Accepted Manuscript

Title: Experimental Study on the Adsorptive Behavior of

Congo Red in Cationic Surfactant-Modified Tea Waste

Author: Mohammad Foroughi-dahr Hossein Abolghasemi

Mohamad Esmaieli Ghadir Nazari Bettina Rasem

PII: S0957-5820(15)00053-1
DOI: http://dx.doi.org/doi:10.1016/j.psep.2015.03.005
Reference: PSEP 544

To appear in: Process Safety and Environment Protection

Received date: 4-12-2014

Revised date: 2-3-2015
Accepted date: 7-3-2015

Please cite this article as: Foroughi-dahr, M., Abolghasemi, H., Esmaieli, M., Nazari, G.,
Rasem, B.,Experimental Study on the Adsorptive Behavior of Congo Red in Cationic
Surfactant-Modified Tea Waste, Process Safety and Environment Protection (2015),
http://dx.doi.org/10.1016/j.psep.2015.03.005

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 Highlights

 We investigated several modifications for the adsorption of Congo red.

 Surfactant modification dramatically influences the adsorption behavior of

the adsorbent.

t
ip
 CTAB-modified tea waste shows superior adsorption capacity for the
adsorption of Congo red.

cr
 Adsorption mechanism includes - stacking, hydrophobic, van der Waals,
and electrostatic interactions.

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 Several characterization analyses confirm the surfactant impregnation of the
adsorbent.

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M
d
p te
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Page 1 of 48
 Experimental Study on the Adsorptive Behavior of Congo Red in

Cationic Surfactant-Modified Tea Waste

Mohammad Foroughi-dahr1, Hossein Abolghasemi1,2,*, Mohamad Esmaieli1, Ghadir Nazari1,

t
Bettina Rasem3,

ip
cr
1- Center for Separation Processes Modeling and Nano-Computations, School of Chemical

us
Engineering, College of Engineering, University of Tehran, P.O. Box 11365-4563, Tehran, Iran.
2- Oil and Gas Center of Excellence, University of Tehran, Tehran, Iran.

an
3- Chemical Engineering Department, Faculty of Process Engineering, Technical University of
Berlin, Berlin, Germany. M
Email addresses: mfd.foroughi@gmail.com; mfd.foroughi@ut.ac.ir (M.Foroughi-dahr),
d

abolghasemi.ha@gmail.com; hoab@ut.ac.ir (H.Abolghasemi), esmaili@ut.ac.ir (M.Esmieli),

ghadir_nazari@ut.ac.ir (G. Nazari), bettina.rasem@tu-berlin.de (B.Rasem)
te

*
Corresponding Author’s Contact: Hossein Abolghasemi (Associate Professor), Email:
p

abolghasemi.ha@gmail.com; hoab@ut.ac.ir, Fax: +98 21-66954051, Tel: +98 21-61112186

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Abstract

The adsorption of Congo red (CR), an anionic dye, from aqueous solution by a cationic

surfactant-modified tea waste (TW) was studied in batch experiments. Cetyl trimetyl ammonium

bromide (CTAB) and Cetyl pyridinium bromide (CPB) was used for the modification of TW and

ground TW. CTAB-modified TW exhibited the highest adsorption capacity with respect to the

Page 2 of 48
other prepared adsorbents. The adsorption of CR on CTAB-TW as a function of adsorbent

dosage, pH of the solution, contact time, and initial dye concentration was investigated. The

optimum amount of CTAB-TW was found to be 0.2 g. The equilibrium CR adsorption data on

CTAB-TW were best described by the Langmuir isotherm model. The adsorption capacity of CR

t
ip
on CTAB-TW was found to be 106.4 mg/g which is relatively high with respect to the other

adsorbents. The adsorption kinetics of CR on CTAB-TW followed a pseudo-second-order

cr
model. Moreover, the intraparticle diffusion model was used to describe the kinetic data. It was

us
found that diffusion is not the only rate controlling step. The adsorbent was characterized by the

Brunauer–Emmett–Teller (BET) analysis, Fourier-transform-infrared (FTIR) spectroscopy, and

scanning-electron-microscopy (SEM).

an
The mechanism for the adsorption of CR on the

surfactant modified TW may include hydrophobic interaction, van der Waals interaction, -
M
stacking and electrostatic interaction.
d

Keywords: Adsorption; Anionic dye; Surfactant; CTAB; CPB; Modified tea waste.
p te
ce

1. Introduction
Ac

Nowadays, wastewater effluents from different industries have become a major environmental

concern. Synthetic dyestuffs exist in fertilizer, pharmaceutical, leather tanning, petroleum

refinery, metal processing and dyeing related industries(Namasivayam et al., 2007) . Most of the

dyes cause damage either to the aquatic life or human beings because of its toxic, mutagenic, and

carcinogenic effects (Gong et al., 2005a). The dyes are stable to light and oxidation agents, and

are resistant to aerobic digestion, which makes them difficult to be treated (Chatterjee et al.,

2009d; Sun and Yang, 2003). Several methods including membrane separation, coagulation,
3

Page 3 of 48
anaerobic treatment, electrocoagulation, flotation, filtration, and ion exchange have been

developed for the removal of dyestuff from water effluents (Chatterjee et al., 2009b; Oei et al.,

2009). However, these methods suffer from some disadvantages which restrict the employment

of such methods in completely removing dye molecules from aqueous solutions. Adsorption

t
ip
technique has been found as a more competitive treatment process for the removal of dyes

(Salleh et al., 2011). However, the cost of the adsorbent, difficulties in the regeneration and

cr
disposal of the used adsorbent is a real challenge. Recently, considerable efforts have been

us
devoted to employing the natural and low-cost adsorbent such as tea waste (Nasuha and Hameed,

2011), orange peel (Namasivayam et al., 1996), peanut hull (Gong et al., 2005b), and beech

an
wood sawdust (Dulman and Cucu-Man, 2009). But the adsorption capacities of most of the

mentioned adsorbents are limited. Therefore, several modifications have been applied in order to
M
enhance the adsorption capacities of the adsorbents such as converting to activated carbon
d

(Arulkumar et al., 2011), acid modification (Nasuha and Hameed, 2011), and cross-linking
te

(Chiou et al., 2004). In the recent years, surfactant impregnation has been developed for

modification of several adsorbents including Chitosan (Chatterjee et al., 2009b), barley straw
p

(Oei et al., 2009), bentonite (Khenifi et al., 2009; Özcan et al., 2007), coir pith (Namasivayam
ce

and Sureshkumar, 2006; Namasivayam and Sureshkumar, 2007), Pillared clays (Wibulswas et
Ac

al., 1999), and sepiolite (Özcan and Özcan, 2005).

In our previous report, tea waste (TW) was used for the adsorption of Congo red (CR) from

aqueous solution (Foroughi-dahr et al., 2014). We found that TW could be considered as a

potential low-cost adsorbent for the removal of CR. In addition, applying a mechanical treatment

to the adsorbent, namely vibratory mill improved the adsorption capacity of TW, in which the

adsorption capacity increased from 32.26 to 43.46 mg CR g adsorbent . Our aim in this paper is

Page 4 of 48
to investigate the effect of impregnating of TW with surfactants, Cetyl trimethyl ammonium

bromide (CTAB) or Cetyl pyridinium bromide (CPB) for the removal of CR from aqueous

solution. It will be shown that the surfactant modified adsorbent has significantly higher

adsorption capacity. The effects of different parameters such as adsorbent dose, solution pH,

t
ip
contact time, and solution concentration will be studied on the adsorption of CR. Moreover,

several two- and three-parameters isotherm models will be used in order to predict the

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experimental isotherm data and the kinetic models is studied to describe the adsorption kinetics.

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an
2. Experimental

2.1. Materials
M
Congo red (CR) was purchased from Merck Company. The formula weight of CR is 696
d

and its chemical formula is C32H22N6Na2O6S2. The maximum wavelength (max) of CR is 495
te

nm. The molecular structure of CR is illustrated in Fig. 1. Organic surfactants used were Cetyl
p

trimethylammonium bromide (CTAB, formula weight: 364.45, and chemical formula:

ce

C19H42BrN) and cetylpyridinium bromide (CPB, formula weight: 384.44, and chemical

formula: C21H38BrN) were obtained from Sigma-Aldrich. The molecular structure of CPB and
Ac

CTAB are illustrated in Fig. 1. Other chemical reagents, such as NaOH, HCl, and KCl were of

analytical grade.

Figure 1

Page 5 of 48
2.2. Preparation of the adsorbent

The tea leaves used in this work were produced in tea plantations from the northern area of Iran.

Tea waste (TW) was collected and prior to the experiments, it was boiled with water several

t
times until the filtrated water was clear and completely colorless. TW was then washed with

ip
distillated water and was oven dried for 48h at 70 C . The sample was ground and sieved to

cr
obtain a particle size of 125  250 m and stored in an airtight container for further use.

us
In order to apply mechanical treatment, grinding experiments were carried out in batches of 10 g

each using a vibratory mill (ALBORZ company, Iran), which works through the cycles of 7 min

an
at 2000rpm . The milled TW was sifted through a 125m sieve to obtain the desired particle size

of the adsorbent. The mechanically treated adsorbent is named MTW .In our previous work, the
M
SEM and FTIR analysis and the adsorption experiments were used to observe the applicability of
d

the mentioned physical treatment on the adsorbent (Foroughi-dahr et al., 2014).

p te

2.3. Synthesis of the surfactant modified adsorbent

ce

The external cation exchange capacity (CEC) of TW and MTW was determined by Bower

method as 67 meq 100g of TW and 63 meq 100g of MTW (Sparks et al., 1996). It can be
Ac

seen that the value of CEC has decreased as a result of applying the mechanical treatment to the

adsorbent. Theoretically, CEC represents the maximum amount of organic cation that can be

exchanged onto the adsorbent surface(Khenifi et al., 2009).

The surfactant modified adsorbents were prepared by the following procedure: firstly, 10 g of

the adsorbent (TW or MTW) was dispersed in about 1000mL in distillate water. Afterwards, a

Page 6 of 48
desired amount of surfactants (CTAB or CPB) was slowly added. The amounts of each

surfactant were calculated based on the adsorbent CEC and it is considered to be at about 200%

CEC corresponding to each adsorbent for the sake of reaching the critical micelle concentration

(CMC) in order to form the surfactant micelles. The reaction mixtures were mechanically stirred

t
ip
at 40C for 48h . Next, the resulting surfactant modified adsorbent was filtrated and washed with

distillate water until no Br- was detected by AgNO3 solution. The products were dried at 70C

cr
for 12h . Finally, the adsorbent samples were activated at 120 C , for 1h . The adsorbent products

us
were ground in an agate mortar and stored in an airtight glass container and labeled.

2.4. Characterization of the modified adsorbents an

M
Several analyses have been applied in order to better characterize the interaction between the
d

surfactant and the adsorbent molecules and to elucidate the adsorption process of CR on the
te

adsorbent. The modifications of the TW adsorbent by the cationic surfactants were confirmed by

the Brunauer–Emmett–Teller (BET) method with N2 gas in a ChemBET 3000 Quantachrome

p

instrument. Fourier transform infrared (FTIR) spectra of the samples were recorded using an
ce

FTIR Spectrophotometer (BRUKER Tensor, 27, Germany) in the wavenumber range of

Ac

4000  400cm1 . The surface morphology of the samples was studied using Scanning electron

microscope (SEM) images which were taken by an Oxford MV 2300 microscope. The samples

were coated with gold before observation of SEM.

2.5. Determination of the point of zero charge

Page 7 of 48
The zero surface charge of the TW adsorbent in aqueous phase was analyzed using the solid

addition method (Somasekhara Reddy et al., 2012). For this purpose, 0.1M KNO3 solution was

applied and its pH was adjusted in the range of 2 12 by adding either 0.1N HCl or NaOH and

measured by a pH meter (Selecta Lab, PHW 100 Model, China). Next, 50mL of each was

t
ip
transferred into a series of conical flasks and then 0.2 g of the TW adsorbent was taken to each

cr
solution. The solutions were agitated for 48h and the final pH values of the solution were

us
measured.

2.6. Adsorption experiments

an
The adsorption of CR on surfactant modified TW adsorbent was studied using the batch
M
adsorption technique investigating different parameters including the type of the surfactant,

sorbent dosage, the pH of the solution, initial dye concentration, and contact time.
d

The adsorption experiments have been conducted using 50mL of dye solution of different CR
te

initial concentration ( 50  250 mg / L ). The solution was put to 100mL stoppered conical flasks
p

and the desired amount of the adsorbent was added. The flasks were shaken for 12h at a constant
ce

rate of 200rpm at 30 C using an orbital shaking incubator. The samples were withdrawn at

preset time intervals, and the adsorbent was separated from the dye solution by centrifugation at
Ac

6000rpm for 30min and the concentration of the supernatant was measured by a UV-vis

spectrophotometer (UNICAM, 8700 series, USA). The amount of sorption at time t , qt (mg/ g) ,

was calculated by:

(C0 - Ct )V (1)
qt =
W ,

Page 8 of 48
where C0 and Ct (mg L) represent the liquid-phase concentration of dye at initial time and any

time t , respectively. V (L) denotes the volume of the solution and W (g) denotes the mass of the

dry adsorbent used.

t
Similar to the kinetic experiments, the effect of the adsorbent dose was accomplished by taking

ip
different amounts of the adsorbent ( 0.05  0.8 g ) and it was stirred with 50mL of the 100mg L

cr
CR solution for 12h .

us
The effect of pH on the adsorption process was studied over a pH range of 3 13 which was

adjusted by a few drops of 0.1N HCL or NaOH. The prepared solution was agitated with the

desired amounts of the adsorbents.

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M
3. Results and discussions
d
te

3.1. The study of the point of zero charge

p

The point of zero charge ( pH PZC ) is an important property identifying the surface electrical
ce

neutrality of the adsorbent. In order to determine pH PZC , the deference between the final and

initial pH values ( pH  pH f  pHi ) was plotted versus the initial pH values ( pHi ). The
Ac

results are depicted in Fig. 2. The intersection of the curve with the x-axis is known as pH PZC at

which pH is zero. According to Fig. 2, pH PZC is 4.75 . Therefore, the surface charge of the

TW at about 4.75 is zero. It can be concluded that at the pH above the pH PZC value, the TW

surface is considered to have a predominantly negative charge, more likely for the impregnation

of the cationic surfactants.

Page 9 of 48
 Figure 2

t
3.2. Initial Considerations

ip
In order to determine the best adsorbent for the removal of CR, several adsorption experiments

cr
have been conducted by using 0.1g of six different prepared adsorbent. Each adsorbent was

us
added to 50mL of 100mg L CR dye at 30 C and the solution was agitated at the rate of

an
200rpm for 12h . The results are illustrated in Fig. 3. It can be seen that the surfactant modified

adsorbents have significantly higher capacity for the adsorption of CR compared to TW and
M
MTW. As a matter of fact, intercalation of the adsorbents by the surfactant cations has improved

the adsorption capacity of the adsorbents. This is consistent with the results of the other
d

researchers (Chatterjee et al., 2009a; Chatterjee et al., 2009c; Taffarel and Rubio, 2010; Xia et
te

al., 2011).
p

According to Fig. 3, the surfactant modified TW has slightly higher adsorption capacity with
ce

respect to the surfactant modified MTW which may be ascribed to the higher value of CEC for

TW. The CEC value is a characterization parameter which represents that the adsorbent with
Ac

higher amount of CEC is more likely to be able to exchange its cations with the cationic

surfactants (Sadeghi Pouya et al., 2015). We continue the rest of the experiments with CTAB-

TW because of its high adsorption capacity with respect to the other adsorbents.

10

Page 10 of 48
3.3. The Adsorption Mechanism

Technically, the adsorption of cationic surfactant onto the surface of adsorbent may follow two

approaches. The first approach: the surfactant molecules interact with TW through their non-

t
polar (alkyl) groups; hence the positive head of the surfactants points towards the bulk of the

ip
solution. The second approach (Chatterjee et al., 2009b): in this approach, the adsorption of the

cr
cationic surfactant onto the negatively charged surface of the adsorbent can be considered to be

controlled by two steps; (1) the formation of surfactant monolayer through the ion exchange and

us
electrostatic attraction and (2) the formation of surfactant bilayer via hydrophobic interactions

an
(S. K. Ghadiri and Nazmara, 2010; Seifi et al., 2011; Torabian et al., 2010). As a matter of fact,

firstly, the positive head of the surfactants are exchanged with the interlayer exchangeable
M
cations within the TW, thereby forming a surfactant monolayer with outward pointing head

groups. Secondly, the bilayer is organized by the attachment of the of surfactant alkyl chains to
d

the outer surface of the monolayer by means of the hydrophobic-hydrophobic interactions.

te

Therefore, the external surface of the modified adsorbent has become positive and accordingly,
p

more appropriate for the adsorption of the anionic adsorbates like the CR molecules.
ce

The first stage is more probable to occur at low surfactant concentrations (at about 100% CEC or

below) and the second stage takes place at higher concentrations hemimicelles or micelles (more
Ac

than 100% CEC) (Guan et al., 2010; Lin et al., 2011). In the present research, the amount of the

surfactant is provided at about 200% of CEC; hence it can be assured that the bilayer is formed.

Fig. 4 best schematizes the modification procedure of TW using cationic surfactant.

Owing to the different configurations of the CPB and CTAB surfactants on TW or MTW,

various interactions may be involved in the adsorption of the CR from aqueous solution. On the

one hand, the positive head of the surfactants covering the exterior surface of the adsorbent may

11

Page 11 of 48
be the main responsible for the increase of CR sorption in the case of organically modified

adsorbents. In fact, the electrostatic attraction between the anionic SO3- group of CR molecules

and positively charged adsorbent is the dominant phenomenon for the adsorption of CR. On the

other hand, as reported in the literature, the hydrophobic portion of the adsorbent surface has

t
ip
more preference for dissociated species of CR in aqueous solution. Furthermore, the van der

Waals interaction between the phenyl ring of CR and –CH2 group of the modified adsorbent can

cr
be considered as one of the driving forces through the adsorption process (Xia et al., 2011).

us
It should be pointed out that in the case of the CPB modified adsorbent, the phenyl ring of CR

can be bound to the pyridine ring of CPB molecules via the - stacking interaction. But then, it

an
can be questioned that why the CTAB modified adsorbent is superior to the CPB modified
M
adsorbent in the adsorption of CR if the latter adsorbent take advantage of the - stacking

interaction. This can be justified by the spatial hindrance arising from the pyridine ring around
d

the CPB head. The way in which CR molecules are adsorbed on the surfactant modified
te

adsorbent is briefly narrated in Fig. 4.

p
ce

Figure 3
Ac

Figure 4

3.4. The study of the adsorbent dosage on the sorption of CR

Fig.5 shows the effect of the adsorbent dose on the removal of CR from aqueous solution. It can

be seen that the adsorption of CR has rapidly increased with the increase of the adsorbent dose.

The optimum amount of the adsorbent is 0.7, 0.4, and 0.2 for TW, CPB-TW, and CTAB-TW,

12

Page 12 of 48
respectively, and after the optimum amount of each adsorbent, the increase of the adsorbent do

not effect on the removal of CR and the adsorption is nearly constant. The sharper adsorption

curve was observed in the case of the modified adsorbent with the cationic surfactants. It is

revealed that the implementation of the surfactant has an influential effect on the adsorption of

t
ip
CR and the optimum amount of the adsorbent has decreased.

cr
us
Figure 5

an
3.5. The study of the initial pH of the solution on the sorption of CR
M
The effect of different pH levels ranging from 3 to 13 has been studied for the removal of CR

from aqueous solution with simple TW adsorbent and its modified form, CPB-TW and CTAB-
d

TW. The results are shown in Fig. 6. The amount of the adsorbent was the optimum amount
te

obtained from the last section. Solution pH meaningfully affects CR structural stability and its
p

color intensity. Therefore, pH experiment is necessary to be studied. It was observed that the
ce

original red color of CR was nearly constant in the pH range of. However, the solution

noticeably changed its color from red to dark blue over the pH range of 3  5 and red color of
Ac

the solution with pH values higher than 10 was different from its original red color. It should be

noted that CR was slightly soluble in water below pH  2 . Hence, the experiment at this pH

range was not done since the results are not reliable (Foroughi-dahr et al., 2014; Xia et al., 2011).

Foroughi-dahr et al. mentioned that based on the reports of the research works of the effect of

13

Page 13 of 48
pH on the adsorption of CR, there is no unique conclusion and the results seem contradictory to

each other (Foroughi-dahr et al., 2014).

According to Fig. 6, the pH of the solution has highly influence on the adsorption of CR on

t
TW. Although, the adsorption of CR was nearly constant over the pH range of 4-10, the

ip
adsorption content extremely decreased at both the lower and higher pH values. In order to have

cr
more discussion on this subject, one can find in our previous paper (Foroughi-dahr et al., 2014).

It can be seen that the effect of solution pH on the adsorption of CR on CTAB-TW and CPB-TW

us
is weak and comparatively high adsorption capacity of CR on the surfactant modified adsorbents

an
can be attributed to the high electrostatic attraction between the anionic dye and the positive head

of the surfactant and/or the van der Waals interaction between the dye molecules and surfactants.
M
Figure 6
d
p te

3.6. The study of agitation time and concentration of dye on the adsorption
ce

The adsorption of CR on CTAB-TW as a function of contact time for different initial

concentration ( 50  250mg L ) is shown in Fig. 7. The adsorption rate dramatically increased in

Ac

the early stages of the adsorption; afterwards it gradually decreased with the progress of the

adsorption until reaching the equilibrium. The equilibrium time for the sorption of CR on CTAB-

TW was found to be 30 , 45 , 300 , 300 , and 480min for 50 , 100 , 150 , 200 , and 250 mg L of

dye, respectively. The amount of CR uptake ( mg g ) increased from 11.45 to 53.73 with the

14

Page 14 of 48
increase of dye concentration from 50 to 250 mg L which can be attributed to the fact that

increasing the initial dye concentration caused an increase in the adsorption driving force.

t
ip
Figure 7

cr
us
3.7. Adsorption Isotherms

an
The Adsorption isotherm is an important technique providing precious information to predict the

adsorbent efficiency for the removal of a specific adsorbate.

M
It is reported in several studies that non-linear analysis should be considered as a better approach
d

to obtain the isotherm parameters as sometimes linearization of non-linear experimental data

te

may distort the error distribution structure of isotherm (Ho, 2004; Kumar and Porkodi, 2006;

Kumar et al., 2008). Hence, the non-linear procedure was carried out for describing the
p

adsorption isotherms and predicting the overall sorption behavior for the removal of CR using
ce

CTAB-TW adsorbent. In this section two-parameter isotherm models (Freundlich and Langmuir)
Ac

and three-parameter isotherm models (sips and Redlich-Peterson) were examined to find out the

best fit for the experimental data.

The experimental adsorption isotherm of CR on TW and CTAB-TW are illustrated in Fig. 8. It

is apparent from Fig. 8 that CTAB-TW has higher adsorption capacity compared to TW for the

removal of CR from aqueous solution. It is important to be noted that the shape of the isotherm

can be used for the interpretation of the adsorption process. According to classification of Giles

15

Page 15 of 48
et al. (Giles et al., 1960), the adsorption isotherms are classified into four groups: L, S, H, and C.

According to the aforementioned classification, the adsorption of CR onto TW and CTAB-TW

followed the L curve pattern which indicates that there is no strong competition between solvent

and the adsorbate to occupy the adsorbent surface sites.

t
ip
Figure 8

cr
us
3.6.1. The Freundlich isotherm is an exponential equation and assumes that as the adsorbate

an
concentration increases, the concentration of adsorbate on the adsorbent surface also increases

(Freundlich, 1906; Oubagaranadin and Murthy, 2010). The Freundlich expression can be
M
represented as:

qe  K F Ce1/n , (2)
d
te

where K F ( mg 1(1 n ) L1 n g 1 ) is the Freundlich constant related to the bonding energy and n is a
p

constant indicative of the intensity of the adsorption. This model is applicable to the adsorption
ce

on heterogeneous surfaces assuming different binding energies for the adsorption sites

3.6.2. The Langmuir isotherm is one of the most frequently used isotherm model and assumes
Ac

uniform energies of adsorption (Hamdaoui and Naffrechoux, 2007; Langmuir, 1918). The

Langmuir equation can be written as:

qe 
qmbCe
, (3)
1  bCe

where qm ( mg g ) denotes the maximum adsorption capacity and b ( L mg ) is the constant

related to the free energy of adsorption.

16

Page 16 of 48
3.6.3. The Sips isotherm is the combined form of Langmuir and Freundlich models which

assumes the heterogeneous adsorption and circumvents the limitation of the rising adsorbate

concentration associated with Freundlich isotherm model (Foo and Hameed, 2010; Sips, 1948).

The Sips equation is as follows:

t
ip
qmS K S CemS (4)
qe  ,
1 KSC mS

cr
e

where qmS ( mg g ) indicates the Sips maximum adsorption, K S (  L mg  S ) is the Sips

m

us
equilibrium constant, and mS is the sips model exponent.

an
3.6.4. Redlich-Peterson isotherm is a hybrid isotherm featuring both Langmuir and Freundlich

isotherms, which incorporates three parameters into an empirical equation. This model can be
M
employed either in homogeneous or heterogeneous systems due to its versatility (Krishna Prasad
d

and Srivastava, 2009; Redlich and Peterson, 1959). The Redlich-Peterson equation is given as:
te

K R Ce (5)
qe  g ,
1  a R Ce
p
ce

where K R ( L / g ) and a R ( (L/ mg) g ) are the Redlich-Peterson isotherm constants and g is an

exponent which lies between 0 and 1.

Ac

The non-linear isotherm models have been analyzed with respect to O.L.S method by Eviews

software. The model parameters have been evaluated at 95% confidence interval. The isotherm

model parameters and the statistical results are presented in Table 1. The correlation coefficient

(R2), adjusted- R2, and the root-mean-square error (RMSE) have been applied to gauge the

fitness of the models.

17

Page 17 of 48
 Table 1

t
Figure 9

ip
cr
Fig. 9 represents the experimental data as well as the isotherm models for the adsorption of CR

us
on CTAB-TW. According to Table 1, all of the isotherm models properly describe the adsorption

of CR on the adsorbent; however, the amounts of the statistical parameters R2 and Adjusted-R2

an
related to the Langmuir model (R2=0.9997 and Adjusted- R2=0.9997) are greater than those of

the other isotherm models which are more close to the unity. Moreover, the Langmuir has the
M
lowest RMSE value (RMSE=0.413).
d

Table 2 lists some of the previous studies of the removal of CR on various adsorbents. It is
te

evident that the maximum adsorption capacity of surfactant modified adsorbent (CTAB-TW,
p

106.4 mg g ) was clearly higher than that of (TW, 23.26 mg g ). Moreover, it is observed that
ce

the CR adsorption capacity of CTAB-TW is relatively high with respect to the other adsorbents

reported in the literature which indicates that CTAB-TW is a promising adsorbent for the
Ac

removal of CR.

Table 2

3.8. Adsorption kinetics

18

Page 18 of 48
The modeling of the adsorption kinetics of the removal of CR on CTAB-TW was studied by the

two most common models, namely pseudo-first-order model and pseudo-second-order model.

The pseudo-first-order model is represented by the following equation:

 k  (6)

t
log  qe - qt  = log  qe  -  1  t ,

ip
 2.303 

cr
where k1 ( 1 min ) is the rate constant of pseudo-first-order adsorption. A linear plot of

log  qe - qt  versus t were used to determine the values of k1 and the equilibrium adsorption

us
capacity ( qe ). The model parameters used to evaluate the experimental data and the

an
corresponding correlation coefficient are presented in Table 3. A comparison between the

resulted correlation coefficients (Table 3) implies that the pseudo-first-order model cannot
M
provide a suitable description for the adsorption of CR on CTAB-TW adsorbent. Besides, the

calculated qe resulted from the pseudo-first-order model were obviously different from that of
d
te

the experimental values.

p

The pseudo-second-order model can be expressed as:

ce

t 1 t (7)
= 2
+ ,
qt k2qe qe
Ac

where k2 ( g mg.min ) relates to the constant of pseudo-second-order adsorption. The straight line plots

of t qt versus t permits the calculation of k2 and qe (Fig. 10). The results are shown in Table 3.

According to Fig. 10, the pseudo-second-order model was found to be most appropriate and accommodate

with the experimental results. It can also be observed from the correlation coefficient values from

Table 3 that R2 values were tending towards unity. In addition, the calculated qe values from

19

Page 19 of 48
the pseudo-second-order model fairly agree the experimental ones better than the pseudo-first-

order. All in all, this can be concluded that the adsorption of CR on CTAB-TW obeys the

pseudo-second-order kinetic model.

t
ip
Table 3

cr
us
Figure 10

3.9. Structural characteristics an

M
3.9.1. BET analysis of TW and surfactant modified TW
d

2 3
Table 4 showed the BET surface area ( m g ), total pore volume ( cm g ) and average pore
te

diameter ( nm ) of the adsorbent samples of TW, MTW, and CTAB-TW. The BET surface area
p

2
decreased from 4.6 to 2.87 m g during the modification of TW with CTAB which may be
ce

ascribed to the blocking and screening of TW pores by surfactant alkyl chains (Gładysz-Płaska et
Ac

al., 2012). It should be noted that, despite of our supposition, the average pore diameter slightly

increases from 4.7 to 5.5 nm which is presumably because of the complete elimination of micro

pores from the adsorbent structure (Gładysz-Płaska et al., 2012). It can be seen that the ground

TW has larger a surface area with respect to TW.

Table 4

20

Page 20 of 48
3.9.2. FTIR analysis of TW and surfactant modified TW

Fig. 11 shows the FTIR spectra of TW and CTAB-TW samples. It is observed that IR spectrums

t
of two samples are nearly the same which is due to the fact that the internal unit structure of TW

ip
framework is identical to that of the modified one (Mohamed, 2004). The absorption peaks at

cr
1
around 3417 cm refers to –OH stretching vibrations refers to the inter- and intra-molecular

us
hydrogen bonding of polymeric compounds such as alcohols, phenols and carboxylic acids, as in

pectin, cellulose and lignin, hence it reveals the presence of free hydroxyl groups on the

an
adsorbent surface (Nasuha and Hameed, 2011). This absorption band weakens and shifts to a

1 1
lower wave number 3414 cm for CTAB-TW. The bands at 2858 and 2924 cm are assigned
M
to the symmetric and asymmetric C-H stretching vibration of methylene groups and their

1 1
d

bending vibrations of TW at 1456 and 1388 cm move to 1450 and 1377 cm for CTAB-TW.
te

The intensity decrease of these bands manifests that the number of aliphatic C-H groups reduces

due to the replacement of the H+ cations by the surfactant cations (Özcan and Özcan, 2005). The
p

FTIR spectra of CTAB-TW before and after the adsorption are shown in Figs. 12. IR absorption
ce

bands and the corresponding possible functional groups are presented in Table 5.
Ac

Figure 11

Figure 12

21

Page 21 of 48
 Table 5

t
3.9.3. SEM analysis of TW and surfactant modified TW

ip
The scanning electron microscope (SEM) images of TW (a), CTAB-TW before adsorption (b),

cr
and CTAB-TW after adsorption (c) are shown in Fig. 13. The micropores can be observed in fig.

us
13(a). The surface morphology of CTAB-TW was different from that of TW. The introduction of

surfactant modification leads to a coverage of CTAB molecules on TW surfaces and as a result

an
large particles and several cavities can be observed which may be convenient for adsorbing of

the dye molecules. The high adsorption capacity of CTAB-TW can be attributed to this fact
M
(Wang and Wang, 2008).
d
te

Figure 13
p

Aknowledgment
ce

The hige
Ac

4. Conclusions

The equilibrium and dynamics of the adsorption of Congo red (CR) onto surfactant-modified

adsorbent was investigated in this paper. It was found that the surface zero charge of tea waste

(TW) is at about 4.74 and above that, the surface of the adsorbent is negative. Several adsorbents

such as TW, Ground TW, and CTAB and CPB modified of TW and Ground TW have been

22

Page 22 of 48
employed for the adsorption of CR from aqueous solutions. CTAB modified TW presented

remarkably the highest adsorption capacity with respect to the other prepared adsorbents. It was

observed that the CR adsorption capacity for TW increased with contact time and initial dye

concentration. The equilibrium data were found to be well described by the Langmuir model

t
ip
with the maximum adsorption capacity of 106.4 mg/g. The kinetic studies of the adsorption of

CR on TW indicated that the pseudo-second-order kinetic model agrees very well with the

cr
adsorption experimental data. The intraparticle kinetic model was used to study the whole

us
adsorption process. According to the intraparticle model, different mechanisms are involved in

the adsorption of CR on CTAB-TW in which intraparticle diffusion and/or external mass transfer

an
and/or boundary layer diffusion were concurrently operating during the CTAB-TW interaction.

Several characterization analyses, including BET, FTIR, and SEM confirmed the surfactant
M
modification of the adsorbent. The results revealed that CTAB modified TW could be applied as
d

low-cost material for the adsorption of CR dye from aqueous solutions.

te

Acknowledgment
p

The authors sincerely thank Professor S.H. Jafari, University of Tehran, Faculty of Chemical
ce

Engineering and Dr. M. Hosseinbakim, University of Tehran, Faculty of Chemistry whose

Ac

invaluable suggestions and constructive discussions have improved the quality of the initial draft

of this paper.

23

Page 23 of 48
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t
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ip
Chatterjee, S., Lee, D.S., Lee, M.W., Woo, S.H., 2009b. Enhanced adsorption of congo red from aqueous
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cr
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an
M
d
p te
ce
Ac

26

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 Captions for Figures

Figure 1. Molecular structure of CR, CTAB, and CPB.

t
Figure 2. The investigation of the point of zero charge of TW

ip
Figure 3. The effect of the adsorbent type on the removal of the CR

cr
Figure 4. (a) Surfactant monolayer formation on the adsorbent surface, (b) Surfactant bilayer

us
formation on the adsorbent surface, (c) Schematic representation of the interactions of CR molecules

with the surfactant modified adsorbent

an
Figure 5. The effect of the adsorbent dosage on the adsorption of CR on three different

adsorbent
M
Figure 6. The effect of pH on the adsorption of CR on three different adsorbent
d

Figure 7. The effect of contact time on CR adsorption onto CTAB-TW

te

Figure 8. Adsorption isotherms of CR onto TW and CTAB-TW

p

Figure 9. Isotherms models for the adsorption of CR onto CTAB-TW

ce

Figure 10. Pseudo-second-order model for adsorption of CR onto CTAB-TW

Figure 11. FTIR spectra of TW and CTAB-TW

Ac

Figure 12. FTIR spectra of CTAB-TW before and after the adsorption

Figure 13. SEM images of (a)TW, (b)CTAB-TW before adsorption, and (c) CTAB-TW after

adsorption

27

Page 27 of 48
 Captions for Tables

Table 1. The isotherm constants and coefficients and the statistical result for the adsorption of
CR on CTAB-TW
Table 2. The comparison of maximum CR adsorption capacities of various adsorbents

t
Table 3. Kinetic parameters of pseudo-first and pseudo-second order models for the adsorption

ip
of CR on TW

cr
Table 4. The BET surface area, total pore volume, and average pore diameter for TW, MTW,

us
and CTAB-TW.

Table 5. IR peaks of CTAB-TW before and after adsorption

an
M
d
p te
ce
Ac

28

Page 28 of 48
Table 1. The isotherm constants and coefficients and the statistical result for the adsorption of
CR on CTAB-TW
Model Model parameter R2 Adjisted-R2 RMSE

Freundlich K F  5.11 , n  1.498 0.9964 0.9955 1.354

t
Langmuir qm  106.4 , b  0.029 0.9997 0.9996 0.413

ip
Sips K S  0.029 , mS  0.983 , qmS  109.9 0.9997 0.9995 0.471

cr
Redlich- K R  3.174 , aR  0.036 , g  0.953 0.9257 0.8762 7.091
Peterson

us
an
M
d
p te
ce
Ac

29

Page 29 of 48
Table 2. The comparison of maximum CR adsorption capacities of various adsorbents

Adsorbent q m (mg g ) References

Chitosan/SDS beads 243.9 [24]
Chitosan beads 182.7 [24]

t
CTAB-Hectorite 182 [23]

ip
Treated sunflower stalk 155.2 [44]
CTAB-TW 106.4 present work
Groundnut shell carbon 110.8 [45]

cr
Bamboo dust carbon 101.9 [45]
Vibratory mill treated tea waste 43.48 [20]

us
Neem leaf 41.2-28.3 [46]
Cattail root 38.79 [47]
Tea waste 23.26 [20]
Myrtus communis 19.23 [48]

an
Banana peel 11.2 [49]
pomegranate 10 [48]
Kaoline (Ceram) 7.27 [50]
Cashew nut shell 5.18 [51]
M
Acid activated red mud 4.05 [52]
d
p te
ce
Ac

30

Page 30 of 48
Table 3. Kinetic parameters of pseudo-first and pseudo-second order models for the adsorption

of CR on TW

Initial qe ,exp Pseudo-first-order kinetic Pseudo-first-order kinetic model

t
ip
concentration (mg/ g) model

(mg/ L) k1 (1 min) qe ,cal R2 k 2 ( g mg.min) qe ,cal R2

cr
103 (mg/ g) 103 (mg/ g)

us
50 4.20 11.52 0.69 0.910 53.99 11.63 0.999

100 9.08 0.02 0.88 0.071 16.13 22.73 0.999

150 16.19 13.82 24.27

an
0.994 1.20 40.00 0.999
M
200 24.04 29.94 570.16 0.563 0.68 47.62 0.999

250 35.09 9.21 54.20 0.826 0.35 58.82 0.997

d
p te
ce
Ac

31

Page 31 of 48
Table 4. Intraparticle diffusion constants of the adsorption of CR on CTAB-TW for different

initial concentration

Initial First adsorption stage second adsorption stage third adsorption stage

t
ip
concentration kid,1 I1 R12 kid,2 I2 R22 kid,3 I3 R32
(mg.g 1. (mg.g 1. (mg.g 1.

cr
min1 2 ) min1 2 ) min1 2 )

us
50 0.237 9.626 1.0 0.0255 11.01 0.949 0.005 11.48 0.211

100 2.425 6.323 1.0 0.646 18.32 0.582 0.058 21.48 0.226

an
150 2.811 6.815 1.0 1.779 12.64 0.959 0.04 35.67 0.371

200 2.785 8.528 0.995 2.131 12.21 0.979 0.235 43.09 0.899

250 2.745 11.96 1.0 2.115 13.87 0.997 0.514 40.21 0.989
M
d
p te
ce
Ac

32

Page 32 of 48
Table 5. The BET surface area, total pore volume, and average pore diameter for TW, MTW,

and CTAB-TW.

Adsorbent Samples Surface area Total pore volume Average pore diameter

t
2
(m g )
3
( cm g ) (nm)

ip
TW[20] 4.60 0.0052 4.70

cr
MTW 26.68 0.0293 12.2

us
CTAB-TW 2.87 0.0182 5.5

an
M
d
p te
ce
Ac

33

Page 33 of 48
Table 6. IR peaks of CTAB-TW before and after adsorption

IR peak Frequency (cm-1)

Assignment
CTAB-TW CTAB-TW Differences

t
ip
Before adsorption After adsorption

cr
1 3314 3410 -4 Bonded –OH groups

2 2924 2926 +2 Aliphatic –C–H

us
group

3 2857 2857 0 Aliphatic –C–H

an
group

4 2358 2357 -1 -C=N stretching

M
5 1639 1650 +11 –C=O stretching

6 1527 1526 -1 Secondary amine

group
d

7 1450 1456 +6 Symmetric bending

te

of CH3
p

8 1377 1378 +1 Symmetric bending

of CH3
ce

9 1232 1243 +11 –SO3 stretching

10 1040 1054 +14 C=O stretching

Ac

34

Page 34 of 48
 Materials Molecular structure

Congo red (CR) C32H22N6Na2O6S2

t
ip
cr
us
an
Cetyl CH3(CH2)15N(CH3)3Br
-
trimethylammonium
Br CH3
M
bromide (CTAB) +
H 3C N
CH3
d

H 3C
Cetylpyridinium C21H38BrN
te

bromide (CPB)
p

+
H 3C - N
ce

Br
Ac

Fig. 1. Molecular structure of CR, CTAB, and CPB.

35

Page 35 of 48
 t
ip
cr
us
Fig.2. The investigation of the point of zero charge of TW

an
M
d
p te
ce
Ac

36

Page 36 of 48
 t
ip
cr
us
an
M
Fig. 3. The effect of the adsorbent type on the removal of the CR
d
p te
ce
Ac

37

Page 37 of 48
 t
ip
cr
us
an
M
d
p te

Fig.4. (a) Surfactant monolayer formation on the adsorbent surface, (b) Surfactant bilayer
ce

formation on the adsorbent surface, (c) Schematic representation of the interactions of CR molecules
with the surfactant modified adsorbent
Ac

38

Page 38 of 48
 t
ip
cr
us
an
Fig. 5. The effect of the adsorbent dosage on the adsorption of CR on three different adsorbent
M
d
p te
ce
Ac

39

Page 39 of 48
 t
ip
cr
us
an
Fig. 6. The effect of pH values on the adsorption of CR on three different adsorbent
M
d
p te
ce
Ac

40

Page 40 of 48
 t
ip
cr
us
an
Fig. 7. The effect of contact time on CR adsorption onto CTAB- TW
M
d
p te
ce
Ac

41

Page 41 of 48
 t
ip
cr
us
an
Fig. 8. Adsorption isotherms of CR onto TW and CTAB-TW
M
d
p te
ce
Ac

42

Page 42 of 48
 t
ip
cr
us
an
Fig. 9. Isotherms models for the adsorption of CR onto CTAB-TW
M
d
p te
ce
Ac

43

Page 43 of 48
 t
ip
cr
us
an
Fig. 10. Pseudo-second-order model for adsorption of CR onto CTAB-TW
M
d
p te
ce
Ac

44

Page 44 of 48
 t
ip
cr
us
an
Fig. 11. FTIR spectra of TW and CTAB-TW
M
d
pte
ce
Ac

45

Page 45 of 48
 t
ip
cr
us
an
Fig. 12. FTIR spectra of CTAB-TW before and after the adsorption
M
d
p te
ce
Ac

46

Page 46 of 48
 (a)

t
ip
cr
us
(b) an (c)
M
d
p te
ce
Ac

Fig. 13. SEM images of (a)TW, (b)CTAB-TW before adsorption, and (c) CTAB-TW after

adsorption

47

Page 47 of 48
Graphical Abstract (for review)

i
cr
us
an
M
ed
pt
ce
Ac

Page 48 of 48