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Indian Chemical Engineer

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Modelling of Binary Isotherm Behaviour for the


Adsorption of Catechol with Phenol and Resorcinol
onto Rice Husk Ash

Chandrakant Thakur, Vimal Chandra Srivastava, Indra Deo Mall & Ajay
Devidas Hiwarkar

To cite this article: Chandrakant Thakur, Vimal Chandra Srivastava, Indra Deo Mall & Ajay
Devidas Hiwarkar (2017): Modelling of Binary Isotherm Behaviour for the Adsorption of
Catechol with Phenol and Resorcinol onto Rice Husk Ash, Indian Chemical Engineer, DOI:
10.1080/00194506.2017.1281770

To link to this article: http://dx.doi.org/10.1080/00194506.2017.1281770

Published online: 01 Feb 2017.

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Download by: [University of Newcastle, Australia] Date: 20 February 2017, At: 10:09
INDIAN CHEMICAL ENGINEER © 2017 Indian Institute of Chemical Engineers
http://dx.doi.org/10.1080/00194506.2017.1281770

Modelling of Binary Isotherm Behaviour for the


Adsorption of Catechol with Phenol and Resorcinol
onto Rice Husk Ash

Chandrakant Thakura,b*, Vimal Chandra Srivastavab, Indra Deo Mallb,c and


Ajay Devidas Hiwarkarb,d
a
Department of Chemical Engineering, National Institute of Technology, Raipur, Chhattisgarh 492010,
QA: MSK Coll: MS

India
b
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand
247667, India
c
Department of Chemical Engineering, University of Petroleum and Energy Studies, Dehradun,
Uttarakhand 248007, India
d
Department of Chemical Engineering, Bundelkhand Institute of Engineering and Technology, Jhansi,
Uttar Pradesh 284128, India

Abstract: The present paper assesses the adsorption capability of rice husk ash (RHA) to adsorb catechol
(C) along with phenol (P) and resorcinol (R) individually and simultaneously from aqueous solution in
both single and binary solutions using batch experiments. Equilibrium isotherm data were collected at
30°C by carrying out experimental runs for 24 h contact time with pre-optimized RHA dosage of
20 mg/L and initial concentration variation of individual components in the range of 50–500 mg/L.
The equilibrium adsorption data for single component were fitted in three adsorption isotherm models,
namely the Langmuir, the Freundlich and the Redlich–Peterson. Equilibrium adsorption data of binary
aqueous solution of catechol–phenol, catechol–resorcinol and the parameter evaluated from single
adsorption isotherm were fitted in various multi-component adsorption isotherm models. Extended
Langmuir model which assumes overlapping of sites for different adsorbates better represented the
binary isotherm data for both catechol–phenol and catechol–resorcinol systems.

Keywords: Isotherm modelling, Phenolic compounds removal, Simultaneous adsorption, RHA.

*Author for Correspondence. Email: chandrakant.thakur@gmail.com


2 THAKUR ET AL .

Nomenclature
aij competition coefficients of component i by component j, dimensionless
aR constant of Redlich–Peterson isotherm, L/mg
Co initial concentration of adsorbate in solution, mg/L
Co,i initial concentration of each component in solution, mg/L
Ce unadsorbed concentration of the single component at equilibrium, mg/L
Ce,i unadsorbed concentration of each component in the ternary mixture at
equilibrium, mg/L
Ki individual extended Langmuir isotherm constant of each component, L/mg
KF mono-component (non-competitive) constant of Freundlich isotherm of the
single component (mg/g)(L/mg)−1/n
KF ,i individual Freundlich isotherm constant of each component (mg/g)(L/mg)−1/n
KL constant of Langmuir isotherm, L/mg
KL,i individual Langmuir isotherm constant of each component, L/mg
KR constant of Redlich–Peterson isotherm, L/g
m mass of adsorbent per litre of solution, mg/L
n mono-component (non-competitive) Freundlich heterogeneity factor of the
single component, dimensionless
ni individual Freundlich heterogeneity factor of each component, dimensionless
N number of data points
SSE Sum of Square of the Error
qe equilibrium single-component solid phase concentration, mg/g
qe,i equilibrium solid phase concentration of each component in ternary mixture, mg/g
qe,cal calculated value of solid phase concentration of adsorbate at equilibrium, mg/g
qe, exp experimental value of solid phase concentration of adsorbate at equilibrium, mg/g
qm maximum adsorption capacity of adsorbent, mg/g
qmax constant in extended Langmuir isotherm, mg/g
ai constant in SRS model for each component, dimensionless
b constant of Redlich–Peterson isotherm (0 < b < 1)
hi multi-component (competitive) Langmuir adsorption constant of
each component, dimensionless

1. Introduction
Phenol (P) and its derivatives such as catechol (C), resorcinol (R) are widely used as intermedi-
ate and basic products of various chemical industries. Phenol, catechol and resorcinol are
widely present in effluents generated from various industries such as paint, pesticide, coal con-
version, polymeric resin, petroleum refinery, petrochemical and textile [1]. These compounds
are considered to be toxic to aquatic organisms at 5–25 mg/L and impart taste and odour
above 2 μmg/L concentration [2]. United States environmental protection agency (USEPA)
has put phenol in priority pollutants list and proposed stringent limits on the discharge of
phenol [3]. According to usage of water, some of the agencies have recommended phenol con-
centration limit. For drinking water, Bureau of Indian Standards (BIS) recommends phenol
limit of 0.001 mg/L. For potable water, World Health Organization (WHO) recommends
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Modelling of Binary Isotherm Behaviour 3

0.001 mg/L maximum phenol, whereas for wastewater, EPA has put a permissible limit of
0.1 mg/L [4]. Considering the toxicity and maximum permissible limits set by various agencies
all over the world, it is necessary to remove phenolic impurities from wastewater prior to
discharge.
Various conventional treatment methods such as chemical and photo-oxidation, coagu-
lation, aerobic or anaerobic biodegradation, solvent extraction, liquid membrane permeation
and adsorption have been used previously for treatment of organic and phenolic compounds
containing wastewater [5–15]. Compared to all these methods, adsorption is the most attractive
because of its relative simplicity of design, operation and scale up, insensitivity to toxic sub-
stances, low cost and has gained a lot of popularity [1,16–19]. Many researchers have reported
that activated carbon is an efficient material for removal of organic compounds [8–10,20–22].
However, its high initial cost and the need for a costly regeneration system makes it less econ-
omically viable as an adsorbent. Taking these criteria into consideration, many investigators
have done research on more economical adsorbents such as those which can be obtained as
agricultural or industrial wastes/by-products.
India is an agriculture-based economy and huge quantities of agricultural wastes such as
rice husk, baggase are used as fuel in the boilers of various industries such as sugar, pulp
and paper mills. During the burning of these wastes, particles emitted are captured by air par-
ticulate devices. These fly ash particles, such as rice husk ash (RHA) and bagasse fly ash (BFA),
have been tested as an adsorbent by a number of researchers for single and multi-adsorbates
adsorption [23].
RHA has good porosity, high amount of silica and a number of functional groups on its
surface, which make it a good adsorbent. Besides its availability in abundance, make it
highly economical as the only cost involved is the transportation cost from the place of gener-
ation to its place of use as an adsorbent [24]. Consequently, various researchers have used RHA
for adsorptive removal of various types of adsorbates such as metal ions, dyes and organics [25–
29]. Only few studies are reported in the open literature for the multi-component adsorption of
phenolic compounds on various types of adsorbents. Since, actual effluents generated in indus-
tries such as petroleum refineries contain several phenolic compounds; therefore, equilibrium
adsorption data for closely related binary compounds is of utmost importance for the design
of adsorption systems.
The present research work aims to examine individual and simultaneous adsorption behav-
iour of catechol onto RHA from its binary solutions with phenol and resorcinol various multi-
component isotherm models.

2. Materials and Methods


2.1. Adsorbent and Adsorbate
RHA obtained from a nearby paper mill (Rana paper mill, Muzaffarnagar, India) was used as
such without any pretreatment. Textural characterization of RHA was done using Micromeri-
tics ASAP 2020 apparatus. Surface functional groups of the samples were determined using
Fourier transform infra-red (FTIR) instrument Thermo Nicolet, Model Magna 760.
Analytical (AR) grade phenol (C6H6O) and catechol (C6H6O2) were procured from s.d.
Fine Chemicals, Mumbai, India, and resorcinol (C6H6O2) was procured from E. Merck,
INDIAN CHEMICAL ENGINEER 2017
4 THAKUR ET AL .

Table 1. Characteristics of adsorbates

Adsorbate Phenol Catechol Resorcinol Reference

Formula C6H6O C6H6O2 C6H6O2 [52,53]


Molar mass (g/mol) 94.11 110.1 110.1
Density (g/cm3) 1.07 1.344 1.28
Solubility in water (g/100 ml, 20°C) 8.3 43 110
λmax (nm) 270 275 273
Dipole 1.7 D 2.62 D 2.07 D
Chemical structure

Mumbai, India. Various properties of these adsorbates have been listed in Table 1 for compari-
son. The experimental solutions were prepared by diluting the respective stock solution of
phenol, catechol and resorcinol with double distilled water (DDW) and mixing them in the
desired proportion. The concentrations of all the three components were varied between 50
and 1000 mg/L.

2.2. Batch Adsorption Equilibrium Study


Batch adsorption experiments were carried out to generate the adsorption equilibrium isotherm
data. Each experiment was conducted on 250 mL flask contain 150 mL aqueous solution of
known concentration and 3 g of RHA. Thus, adsorbent dose was kept constant at 20 g/L.
Initial concentration for single compound (phenol, catechol and resorcinol) and binary
mixture of resorcinol–catechol and catechol–phenol of the solutions ranged from 50 to
500 mg/L. Initial concentration of compounds was kept in the range of 50–500 mg/L for
single-component adsorption study. For binary study, individual concentrations were made
in the range of 100–1000 mg/L, which upon mixing in equal volume, became in the range of
50–500 mg/L for binary study. The flask was kept in a constant temperature orbital shaker
(CIS-24 BL, Remi Instrument, Mumbai) at 150 rpm for 24 h to ensure that the adsorption
process reach equilibrium. Residue solution concentrations of single and binary component
system were analysed.

2.3. Analysis of Phenol, Catechol and Resorcinol


The initial and final concentration of single component (phenol, catechol and resorcinol) and
binary components (catechol–phenol and resorcinol–catechol) were determined using high per-
formance liquid chromatography (HPLC) purchased from Waters (India) Pvt. Ltd., Bangalore
at a wavelength of 270, 275 and 273 nm, respectively, for single component and 260 nm for
binary component system. The solvent was prepared by mixing methanol, acetic acid and dis-
tilled water in the ratio 4:0.1:5.9, which were used as a mobile phase in a symmetry C18 column
having size (4.6 mm × 150 mm). Flow rate of solvent in the column was 5 × 10−4 L/min.
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Modelling of Binary Isotherm Behaviour 5

The compound was identified by its peak retention time of the components. The calibration
curve between peak areas of HPLC reading versus concentration prepared for both single
and binary components with a correlation coefficient (R2 ) equal to 0.99.
The total amount of adsorbate adsorbed per g of RHA (qe,i ); individual adsorption yield
(Adi %) and total adsorption yields (AdTot %) were calculated using the following expressions
(Equations (1)–(3)):

(Co,i − Ce,i )V
qe,i = , (1)
w

100(Co,i − Ce,i )
Adi % = , (2)
Co,i

100 (C − Ce,i )
AdTot % =  o,i , (3)
Co,i

where qe is the amount of adsorbent (mg/g); Co and Ce are the initial and equilibrium concen-
trations of adsorbate, i, in liquid phase (mg/L), respectively; V is the volume of the adsorbate
containing solution and w is the mass of the adsorbent (g).

2.4. Adsorption Equilibrium


The single and binary equilibrium of adsorption of phenol, catechol and resorcinol onto RHA
was determined at 30°C in batch mode. The competitive adsorption equilibrium of two binary
mixtures (catechol–phenol and catechol–resorcinol) with different concentrations were studied
to determine the effect of the phenol and resorcinol on the adsorption of catechol onto
RHA. Many researchers have reported several isotherm models for single component, of
which the most commonly used models are Langmuir model, Freundlich model and
Redlich–Peterson (R–P) model. The best isotherm model was selected on the basis of corre-
lation coefficient (R2 ), and sum of the squares of the errors (SSE) function. The SSE error func-
tion is given as


n
SSE = (qe,i, exp − qe,i,cal )2 . (4)
i=1

In this equation, the subscripts “exp” and “calc” show the experimental and calculated
values, and n indicates the number of measurements. The constants of single-component iso-
therm were further used in the multi-component adsorption model. Many multi-component
isotherm models such as non-modified Langmuir model, modified Langmuir model, extended
Freundlich model were used to analyse the multi-component adsorption behaviour. Single and
multi-component isotherm models used in the present isotherm modelling are listed in the
Table 2.

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6 THAKUR ET AL .

Table 2. Mono- and multi-component isotherm models

Mono-component isotherms models Reference

Freundlich qe = KF Ce1/n [41]


q m KL Ce
Langmuir qe = [40]
1 + KL Ce
KR Ce
R–P qe = [42]
1 + aR Ceb
Multi-component isotherm models
qm,i KL,i Ce,i
Non-modified Langmuir qe,i =  [44]
1 + Nj=1 KL,j Ce,j
qm,i KL,i (Ce,i /hL,i )
Modified Langmuir qe,i = N [44]
1+ j=1 KL,j (Ce,j /hL,j )

qmax KEL,i Ce,i


Extended Langmuir qe,i = N [45]
1+ j=1 KEL,j Ce,j
(1/ni )+xi
KF,i Ce,i
Extended Freundlich qe,i = [50]
Ce,i + yi Ce,j
x1 z1

 (1/ni )−1
N
SRS qe,i = KF,i Ce,i j=1 aij Ce,j [46]
KR,i Ce,i
Non-modified R–P qe,i = N b,j
[47]
1 + j=1 aR,j Ce,j
KR,i (Ce,i /hR,i )
Modified R–P qe,i = N b,j
[47]
1+ j=1 aR,j (Ce,j /hR,j )

3. Results and Discussion


3.1. Characterization of the Adsorbent
Average particle size of RHA used in this study was 150 µm. Bulk density and the heating
values were 109.9 kg/m3 and 9.88 MJ/kg, respectively. The Brunauer–Emmett–Teller (BET)
surface area was 47.19 m2/g, and single point adsorption total pore volume of pores was
0.033 cm3/g. Average pore width was 28.2 Å, whereas Barrett–Joyner–Halenda (BJH)
average pore diameter was 38.7 Å.
The FTIR spectra analysis of blank RHA and individually loaded phenol catechol as well
as resorcinol on RHA have been studied in the range of 400–4000 cm−1 wave numbers (Fig. 1)
so as to understand the change of functional group after loading of phenol, catechol and resor-
cinol onto RHA. The analysis shows peaks in the region 3320–3600 cm−1 in blank RHA. The
bands for the hydroxyl group are due to –OH deformation vibrations and –OH stretching fre-
quencies, which suggested the presence of alcoholic or phenolic components [30]. This peak is
also due to the presence of amine group (–NH), which generally show peaks in the range of
3300–3500 cm−1. The peaks at 2815 cm−1 in blank RHA may be due to the –CH stretching

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Modelling of Binary Isotherm Behaviour 7

Fig. 1. Equilibrium adsorption isotherms for the individual adsorption of phenol, catechol and resorci-
nol onto RHA. Experimental data represented by points and R–P isotherm fitting represented by lines.

of phenolic rings or due to the symmetric CH3 stretch of the methoxyl group. These peaks get
shifted to higher wave numbers in 2830, 2834 and 2854 cm−1 in phenol-, resorcinol- and cate-
chol-loaded RHA. Blank RHA shows peaks at 1355 and 1593 cm−1. These peaks may be due
to OH deformation and stretch of C = C aromatic rings or due to NH bending, respectively
[30,31]. The band at 1355 cm−1could also be due to both OH in-plane bending and CH

Fig. 2. FTIR analysis of raw RHA, phenol-, catechol- and resorcinol-loaded RHA.

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8 THAKUR ET AL .

Table 3. Individual adsorption equilibrium uptakes and yields of phenol, catechol and resorcinol
adsorption at different initial concentrations onto RHA

Co Ce qe Ad%
(mmol/L) (mmol/L) (mmol/g) –

Phenol
0.266 0.212 0.003 20.250
2.597 1.421 0.059 45.294
5.173 3.254 0.096 37.112
7.830 5.300 0.127 32.316
10.480 6.774 0.185 35.361
13.510 9.083 0.221 32.773
Catechol
0.229 0.162 0.003 29.434
0.865 0.368 0.025 57.450
2.141 0.906 0.062 57.677
6.747 3.767 0.149 44.167
8.952 4.757 0.210 46.860
13.525 7.430 0.305 45.068
Resorcinol
0.239 0.169 0.004 29.454
0.465 0.238 0.011 48.718
1.164 0.519 0.032 55.448
2.553 1.270 0.064 50.262
5.225 2.960 0.113 43.346
6.687 4.093 0.130 38.795
8.958 5.092 0.193 43.156
13.510 7.947 0.278 41.176

bending [32]. The strong band observed around 1091 cm−1 may be assigned to C–O stretching.
In the adsorbate-loaded RHA spectra, not only the intensity of these bands increases but also
shift in peaks is observed indicating utilization of these groups for adsorption purpose [33]. Two
different types of electron donor–acceptor interactions may occur on the RHA surface. RHA
surface has both carbonyl and amine groups, which are electron donors. These may interact
with aromatic ring (electron acceptors) of the phenolic adsorbates [34,35]. It may be seen
that the adsorbate-loaded RHA has a much sharper peak in the range of 3200–3400 cm−1
when compared to blank RHA, which has a broader peak (3320–3600 cm−1). Thus, amine
group seems to be more helpful in the adsorption of phenolic adsorbates.

3.2. Individual Adsorption of Phenol, Catechol and Resorcinol


The equilibrium uptakes and the adsorption yields obtained for single-component phenol, cate-
chol and resorcinol solutions are shown in Table 3 and Fig. 2. Fig. 2 illustrates that an increase
in the initial concentration of phenol, catechol and resorcinol increased the equilibrium uptake.
Generally, the amount of adsorbate adsorbed per unit mass of adsorbent (q) increases, and
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Modelling of Binary Isotherm Behaviour 9

adsorption removal efficiency (Ad%) decreases with an increase in the initial concentration. At
higher concentrations, the driving force required to overcome the resistance to the mass transfer
of adsorbate between the solution and the solid phases becomes greater, and thus the equili-
brium uptake increases. For higher initial concentration, the trend was similar in the present
study for all the adsorbates (phenol, catechol and resorcinol) adsorption onto RHA. At high
initial concentrations, adsorbate molecules already adsorbed resist adsorption of new mol-
ecules and the Ad% decreases. However, at lower initial concentration, Ad% increased with
an increase in initial concentration (up to a certain value) because of the higher driving force
and very small presence of adsorbate on the adsorbent.
It may also be seen in Fig. 2 that the adsorption capacity of RHA for catechol is greater
than that of resorcinol and phenol. Adsorption process is mainly influenced by solubility,
polarity, position of the hydroxyl group and interactive force between the adsorbate in the
aqueous phase and the RHA [7,25,26,28]. Solubility of resorcinol is much higher than catechol
[9]. This may be the reason for lower adsorption capacity of resorcinol compared to that of cate-
chol. In addition, the polarity of adsorbates influences the adsorption of phenolic derivatives.
The dipole moment of catechol (2.620 D) is much larger than that of resorcinol (2.071 D) and
phenol (1.22 D), respectively [36]. Therefore, the interaction between the RHA with catechol is
expected to be much stronger than that of resorcinol and phenol. Suresh et al. [9] found that the
ortho-position greatly enhances the adsorption energy of compound such as catechol. Thus

Table 4. Isotherm parameter fitted on isotherm model for the removal of phenol, catechol and resorcinol
by RHA

Adsorbate Langmuir R2 SSE


0.85 × 0.038Ce,P
Phenol qe,P = 0.980 0.0006
1 + 0.038Ce,P
2.22 × 0.0212Ce,C
Catechol qe,C = 0.990 0.0007
1 + 0.0212Ce,C
0.81 × 0.056Ce,R
Resorcinol qe,R = 0.972 0.0008
1 + 0.056Ce,R
Adsorbate Freundlich R2 SSE
Phenol qe,P = 0.036Ce,P
0.819
0.983 0.0005
Catechol qe,C = 0.052Ce,C
0.88
0.991 0.0006
Resorcinol qe,R = 0.046Ce,R
0.841
0.975 0.0007
Adsorbate R–P R2 SSE
1.08Ce,P
Phenol qe,P = 0.983 0.0005
1 + 28.72Ce,P
0.186

3.32Ce,C
Catechol qe,C = 0.991 0.0006
1 + 63.34Ce,C
0.121

2.87Ce,R
Resorcinol qe,R = 0.975 0.0007
1 + 61.86Ce,R
0.161

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10 THAKUR ET AL .

cumulative effects of solubility, polarity and position of the hydroxyl group probably increased
the absorbability of catechol when compared to resorcinol and phenol onto RHA [37].
Substitution of functional groups on benzene ring provides different inductive and reson-
ance effects [38]. π-donating strength of the host aromatic ring is known to be enhanced by the
substitution of hydroxyl group, which is an electron-donating functional group. This increases
the adsorption affinity of the phenolic compounds to the RHA [39]. FTIR analysis shows that
the interaction between RHA and adsorbates, and between phenol catechol and resorcinol
happens with the help of aromatic ring (electron acceptor) and –OH groups. Since π–π disper-
sive interactions become stronger with an increase in the number of hydroxyl groups [8,9],
therefore, the adsorption of phenol is less than the catechol and resorcinol onto RHA.

3.2.1. Single-component Adsorption Isotherm


The Langmuir, Freundlich and R–P isotherms are widely used for single-component adsorp-
tion data analysis. Equilibrium adsorption data for single-component aqueous solutions con-
taining phenol, catechol and resorcinol were fitted to these three isotherm models. Results
are shown in Table 4 along with the regression coefficients (R2 ) and SSE values. The single-
component Langmuir constant, qm , is the monolayer saturation at equilibrium [40]. The
values of qm in Table 4 indicate that the amount of catechol adsorbed per unit mass of RHA
for the complete monolayer surface coverage was little higher than that of phenol and resorci-
nol. A large value of constant KL , which is related to adsorbate affinity for the RHA, indicates
strong bonding of catechol to RHA. The value of constant n in Freundlich isotherm [41] indi-
cates affinity to RHA. It also indicates the heterogeneity of the adsorbent sites. RHA shows
greater heterogeneity for catechol than that for phenol and resorcinol (Table 4). The magnitude
of KF also showed the higher uptake of catechol than that of resorcinol and phenol by RHA.
R–P [42] isotherm is an empirical model which combines elements from both the Langmuir and
Freundlich equations, and the mechanism of adsorption is a hybrid and does not follow ideal
monolayer adsorption. For favourable adsorption, the R–P constant b normally lies between 0
and 1.
It may be seen in Table 4 that the SSE values are lower for R–P or Freundlich isotherm than
that for Langmuir. The R2 values are higher for R–P or Freundlich isotherm fitting, indicating
better representation of isotherm data by R–P or Freundlich isotherms. However, the difference
in SSE or R2 values for any of the isotherms is marginal and isotherm can be represented by any
of the R–P, Freundlich or Langmuir isotherms. Allen et al. [43] mentioned that Freundlich and
Langmuir equation show good fit for moderate concentration range data with two constants;
however, wide concentration range cannot be fitted with a two constants. R–P equation con-
tains three parameters and it well represents that wide concentration range data.

3.3. Multi-component Adsorption Models


Binary adsorption isotherm data for catechol–phenol and catechol–resorcinol systems onto
RHA were collected by taking four solutions of each adsorbate having different initial concen-
trations. Thus, a total of 16 experiments were performed for both catechol–phenol and cate-
chol–resorcinol systems. These initial concentrations along with equilibrium adsorption
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Modelling of Binary Isotherm Behaviour 11

Table 5. Comparison of individual and total adsorption equilibrium uptakes and yields found at different
catechol (C) concentrations in the absence and presence of increasing concentrations of phenol (P)

Co,C Co,P Ce,C Ce,P qe,C qe,P AdC % AdP % AdTot %


(mmol/L) (mmol/L) (mmol/L) (mmol/L) (mmol/g) (mmol/g) – – –

0.496 0.459 0.140 0.179 0.018 0.014 71.810 60.940 66.590


0.552 1.019 0.157 0.495 0.020 0.026 71.640 51.410 58.520
0.454 2.511 0.119 1.171 0.017 0.067 73.800 53.340 56.470
0.508 5.470 0.143 2.318 0.018 0.158 71.750 57.620 58.820
0.916 0.586 0.359 0.229 0.028 0.018 60.840 60.920 60.870
0.860 1.042 0.286 0.525 0.029 0.026 66.770 49.590 57.360
0.908 2.589 0.327 1.333 0.029 0.063 64.040 48.530 52.560
0.871 4.949 0.286 2.505 0.029 0.122 67.150 49.390 52.040
2.237 0.572 1.082 0.200 0.058 0.019 51.620 64.990 54.340
2.082 1.021 0.935 0.470 0.057 0.028 55.090 53.970 54.720
2.061 2.490 0.984 1.322 0.054 0.058 52.250 46.900 49.320
2.191 5.232 1.055 2.385 0.057 0.142 51.830 54.420 53.650
3.919 0.555 2.145 0.243 0.089 0.016 45.270 56.130 46.610
4.257 1.082 2.260 0.682 0.100 0.020 46.910 37.000 44.900
4.563 2.822 2.286 1.476 0.114 0.067 49.900 47.700 49.060
4.171 5.067 2.208 2.362 0.098 0.135 47.060 53.380 50.530

Table 6. Comparison of individual and total adsorption equilibrium uptakes and yields found at different
catechol (C) concentrations in the absence and presence of increasing concentrations of resorcinol (R)

Co,C Co,R Ce,C Ce,R qe,C qe,R AdC % AdR % AdTot %


(mmol/L) (mmol/L) (mmol/L) (mmol/L) (mmol/g) (mmol/g) – – –
0.511 0.470 0.147 0.120 0.018 0.018 71.280 74.500 72.820
0.486 0.963 0.126 0.438 0.018 0.026 74.000 54.500 61.040
0.537 2.244 0.154 0.892 0.019 0.068 71.430 60.240 62.400
0.506 4.505 0.144 2.250 0.018 0.113 71.560 50.060 52.230
0.896 0.482 0.273 0.179 0.031 0.015 69.580 62.760 67.190
0.962 0.922 0.342 0.419 0.031 0.025 64.410 54.570 59.590
0.917 2.253 0.309 0.909 0.030 0.067 66.280 59.650 61.570
0.921 4.477 0.363 2.069 0.028 0.120 60.570 53.790 54.950
2.275 0.476 1.119 0.166 0.058 0.015 50.810 65.090 53.280
2.228 0.927 0.939 0.438 0.064 0.024 57.870 52.710 56.350
2.259 2.336 0.943 0.883 0.066 0.073 58.260 62.180 60.260
2.272 4.462 0.981 1.948 0.065 0.126 56.820 56.350 56.510
4.473 0.408 2.410 0.122 0.103 0.014 46.120 70.040 48.120
4.501 0.892 2.341 0.390 0.108 0.025 47.980 56.270 49.350
4.508 2.331 2.175 0.906 0.117 0.071 51.750 61.130 54.950
4.481 4.479 2.519 2.190 0.098 0.114 43.780 51.100 47.440

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12 THAKUR ET AL .

values for catechol–phenol and catechol–resorcinol systems are summarized in Tables 5 and 6,
respectively.
It may be seen that the equilibrium uptake of catechol decreases with an increase in phenol
and resorcinol concentration and vice versa. For instance, at 2.14 ± 0.01 mmol/L initial cate-
chol concentration, in the absence of phenol and resorcinol concentration, adsorbed catechol
quantities at equilibrium are found to be 0.062 (Table 3). However, in the presence of
5.232 mmol/L phenol, adsorbed catechol quantities at equilibrium are found to be
0.057 mmol/g (Table 5). Similarly, in the presence of 4.462 mmol/L of resorcinol, adsorbed
catechol quantities at equilibrium are found to be 0.065 mmol/g (Table 6). Thus, the combined
effect of catechol–phenol and catechol–resorcinol on the total sorption is antagonistic.
During individual adsorption, the adsorption capacity of RHA for catechol is greater than
that of resorcinol and phenol. Therefore, it is expected that the adsorption removal efficiency
(AdC%) of catechol will be higher than the Adtol% in the binary adsorption. However, at
some experimental points (Tables 5 and 6), Adtol% > AdC%. It may be noted that at some of
these points, the difference is marginal and within experimental error. Significant difference
is observed only for those experimental runs in which the initial concentration of catechol is
high and that the initial concentration of other adsorbate is low. At higher initial concentration,
significant amount of catechol adsorption takes place in short time due to higher driving force;
however, adsorbed catechol molecules repel more adsorption of catechol and AdC% decreases.
For the other adsorbate, since its initial concentration is lower, its Ad% is higher and it overall
increases the Adtol%.
The binary adsorption data of catechol–phenol and catechol–resorcinol aqueous solution
onto RHA have been fitted to the various multi-component isotherm models using SSE error
function. The multi-component non-modified R–P model (Equations (5) and (6)) showed poor
fit to catechol–phenol and catechol–resorcinol experimental data.

3.321Ce,C
qe,C = ; qe,P
1 + (63.336Ce,C
0.121
+ 28.722Ce,P
0.186
)
1.080Ce,P
= , SSE = 0.0682, (5)
1 + (63.336Ce,C
0.121
+ 28.722Ce,P
0.186
)

3.321Ce,C
qe,C = ; qe,R
1 + (63.34Ce,C
0.121
+ 61.86Ce,R
0.161
)
2.87Ce,R
= , SSE = 0.048, (6)
1 + (63.34Ce,C
0.121
+ 61.86Ce,R
0.161
)

To improve the accuracy of non-modified R–P model, Bellot and Condoret [44] incorpor-
ated an interaction term, hRP,i , in the competitive non-modified R–P model to formulate the
modified competitive R–P model. All the modified R–P coefficients (hRP,i ) estimated were
found to be slightly less than 1.0, indicating that the use of hRP,i increased the fitting in modified

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Modelling of Binary Isotherm Behaviour 13

R–P model (Equations (7) and (8)).

3.321(Ce,C /0.67)
qe,C = ; qe,P
1 + (63.336(Ce,C /0.67)0.121 + 28.722(Ce,P /0.163)0.186 )
1.08(Ce,P /0.163)
= , SSE = 0.0040, (7)
1 + (63.336(Ce,C /0.675)0.121 + 28.722(Ce,P /0.163)0.186 )

3.321(Ce,C /0.49)
qe,C = ; qe,R
1 + (63.34(Ce,C /0.49)0.121 + 61.86(Ce,R /0.323)0.161 )
2.871(Ce,R /0.323)
= , SSE = 0.0051. (8)
1 + (63.34(Ce,C /0.49)0.121 + 61.86(Ce,R /0.323)0.161 )

Similarly, use of interaction terms for Langmuir model (hL,i ) in the modified Langmuir
model (Equations (11) and (12)) significantly improved the fit of the non-modified Langmuir
model (Equations (9) and (10)) as shown by decrease in SSE values:

2.22 × 0.021Ce,C 0.85 × 0.04Ce,P


qe,C = ; qe,P = , SSE = 0.0251, (9)
1 + (0.04Ce,P + 0.021Ce,C ) 1 + (0.04Ce,P + 0.021Ce,C )

2.224 × 0.0212Ce,C
qe,C = ; qe,R
1 + (0.056Ce,R + 0.0212Ce,C )
0.805 × 0.056Ce,R
= , SSE = 0.0135, (10)
1 + (0.0212Ce,C + 0.056Ce,R )

2.23 × 0.021(Ce,R /0.51)


qe,C = ; qe,P
1 + (0.021(Ce,C /0.51) + 0.04(Ce,P /0.87))
0.85 × 0.04(Ce,P /0.87)
= , SSE = 0.0047, (11)
1 + (0.021(Ce,C /0.51) + 0.04(Ce,P /0.87))

2.224 × 0.0212(Ce,C /0.861)


qe,C = ; qe,R
1 + (0.0212(Ce,C /0.861) + 0.056(Ce,R /0.64))
0.81 × 0.056(Ce,R /0.64)
= , SSE = 0.0044. (12)
1 + (0.056(Ce,R /0.64) + 0.0212(Ce,C /0.861))

Extended Langmuir multi-component isotherm model assumes the surface sites to be


uniform. It also assumes that all the adsorbate molecules in the solution compete for the
same surface sites [45]. The use of the extended Langmuir model on binary system of cate-
chol–phenol and catechol–resorcinol (Equations (13) and (14)) improved the fit of the binary

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14 THAKUR ET AL .

adsorption data over non-modified and modified competitive Langmuir model.

2.96 × 0.017Ce,C 2.96 × 0.02Ce,P


qe,C = ; qe,P = , SSE = 0.0041, (13)
1 + (0.017Ce,C + 0.02Ce,P ) 1 + (0.017Ce,C + 0.02Ce,P )

0.51 × 0.137Ce,C
qe,C = ; qe,R
1 + (0.137Ce,C + 0.167Ce,R )
0.51 × 0.167Ce,R
= , SSE = 0.0039. (14)
1 + (0.137Ce,C + 0.167Ce,R )

Constant Ki in the extended Langmuir model reflects the affinity between RHA and the
adsorbates in the binary system. The value of Ki for catechol–phenol was found to be 0.017
and 0.02 L/mmol and for catechol–resorcinol was found to be 0.137 and 0.1667 L/mmol,
respectively. The overall total adsorbate uptake (qmax ) for catechol–phenol and catechol–resor-
cinol by RHA was found to be 2.96 and 0.51 mmol/g respectively, which is much lower than the
sum of the maximum total capacities of catechol–phenol (2.22+0.85 = 3.07 mmol/g) and cate-
chol–resorcinol (2.22+0.81 = 3.03 mmol/g) resulting from the single-component adsorption.
Thus, it seems that catechol and resorcinol compete more when compared to catechol and
phenol for same adsorption sites present on RHA.
Sheindorf–Rebhum–Sheintuch (SRS) model is applicable to those systems where each
component individually obeys the single-component Freundlich isotherm and that the
adsorption energies of sites are exponentially distributed [46]. The adsorption competition
coefficient (aij ) describes the inhibition to the adsorption of component i by component j.
For systems which are represented by the SRS model, product of the competition coefficients
aij and a ji is close to unity [25,47–49]. The binary adsorption of catechol–phenol and catechol–
resorcinol onto RHA can be represented by following form of SRS equations (Equations (15)
and (16)):

qe,C = 0.052Ce,C (0.001Ce,P + Ce,C )(0.88−1) ; qe,P


= 0.036Ce,P (Ce,P + 0.001Ce,C )(0.82−1) , SSE = 0.0205, (15)

qe,C = 0.052Ce,C (Ce,C + 0.001Ce,R )(0.88−1) ; qe,R


= 0.046Ce,R (0.001Ce,C + Ce,R )(0.841−1) , SSE = 0.010. (16)

For the simultaneous adsorption of catechol and phenol onto RHA, product of aPR and
aRP was found to be much less than 1; therefore, SRS model was not able to satisfactorily rep-
resent the binary sorption data for the catechol and phenol. Results are similar for catechol–
resorcinol system.
Fritz and Schlunder [50] gave an extended Freundlich isotherm for binary mixtures of phe-
nolic substitutes on activated carbon. Extended Freundlich isotherm gives better fit for systems
with significant non-ideal effects and heterogeneous surfaces [51]. Since RHA surface is hetero-
geneous and Freundlich model represented the mono-component isotherm data, therefore,

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Modelling of Binary Isotherm Behaviour 15

Fig. 3. Comparison of the experimental and calculated qe values for catechol and phenol adsorption
from a binary mixture of catechol and phenol.

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16 THAKUR ET AL .

Fig. 4. Comparison of the experimental and calculated qe values for catechol and resorcinol adsorption
from a binary mixture of catechol and resorcinol.

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Modelling of Binary Isotherm Behaviour 17

Fig. 5. Binary adsorption isotherms of simultaneous catechol and phenol adsorption onto RHA. The
surfaces are predicted by the extended Langmuir model and the symbols are experimental data: (a) cate-
chol uptake and (b) phenol uptake.

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18 THAKUR ET AL .

Fig. 6. Binary adsorption isotherms of simultaneous catechol and resorcinol adsorption onto RHA. The
surfaces are predicted by the extended Langmuir model and the symbols are experimental data: (a) cate-
chol uptake and (b) resorcinol uptake.

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Modelling of Binary Isotherm Behaviour 19

Table 7. Comparison of surface area of low-cost adsorbents and their capacity for the adsorption of
phenolic compounds

Surface Area Adsorption Capacity


Adsorbent (m2/g) Adsorbate (mg/g) Reference

SD 3.0 Phenol 5.24 [54]


SDC 4.39 Phenol 7.13 [54]
CFA 69 Phenol 11.39 [55]
Jordanian Zeolitic 49 Phenol 34.5 [56]
Tuff
HDTMA-Mt 27.8 4-chlorophenol 29.96 [57]
RHA 50.14 Phenol 83.3 [58]
RHA 65.36 α-picoline 29.8 [59]
RHA 92.08 2,4-dichlorophenoxy 7.07 [60]
acetic acid
RHA 47.19 Phenol 80 Present
Study
RHA 47.19 Catechol 244 Present
Study
RHA 47.19 Resorcinol 89 Present
Study

Notes: SD: saw dust; SDC: saw dust carbon; CFA: coal fly ash; HDTMA-Mt: hexadecyl trimethyl ammonium bromide,
montmorillonite; RHA: rice husk ash.

extended Freundlich model also gave satisfactory fit to the binary experimental equilibrium
data (Equations (17) and (18)).

0.89 0.82
0.052Ce,C 0.036Ce,P
qe,C = ; qe,P = , SSE = 0.0797, (17)
0.01
Ce,C + 14.985Ce,P465.22 0.001
Ce,P + 1.55Ce,C
1.55

10.671 77.474
0.0517Ce,C 0.0457Ce,R
qe,C = ; qe,R = , SSE = 0.034. (18)
9.791
Ce,C + 0.001Ce,R 0.2040 76.634
Ce,R + 11.669Ce,C
205.117

The comparisons of the experimental and calculated qe values of catechol–phenol and cate-
chol–resorcinol in mixtures are also presented by the parity plots in Figs. 3 and 4, respectively.
To determine the best fit model for both binary adsorption system SSE values of different iso-
therm models were compared. Extended Langmuir model (SSE = 0.0041 and SSE = 0.0039)
showed best-fits for the experimental adsorption data of catechol–phenol and catechol–resor-
cinol, respectively, for binary systems onto RHA. It seems that component of both binary
compete for the same adsorption sites on RHA. Thus, extended Langmuir model which
assumes overlapping of sites for different adsorbates better represents the isotherm data.
Figs. 5 and 6 show a 3D diagram plotted on the basis of smooth surface generated from the

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20 THAKUR ET AL .

multi-component extended Langmuir model. The experimental data are shown by points on
the same surface. The fit of the surface to the experimental data points is satisfactory.
Table 7 compares the adsorption capacity for removal of phenolic compounds and surface
area of some low-cost adsorbents. It may be seen that the adsorption capacity and surface area
differ widely in their values for different adsorbents. RHA used in the present study shows good
adsorption for phenol, resorcinol and catechol.

4. Conclusion
The equilibrium adsorption of phenolic compounds was studied for single components and for
binary component catechol–phenol and catechol–resorcinol systems onto low-cost adsorbent
RHA. Adsorption equilibrium data were obtained by batch mode experiment performed at
30°C. Various isotherm models were used to interpret the adsorption data of the investigated
single and binary systems. Langmuir, Freundlich and R–P isotherm models shows quite
similar results, of which R–P was found to be marginally better isotherm model for the
single-component adsorption. Extended Langmuir model showed better fit for binary com-
ponent adsorption for catechol–phenol and catechol–resorcinol systems among various
multi-component isotherm models. RHA showed higher adsorption capacity for catechol
when compared to resorcinol and phenol. The binary adsorption equilibrium data showed
competitive adsorption behaviour.

Disclosure statement
No potential conflict of interest was reported by the authors.

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