid concentration.

and equal phase volumes ratio of the organic and aqu-
eous phases (Vorg/Vaq = 1).From the slope of Fig. 7, the
value of kL was calculated to be 1.79 × 10−5 m.s−1.
Effect of stirring speed (N) on RHA0
The phenomenon of reactive extraction in Lewis type
stirred cell is controlled either by chemical reaction rate
kinetics or by diffusion rate with which the reactants
such as acid and extractant (TBP) approaches toward
each other. In diffusion-controlled system, the rate
increases with an increase of agitation speed whereas
in the other case where the diffusion influence is slight,
and the rate of extraction is chiefly controlled by the
chemical reaction. In the present work, the agitation or
stirring speed was changed from 40 to 80 rpm and its
influence on the initial rate of extraction were observed,
as shown in Fig. 8. The interfacial area between the
aqueous and organic phases gets disturbed (changes) if

Figure 7. Determination of physical mass transfer coefficient(kL)
.
the agitation speed is further increased. For the chosen
range of agitation speeds, it can be seen from Fig. 8 that
RHA0 was almost constant (7.31 × 10−7-7.58 × 10−7
kmol.m−2.s−1) and agitation speed has hardly got any
effect the rate of extraction of gallic acid. This tells that
extraction is primarily governed by chemical reaction.
The kinetics of chemical reaction belongs to either
regime 1 or regime 3.
Effect of the phase volume ratio (Vorg/Vaq) on RHA0
To know whether the reaction follows regime 1 or regime
3, the influence of phase volume ratio (Vorg/Vaq) on the
initial specific rate of extraction was observed. From Fig.
0:14
9, one can observe that the RHA,0 value varies in linear
proportion when Vorg/Vaq was altered from 0.5 to 1.5.
Figure 8. Variation of Initial rate of reaction RHA0 with speed of
stirring (RPM).
SEPARATION SCIENCE AND TECHNOLOGY 9
Thus, the reactive extraction of gallic acid with TBP in
isoamyl alcohol was determined to be taking place in
regime 1 (very slow chemical reaction).
Order of the reaction (m,n)
To evaluate the reaction order with respect to gallic
acid (m) the gallic acid concentration was varied from
0.01 to 0.06 kmol.m−3. The concentration of TBP was
held constant at 0.3652 kmol.m−3 in isoamyl alcohol
and agitation speed was set at 80 rpm. The observed
values of reaction rate at different initial acid concen-
tration of gallic acid are plotted in Fig. 10. It can be
observed from Fig. 10 that the value of RHC,0 increased
linearly with initial gallic acid concentration (at fixed
TBP concentration).
The order with respect to gallic acid was evaluated
from Fig. 10 to be 0.86. Likewise, for calculating reac-
tion order with respect to extractant TBP (n), the values
of initial rate of reaction RHC,0 were measured as the
TBP concentration was changed from 0.3652 to 1.4692
kmol.m−3 at a fixed gallic acid concentration of 0.06
kmol.m−3 and at a constant agitation speed of 80 rpm.
The order with respect to TBP (n) was observed to be
0.17 from Fig. 11.
The forward reaction rate constant (k) was deter-
mined from slope of Fig. 12 as 1.008 × 10−5 (s−1). Then
from equilibrium constant, the backward reaction rate
constant (k−1) was found to be 1.53 × 10−6 (s−1).
Criteria for the Reaction Regime.
For m = 0.17 and n = 0.86, the Hatta number (Ha) is
stated as given in Eq.(22)
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
eq
1:07k HAorg ½Eorg 0:17 DHC
Ha ¼ (22)
kL
Figure 9. Variation of initial rate of reaction RHA0 with phase
volume ratio(Vorg/Vaq).
10 N. JOSHI ET AL.
Figure 10. Variation of initial rate of reaction RHA0 with extractant
concentration at fixed initial acid concentration(0.06 kmol.m−3).
Figure 11. Variation of initial rate of reaction RHA0 with initial
concentration of gallic acid at fixed extractant concentration
(0.3652 kmol.m−3).
The value of diffusivity DHC was estimated using the
Reddy Doraiswamy Equation[30] and Wilke−Chang
Equation[31] and was obtained as 0.302 × 10−9 m2.s−1
and 0.276 × 10−9 m2.s−1 respectively. The average value
of the diffusivity was used for the calculation of Hatta
number, which compares the rate of reaction with rate
of diffusion through the film, which is used for the
classification of the regime. The values of Ha were
found to be in the range of 0.0039–0.0041, Thus, it
was confirmed that the reaction belongs to regime 1.
Back extraction
It was observed that with the temperature swing
method, 58% of acid present in the loaded organic
Figure 12. Determination of reaction rate constant.
phase (60% isoamyl alcohol and 40% TBP) was trans-
ferred to the aqueous phase. The distribution coeffi-
cient for the back-extraction process was observed to be
1.38. Though NaOH contact method results in better
recovery of acid (95% of acid present in organic phase)
but in the form of sodium salt of gallic acid which
needs further treatment (reacidification), if the acid is
to be obtained in pure form.
Equilibrium and kinetic studies presented in the
above work will be helpful in design of the reactive
extraction process. These equilibrium study of the reac-
tive extraction process gives an indication of the che-
mical potential of the solute in the both the organic
phase and aqueous phase at equilibrium. The kinetic
study tells the time and volume of reactor required to
get to the equilibrium state. Although the reaction
regime was found to be very slow a Rotating Disc
Contactors (RDC) can be utilized which will be able
to provide turbulence and high interfacial areas so that
reactor volume can be small. In the above study various
adsorption isotherm models have been applied. The
optimization can be done by various methods such as
RSM, ANN, GE, and DE etc. Of all these processes, the
RSM can be used for the optimization of equilibrium
extraction process.
Conclusions
Equilibrium studies of gallic acid with TBP as extrac-
tant and isoamyl alcohol as diluent have been carried
out at temperature of 303 K. The equilibrium results
show that the formation of 1:1 acid/TBP complexes.
Various models such as modified Langmuir,
Freundlich and Temkin were applied to describe the
chemical extraction process. It was observed that
Freundlich describes the system best. Kinetic studies

were also carried out. Physical mass transfer coefficient
was determined as 1.79 × 10−5 m.s−1. For the classifica-
tion of reaction in various regime effect of parameters
such as speed of stirring and ratio of volume of organic
phase to aqueous phase on initial rate of reaction was
observed and reaction was found to be very slow. The
order with respect to extractant and with respect to
initial acid concentration was calculated as 0.17 and
0.86 respectively. Overall order of the reaction can be
taken as 1. Rate constant was determined to be
1.008 × 10−5 s−1. RSM was used to optimize the extrac-
tion efficiency.
Conflict of interest
The authors have declared no conflict of interest.
Abbreviations
TBP Tributyl phosphate
Symbols Used
[HA]0 [kmol.m−3] Initial Gallic acid concentration
[HA]org [kmol.m−3] Equilibrium Gallic acid in organic
phase
[HA]aq [kmol.m−3] Equilibrium Gallic acid in aqueous
phase
KHA - ionization constant
P Partition Coefficient
D [m3.kmol−1] Dimerization Coefficient
KD-Distribution Coefficient
Ha - Hatta Number
DHC [m2s−1] Diffusivity
kL physical mass transfer coefficient
k s−1 first order forward rate constant
k−1 s−1 first order backward rate constant
RHA0 [kmol.m−2s−1] Initial rate of reaction
pKa Acid Dissociation Constant
KE Overall equilibrium extraction complexation
constant
Z loading ratio
Ee Extraction Efficiency
[E]0 [kmol.m−3]Initial Extractant Concentration of TBP
Subscript
org organic
aq aqueous
Novelity statement
The equilibrium for the reactive extraction of gallic acid with
isoamyl alcohol is presented for the first time. Literature
SEPARATION SCIENCE AND TECHNOLOGY 11
review reveals that although some equilibrium studies have
been carried out, iso amyl alcohol have never been used.
Kinetic study is also presented for the first time. Results
obtained from equilibrium and kinetic studies can be useful
for design of extraction column.
Adsorption Isotherm Modeling has also been carried out
for the extraction process of gallic acid.
Optimization by response surface methodology is also
carried out for finding out the optimum operating para-
meters for the process.
ORCID
Nishant Joshi http://orcid.org/0000-0003-4513-8030
Amit Keshav http://orcid.org/0000-0002-4911-8865
A.K. Poonia http://orcid.org/0000-0003-0262-0871
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