Journal of Molecular Liquids 285 (2019) 375–385

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Journal of Molecular Liquids

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

Enhanced adsorption performance of Reactive Red 120 azo dye from

aqueous solution using quaternary amine modified orange peel powder
Venkata Subbaiah Munagapati a, Jet-Chau Wen a,b,⁎, Chih-Long Pan c, Yuvaraja Gutha d, Jyh-Horng Wen e
a
Research Centre for Soil & Water Resources and Natural Disaster Prevention (SWAN), National Yunlin University of Science & Technology, 123, Section 3, University Road, Douliou, Yunlin 640,
Taiwan, ROC
b
Department and Graduate School of Safety and Environment Engineering, National Yunlin University of Science & Technology, 123, Section 3, University Road, Douliou, Yunlin 640, Taiwan, ROC
c
Bachelor Program in Interdisciplinary Studies, College of Future, National Yunlin University of Science & Technology, 123, Section 3, University Road, Douliou, Yunlin 640, Taiwan, ROC
d
School of Civil Engineering, Guangzhou University, Guangzhou 510006, PR China
e
Department of Electrical Engineering, Tunghai University, 1727, Section 4, Taiwan Boulevard, Xitun District, Taichung 407, Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: Orange peel powder was chemically modified to enhance quaternary amine type content on the surface of adsor-
Received 5 February 2019 bent which was named as quaternary amine modified orange peel powder (QAMOPP). The effecting parameters
Received in revised form 15 April 2019 on adsorption of Reactive Red (RR) 120 such as pH (2.0–9.0), contact time (0–300 min), adsorbent dosage
Accepted 15 April 2019
(0.01–0.07 g/30 mL), initial RR120 concentration (100–1000 mg/L) and temperature (298–338 K) were studied.
Available online 18 April 2019
The QAMOPP was extensively characterized for its surface chemical bonding, morphological structure, and spe-
Keywords:
cific surface area, total pore volume and average pore diameter by employing FTIR, SEM and BET analysis. The ex-
Adsorption perimental adsorption kinetic data followed the pseudo-second-order kinetic model equation with a regression
Reactive Red 120 coefficient of N0.9941 for all studied temperatures. The activation energy (Ea) is calculated to be 12.1 kJ/mol by
Isotherms using the Arrhenius equation. Adsorption isotherms of RR120 on QAMOPP were correlated with two- and
Kinetics three-parameter non-linearized isotherm equations viz. Langmuir, Freundlich, Dubinin-Radushkevich (D-R),
Thermodynamics Temkin, Sips, Toth, Khan and Redlich-Peterson (R-P). It was observed that the Langmuir (R2 = 0.9996) and
Temperature Khan (R2 = 0.9991) were the best fit isotherm models to predict RR120 adsorption onto QAMOPP. pH study re-
vealed that the adsorption capacity decreased with an increase in pH of the solution. Optimum adsorption of
RR120 onto QAMOPP was observed at pH 2.0 (344.8 mg/g). The adsorption performance of QAMOPP increased
with contact time until 110 min, when it became nearly constant. The negative values (−1.9114 to
−5.9208 kJ/mol) of ΔGo, the positive values (0.102 kJ/mol K and 28.4 kJ/mol) of ΔSo and ΔHo parameters indicate
that the adsorption of RR120 onto QAMOPP was spontaneous, feasible and endothermic, respectively. Desorption
experimental studies showed optimum RR120 recovery (92%) when 0.1 M NaOH was used as an eluent.
Hence to remove RR120 from aqueous media QAMOPP can be considered as a powerful alternative adsorbent
material.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction as plastic carpet weaving, food processing, dyeing, leather tanning,

pulp, paper, textile, cosmetics, pharmaceutical, etc. consist dyes as
Among the several wastewaters from agricultural, domestic and common pollutants [1]. Mainly dyes are divided into three main
industrial resources enters into the environment in different sea- groups; anionic, non-ionic and cationic dyes. Reactive azo dyes
sons throughout the year, comprising a huge concentration of pol- are commonly used in textile industries. During the textile dyeing
lutant chemicals such as heavy metals, dyes, insecticides, cyanide process, the estimated loss is about 10–60%, which was highest re-
and hydrocarbon solvents. The effluents of many industries such sponsible for the large quantities of dye wastewater into the envi-
ronment. Reactive azo dyes are, the most problematic than the
other type of dyes hence their removal from wastewater is must
⁎ Corresponding author at: Research Centre for Soil & Water Resources and Natural
Disaster Prevention (SWAN), National Yunlin University of Science & Technology, 123,
and extremely important. The higher concentrations of them lead
Section 3, University Road, Douliou, Yunlin 640, Taiwan, ROC. to skin irritation, dermatitis, carcinogenicity, mutagenicity and
E-mail address: [email protected] (J.-C. Wen). also toxic to aquatic life [2–4].

https://doi.org/10.1016/j.molliq.2019.04.081
0167-7322/© 2019 Elsevier B.V. All rights reserved.
376 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385

Current treatment technologies like membrane filtration [5], (100–1000 mg/L) and temperature (298–338 K) have been investi-
electrochemical destruction [6], photochemical degradation [7], gated and optimized. In addition to this, the adsorption equilibrium
ion exchange [8], oxidation [9], coagulation [10,11] and adsorption data were evaluated using the two- and three-parameter non-
[12] have been employed in treating effluents containing dyes. linearized isotherm models. Kinetics and thermodynamics of the ad-
Among all these techniques, adsorption is generally the most feasi- sorption at different temperatures (298–338 K) were also studied.
ble and adaptable technique due to its relatively low initial cost, Desorption experiment studies were conducted to identify the re-
lower waste production, simple operation design, reusability, covery of RR120 and the QAMOPP for reuse.
easy operation, a broad range of adsorbents availability and excel-
lent quality of the treated substances, particularly in well-designed 2. Materials and methods
adsorption processes. Materials locally available in large quantities
such as industrial byproducts or agricultural wastes, natural mate- 2.1. Chemicals and equipment
rials can be utilized as low-cost adsorbent materials. Various low-
cost adsorbents such as tea waste [13], cucumber peel [14], wood In the present study, all reagents used were of analytical reagent (AR)
apple shell [15], rice bran [16], walnut and poplar woods [17], ba- grade and were used as without further purification. The pH of the solu-
nana peel powder [18], dried prickly peal cactus (Opuntia ficus tions was determined by using digital pH meter (Elico, LI-129).
indica) cladodes [19], breadnut peel [20], barberry stem [21], bottle Standard buffer (4.0, 7.0 and 10.0) solutions are used to calibrate
ground peel [22], jackfruit peel [23], mosambi (Citrus limetta) peel the pH meter. The RR120 concentrations were analyzed by UV–
[24] sugarcane bagasse [25] and cashew nut shell [26,27] were visible spectrophotometer (JASCO, V-750, Japan) at a maximum
successfully used in treatment of dyes as well as metal ions from wavelength of 515 nm.
aqueous media.
Orange peels, which are abundant, cheap and widely available 2.2. Adsorbate
biomaterials that are discarded in fresh fruit stalls/juice shops,
could be used as an appropriated economic adsorbent for the re- Reactive Red (RR) 120 [Dye content ≥50%; Molecular weight:
moval of many different pollutants like dyes and heavy metal 1469.98; Linear formula: C 44 H 24 Cl 2 N 14 O 20 S 6 Na 6 ; λ max : 515 nm]
ions from aqueous solutions [28]. It in general consists of cellu- was purchased from Sigma-Aldrich (India). The molecular struc-
lose, lignin, pectin (galacturonic acid), hemicelluloses and chloro- ture of RR120 is presented in Fig. 1. To prepare RR120 stock solu-
phyll pigments. These components have different functional tion (1000 mg/L) a desired amount of RR120 was dissolved in
groups for example amide, carboxyl and hydroxyl which can double deionized water (Milli-Q Millipore 18.2 Ω cm −1-
play an important role in the removal of dyes from wastewaters conductivity). A stock solution was further diluted to obtain the
[29]. Recently, research has been focused on improving the ad- desired concentrations (100 to 1000 mg/L) were used in all the ad-
sorption capacity of adsorbents through chemical modifications sorption experiments.
[30–38]. These modifications used to adsorbents may introduce
functional groups (amine, amide, carboxylate, hydroxyl, phos- 2.3. Preparation of QAMOPP
phate, etc.) in the structure of the adsorbents or increase their po-
rosity, with an increase in their adsorption capacity. Many Waste orange peel (OP) materials were collected from a Pullampeta
researchers developed chemical modified orange peel that has (Kadapa district, Andhra Pradesh, India) town fruit and juice shops. The
been fruitfully applied for the elimination of dyes and metal ions OP was washed with a tap as well as deionized water several times to
from aqueous solution, some of which are sodium hydroxide- remove dirt and other contaminants and air dried for 24 h. The dried
treated orange peel [39], CTAB modified orange peel [39], acti- OP was cut into small pieces and dried at 70 °C inside an oven for
vated carbon prepared by orange peel [40], HCl treated orange 24 h. The oven dried OP was grinding well to a fine powder. This ob-
peel [41], activated carbon from orange peel [42], sulfuric acid- tained powder named as OPP.
treated orange peel [43], aminated pumpkin seed powder [44], Quaternary amine modified orange peel powder (QAMOPP) was
calcined magnetic orange peel [45], chemically modified orange prepared according to the method proposed by Gurung et al. [48]. In
peel [46] and grafted copolymerization-modified orange peel a typical run, the mixtures of 10.0 g dry OPP, 10.0 g formaldehyde
[47]. In this study, we have chosen QAMOPP as an adsorbent ma- (HCHO) and 40 mL of Conc. HCl was stirred for 24 h at 90 °C in a
terial for the removal of RR120 from aqueous media. three-neck round bottom flask. The product of chloromethylation
This study aims to determine the adsorption behavior of RR120 was diluted with double deionized water and the solid was filtered
using QAMOPP. The different controlling experimental conditions and washed with double deionized water a number of times to
such as an effect of pH (2.0–9.0), contact time (0–300 min), adsor- ensure the filtrate became neutral. The obtained chloromethylated
bent dosage (0.01–0.07 g/30 mL), initial RR120 concentration product was dried in an oven at 50 °C for overnight. Then, 9.0 g
of the product was mixed with 40 mL of 50% dimethylamine
((CH3)2NH) solution and 20 mL of 37% HCHO solution and heated
at 90 °C with continuous string for 12 h to get dimethylamine mod-
ified OPP. The product was filtered and washed with 0.1 M HCl
solution followed by several washings with water and dried for
24 h at 50 °C. The obtained dimethylamine ((CH 3) 2 NH) modified
OPP was further mixed together with 0.6 mL methyl iodide (CH3I),
0.2 g sodium carbonate (Na2CO3) and 0.6 g sodium iodide (NaI) in
10 mL methanol (CH3OH) to remove any unreacted methyl iodide
and successively washed with double deionized water until a neu-
tral pH was reached. The obtained residue was further washed
with 0.1 M NaCl to get the chloride salt of quaternary amine modi-
fied OPP which as dried at 50 °C inside an oven for 24 h. Finally,
the oven dried product was ground and sieved into smaller particles
by a 50 mesh size. The modified OPP is called as QAMOPP. The reac-
Fig. 1. Molecular structure of RR120. tion occurs as follows:
 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385 377

24 h. For the desorption process, the RR120-loaded adsorbents were

2.4. QAMOPP characterization added into 30 mL of 0.1, 0.3, 0.5, 0.7 and 1.0 M NaOH eluents. The mix-
tures were agitated at 180 rpm for 4 h. Subsequently, the adsorbent was
The FTIR spectra of the QAMOPP and RR120-loaded QAMOPP were separated magnetically. The amount of RR120 desorbed into the solu-
done on FTIR spectrometer (Nicolet IS10, Thermo Scientific, USA). tions was analyzed by UV–visible spectrophotometer. The efficiency of
Pure KBr pellet and 1:10 (sample with KBr) pellets were used as blank RR120 desorbed from the QAMOPP was calculated using the following
and samples for FTIR measurement. The functional groups of the sam- Eq. (2):
ples were recorded in the frequency range of 400–4000 cm−1. The spe-
cific surface area, total pore volume and average pore diameter of Amount of RR120 desorbed
Desorption efficiency ¼  100 ð2Þ
QAMOPP were analyzed by adsorption-desorption of N2 at 77 K using Amount of RR120 adsorbed
BET surface analyzer (BELSORP, BEL Japan). The sample was degassed
at 323 K for 12 h to obtain a residual pressure b 10−6 mm Hg. The
QAMOPP before and after RR120 adsorption was loaded onto the copper 2.6. Chi-square (χ2) analysis
substrate after sputter-coated with a homogeneous gold layer for mea-
suring surface morphologies using SEM (JEOL, JSM-7600F, Japan). The equivalent mathematical statement of χ2 test can be repre-
sented as:
2.5. Adsorption and desorption studies
 2 !
X qe −qe;m
Batch sorption experiments were carried out in falcon tubes (50 mL) χ2 ¼ ð3Þ
qe;m
by adding a fixed quantity of QAMOPP with 30 mL of RR120 solution.
The pH value was adjusted (using 0.1 M HCl or NaOH) between 2.0 where qe,m and qe are equilibrium adsorption capacities (mg/g) ob-
and 9.0. The adsorbent dosage on RR120 adsorption was performed by tained from the experimental and calculated data by the isotherm
varying the amount of adsorbent from 0.01 to 0.07 g/30 mL. The kinetic model, respectively. The best fitting of the non-linear isotherm model
experiment was conducted in 250 mL conical flask containing 0.2 g of to the experimental data was evaluated on the basis of the lower
QAMOPP and 120 mL RR120 solution with an initial concentration of value of χ2.
300 mg/L. The experiment was repeated at 308 and 318 K temperatures
also. The contact time was varied from 0 to 300 min. The equilibrium 3. Results and discussion
isotherm of RR120 onto QAMOPP was carried out at 298 K. A 0.05 g of
QAMOPP with 30 mL RR120 solution (of different initial concentrations 3.1. Characterization of the adsorbent
100 to 1000 mg/L) was agitated at 180 rpm for 4 h at 298 K. The adsorp-
tion studies were also carried out at five temperatures (298–338 K) in The FTIR spectrums of the QAMOPP and RR120 loaded on QAMOPP
order to estimate the thermodynamic (ΔGo, ΔHo and ΔSo) parameters. are shown in Fig. 2. The spectrum of QAMOPP before adsorption
The average value (done twice) of every experiment was taken for (Fig. 2(a)) showed the distinct major bands at 3469, 2971, 1589, 1490,
data analysis. The remaining concentration of RR120 within the solution 1247, 1153, 1015, 836 and 695 cm−1. In particular, the strong broad
was measured by means of an UV–visible spectrophotometer after peak at 3469 cm−1 is associated to the stretching vibration of hydroxyl
proper dilution. Based on the initial and final concentrations of the (-OH) and amine (-NH) functional groups of the QAMOPP surface, while
RR120, the adsorption capacity and removal efficiency of the QAMOPP the band at 2971 cm−1 corresponds to the –C-H stretching vibration.
was measured using the following Eq. (1): The remaining major bands of QAMOPP could be attributed as below:
1589 cm−1 (N\\H bending vibrations of amine), 1490 cm−1 (N_N
ðC o −C e ÞV stretching vibrations of azide), 1247 cm−1 (stretching vibration of –
qe ¼ ð1Þ
m S=O group), 1153 cm−1 (stretching vibration of the –C-N),
1015 cm−1 (stretching vibrations of C\\O), 831 cm−1 (aromatic C\\H
For the desorption study, 0.1 g of QAMOPP was added to 30 mL bending vibrations) and 695 cm−1 (–S-O stretching). After the adsorp-
(300 mg/L, pH = 2.0) of RR120 solution and the mixtures were agitated tion of RR120, the peaks at 3457, 2928, 1588, 1476, 1246, 1152, 1013,
on a reciprocating shaker at a constant speed of 180 rpm and 298 K for 836 and 689 cm−1 was found on the spectrum (Fig. 2(b)). Comparison
4 h. Afterwards, the RR120-loaded adsorbents were magnetically sepa- of FTIR spectra of RR120 loaded QAMOPP with unloaded QAMOPP
rated and the remaining RR120 concentration in the solutions was de- displayed considerable changes in some peaks. A small number of
termined using UV–visible spectrophotometer. After then, RR120- bands (1589, 1247, 1153 and 1015 cm−1) on the QAMOPP were not
loaded adsorbents were filtered and dried at 70 °C inside an oven for shifted mean that they were not participated in the adsorption process.
378 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385

100
high porosity and surface areas those are favorable for molecular diffu-
95 (b) sion and the adsorption of contaminants. The EDAX spectrum of the
90 QAMOPP shown in Fig. 3(c) clearly indicates that the composite chiefly
contains C (56.25 wt% 62.77 at.%), N (15.43 wt% 14.77 at.%), O (25.16 wt
85
% 21.08 at.%), Mg (0.64 wt% 0.35 at.%), P (1.49 wt% 0.64 at.%), S (0.39 wt%
Transmittance (%)

80 (a) 0.16 at.%) and K (0.64 wt% 0.22 at.%).

The specific surface area, total pore volume and average pore diam-
75
eter play an essential role in the adsorption capacity and adsorption rate
70 of the QAMOPP. The reason is that these properties can provide more
65 active adsorption sites, which improve the adsorption rate of QAMOPP.
The specific surface area, total pore volume and average pore diameter
60
of the QAMOPP were found to be 38.6 m2/g, 0.291 cm3/g and
55 11.13 nm, respectively. These properties increased the possibility of
50
the RR120 to be adsorbed onto QAMOPP.

45
3.2. Effect of pH
40
4000 3500 3000 2500 2000 1500 1000 500
One of the vital factors that affect adsorption process is solution pH
-1
Wavenumber (cm ) due to its control on surface charge and solubility of adsorbent. The ef-
fect of pH on the adsorption capacity of RR120 onto QAMOPP was stud-
Fig. 2. FTIR spectra of QAMOPP: (a) before adsorption and (b) after adsorption. ied in various pH conditions ranging from 2.0 to 9.0 at 298 K, constant
initial RR120 concentration of 300 mg/L, adsorbent dosage of 0.05 g
and contact time of 110 min. As can be seen from Fig. 4, the adsorption
A number of bands showed shift like 3457, 2928, 1476, 836 and
of RR120 onto QAMOPP is intimately dependent on the pH of the solu-
689 cm−1 (Fig. 2(b)) indicates the bonds formation between QAMOPP
tion. The adsorption capacity of RR120 decreased from 143.9 to
and RR120 dye molecules. Therefore, it can be concluded that hydroxyl
3.87 mg/g with increasing pH solution from 2.0 to 9.0, and a maximum
and amine functional groups may play a considerable role in the adsorp-
adsorption capacity was reached at an equilibrium pH of around 2.0 and
tion of RR120 on the QAMOPP surface.
this pH was chosen for the further sorption experiments. RR120 has six
The morphological pattern of QAMOPP before and after RR120 ad-
sulphonate (R-SO3−) groups, which are easily dissociated in aqueous
sorption is studied using SEM. The SEM/EDAX images of the samples
solution, leaving the dye molecule with a net negative charge.
are shown in Fig. 3. Before the adsorption a smooth surface morphology
as observed (Fig. 3(a)), while after the adsorption of RR120 on the
QAMOPP, a layered structure on the surface of adsorbent and rough
morphology was observed (Fig. 3(b)). In general rough surfaces provide RR120−SO3 Na→RR120−SO−
3 þ Na
þ

Fig. 3. SEM images of (a) QAMOPP (b) RR120 loaded QAMOPP and (c) EDAX spectrum of QAMOPP.
 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385 379

160
3.3. Effect of adsorbent dosage

140
Adsorbent dosage also plays an important role in the adsorption of
RR120 from aqueous solution. Experiments were carried out at different
120
adsorbent dosages (0.01, 0.02, 0.03, 0.04, 0.05, 0.06 and 0.07 g/30 mL)
Adsorption capacity [mg/g]

and fixed initial RR120 concentration (300 mg/L). The results of the dos-
100
age of QAMOPP for the adsorption of RR120 are shown in Fig. 5. This fig-
ure shows that the removal efficiency of RR120 increased (32.4 to 91%)
80
when the adsorbent dose was increased (0.01 to 0.07 g/30 mL). This
condition may be due to higher surface area and the quantity of adsorp-
60
tion exchangeable active sites that are available for adsorption. If the ad-
40
sorption capacity was articulated as the quantity of dye adsorbed per
unit mass of the adsorbent (mg/g), the adsorption capacity of
20
QAMOPP for RR120 decreased (290.7 to 118.7 mg/g) with increasing
adsorbent dosage (0.01 to 0.07 g/30 mL) (Fig. 5). This may be due to re-
0 duce in total available surface area of adsorbent as of overlapping or ag-
gregation of adsorption sites resulting in an increase in diffusion path
2 3 4 5 6 7 8 9 10 length for the RR120. In this study, the maximum removal efficiency
pH 91% was found at 0.05 g/30 mL. This adsorbent dosage was considered
for all the adsorption studies.
Fig. 4. Effect of pH on RR120 adsorption onto QAMOPP.

Hþ 3.4. Effect of contact time on RR120 uptake

S−OH → S−OH þ − þ −
2 þ RR120−SO3 →S−OH 2 〉 −−− 〈 RR120−SO3

Contact time studies are vital in describing the adsorption rate

OH− − and estimation of equilibrium time for dye adsorption. The impact
S−OH → S−O þ RR120−SO−
3 þ H 2 O→S−O −
h−−−iRR120−SO−
3
of contact time (different time intervals ranging from 0 to 300 min)
on the adsorption of RR120 using QAMOPP was studied under the
where S denotes the surface of QAMOPP. optimal conditions: pH 2.0, initial RR120 concentration 300 mg/L,
At lower pH, the positively charged surface (active sites) of the adsorbent dosage 0.3 g and different temperatures. As shown in
QAMOPP attracts the negatively charged RR120 that enhances the up- Fig. 6, the adsorption capacity of RR120 was gradually increased
take. Whereas at higher pH the abundance of hydroxide ions competes with time and reached equilibrium condition after 110 min due to
with RR120 and the ionic repulsions between the negatively charged the presence of highly available surface area and active adsorption
surface and RR120 molecule results lower adsorption of RR120. The sites. However, after this time, an equilibrium was achieved when
outer surface of the QAMOPP does not have exchangeable anions at the adsorbent surface becomes saturated. Thus, the contact time of
higher pH values. The lower pH of the solution is suitable for the adsorp- 110 min was considered as an equilibrium time and was used for fur-
tion of reactive dyes [49–51]. ther experiments.

100
300

90 280

260
Adsorption capacity [mg/g]

80
% Removal efficiency

240

70 220

200
60
180

50
160

140
40
% Removal efficiency
120
Adsorption capacity [mg/g]
30
100
0.01 0.02 0.03 0.04 0.05 0.06 0.07

Amount of adsorbent dosage [g/30 mL]

Fig. 5. Effect of adsorbent dosage for RR120 adsorption onto QAMOPP.

380 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385

180 180

160
160

140
140
120
120

q [mg/g]
100
100 Experimental
q [mg/g]

80 Experimental
Experimental
80
60 Pseudo-first-order (298 K)
Pseudo-second-order (298 K)
60 40 Pseudo-first-order (308 K)
Pseudo-second-order (308 K)
Pseudo-first-order (318 K)
40 20
Pseudo-second-order (318 K)
298 K
0
20 308 K
0 100 200 300
318 K
0 Time [min]
0 50 100 150 200 250 300
Fig. 7. Kinetic parameters on RR120 adsorption onto QAMOPP at different temperatures.
Time [min]

Fig. 6. Effect of contact time on RR120 adsorption onto QAMOPP at different temperatures.
model at all temperatures. The non-linear adsorption kinetic curves
for RR120 are shown in Fig. 7.

3.5. Adsorption kinetics

3.6. Adsorption activation energy
To evaluate the performance of an adsorbent and the mechanism of
adsorption process adsorption kinetic studies are necessary. In the case The values of the pseudo-second-order rate constant k2 at different
of pollutant uptake, kinetics helps to select the optimum operating con- temperatures are given in Table 1 were applied to approximate the ac-
ditions for extending the process to large-scale adsorption systems [23]. tivation energy of the adsorption process of RR120 onto QAMOPP by the
To analyze the adsorption kinetics of RR120 onto QAMOPP two kinetic Arrhenius equation can be expressed in Eq. (6):
models, which are pseudo-first-order and pseudo-second-order models
have been used for their validity with the experimental data. The non-
Ea
linear kinetic models are generally expressed as follows: ln k2 ¼ ln Ao − ð6Þ
RT
Pseudo-first-order [52]:

qt ¼ qe1 ð1− expð−k1 t ÞÞ ð4Þ Ea can be obtained by plotting ln k2 against the reciprocal of the ab-
solute temperature (Fig. 8). Whether the adsorption process is physical
Pseudo-second-order [53]: or chemical can be known by the magnitude of Ea. The value of Ea ob-
tained for the adsorption of RR120 onto QAMOPP is 12.1 kJ/mol. In gen-
q2e2 k2 t eral, 5 to 40 kJ/mol, is the range of activation energy for physical
qt ¼ ð5Þ adsorption. From the results, the adsorption of RR120 onto QAMOPP is
1 þ qe2 k2 t
a physical adsorption process.

The kinetic parameters (qe1, qe2, k1, k2, and R2) obtained by non-
linear regression method are presented in Table 1. As seen from this 3.7. Adsorption isotherms
table, the low R2 values (in the range of 0.9484–0.9740) and there is
not a quite good agreement between the values of experimental qe,exp The information regarding the distribution of adsorbate molecules at
and calculated qe1,cal showed that the pseudo-first-order model is un- the solid/liquid interface was obtained from numerous adsorption iso-
suitable for modeling the adsorption of RR120 onto QAMOPP for the therm models. In this work, various two- and three-parameter non-
studied temperature range. On the other hand, the high R2 values (in linearized isotherm models such as Langmuir, Freundlich, Dubinin-
the range 0.9967–0.9982) and excellent conformity between the qe,exp Radushkevich (D-R), Temkin, Sips, Toth, Khan and Redlich-Peterson
and qe2,cal values exposed that the adsorption mechanism of RR120 (R-P) models were employed for testing the experimental equilibrium
onto QAMOPP could be well modeled with the pseudo-second-order adsorption data.

Table 1
Kinetic parameters obtained from pseudo-first-order and pseudo-second-order at different temperatures.

Adsorbent Temp. (K) qe,exp Pseudo-first-order model Pseudo-second-order model

(mg/g) 2
qe1,cal k1 (1/min) R qe2,cal k2 R2
(mg/g) (mg/g) (g/mg min)

QAMOPP 298 136.2 128.9 0.1065 0.9740 138.9 0.0013 0.9982

308 148.6 141.2 0.1277 0.9621 150.9 0.0015 0.9967
318 165.1 157.6 0.1600 0.9484 167.2 0.0017 0.9941
 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385 381

-6.30
Table 2
Isotherm parameters for RR120 adsorption onto QAMOPP.
-6.35
Isotherm Parameters Values

Two-parameter isotherm models

-6.40 Langmuir qm (mg/g) 344.8
KL (L/mg) 0.0352
R2 0.9996
-6.45
χ2 3.8
Freundlich Kf (mg/g) 69.9
ln k2

-6.50 n 3.832
R2 0.9287
χ2 32.4
-6.55 Temkin b (J/mol) 0.039
α (L/mg) 0.5472
R2 0.9676
-6.60
χ2 19.5
Dubinin-Radushkevich qm (mg/g) 287.9
-6.65 K (mol2/J2) 0.0204
E (kJ/mol) 4.95
R2 0.8463
0.00315 0.00320 0.00325 0.00330 0.00335 χ2 53.6
1/T
Three-parameter isotherm models
Sips KS (L/g) 12.11
Fig. 8. Plot of ln k2 versus 1/T for the estimation of activation energy for RR120 adsorption aS (L/mg) 0.0352
onto QAMOPP. βS 0.9999
R2 0.9925
χ2 7.3
Toth qmax (mg/g) 342.9
bT (L/mg) 0.0347
3.7.1. Two-parameter isotherms nT 0.9849
R2 0.9896
3.7.1.1. Langmuir isotherm. Langmuir isotherm [54] model predicts the χ2 11.2
monolayer coverage at the outer surface of adsorbent by assuming Khan qmax (mg/g) 344.2
bK (L/mg) 0.033
monolayer adsorption occurs at structurally and energetically homoge-
aK 0.986
neous active sites. The non-linearized form of Langmuir isotherm is R2 0.9991
expressed by the following Eq. (7): χ2 6.5
Redlich-Peterson KRP (L/g) 11.723
qm K L C e aRP (L/mg) 0.0531
qe ¼ ð7Þ βRP 0.995
1 þ K LCe
R2 0.9825
χ2 13.2
The maximum RR120 uptake by QAMOPP was 344.8 mg/g.
The Eq. (8) describes the dimensionless constant separation fac-
tor or equilibrium parameter (RL) that indicates the adsorption
capacity. adsorption process. The non-linearized form of D-R isotherm is repre-
sented by the following Eqs. (10) and (11):
1
RL ¼ ð8Þ  
ð1 þ K L C o Þ qe ¼ qm exp −Kε2 ð10Þ

If 0 b RL b 1, the isotherm will be favorable adsorption; for RL N where

1, the isotherm will be unfavorable adsorption; for RL = 1, the iso-
 
therm will be linear adsorption and for RL = 0, the isotherm will be 1
ε ¼ RT ln 1 þ ð11Þ
irreversible adsorption. The values of RL lay in the range of Ce
0.03–0.22, indicating that adsorption of RR120 onto QAMOPP is
favorable. The mean free energy of adsorption process (E) is determined using
following Eq. (12):
3.7.1.2. Freundlich isotherm. Freundlich isotherm [55] mainly considers
that during the adsorption process the adsorption surface becomes het- 1
E ¼ pffiffiffiffiffiffiffi ð12Þ
erogeneous. The non-linearized from of Freundlich isotherm is given by 2K
Eq. (9):
Depending on the values of E, the adsorption process may be
qe ¼ K f C 1=n ð9Þ physical or chemical. The magnitude of E determines the adsorption
e
process. The range of E known for chemical adsorption is 8 to
16 kJ/mol, physical in nature is b8 kJ/mol and chemisorption is E
The values of exponent n are in the range (1 b n b 10) of favorable N 16 kJ/mol. Based on the value of E (4.95 kJ/mol) we can justify the
adsorption. In this study, the n value was observed to be 3.832 physical adsorption process plays a significant role in the adsorption
(Table 2). The n value was between 1 and 10, indicates that the adsorp- of RR120 on QAMOPP surface.
tion of RR120 onto QAMOPP is favorable.
3.7.1.4. Temkin isotherm. Temkin isotherm [57] model explains about the
3.7.1.3. Dubinin-Radushkevich (D-R) isotherm. The D-R isotherm [56] interactions between adsorbate and adsorbent. Assuming the linear (in-
model gives the characteristic porosity and apparent energy of stead of logarithmic) decrease of heat of adsorption of all the molecules
382 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385

in the layer and the binding energy distribution is uniform across the
from both Langmuir and Freundlich isotherm models. The non-
surface. The non-linearized form of Temkin isotherm has been used in
linearized form of R-P isotherm can be expressed as the following
the following Eqs. (13) and (14):
Eq. (18):
qe ¼ β ln α þ β lnC e ð13Þ
K RP C f
q¼ β
ð18Þ
where 1 þ aRP C f RP

RT
β¼ ð14Þ
b When the value of βRP = 0, the R-P model reduces to the Henry's law
equation which is a linear isotherm, and to the Langmuir isotherms for
The value of b indicates whether it is physical (b8 kJ/mol) or chem- βRP = 1. For high adsorbate concentration, the R-P model reduces to the
ical (between 8 and 16 kJ/mol) adsorption process. The value of b Freundlich isotherm. The βRP value was close to 1 (Table 2), which indi-
(0.039 kJ/mol) in the present study was lower than 8 kJ/mol, indicated cates that the adsorption of RR120 onto QAMOPP equilibrium data can
that the adsorption of RR120 onto QAMOPP is physical adsorption be approximated to fit the Langmuir isotherm.
process. The comparison results of the values of the Langmuir, Freundlich,
Dubinin-Radushkevich (D-R), Temkin, Sips, Toth, Khan and Redlich-
3.7.2. Three-parameter isotherms Peterson (R-P) model rate constants with correlation coefficients (R2)
and Chi-square (χ2) are given in Table 2. As can be seen from Table 2,
3.7.2.1. Sips isotherm. Sips isotherm [58] is generally known as the com- the correlation coefficient (R2) and Chi-square (χ2) values of all the iso-
bination of the Langmuir and Freundlich isotherm models that de- therm models, it can be concluded that the Langmuir (two-parameter)
scribes heterogeneous surface much better. Depending on the and Khan (three-parameter) isotherm models are the best fitted models
adsorbate concentrations low and high, the Sips isotherm approaches for the experimental data of RR120 adsorption on the QAMOPP because
the Freundlich and Langmuir isotherms respectively. The non- those displayed the higher R2 and lower Chi-square (χ2) values.
linearized form of Sips isotherm can be expressed as the following
Eq. (15): 3.8. Comparison of the adsorption capacity with other adsorbents

K S C βs The comparison of monolayer adsorption capacities of various ad-

q¼ e
ð15Þ
1 þ aS C βs
e sorbents was reported in the literature [3,62–72] and the qmax (mg/g)
values are listed in Table 3. From the results, it was observed that the
When the value of βS is 0 and 1 then the Sips isotherm become a maximum monolayer adsorption capacity of QAMOPP is superior to
Freundlich isotherm and Langmuir isotherm respectively which can be the literature, which shows perfect adsorption property and satisfactory
applied for ideal surfaces. The coefficient βS for the present study was performance for the removal of RR120 would be an effectively
close to unity (Table 2), implying the RR120 adsorption was better rep- adsorbent.
resented by the Langmuir isotherm.
3.9. Effect of temperature and thermodynamic study
3.7.2.2. Toth isotherm. When the adsorbate concentration is low and high
then the Toth isotherm [59] model is very useful in describing the ad- The effect of temperature on the adsorption of RR120 onto QAMOPP
sorption process as this model gives a wide range of fit than Langmuir was studied and presented in Fig. 9, for five different temperatures of
or Freundlich isotherm equation. The non-linearized form of Toth iso- 298, 308, 318, 328, and 338 K, at 300 mg/L initial RR120 concentration
therm is determined from the following Eq. (16): and pH 2.0. The equilibrium adsorption capacity of RR120 was increased
(132.3 to 172.4 mg/g) with an increase in temperature (298 to 338 K)
qmax bT C e which is a sign of endothermic in nature of the adsorption. The in-
q¼h inT ð16Þ
1=nT creased adsorption capacity at higher temperatures may be due to the
1 þ ðbT C e Þ
availability of the high surface area or exchangeable sites and high po-
rosity. From these results, thermodynamic parameters (ΔGo, ΔHo and
If nT = 1, Toth isotherm is reduced to the Langmuir isotherm equa-
ΔSo) were calculated using the following Eqs. (19)–(22):
tion. The estimated nT value (Table 2) is close to unity, which suggest
the RR120 adsorption fit the Langmuir isotherm model.
ΔGo ¼ −RT ln K c ð19Þ
3.7.2.3. Khan isotherm. The Khan isotherm [60] model describes the ex-
perimental data with the minimum average percentage error by com-
Table 3
paring several multicomponent adsorption isotherms. The non-
Comparison of adsorption capacity of QAMOPP with different adsorbents.
linearized form of Khan isotherm is expressed as following Eq. (17):
Adsorbent Adsorption capacity pH References
q bK C f (mg/g)
q ¼  max aK ð17Þ
1 þ bK C f Nanoparticles of Fe3O4 166.67 2.5 [3]
Chitosan/zeolite 19.14 5.0 [62]
Chara contraria 92.35 1.0 [63]
If aK = 1, Khan equation reduces to the Langmuir isotherm, whereas Chitosan beads 114.9 4.0 [64]
the term bKCf is much greater than unity it can be simplified to a Hydrilla verticillata 120.85 2.0 [65]
Freundlich type isotherm. In this study, the aK value was close to unity Jatropha curcas shells 42.5 2.0 [66]
Agave sisalana 110 2.0 [67]
(Table 2), which suggests that the adsorption of RR120 onto QAMOPP
Pumpkin husk 98.61 1.0 [68]
fit the Langmuir isotherm model. Cetylpyridinium-bentonite 81.97 2.0 [69]
Chitosan/modified montmorillonite 5.6 5.0 [70]
3.7.2.4. Redlich-Peterson (R-P) isotherm. The R-P [61] isotherm model is Activated carbon 267.2 2.0 [71]
generally studied in large concentration intervals in the various systems Cumin herb wastes 47.88 2.0 [72]
QAMOPP 344.8 2.0 This study
(homogeneous and heterogeneous). This model uses hybrid elements
 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385 383

175

170
80
165
Adsorption capacity [mg/g]

Desorption rate [%]

160 60

155

40
150

145
20

140

135 0
290 300 310 320 330 340 0.0 0.2 0.4 0.6 0.8 1.0
Temperature (K) NaOH Concentration [M]

Fig. 9. Effect of temperature on RR120 adsorption onto QAMOPP. Fig. 11. Effect of NaOH concentration on desorption of RR120 from the QAMOPP.

QAMOPP. The magnitude of ΔGo is between −20 and 0 kJ/mol means

C Ae physisorption and between −400 and −80 kJ/mol. ΔHo due to
Kc ¼ ð20Þ
Ce physisorption is lower than 84 kJ/mol, while ΔGo due to chemisorption
takes a value between 84 and 420 kJ/mol [73]. Therefore, the values of
ΔGo ¼ ΔHo −TΔSo ð21Þ ΔGo and ΔHo suggest that adsorption of RR120 onto QAMOPP was
driven by a physisorption. The positive value of ΔSo (0.102 kJ/mol K) in-
ΔGo ΔH o ΔSo dicated an increased degree of disorderness at the solid-solution inter-
ln K c ¼ − ¼− þ ð22Þ
RT RT R face during the adsorption of RR120 on the active sites of QAMOPP.

The values of ΔHo and ΔSo were determined from the slope and in- 3.10. Desorption studies
tercept of the linear plot of ln Kc versus 1/T (Fig. 10) using the Van't
Hoff equation (Eq. (22)). The negative values of ΔGo (−1.9114, Desorption experiments reveal the recovery of RR120 from
−2.7935, −3.8229, −4.9472 and −5.9208 kJ/mol) at all temperatures QAMOPP. NaOH solution was selected as a desorbing agent to desorb
(298, 308, 318, 328 and 338 K, respectively) indicated that the feasibility RR120 from the RR120-loaded QAMOPP. Various concentrations of
and spontaneity of the RR120 adsorption process onto QAMOPP. More- NaOH (0.1, 0.3, 0.5, 0.7 and 1.0 M) were used as desorbing media for
over, the ΔGo was inversely proportional to temperature and more fa- the regeneration of RR120-loaded QAMOPP and the results are offered
vorable at higher temperatures and the reaction rate increases. The in Fig. 11. The Efficiency of desorption was decreased, with increasing
positive value of ΔHo (28.4 kJ/mol) reveals that the RR120 adsorption NaOH concentration (Fig. 11). The maximum desorption (92%) of
onto the QAMOPP was endothermic, which means a portion of total en- RR120 from QAMOPP was achieved with 0.1 M NaOH, indicating that
ergy is released when RR120 anions adsorbed on the active sites of a lower concentration of NaOH was more efficient in releasing RR120.
From the desorption studies, it is concluded that QAMOPP has shown
better restorative potential and effectual for the elimination of RR120
from aqueous solution.
2.2
3.11. Adsorption mechanism
2.0

The adsorption of RR120 on QAMOPP depends on dye (RR120)

1.8
structure and adsorbent surface properties. The main mechanism in-
volved is an electrostatic attraction (major contribution) along with
1.6
physisorption (minor contribution). The high anionic nature of dye
varies depends on pH. In low pH solutions to high pH solutions the an-
ln Kc

1.4
ionic nature decreases, correspondingly the adsorption capacity also fol-
lows the same trend (high at low pH and low at high pH). Because of the
1.2
easily protonated nature of the hydroxyl groups (-OH) present on the
1.0
surface of QAMOPP, they behave as positive groups (-OH+ 2 ) in acidic
medium (pH = 2.0) where high adsorption capacity was observed in
0.8 the present study. This is the common trend observed when electro-
static interactions play a significant role in the adsorption mechanism.
0.6
0.0029 0.0030 0.0031 0.0032 0.0033 0.0034 4. Conclusions
1/T
The QAMOPP used in the present study is an alternative adsorbent for
Fig. 10. Thermodynamic parameters on RR120 adsorption onto QAMOPP. RR120 removal from aqueous solution. The results showed that pH
384 V.S. Munagapati et al. / Journal of Molecular Liquids 285 (2019) 375–385

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