Dyes and Pigments 224 (2024) 112047

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Dyes and Pigments

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

Insights into application of aqueous biphasic systems of deep eutectic

solvents composed of benzyltrialkylammonium chloride in dye separation
Emmanuel A. Oke , Sushma P. Ijardar *
Department of Chemistry, Veer Narmad South Gujarat University, Surat, 395007, India

A R T I C L E I N F O A B S T R A C T

Keywords: Deep eutectic solvents (DES) are considered the newest entry in the list of green solvents and they are analogues
Aqueous biphasic systems of ionic liquids (ILs), with excellent solvent characteristics better than commonly used organic solvents and ILs.
Deep eutectic solvents Owing to this, We have prepared DES using benzyltrialkylammonium chloride (BTAAC) including benzyl­
Salts
trimethylammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), and benzyl­
Separation
Anionic azo dyes
tributylammonium chloride (BTBAC) as hydrogen bond acceptors (HBA) and glycols, like ethylene glycol (EG),
diethylene glycol (DEG) and triethylene glycol (TEG) as hydrogen bond donors (HBD). Aqueous biphasic systems
(ABS) were developed using the synthesized DESs and K3PO4, K2HPO4, and K2CO3 at 298.15 K and atmospheric
pressure. The phase-forming ability of DES has been evaluated based on the nature of potassium salts, HBA and
HBD. In most cases, the influence of salts on ABS formation was found to follow the order: K3PO4 > K2HPO4 >
K2CO3, while HBAs follow: BTBAC > BTEAC > BTMAC. The performance of the ABSs was experimentally applied
for the extraction of Methyl orange (MO), Eriochrome black T (EBT), and Eosin Y (EY). In most ABS, the
extraction order for the studied dyes noticed was: MO < EBT < EY, consistent with their hydrophobic nature.
ABS consisting of BTBAC:TEG + K2HPO4 and BTBAC:TEG + K3PO4 was found to lead to the complete extraction
of MO, EBT, and EY. The recovery of extracted EY dye was performed by adsorption method using starch-
modified chitosan as an adsrobent.

1. Introduction
The burgeoning of industrialisation has deprived mankind of the
right to a healthy environment. Water pollution has an extreme effect on
the environment as it indirectly or directly harms both marine and
human lives as compared with other types of pollution [1]. The con­
sumption of contaminated water alone has led to nearly 3.1% or 1.7
million deaths worldwide because more than 40% of the world popu­
lation does not have access to drinkable water [2,3]. Dyes are chemical
substances applied to impart colour to materials. Industries like textile,
paper, cosmetics, food, printing, plastic, drinks, leather, and pharma­
ceuticals are using dyes extensively in their operations [4–7]. Azo dyes
are anionic dyes that possess N–
–N moiety and have been reported to be
the largest type of organic dyes with a high level of toxicity [8]. Methyl
orange (MO), Eriochrome black T (EBT), Eosin Y (EY), and other dyes
are found to be carcinogenic, teratogenic, and mutagenic due to the
presence of aromatic rings in their structures. The availability of sulfo­
nate groups in the structures of these dyes makes them to be potential
risk chemical pollutants [1,9,10]. At high concentrations, dyes could
affect the proper functioning of the central nervous system [11,12].
Therefore, dyes should be recovered from industrial effluents before
discharging into water bodies.
There are many treatment techniques like coagulation, flocculation,
adsorption, ion exchange, membrane, advanced oxidation, and biore­
mediation have been applied to remove dyes from the environment
[13–17]. However, some of these techniques are costly, demand high
energy, and also generate secondary pollutants that must be treated after
the end of the processes. Additionally, certain colours used in the dyeing
industries are difficult to remove via conventional waste treatment
methods due to their resistance towards light, oxidizing agents, and
aerobic digestion [18–20].
ABS fulfils most of the prerequisites of ideal separation techniques
and has been applied to exclude, concentrate, and purify many analytes
[21]. ABS can be fabricated by mixing an aqueous solution of two
components polymer/polymer, polymer/salt, alcohol/salt, ionic liquid
(IL)/salt, IL/polymer, IL/amino acid, IL/carbohydrate, IL/surfactant,
deep eutectic solvents (DES)/salt, DES/DES, DES/polymer, DES/­
carbohydrate. An appropriate selection of the phase-forming

* Corresponding author.
E-mail address: sijardar@vnsgu.ac.in (S.P. Ijardar).

https://doi.org/10.1016/j.dyepig.2024.112047
Received 7 September 2023; Received in revised form 21 January 2024; Accepted 19 February 2024
Available online 20 February 2024
0143-7208/© 2024 Elsevier Ltd. All rights reserved.
E.A. Oke and S.P. Ijardar
constituents is crucial to the formation of two distinct phases at equi­
librium. ABS has been successfully applied for the separation and puri­
fication of dyes, biomolecules, pharmaceuticals, pesticides, and metals
[21–24].
ILs are found to be costly and toxic hence making them unsustainable
from the viewpoint of green chemistry and an economic perspective
[25–28]. Recently, DESs have been introduced as one of the components
of ABS. DES can be prepared through strong hydrogen bond interactions
by mixing bond acceptor (HBA) with hydrogen bond donor (HBD) at a
suitable molar ratio and temperature [29]. DES possess significantly low
toxicity, higher biodegradability and can easily be prepared without any
further purification in comparison to ILs [30,31]. ABS involving DES
have been recently used to separate proteins, amino acids, nucleic acids,
pharmaceuticals, dyes, and polysaccharides with outstanding results
[32,33]. Studies on the extraction of dyes with notable extraction effi­
ciencies using DES-based ABS are rare. Nevertheless, complete extrac­
tion of sudan III and pigment blue were reported using DES-ABS
composed of choline chloride and carboxylic acids DESs in conjunction
with PPG 400 [34]. Also, sudan III, amaranth, and sunset yellow FCF
dyes were successfully separated using DES prepared from PPG 400 and
tetrabutylammonium bromide along with a few phase formers [35].
More than 95% extraction efficiencies were achieved for methylene
blue, sudan III, and sunset yellow FCF when a variety of hydrophobic
and hydrophilic DESs were combined to form ABS [36]. Excellent out­
comes were also seen by utilising multiple DES-based ABSs to partition
sudan III, methylene blue, and tartrazine [37]. ABSs constructed from
tetrabutylammonium bromide and PPG 400 DES in addition to citrate
salts could extract more than 98% of congo red, methylene blue, and
methyl orange from aqueous solution [38]. Higher than 98% extraction
efficiencies of alizarin red S, orange II, and congo red using ABS
composed of benzyltriethylammonium chloride and propanol DES in
combination with K3PO4 salt have been reported recently [39].
ABS study involving the extraction of dyes constituted by benzyl­
trialkylammonium chloride and glycol DESs in combination with po­
tassium salts is not available in the literature. Therefore, this study aims
to use them for the extraction of anionic dyes from an aqueous solution.
In this investigation, ABS were constructed using nine DESs prepared
from HBAs: benzyltrimethylammonium chloride (BTMAC), benzyl­
triethylammonium chloride (BTEAC) and benzyltributylammonium
chloride (BTBAC) and HBDs: ethylene glycol (EG), diethylene glycol
(DEG) and triethylene glycol (TEG) with potassium salts, including
K3PO4, K2HPO4 and K2CO3. The selection of HBAs was based on their
lower hydrophilicity, ascribed to the presence of the benzyl group in
their side chain [39]. Glycols (EG, DEG and TEG) were chosen because of
their high polar nature and outstanding solvation ability [40]. The
choice of inorganic salts was based on the fact that inorganic salts are
more capable of forming phase separation than organic salts [41,42].
Various factors affecting the phase behaviour of the developed ABS were
examined. The efficiencies of the studied ABSs were examined based on
their ability to extract anionic azo dyes: MO, EBT and EY. These dyes
were selected due to the ease of analyzing them using simple analytical
techniques. In addition, we were able to recover EY dye from the DES
phase components successfully using starch-modified chitosan under
different experimental conditions.
2. Materials and methods
2.1. Materials
BTMAC, BTEAC, and BTBAC were obtained from Spectrochem Pvt.
Ltd. India. EG, DEG, TEG, K3PO4, K2HPO4, and K2CO3 were provided by
Merck, India. MO and EBT dyes were obtained from Sisco Research Lab
and EY dye was supplied by Sigma Aldrich. All chemicals were used
without any further purification. The dissolution of all solutes was car­
ried out using double-distilled water. The details of chemicals used in
this study are depicted in Table S1. The chemical structures of the dyes
2
Dyes and Pigments 224 (2024) 112047
are shown in Fig. S1 of the supplementary information.
2.2. Preparation and characterisation of DES
DESs used in this present investigation were synthesized at 1:3 M
ratio of HBA to HBD [43]. The DES constituents (HBA and HBD) were
mixed thoroughly and stirred continuously for 3 h by a thermostatically
controlled magnetic stirrer at 333.15 K and atmospheric pressure until a
clear homogenous liquid was obtained. Metrohm Karl Fischer Titrator
(870 KF Titrino Plus) was utilized for the determination of water content
in the prepared DES (Table S2). Karl Fischer Titrator operates on the
principle of volumetric titration, a well-known classical method. The
equipment was calibrated based on the instructions written in the
operating manual. The synthesized DESs were characterised by the
FT-IR technique (Fig. 1). The synthesized DESs showed –OH stretching
at 3400–3300 cm− 1, aromatic stretching at 3100–3000 cm− 1, aliphatic
stretching at 2900–2850 cm− 1, and C– –C and C–C ring stretching at
1650 cm− 1 and 1470–1450 cm− 1, respectively. In addition, 1410–1400
cm− 1 for C–OH bending, 1120–1050 cm− 1 for C–O, and C–O–C
stretching, 840–800 cm− 1 for –OH wagging, and 750–700 cm− 1 for ar­
omatic –CH wagging.
2.3. Binodal curves determination
The phase diagrams for ABS of benzyltrialkylammonium chloride-
based DES, BTAAC: Glycols + K3PO4/K2HPO4/K2CO3) were deter­
mined using cloud point titration method at 298.15 K and atmospheric
pressure. 60 wt% aqueous solution of DES and 45 wt% aqueous solutions
of salt were used for the construction of different binodal curves. An
appropriate quantity of DES solution was weighed carefully into a
transparent glass vial followed by a drop-wise addition of salt solution
under constant stirring until turbidity (formation of biphasic solution)
was observed. This was thereafter followed by the addition of double-
distilled water drop by drop until a clear solution (monophasic region)
was seen. The clear solution formed was made turbid again by the drop-
wise addition of an aqueous salt solution. The steps taken earlier were
repeated until adequate data needed to plot binodal curves were ob­
tained. The compositions of the systems were determined using Mettler
Toledo JE1103CE (Switzerland) analytical balance with an uncertainty
of ±10− 4 g.
The experimental binodal curve data obtained were fitted into
Merchuk et al. empirical equation (1) [44].
( )]
Y = A exp[(B × X0.5 − C × X3 (1)
Y and X designate the weight fraction percentages of the DES and
inorganic salt, respectively, while A, B, and C are constant, and represent
the fitting parameters obtained by least squares regression of the
experimental data. The fitting constants are listed in Table 1.
2.4. Determination of tie-lines (TLs) experiment
To estimate the TLs from the biphasic zones, points were selected.
The quantities of the components were measured by weighing them into
centrifuge bottles. The weighed constituents were vigorously agitated
and centrifuged at 3000 rpm for about 25 min. The airtight tubes were
during this step and left to equilibrate at 298.15 ± 1 K for ~24 h. A
careful separation of the top and bottom phases was ensured and
weighed accurately. The four unknown equations (2)–(5) below were
solved for the appropriate determination of the TLs:
[( )]
YT = A exp B ∗ XT0.5 − C ∗ XT3 (2)
[( )]
YB = A exp B ∗ XB0.5 − C ∗ XB3 (3)
E.A. Oke and S.P. Ijardar Dyes and Pigments 224 (2024) 112047

Fig. 1. FT-IR spectra of the nine studied DES.

employing equation (6) are presented in Table 2. A TLL represents the

Table 1
difference in the concentration of the top and bottom phases after the
The value of correlation parameters A, B, and C of Eq. (1) along with R2 of the
equilibration of the two phases. This could assist in the appropriate se­
binodal curves for investigated DES-ABS at 298.15 K.
lection of mixture compositions for the extraction of analytes of interest.
5
DES Salt A B C × 10− R2
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
K3PO4 40.307 − 0.1576 0.739 0.9997 TLL = (XT − XB )2 + (YT − YB )2 (6)
BTEAC:EG K2HPO4 47.006 − 0.1515 0.722 0.9989
K2CO3 39.492 − 0.1188 0.693 0.9996
K3PO4 31.209 0.1818 0.898 0.9999
2.5. Partitioning of dyes
−
BTBAC:EG K2HPO4 38.726 − 0.1947 0.622 0.9998
K2CO3 30.493 − 0.1710 0.497 0.9998
K3PO4 46.639 − 0.1424 0.691 0.9995 MO, EBT, and CR dyes of varying polarities were chosen as the target
BTMAC:DEG K2HPO4 55.917 − 0.1468 0.771 0.9996 compounds for determining the extraction ability of studied ABS con­
K2CO3 47.917 0.1084 0.745 0.9992
−
sisting of DES and potassium salts. An appropriate amount of DES, po­
K3PO4 43.165 − 0.1571 0.843 0.9998
BTEAC:DEG K2HPO4 52.391 − 0.1870 0.713 0.9996 tassium salt, and aqueous dye solution of 400 mg/L concentration was
K2CO3 42.375 − 0.1236 0.591 0.9996 introduced into a transparent 10 mL glass vial. The mixture was stirred
K3PO4 31.141 − 0.1568 0.891 0.9996 thoroughly for 15 min to improve the equilibrium and effectiveness of
BTBAC:DEG K2HPO4 39.146 − 0.1723 0.86 0.9999 the extraction platform. The prepared mixture was later allowed to
K2CO3 31.959 0.1611 0.525 0.9995
equilibrate for approximately 48 h in a thermostat at 298.15 K. After
−
K3PO4 46.000 − 0.1646 1.093 0.9990
BTMAC:TEG K2HPO4 56.439 − 0.1911 1.022 0.9991 this, DES-rich top phase and salt-rich bottom phase were separated
K2CO3 47.717 − 0.1323 0.694 0.9990 carefully with syringes. A UV–vis spectrophotometer was used for the
K3PO4 42.973 − 0.1694 1.033 0.9998 concentration determination of dyes by measuring the absorbance of
BTEAC:TEG K2HPO4 56.126 0.2196 0.88 0.9993
−
MO, EBT, and EY at 505 nm, 503 nm, and 517 nm, respectively. For the
K2CO3 41.758 − 0.1259 0.76 0.9994
K3PO4 32.327 − 0.1590 0.122 0.9999 minimization of cross-contamination from phase components, extrac­
BTBAC:TEG K2HPO4 39.283 − 0.1758 1.140 0.9998 tion systems without the compounds of interest were prepared in par­
K2CO3 31.554 − 0.1552 0.649 0.9997 allel and employed for blank determinations. All experiments were
performed twice to get accurate results. The standard calibration curves
for MO, EBT, and EY are shown in Fig. S2 (A-C), respectively.
YM 1− α
YT = − ∗ YB (4) Phase volume ratio (R) and extraction efficiency (EE %) were ob­
α α
tained as follows:
XM 1− α
XT = − ∗ XB (5) Rdye =
VT
(7)
α α VB
In the above equations, the top phase, bottom phase, and the initial C T VT
mixture are represented by T, B, and M respectively; the weight fraction EEDye (%) = × 100 (8)
C T VT + C B VB
percentage of salt and the DES are respectively designated by X and Y;
the ratio between the weight of the top phase and the total weight of the In the above equations, VT and VB denoted the volume of the top phase
mixture is depicted by α; and letters A, B, and C represent the fitted and bottom phase, respectively. CT and CB are designated as the equi­
constants derived from equation (1). librium concentration of dyes after extraction in the top and bottom
Using these compositions, tie-line lengths (TLLs) were obtained by phases, respectively.

3
E.A. Oke and S.P. Ijardar Dyes and Pigments 224 (2024) 112047

Table 2
Weight fraction compositions of salt (X) and DES (Y) in the mixture (M) for bottom phase (B) and top phase (T) and respective tie line lengths for DES ABS systems at
298.15 K.
DES Salt XM YM XB YB XT YT TLL

BTEAC:EG K3PO4 35.69 14.25 42.53 8.45 6.92 26.55 39.95

K2HPO4 35.21 15.5 41.25 11.45 8.54 30.42 37.81
K2CO3 34.78 15.21 46.43 11.85 3.88 32.55 47.32
BTBAC:EG K3PO4 35.47 12.36 46.55 3.3 5.25 21.08 44.96
K2HPO4 34.89 9.45 45.51 6.25 3.56 26.26 46.48
K2CO3 34.35 15.36 46.42 6.38 5.23 20.08 43.41
BTMAC:DEG K3PO4 35.94 17.95 46.16 9.67 4.76 34.22 48.13
K2HPO4 34.98 17.56 42.25 12.53 6.04 38.93 44.81
K2CO3 35.22 19.85 45.2 14.2 4.56 38.23 47.21
BTEAC:DEG K3PO4 35.65 14.65 48.37 6.17 8.09 27.85 45.74
K2HPO4 35.24 16.35 41.68 9.5 6.78 32.43 41.76
K2CO3 35.65 17.95 44.5 12.2 3.95 33.45 45.78
BTBAC:DEG K3PO4 35.22 13.45 46.6 4.56 3.64 22.85 46.69
K2HPO4 34.63 12.34 44.5 6.52 4.33 27.25 45.20
K2CO3 34.83 17.65 46.14 6.84 3.45 25.75 46.69
BTMAC:TEG K3PO4 35.05 12.55 45.55 6.12 8.55 28.13 43.05
K2HPO4 35.12 17.95 46.55 5.95 9.01 31.85 45.61
K2CO3 35.09 18.15 40.25 13.95 6.92 33.52 38.65
K3PO4 35.24 15.05 47.5 4.55 7.47 27.13 45.96
BTEAC:TEG K2HPO4 34.95 16.55 44.79 6.6 7.61 30.15 44.01
K2CO3 35.41 18.5 41.25 14.5 3.75 32.97 41.80
K3PO4 35.05 13.25 43.8 5.25 5.95 22.05 41.41
BTBAC:TEG K2HPO4 35.28 13.06 43.71 4.95 5.52 25.8 43.51
K2CO3 35.15 14.98 46.25 5.95 5.15 22.45 44.29

2.6. Separation of dyes from ABS phase constituents
The system used for the recovery study was composed of 35 wt%
BTBAC:TEG +20 wt% K3PO4 + 45 wt% aqueous solution of EY under
thermostatically controlled temperature (25◦ C). Following the success­
ful separation of dyes using ABS, additional experiments were carried
out to assess the recovery of both the dyes and the components forming
the phases. Recovering EY from the ABS phase post-separation was
achieved by adsorbing it onto starch-modified chitosan, an adsorbent
derived from crab shells using a known procedure [45]. The adsorption
experiments employed a solid-liquid ratio of 1:150 g/mL between chi­
tosan (g) and the DES phase (mL) of the ABS. To evaluate the impact of
agitation on the adsorption efficiency of EY, different parameters: at 60
h: constant stirring (at 300 rpm), vigorous stirring for 2 min (using a
vortex mixer), and no agitation were investigated. Furthermore, the
effect of the adsorbent dosage was investigated by varying the
solid-liquid ratios of 1:75, 1:100, 1:150 and 1:300 (at 300 rpm and
25◦ C). Additionally, three different temperatures (25, 35, 45 and 55 ◦ C)
were examined with a fixed solid-liquid ratio of 1:75 g/mL and constant
stirring at 300 rpm. All experiments were conducted in duplicate and
data analysis was based on the average experimental values.
The concentration of EY dye in the DES-rich phase was determined
with the help of a UV–Vis spectrophotometer at 517 nm absorption
wavelength. The dye recovery efficiency was estimated by Eq. (9) shown
below:
( )
Cw
R (%) = 1 − X 100% (9)
Cwo
where Cwo and Cw represent the concentrations of EY in the DES-rich
phase before and after the recovery process, respectively. The treated
DES phase was thereafter vacuum-dried for some time to remove water
from it. Karl Fischer Titrator (870 KF Titrino Plus) was used to quantify
the water content of the regenerated DES and it was observed not to be
significant.
3. Results and discussion
3.1. Binodal curve
The construction of binodal curves for the extraction of compounds
of interest is crucial in ABS. The binodal curve gives important details
about the amount of each component of ABS needed to form a biphasic
system. In this study, the data utilized to construct binodal curves were
obtained experimentally at 298.15 K and atmospheric pressure. The
compositions of the binodal curves composed of BTMAC: Glyco­
ls+K3PO4/K2HPO4/K2CO3, BTEAC:Glycols+K3PO4/K2HPO4/K2CO3 and
BTBAC: Glycols+K3PO4/K2HPO4/K2CO3 were investigated. The binodal
curves obtained for ABS based on BTAAC: EG, BTAAC: DEG, and BTAAC:
TEG DES are respectively shown in Fig. 2 (A-C), Fig. 3 (A-C) and Fig. 4
(A-C). We observed that the binodal curves of most of the DES-based
ABS began to converge as the inorganic salt concentration increased.
This implies that the phase behaviour, independent of the HBD, essen­
tially reflects that of the HBA at lower concentrations of DESs [46].
Although DES-based ABS were initially classified as ternary systems,
subsequent reports have shown that they are pseudo-ternary systems
because the disruption of hydrogen bonding destroys the integrity of the
DES [34,47]. The excess water present causes components of the DES to
preferentially solvate when it is isolated.
3.1.1. Influence of inorganic salts on phase behaviour
The influence of three potassium salts (K3PO4/K2HPO4/K2CO3) on
the phase behaviour of BTAAC- based-DESs ABSs was investigated. In
this study, the salts employed to form phase separation were noticed to
follow the sequence K3PO4 > K2HPO4 > K2CO3 in almost all the
examined systems. The obtained results show that ABSs constituted by
BTAAC: TEG demonstrated higher phase forming capacity with K3PO4
followed by K2HPO4 while K2CO3 displayed the least phase formation. In
other words, the phase-forming ability of the studied salts in BTMAC:
TEG followed the order: K3PO4 > K2HPO4 > K2CO3 (Fig. 4A). Similar
trend was observed for the other systems studied as illustrated in Fig. 2
(A-C), Fig. 3 (A-C) and Fig. 4 (B & C). Although merging of binodal
curves was noticed in some systems involving K2HPO4 and K2CO3. This
behaviour could be a result of the closeness in the phase-forming ca­
pacity of the concerned salts as evidenced from the Gibbs free energy of
hydration (ΔGhyd) and molar entropy of hydration (ΔShyd) values of
their respective anions. The Hofmeister series is a well-known scale used
to display the salting-out capacity of various salts and the obtained re­
sults followed the same order as given in this series [48]. The ΔGhyd and
ΔShyd of anions like PO3− 2− 2−
4 , HPO4 , and CO3 also play a crucial role in
the phase separation potential of salts. The salting-out potential of the

4
E.A. Oke and S.P. Ijardar
Fig. 2. Effect of salt on the phase behaviour of BTAAC:EG + salts based ABS at 298.15 K and atmospheric pressure (Δ) K3PO4; (O) K2HPO4; (◊) K2CO3.
anions of the salts investigated follows the trend: PO3− 4 (ΔGhyd
kJ⋅mol− 1and ΔShyd J⋅K− 1mol− 1 = − 2835/-421) > HPO2− 4 (ΔGhyd
kJ⋅mol− 1 and ΔShyd J⋅K− 1⋅mol− 1 = − 1125/-272) > CO2− 3 (ΔGhyd
kJ⋅mol− 1 and ΔShyd J⋅K− 1⋅mol− 1 = − 1300/-245). The results obtained
for the phase separation with potassium salts are in accordance with the
previous study that anion with greater values of ΔGhyd and ΔShyd gives
better complex formation and salting-out ability [49–51]. In addition,
the phase formation trend also suggested that salts containing anions
with greater valencies require more water molecules, thereby reducing
the quantity of water available to hydrate DES. Li et al. have noticed that
water molecules were preferred to combine with salt molecules over
DES during phase separation [52]. Therefore, the major driving force for
the phase formation in ABS is the salting out effect by the salts and an
anion of the inorganic salts plays a prominent role in the formation of
ABS. Hence highly charged inorganic salts with small ionic radii
effortlessly induce phase splitting.
3.1.2. Influence of DES HBA and HBD on phase behaviour
The affinity of DES for water molecules is due to their hydrophobic
5
Dyes and Pigments 224 (2024) 112047
nature that depends on HBA and HBD. In this section, the role of HBA of
DES on phase separation of ABS composed of BTAAC: DEG + potassium
salts is discussed and graphically shown in Fig. 5 (A-C). The phase-
forming ability of DESs investigated was observed to follow the HBA
order: BTBAC > BTEAC > BTMAC. As the alkyl chain length of the HBA
decreases, the phase separation capacity of the DES also decreases. i.e.
ABS composed of BTAAC:DEG + K3PO4 (Fig. 5C), DES containing
BTBAC showed higher phase separation potential compared to DES
consisting of BTEAC and BTMAC as HBA. The binodal curve of the
system involving BTBAC is closer to the origin than BTEAC or BTMAC. A
similar trend was observed for BTAAC: DEG + K2CO3 and BTAAC: DEG
+ K2HPO4 as shown in Fig. 5A and 5B, respectively. The phase separa­
tion ability of DES-based ABS relies strongly on the alkyl chain length of
the HBA of the DES. It can be summarised that the hydrophobic char­
acter of BTBAC-based DES is greater than BTEAC and BTMAC. A similar
trend has been reported earlier for the phase-forming order of tetrabu­
tylammonium bromide (TBAB):polyethylene glycol 200 (PEG 200) >
tetrabutylammonium chloride (TBAC):PEG 200 > tetraethylammonium
bromide (TEAB): PEG 200 ≈ tetraethylammonium chloride (TEAC):PEG
E.A. Oke and S.P. Ijardar
Fig. 3. Effect of salt on the phase behaviour of BTAAC: DEG + salts based ABS at 298.15 K and atmospheric pressure. (Δ) K3PO4; (O) K2HPO4; (◊) K2CO3.
200.
The comparison graph for the effect of HBD for common HBA;
BTMAC with all three studied salts (K3PO4/K2HPO4/K2CO3) have been
added in Fig. S3 (A-C). It can be observed that there is no clear sepa­
ration of binodal curve for HBD. The effect of TEG can be distinctly
observed while the EG and DEG are interchanging positions. For other
common HBA like BTEAC and BTBAC, similar results were obtained.
3.2. Extraction of anionic azo dyes
To determine the applicability of ABS involving BTAAC-based DES,
extraction of MO, EBT, and EY (anionic azo dye) was performed.
Considering the phase behaviour of the ABS discussed previously, the
dyes were extracted from an aqueous solution. A common ternary sys­
tem of 35 wt% DES +20 wt% salt +45 wt% aqueous dye solution within
the biphasic region was used for the extraction study at 298.15 K and
6
Dyes and Pigments 224 (2024) 112047
atmospheric pressure. This was done to make the comparison of the
experimental results easy and relatable.
3.2.1. Influence of potassium salts on the extraction of anionic azo dyes
As depicted in Fig. 6 (A-C), the % EEdyes decreases as the salting-out
ability of the potassium salts decreases i.e. K3PO4 > K2HPO4 > K2CO3.
This trend is in accordance with the salting-out effect of the salts
involved as previously discussed. For example, ABS composed of
BTMAC:DEG + K3PO4 resulted in higher extraction efficiency (90.44 ±
2.08%) whereas a system constituted by BTMAC:DEG + K2CO3 resulted
in a lower efficiency (85.82 ± 1.58%) for MO dye (Fig. 6A). Similar
sequence was observed in all the examined systems as presented in Fig. 6
(B & C) for EBT and EY dyes, respectively. The obtained results are
similar to the earlier reports that dealt with the extraction of various
compounds of interest involving ABS technology [53]. Interestingly,
ABS constituted by BTBAC: TEG + K2HPO4 and BTBAC: TEG + K3PO4
E.A. Oke and S.P. Ijardar
Fig. 4. Effect of salt on the phase behaviour of BTAAC:TEG + salts based ABS at 298.15 K and atmospheric pressure. (Δ) K3PO4; (O) K2HPO4; (◊) K2CO3.
demonstrated complete extraction (100%) as shown in Table 3. The
outstanding results displayed by these systems (i.e. BTBAC: TEG +
K2HPO4 and BTBAC: TEG + K3PO4) can be ascribed to their excellent
phase-splitting ability compared to other systems. The dyes investigated
in this study displayed a greater affinity for the hydrophobic phase
(DES-rich upper phase) rather than the hydrophilic phase (salt-rich
phase). This behaviour demonstrated by the three anionic azo dyes is
due to their inherent high hydrophobic character.
3.2.2. Influence of DES composition on the extraction of anionic azo dyes
To investigate the influence of DES composition on the extraction of
MO, EBT, and EY dyes, the effect of the alkyl chain length of HBA and
HBD was considered. For ABS composed of BTAAC + Glycols + K3PO4
(Fig. S4 (A-C)), BTMAC < BTEAC < BTBAC trend was observed for the
influence of HBA on %EEdyes in most studied ABS. This is in agreement
with the phase behaviour of the concerned systems discussed in section
7
Dyes and Pigments 224 (2024) 112047
3.1.2. i.e. ABS composed of BTMAC: EG + K3PO4 resulted in the least
extraction efficiency (86.40 ± 1.54%) and BTBAC:EG + K3PO4 system
with the highest extraction efficiency (97.82 ± 2.56%) for EBT dye
(Fig. S4 B). This can be attributed to the least hydrophobic character of
the former and the higher hydrophobic profile of the latter, thereby
making it highly interacted with the EBT via stronger intermolecular
hydrogen bonding. Hence, BTBAC: EG + K3PO4 system demonstrated
better extraction efficiency for the dye than BTMAC: EG + K3PO4 and
BTEAC:EG + K3PO4 systems. As the alkyl chain length of HBA of the DES
increases, its extraction performance increases as illustrated in Fig. S4
(A-C). To gain insights into the effect of HBD on %EEdye, BTAAC: Gly­
cols + K3PO4 ABS were considered for EY dye only. In this case, the
effect of HBD on the %EEdye follows the order EG < DEG < TEG (Fig. S5).
Previously, Fan et al. indicated that the hydrophobicity or non-polar
nature of chemical substances increases as the alkyl chain length in­
creases [54]. The extraction trend observed in this study follows the
E.A. Oke and S.P. Ijardar
Fig. 5. Effect of HBA on the phase behaviour of BTAAC:DEG + salts based ABS at 298.15 K and atmospheric pressure. (Δ) BTMAC; (◊) BTEAC; (O) BTBAC.
hydrophobicity of EG, DEG and TEG employed as HBD. As the alkyl
chain length of the HBD increases, the %EEdye also increases simulta­
neously. Similar to our observation, the desulphurization of thiophene,
benzothiophene, and dibenzothiophene was carried out by Lee et al.
They demonstrated that the removal rate of analytes increases by
increasing the alkyl chain length of HBA and HBD of the DES [55,56].
Also, an increase in the alkyl chain length of both HBA and HBD was
reported to increase the absorption of CO2 due to an increase in the free
volume mechanism of DES [57–59]. However, Fan et al. posited that an
increase in hydrophobicity does not have any significant effect on the
extraction rates of phenolic compounds. Contrarily, a report by Adeyemi
et al. found that the extraction efficiency of 2-chlorophenol and 3-chlor­
ophenol reduces as the alkyl chain length of HBA increases from hex­
anoic acid to octanoic acid [60]. However, the same author observed
8
Dyes and Pigments 224 (2024) 112047
that the extraction efficiency of 2,4-dichlorophenol remained the same
regardless of the alkyl chain length of the HBA involved. The contra­
dictory results observed by some researchers and ours can be attributed
to the higher viscosity of DES as the alkyl chain length of HBA and HBD
of DES increases which could affect the mass transfer of analytes into the
DES-rich phase.
3.2.3. Influence of the hydrophobicity of anionic azo dyes on extraction
efficiency
The hydrophobicity of chemical substances is usually measured by
the partition between octanol and water, commonly called the “loga­
rithm of the octanol-water partition coefficient (log Kow).” The log Kow
of MO, EBT, and EY dyes are − 0.66, 1.78, and 6.91, respectively, pre­
dicted by using EPI Suite ™ software [61]. As illustrated in Fig. S6, the %
E.A. Oke and S.P. Ijardar Dyes and Pigments 224 (2024) 112047

Fig. 6. Influence of potassium salts on %EEdyes of various DES-based ABS studied: (A) MO (B) EBT and (C) EY.

9
E.A. Oke and S.P. Ijardar Dyes and Pigments 224 (2024) 112047

Table 3 [64–68]. Building upon these successes, the current work adopts the
Extraction efficiencies of dyes (%EEdyes) in various systems investigated at method of adsorption using starch-modified chitosan to regenerate the
298.15 K and atmospheric pressure. BTBAC:TEG DES from dye solution.
ABSs MO EBT EY After a careful separation of ABS phases, the dye in the DES-rich
BTMAC:EG + K2CO3 81.27 ± 1.04 83.56 ± 1.40 86.82 ± 1.46
phase was recovered using starch-modified chitosan. The recovery of
BTMAC:EG + K2HPO4 83.08 ± 1.42 84.98 ± 1.65 89.10 ± 1.22 EY dye from the DES-rich phase was examined which can represent
BTMAC:EG + K3PO4 84.86 ± 1.36 86.40 ± 1.54 90.06 ± 2.06 other extraction of presently studied dyes. We examined various factors,
BTMAC:DEG + K2CO3 85.82 ± 1.58 88.96 ± 1.88 92.24 ± 1.98 including the stirring mode. This involved comparing experiments
BTMAC:DEG + K2HPO4 88.16 ± 1.84 91.44 ± 2.12 92.84 ± 2.22
conducted without agitation to minimize large-scale costs, as well as
BTMAC:DEG + K3PO4 90.44 ± 2.08 93.18 ± 2.24 94.98 ± 2.53
BTMAC:TEG + K2CO3 90.82 ± 2.51 93.06 ± 2.31 94.26 ± 2.36 agitation at 300 rpm and vigorous agitation using a vortex mixer. The
BTMAC:TEG + K2HPO4 91.28 ± 2.17 93.64 ± 2.50 93.98 ± 2.45 solid-liquid ratio (mass/volume) between the adsorbent (g) and the DES-
BTMAC:TEG + K3PO4 94.44 ± 2.65 96.18 ± 2.47 96.38 ± 2.22 rich phase (mL) of ABS and the maximum saturation of the adsorbent in
BTEAC:EG + K2CO3 86.86 ± 1.82 89.34 ± 2.01 90.86 ± 2.08 the phase containing the dye was studies considered. The effect of
BTEAC:EG + K2HPO4 87.28 ± 1.76 91.66 ± 2.24 92.64 ± 2.32
BTEAC:EG + K3PO4 90.90 ± 2.46 94.92 ± 2.58 96.18 ± 2.84
temperature variations ranging from 25 to 55 ◦ C is also studied. All the
BTEAC:DEG + K2CO3 91.48 ± 2.09 93.41 ± 2.41 95.82 ± 2.82 results of these experiments are presented in Fig. 7 (A-C).
BTEAC:DEG + K2HPO4 93.16 ± 2.20 95.82 ± 2.62 96.18 ± 2.76
BTEAC:DEG + K3PO4 95.11 ± 2.48 97.62 ± 2.51 97.98 ± 2.86 4.1. Effect of agitation
BTEAC:TEG + K2CO3 95.68 ± 2.46 96.18 ± 2.62 96.76 ± 2.59
BTEAC:TEG + K2HPO4 95.94 ± 2.80 97.46 ± 2.52 97.42 ± 2.82
BTEAC:TEG + K3PO4 97.60 ± 2.76 97.99 ± 2.94 98.88 ± 2.78 During the 60-h agitation period, the recovery of EY dye from the
BTBAC:EG + K2CO3 92.42 ± 2.02 94.36 ± 2.41 96.84 ± 2.64 DES-rich phase was more substantial (81.86%) when constant agitation
BTBAC:EG + K2HPO4 92.88 ± 1.96 96.44 ± 2.48 96.98 ± 2.61 at 300 rpm was employed, in comparison to 67.15% achieved with
BTBAC:EG + K3PO4 94.14 ± 2.66 97.82 ± 2.56 98.86 ± 2.92 vigorous stirring for 2 min, and 56.96% without any agitation, as
BTBAC:DEG + K2CO3 94.48 ± 2.49 98.41 ± 2.98 99.02 ± 1.22
BTBAC:DEG + K2HPO4 96.62 ± 2.86 98.86 ± 2.62 99.28 ± 2.96
depicted in Fig. 7 (A). The higher percentages of EY recovery during the
BTBAC:DEG + K3PO4 98.58 ± 2.48 99.72 ± 1.06 100.02 ± 0.06 agitation process can be attributed to the reduction in starch-chitosan
BTBAC:TEG + K2CO3 99.58 ± 0.86 100.02 ± 0.02 100.08 ± 0.11 boundary layer resistance and an increase in system mobility [69].
BTBAC:TEG + K2HPO4 100.11 ± 0.22 100.06 ± 0.13 100.14 ± 0.61
BTBAC:TEG + K3PO4 100.04 ± 0.06 100.09 ± 0.04 100.01 ± 0.02
4.2. Effect of solid-liquid ratio

EEdyes follows the sequence: MO < EBT < EY in most scenarios. The
extraction efficiencies of the system composed of BTEAC:EG + K3PO4
were 90.90 ± 2.46%, 94.92 ± 2.58%, and 96.18 ± 2.84% for MO, EBT,
and EY dyes, respectively (Table 3). The value of log Kow for MO is far
less than that of EBT and EY implying that MO is less hydrophobic. In
other words, a stronger hydrogen bond is formed between EBT and EY
compared to MO during the extraction process. This behaviour can be
ascribed to the fewer number of non-polar groups/aromatic groups in
the chemical structure of MO compared to EBT and EY (Fig. S1). Hence,
EBT and EY demonstrating a greater affinity for the DES-rich phase is
justifiable. In addition, the obtained results are in agreement with the
previous study. For example, the extraction order obtained for various
phenolic compounds using liquid-liquids extraction method based on ILs
was resorcinol < guaiacol ≈ phenol < p-nitrophenol ≈ o-cresol with log
Kow of 0.78, 1.37, 1.47, 1.78, and 1.95, respectively. The extraction of
dyes (methylene blue, methyl orange, and congo red) involving
DES-based ABS was also found to be directly related to the hydropho­
bicity of dyes [62].
4. Recovery of ABS phase constituents
In order to attain complete sustainability, it is imperative to establish
a circular process that enables the regeneration and reuse of ABS phase
constituents. One of the previous studies has demonstrated the suc­
cessful recovery of ABS phase components from the extraction phase
using chitosan [63]. Also, starch-modified chitosan has been used to
remove various contaminants such as dyes, metal ions, phthalates, and
heavy oils among others [31,47–49]. Chitosan, a biopolymer, stands as
the world’s second most abundant natural polymer. It is commonly
obtained from seafood waste, particularly the shells of crabs, krill,
prawns, and shrimp. Chitosan is highly regarded for its
cost-effectiveness, biocompatibility, non-toxic and remarkable biode­
gradability [50,51]. Also, starch, a readily available and cost-effective
biopolymer, is a polysaccharide that finds wide applications in water
purification and others. Its biodegradable and non-toxic properties have
led to the development of numerous starch-based composites for highly
effective removal of dyes, heavy metals and oil from wastewater
The solid-liquid ratio was observed to exert a significant influence on
the dye recovery. In all cases, regardless of the adsorbent mass to dye-
containing solution ratio, the adsorptive capacity of the starch-
modified chitosan increased as the solid-liquid ratio increased [Fig. 7
(B)]. Specifically, a solid-liquid ratio of 1:75 (m/v) resulted in the
highest dye recovery percentage of 92.66% after 60 h, whereas a solid-
liquid ratio of 1:30 led to a lower dye recovery percentage of 64.24%. In
other words, the observed dye recovery efficiencies follow the trend
1:75 (92.66%) > 1:100 (84.06%) > 1:150 (75.54%) > 1:300 (64.24%).
This sequence can primarily be attributed to the increase in the
adsorptive surface area and an increased abundance of active adsorption
sites of the starch-modified chitosan as the temperature increases [63,
70].
4.3. Effect of temperature
The role of temperature on the adsorptive recovery of dye was also
investigated and found to be noteworthy. An increase in temperature
from 25 ◦ C to 55 ◦ C amplifies the recovery of dye as illustrated in Fig. 7
(C). For example, the recovery of dye increased from 57.96% at 25 ◦ C to
81.02% at 55 ◦ C after 24 h with constant stirring of 300 rpm. The
behaviour noticed could be due to the enhancement of the surface area
of starch-modified chitosan as the temperature increases. the rise in
temperature leads to the generation of more active sites for the
adsorption of dye [53]. Additionally, the highest dye recovery of 97.26%
was obtained from the DES phase after 60 h at 55 ◦ C at the constant
stirring of 300 rpm, as shown in Fig. 7 (C). Therefore, starch-modified
chitosan could serve as an efficient adsorbent for the recovery of dye
from ABS phase constituents.
5. Conclusion
In this current study, BTAAC-based HBA and glycol-based HBD were
successfully utilized for the synthesis of DES. The synthesized DES were
employed to form ABS with three inorganic potassium salts at 298.15 K
and atmospheric pressure. The influence of salts and DES composition
on the phase equilibria of the constructed systems was investigated. The
effect of these factors on the phase behaviour of the ABS investigated

10
E.A. Oke and S.P. Ijardar
Fig. 7. Recovery (%) of EY dye from DES-rich phase onto starch-modified chitosan adsorbent: (A) effect of agitation, (B) effect of solid-liquid ratio, (C) effect of
temperature.
was found to be significant. Also, the developed systems were applied
for the extraction of anionic azo dyes MO, EBT, and EY. The influence of
salts, DES constituents, and hydrophobicity of dye on the extraction
efficiency of studied DES-based ABS were equally examined. It was
observed he salting-out ability of salts, the alkyl chain length of DES’s
components, and the hydrophobicity of dyes have a significant effect on
the extraction efficiency of the developed ABS. The systems constituted
11
Dyes and Pigments 224 (2024) 112047
by BTBAC: TEG + K2HPO4 and BTBAC:TEG + K3PO4 resulted in 100%
extraction of the three investigated dyes. Most of the DES-based ABS
employed in this study has great potential for extracting different dyes
regardless of their physicochemical properties and complex structures.
In addition, this study demonstrates the efficacy of starch-modified
chitosan as an efficient adsorbent for the recovery of dye from ABS
phase constituents. The findings contribute to the establishment of
E.A. Oke and S.P. Ijardar
circular processes, promoting sustainability in industrial applications by
tackling water pollution.
CRediT authorship contribution statement
Emmanuel A. Oke: Formal analysis, Investigation, Visualization,
Writing – original draft. Sushma P. Ijardar: Conceptualization, Data
curation, Methodology, Project administration, Supervision, Validation,
Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Shared in supporting information
Acknowledgement
Emmanuel A. Oke acknowledges the financial assistance of Africa
Scholarship-MEA under the scheme of the Indian Council for Cultural
Relations (2019–2020).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.dyepig.2024.112047.
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