Arabian Journal of Chemistry (2020) 13, 2766–2777

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Sodium hyroxyethylcellulose adipate: An efficient

and reusable sorbent for cadmium uptake from
spiked high-hardness ground water
Muhammad Ajaz Hussain a,*, Shahana Zaman a, Azhar Abbas a,
Muhammad Nawaz Tahir b,*, Muhammad Amin a, Syed Zajif Hussain c,
Irshad Hussain c

a
Ibn-e-Sina Block, Department of Chemistry, University of Sargodha, Sargodha 40100, Pakistan
b
Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
c
Department of Chemistry, SBA School of Science & Engineering (SSE), Lahore University of Management Sciences
(LUMS), DHA, Lahore Cantt. 54792, Pakistan

Received 7 January 2018; accepted 8 July 2018

Available online 17 July 2018

KEYWORDS Abstract Herein, we report on the evaluation of chemically modified hyrdroxyethylcellulose for its
Hydroxyethylcellulose; sorption efficacy to remove Cd(II) from spiked high-hardness ground water (GW) and distilled
Sodium hydroxyethylcellu- water (DW) solutions. Hyrdroxyethylcellulose was chemically modified using adipic anhydride in
lose adipate; the presence of DMAP as a catalyst under homogeneous reaction conditions. Hyrdroxyethylcellu-
Metal uptake; lose adipate (HEC-Adip) obtained was then converted to its sodium salt as HEC-Adip-Na after
Cadmium; treating with saturated solution of NaHCO3. Structures were thoroughly characterized using FTIR,
Kinetics SEM, EDS and solid-state CP/MAS 13C NMR. The surface charge of the sorbent was monitored
by pHZPC (pH of zero point charge). The sorption data fitted well to Langmuir isotherm and
pseudo-second order kinetic model. Maximum sorption capacity of Cd(II) was calculated to be
114.94 mg g
1 and 112.35 mg g
1 from DW and GW, respectively. Thermodynamic parameters,
i.e., DH°, DS° and DG°, were also calculated and showed negative values indicating spontaneous
and exothermic nature of sorption process. In addition, the synthesized sorbent is more suitable
for repeated use because it shows negligible decrease in its sorption capacity for the uptake of
Cd(II) from aqueous solution after five regeneration cycles.
Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding authors.
E-mail addresses: majaz172@yahoo.com (M.A. Hussain), muhammad.tahir@kfupm.edu.sa (M.N. Tahir).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

https://doi.org/10.1016/j.arabjc.2018.07.007
1878-5352 Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Sodium hyroxyethylcellulose adipate: An efficient and reusable sorbent
1. Introduction
Worldwide, there are a number of water pollution sources:
among them organic and inorganic pollutants are more haz-
ardous (Zhang et al., 2016; Ahmad et al., 2018). Globally
due to industrial revolution, the rate of inorganic pollutants
production increases many times which is being considered
as the dominant and permanent pollutant for drinking and
ground water (Negm et al., 2018). During past few decades,
people learned that industrial processes such as metallurgy,
petrochemical refining, leather tanneries, mining activities
and paints and pigment manufacturing (Nguyen et al., 2013;
Duan et al., 2014) resulted in severe pollution of ground and
surface water which have reached to alarming situation
(Morales et al., 2016). From the eco-toxicological point of
view, the most hazardous inorganic pollutants coming out of
above mentioned industries are heavy metals like lead, cad-
mium, mercury, and chromium, etc. Among heavy metal ions,
cadmium is a highly toxic metal which causes breakdown of
immune system which further leads to cancer, diarrhea, renal
failure, lungs disorder, skeletal deformation and damage of
central nervous system (Oelkers et al., 2011; Khan et al.,
2013; Tellez-Plaza et al., 2008).
A large number of techniques have been used for the
removal of heavy metals from water which include solvent
extraction, ion-exchange, reverse osmosis, precipitation and
nanofiltration (Williams et al., 1998; Kadirvelu et al., 2001;
Cheng et al., 2014; Kim et al., 2006). But, these expensive tech-
nologies are hazardous to environment and efficiency of the
method become compromised afterward. Consequently, cost
effective and environmental friendly procedures for water
purification should be developed. Recently, research consider-
ation has been dedicated to ion-exchange process which is
being considered to be more efficient, economical and eco-
friendly for the purification of water containing sewage water,
tannery and industrial effluents (Guo et al., 2015; Suteu et al.,
2015).
Most valuable ion-exchangers/sorbent are chemically mod-
ified cellulosic biomaterials because of their economical and
biodegradable nature, water insolubility, reusability and non-
toxicity (Abbas et al., 2015; Babel and Kurniawan, 2003;
Suteu et al., 2015). Among chemical modified cellulosic mate-
rials, esterified polysaccharides (getting COOH functionalities
as termini) are current topic of interests for the removal of
metal ions (Abbas et al., 2017; Lima et al., 2006; Zhong
et al., 2012).
In the present work, we are aimed to synthesize an efficient
and novel sorbent of commercially available biomaterial,
i.e., hydroxyethylcellulose (HEC), after its modification by
esterification with adipic anhydride to form HEC-adipate
(HEC-Adip). HEC-Adip will be having single kind of COOH
functionalities suitable to be converted to its sodic form
(HEC-Adip-Na) after treating with NaHCO3. We are aimed
to report appraisal of HEC-Adip-Na as a new and efficient
ion exchanger in terms of Cd(II) uptake from DW and GW.
Present investigation also dealt with metal ions uptake under
equilibrium conditions using HEC-Adip-Na and their kinetic
evaluation to establish the mechanism of metal ion uptake.
The present work is also evaluating the reusability of HEC-
Adip-Na for Cd(II) uptake. Calculation of different kinetic
parameters and thermodynamic triplet (DH°, DS° and DG°)
2767
are also aimed to check the nature and spontaneity of the
adsorption process.
2. Materials and methods
2.1. Materials
Hydroxyethylcellulose was obtained from Natrosol hydrox-
yethylcellulose, HE10K, Belgium. NaHCO3, NaOH and
HNO3 were obtained from Fluka. Adipic anhydride, solvents
and other reagents were procured from Sigma-Aldrich. All
the organic solvents used in the laboratory were of analytical
grade. Chemical characterization of GW (from District Sar-
godha) was done using available analytical techniques and fol-
lowing information was obtained: pH 7.2, calcium hardness
490.5 mg L
1 , magnesium hardness 885 mg L
1 , total hard-
ness (MgCO3 and CaCO3) 1375.5 mg L
1 , P-alkalinity
(CO
2
1
1
3 ) 0.00 mg L , M-alkalinity (HCO3 ) 560.2 mg L ,

1

1
total alkalinity 560.3 mg L , concentration of sulphate
(SO
2
1
1
4 ) 187.5 mg L , nitrates conc. (NO3 ) 27.5 mg L ,

1

3
1
1
phosphate conc. (PO4 ) 21.2 mg L , chlorides conc. (Cl )
1425.2 mg L
1 and iron conc. (Fe) is 0.12 mg L
1.
2.2. Synthesis and characterization of sorbent (HEC-Adip-Na)
2.2.1. Synthesis of HEC-adipate and its sodium salt
For the synthesis of HEC-Adip, dried (at 10° C for 5 h in vac-
uum oven) hydroxyethylcellulose (HEC, 10 g, 36 mmol) was
dissolved in 80 mL of DMAc and the mixture was continu-
ously stirred for 2 h at 353 K temperature to get its clear solu-
tion. Adipic anhydride (29.8 g, 108 mmol) was added into the
solution by parts and stirred at the same temperature (353 K)
for 24 h. The product of the reaction was then precipitated and
washed thrice with diethyl ether (250 mL). The product
obtained was dried in vacuum oven at 50 °C for 24 h.
DS: 1.02; Yield: 12.6 g (85%)
FTIR: 3292 cm
1 (OAH), 2889 cm
1 (CAH), 1712 cm
1
(C‚OEster) and 1045 cm
1 (CAOAC).
The HEC-Adip was treated with NaHCO3 (saturated
solution) and stirred for 2.0 h to get the final product HEC-
Adip-Na. The HEC-Adip-Na was separated from solution
by filtration and then dried.
FTIR: 3483 cm
1 (OAH), 2879 cm
1 (CAH), 1724 cm
1
(C‚OEster), 1564 cm
1 (COO
), 1056 cm
1 (CAOAC).
2.2.2. Measurements
FTIR spectrometer (IR Prestige-21, Shimadzu, Japan) was
used for the spectroscopic analysis and spectrum was recorded
between the scanning range 5000–500 cm
1 on the frequency
of 400 MHz. KBr pellets of samples were prepared and dried
in an oven for 30 min at 60 °C before analysis. The 13C
NMR (solid state CP/MAS) of the HEC-Adip-Na (sorbent)
was obtained at room temperature, 100 MHz, acquisition time
0.032 s, NS 5000, Delay time 4.85 ms at proton 90° using DRX-
400, Bruker instrument. SEM-EDS (scanning electron
microscopy-energy dispersive spectroscopy) image of the sam-
ples were recorded on 1530 Gemini LEO (Carl Zeiss) by mak-
ing a thin coating of dry sample pasted on carbon tape. FAAS
analysis was performed using flame absorption spectrometer
(AA 6300, Shimadzu, Japan) with a supply air-acetylene
2768
mixture. The sample was irradiated with radiation of wave-
length 228.8 nm for the determination of Cd(II) ion concentra-
tion in GW and DW before and after the action of adsorbent.
2.2.3. Determination of degree of substitution (DS)
In order to calculate the degree of substitution (DS) of
HEC-Adip, 100 mg of the product was mixed with 100 mL
of saturated solution of NaHCO3 for about 2 h at room tem-
perature. The solution was filtered and a known volume of
sodium bicarbonate (NaHCO3) was titrated against 0.02 M
hydrochloric acid (HCl) with methyl orange indicator. The
volume of HCl required for the neutralization of NaHCO3
was used for the determination of DS of HEC-Adip with the
help of following (Eq. (2)) relation;
nAdip ¼ VNaHCO3  MNaHCO3
VHCl  MHCl ð1Þ
276:14  nAdip
DS ¼ ð2Þ
mHEC
Adip
100  nAdip
where mHEC-Adip is the mass of HEC-Adip, nAdip is the number
of moles of carboxylate moieties conjugated with HEC-Adip,
276.14 is the mass of HEC repeating unit.
2.2.4. Calculation of yield
In order to calculate the theoretical yield of HEC-Adip, fol-
lowing equation is used (Hussain et al., 2010);
 
WP
Theoretical Yield ¼ WP þ  DS  MAdip ð3Þ
MwofHEC
where WP is mass of polymer used for reaction, Mw of HEC
denotes the mass of HEC repeating unit, DS is the degree of
substitution of adipate moiety and MAdip is molar mass of
adipic acid.
2.2.5. Determination of pHZPC (pH corresponding to zero point
charge)
The value of pHZPC, pH corresponding to zero point charge
(ZPC) of the sorbent HEC-Adip-Na was determined by using
solid addition method (Kumar et al., 2008). NaNO3 solution
(50 mL, 0.1 M) were taken and their initial pH values (pHi)
were adjusted between the range of 2–10 by using 0.1 M HCl
or 0.1 M NaOH. Sorbent (50 mg) was added to each solution
and shaken for 2 h at 200 rpm at room temperature. The mix-
tures were then filtered after 2 h and final pH values (pHf) of
filtrate were again determined. A graph was plotted between
pHi and pHf -pHi. The point at which it intersected the
X-axis showed the value of pHZPC. The surface of the sorbent
will be negatively charged at pH greater than its pHZPC which
favors uptake of Cd(II) ions by the sorbent.
2.3. Sorption kinetics
Batch experiments were conducted by adding of the sorbent
(50 mg) into Cd(II) ions solution (100 mL) of known concen-
trations (both DW and GW). The extent of Cd(II) ion uptake
by the sorbent, qe in mg g
1 was figured out by using the
following relation (Eqs. (4) and (5);
Ci
Ce
qe ¼ V ð4Þ
m
M.A. Hussain et al.
Ci
Ce
Percentage uptake ¼  100 ð5Þ
Ci
In this equation, Ci and Cf are the initial and final concen-
trations of Cd(II) ions in mg L
1, respectively. V (L) and m (g)
are the volume of solution and mass of adsorbent, respectively.
2.3.1. Effect of the initial metal ion concentration
For the determination of effect of metal ion concentration on
the adsorption of Cd(II) ions, solution of different concentra-
tions, i.e., 20, 40, 60, 80, 100, 120 and 140 mg L
1 were pre-
pared in both GW and DW. Experiments were performed by
adding of sorbent (HEC-Adip-Na, 50 mg) in each solution
and stirring for 30 min at 200 rpm speed and temperature of
298 K.
2.3.2. Effect of sorbent dosage
For the investigation of the effect of sorbent on sorption
capacity of HEC-Adip-Na, varied amounts of sorbent (30–
100 mg) were added to Cd(II) ions solution (100 mL) having
optimized concentration, i.e., 60 mg L
1 in both GW and
DW and stirred continuously for 30 min at 200 rpm and 298
K temperature.
2.3.3. Effect of contact time
Optimum time for maximum sorption capacity was deter-
mined by stirring the mixture having metal ions and sorbent
at room temperature for time intervals between the range 5–
120 min under optimized conditions of initial metal ion con-
centration (60 mg L
1) and sorbent dosage (50 mg).
2.3.4. Effect of initial pH
The effect of pH on the sorption of HEC-Adip-Na was deter-
mined by preparing solutions of Cd(II) ions (both GW and
DW) having a range of pH between 2 and 7 using 1 M NaOH
or 1 M HCl solutions and then treating with sorbent at opti-
mized conditions. The sorbent was allowed to settle and then
it was filtered by applying vacuum suction. The filtrate was
analyzed through FAAS.
2.3.5. Effect of temperature
The effect of temperature on the sorption of Cd(II) ions by
HEC-Adip-Na was also studied. For this purpose the same
sorption process was carried out at different temperatures
ranging from 298 to 338 K. Kinetic studies were performed
by analyzing the contents of mixture at different time intervals
before the achievement of equilibrium. Adsorption isotherms
were also plotted for the adsorption of Cd(II) ions by the sor-
bent (HEC-Adip-Na) at above mentioned optimal parameters.
2.4. Regeneration studies
Regeneration studies were also performed on the sorbent. Sor-
bent (50 mg) was stirred with 100 mL of both GW and DW
solution with 60 mg L
1 initial concentration of Cd(II) ions
for 30 min. The mixture was filtered and recovered sorbent
was then agitated with 100 mL of freshly prepared saturated
solution of NaCl (brine) for 24 h. The mixture was then filtered
and washed with DW repeatedly until it gave negative result
Sodium hyroxyethylcellulose adipate: An efficient and reusable sorbent 2769

with AgNO3 test. The recovered sorbent was then air-dried. The obtained chemically modified product was then treated
The regenerated sorbent was used for the uptake of Cd(II) ions with saturated solution of NaHCO3 to get its sodium salt
again. The same sorption and desorption experiment was con- (HEC-Adip-Na). Fig. 1 shows the schematic diagram of syn-
ducted for five times repeatedly and sorbent was washed with thesis of HEC-Adip and HEC-Adip-Na.
distilled water each time till neutralization, before proceeding
to next cycle. Sorption experiment was also carried out on 3.1.2. FTIR spectroscopic analysis
the acidic form of the sorbent (HEC-Adip) by stirring sorbent
Fig. 2 shows the FTIR (KBr) spectrum of HEC-Adip and
(50 mg) with GW and DW solutions (100 mL) containing Cd
HEC-Adip-Na, HEC-Adip-Cd. The spectra show that multi-
(II) solution for metal-uptake at specified pH and 298 K.
ple functionalities are present in the sorbent. The band at
All the experiments were performed in triplicates and the
1712 cm
1 in the spectrum of HEC-Adip shows presence of
concurrent values were taken to present results.
ester carbonyl functional group which indicate effective link-
age of HEC with adipic anhydride. Spectrum of HEC-Adip
3. Results and discussions
shows that after the formation of sodium salt of HEC-Adip,
this signal transferred to a higher value of 1724 cm
1 and a
3.1. Synthesis and characterization of the sorbent (HEC-Adip- typical peak at 1564 cm
1 confirms the presence of carboxylate
Na) anion showing successful formation of sodium salt of HEC-
Adip. In FTIR spectrum of HEC-Adip-Cd, a shift in peak
3.1.1. Synthesis of HEC-Adip and its sodic form positions especially in finger print region and from 1724 to
HEC-Adip (hydroxyethylcellulose adipate) was synthesized by 1548 cm
1 was observed. This change in FTIR spectra in mov-
the reaction of HEC with adipic anhydride in DMAc solvent ing from HEC-Adip-Na to HEC-Adip-Cd was due to the bind-
in the presence of DMAP (4-dimethylamino pyridine) catalyst. ing of cadmium with carboxylic acid group of the adsorbent.
Shifting of these peaks is an evidence of successful adsorption
O of Cd(II) on the surface of the adsorbent. The intense bands
OH
O appeared at 857 and 571 cm
1 in the spectrum of HEC-
Adip-Cd are also characteristic for Cd to oxygen bond.
O R=H or hydroxyethyl
13
RO O 3.1.3. Solid-state C NMR spectroscopic analysis (CP/MAS)
Solid state (CP/MAS) 13C NMR spectroscopic analysis of
O OR HEC-Adip-Na was performed to confirm the adipate forma-
HEC O tion (Fig. 3). The signal at 174.94 ppm (C-11) showed ester sig-
nal for successful adipate formation wherewas signal at 182.54
Adipic anhydride
80°C, 24 h
ppm (C-16) showed sadium salt formation of terminal COOH
group of HEC-Adip. Another peak at 27.15 ppm (C-12-15)
exhibits CH2 groups in adipate moiety of HEC-Adip-Na.
O
Peaks at 104.15 ppm and 62.08 ppm show C-1 and C-6 in
O OH the HEC-Adip-Na respectively. Signals of methylene protons
O of hydroxyethyl group are overlapped with signals of polymer
O
O backbone. Other signals in the range of 71.28–83.10 ppm
O showed C-2-5 and C-7-10 of HEC-Adip-Na.
R=H or
RO O
Adipate moities 3.1.4. SEM-EDS analyses
O OR SEM analysis was carried out to investigate the surface
HEC-Adip O morphology of acidic form (HEC-Adip), sodic form (HEC-
Adip-Na) and sodic form of sorbent after Cd(II) uptake.
NaHCO3 SEM analyses showed that the surface topology of the sorbent
RT, 2h (HEC-Adip-Na) was rigid and rough (Fig. 4a–c). EDS plots
show the presence of Na ions and Cd ions in the sorbent before
O and after sorption, respectively (Fig. 4d–f).
O ONa
O 3.2. Determination of the pH of zero-point charge (pHZPC)
O
O
O The pHZPC of the sorbent was also investigated to determine
RO R=H or the charge on the surface of the sorbent (HEC-Adip-Na) and
O
Adipate-Na moities it was found to be 5 (Fig. 5). This value shows that the sorbent
O OR has weak acidic character due to COOH groups of adipate
O moieties of the sorbent. This means that at pH 5, i.e., pHZPC,
HEC-Adip-Na the surface of the sorbent is neutral while above and below this
pH surface of the sorbent has negative and positive charge,
Fig. 1 Schematic diagram for the synthesis of HEC-Adip and its respectively. Any pH value greater than 5 will favour metal
conversion to HEC-Adip-Na. uptake.
2770 M.A. Hussain et al.

HEC-Adipate

1634
2889

1713
3229

1045
HEC-Adipate-Na

1645
1724

1564
3292

2880

HEC-Adip-Na after

1057
Cd(II) uptake

1641
1548
1722
3258

571
1062
2892

857
3500 3000 2500 2000 1750 1500 1250 1000 750 500
Wavenumber, cm-1

Fig. 2 FTIR (KBr) spectra of HEC-Adip, HEC-Adip-Na and HEC-Adip-Na after Cd(II) uptake.

13
Fig. 3 Solid-state CP/MAS C NMR spectra of HEC-Adip-Na.

3.3. Sorption studies
3.3.1. Effect of the initial metal ion concentration
The effect of initial metal ion concentration on the sorption
capacity of HEC-Adip-Na for the uptake of Cd(II) ions was
investigated both from GW and DW. Sorbent (50 mg) of
was added into the solutions having different metal ion con-
centration ranging from 20 to 140 mg L
1. A graph was plot-
ted between initial metal ion concentration and sorption
capacity (Fig. 6a). It is evident from the graph that in start,
the sorption capacity of sorbent increased with increase in
metal ion concentration but later it became constant. The rea-
son behind might be that at the start more sites of the sorbent
were available for the uptake of metal ions but later on all the
sites were occupied so the rate becomes constant. The sorbent
showed maximum sorption capacity at 60 mg L
1 for both
GW and DW solutions. This optimized concentration was
used for further studies.
3.3.2. Effect of the sorbent dosage
The effect of sorbent dosage on the sorption capacity was
investigated by varying the amount of sorbent in the range
Sodium hyroxyethylcellulose adipate: An efficient and reusable sorbent 2771

a
d

100µm

b e

100µm

c
f

100µm

Fig. 4 SEM images of HEC-Adip (a), HEC-Adip-Na (b), HEC-Adip-Na after Cd(II) uptake (c), EDS of HEC-Adip (d), HEC-Adip-Na
(e) and HEC-Adip-Na after Cd(II) uptake (f).

5 early 25 min. This fact can be explained in such a way that

greater amount of sorption sites were present in the start but
4 after some time reaction attained equilibrium because all sorp-
3 tion sites were occupied.
pHi-pHf

2 3.3.4. Effect of initial pH on Cd(II) ions uptake

1 The effect of initial pH on the sorption capacity of sorbent
0 (HEC-Adip-Na) was also observed at 60 mg L
1 of initial
0 2 4 6 8 10
-1
pHi
-2
Fig. 5 Zero point charge pH (pHZPC) of HEC-Adip-Na sorbent.
30–100 mg. The graph showed an increase in the sorption
capacity with an increase in the sorbent dosage due to the
increase in the availability of active sites of the sorbent but
decreases at later stage due to the reason that all Cd(II) ions
have been adsorbed and exchange sites are still available.
Moreover, it was also inferred that uptake of Cd(II) ions from
distilled water (DW) was greater than ground water (GW).
The reason behind this fact is the competition for the sorption
sites between the alkaline earth metal ions and Cd(II) ions. The
plot (Fig. 6b) shows that maximum sorption capacity was
observed for 50 mg of sorbent for both GW and DW solutions
and this amount was used for further studies.
3.3.3. Effect of contact time
Fig. 6c illustrates the effect of contact time on the sorption
capacity of sorbent. The uptake of Cd(II) ions was estimated
between the time range 5–120 min. The plot showed that max-
imum level of uptake of about 95% was achieved within the
Cd(II) ion concentration and 50 mg sorbent dosage (Fig. 6d).
The pH of solution was varied between the ranges 2–7. The
uptake of Cd(II) was found to be highly pH dependent. At
acidic pH, sorption of Cd(II) ions was very low but it acceler-
ated rapidly when the pH increased from 5 onwards. This was
due to the reason that lower pH causes the protonation of
HEC-Adip-Na to form its acidic derivative (HEC-Adip) leav-
ing no more Na ions to be exchanged with Cd(II) ions. At pH
greater than 5.0 (pHZPC for HEC-Adip-Na) the carboxylic
moiety was deprotonated to favor the uptake of Cd(II) ions
because at pH greater than 5 surface of the sorbent become
negatively charged which favors metal uptake. The maximum
sorption capacity was observed at pH 6.0 for GW and DW
both.
3.4. Kinetic and isothermal modeling
3.4.1. Kinetic modeling
Kinetic study of the sorption process was done to investigate
the mechanism of the process because it is necessary to know
the exact mechanism of process before designing a system of
water purification. Two different kinetic models (pseudo-first
order and pseudo-second order) were applied to the sorption
data.
2772 M.A. Hussain et al.

120 120
(a) (c)
Sorption capacity, mg g-1 100 100

Sorption capacity, mg g-1

80
80
60
60
DW 40 DW
40 GW GW
20

20 0
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120
Initial metal ion concentration, mg L-1 Time, min
135 140

120 (b) 120 (d)

Sorption capacirty, mg g-1

Sorption capacity, mg g-1

105 100

90 80

75 60 DW
GW
60 40
DW
45 GW 20

30 0
20 40 60 80 100 2 3 4 5 6 7
Sorbent dosage, g pH

Fig. 6 Sorption capacity of HEC-Adip-Na as a function of initial Cd(II) concentration from DW and GW (sorption conditions: sorbent
dose = 50 mg in 100 mL Cd(II) solution, Cd(II) concentration both in DW and GW = 20–140 mg L
1, temperature = 298 K, contact
time = 30 min, pH was kept at 6.0 for both DW and GW) (a). Sorption capacity of HEC-Adip-Na as a function of sorbent dosage
(sorption conditions: sorbent dose = 30–100 mg in 100 mL Cd(II) solution, Cd(II) concentration both in DW and GW = 60 mg L
1,
temperature = 298 K, contact time = 30 min, pH was kept at 6.0 for both DW and GW) (b). Sorption capacity of HEC-Adip-Na as a
function of contact time (sorption conditions: sorbent dose = 50 mg in 100 mL Cd(II) solution, Cd(II) concentration both in DW and
GW = 60 mg L
1, temperature = 298 K, contact time = 5–120 min, pH was kept at 6.0 for both DW and GW) (c). Sorption capacity of
HEC-Adip-Na as a function of pH of solution (sorption conditions: sorbent dose = 50 mg in 100 mL Cd(II) solution, Cd(II)
concentration both in DW and GW = 60 mg L
1, temperature = 298 K, contact time = 30 min, pH was changed from 2 to 7 for both
DW and GW) (d).

Pseudo-first order kinetic model can be explained in terms t 1 t

of the following linear equation (Eq. (6));
k1
logðqe
qt Þ ¼ logqe
t ð6Þ
2:303
In this equation, qe and qt denotes the amounts of metal
ions adsorbed at equilibrium and the time t, respectively; k1
(g mg
1 min
1) is the rate constant of the reaction. If straight
line is obtained by plotting logðqe
qt Þ against t then it would
indicate that the same model is applicable to the given situa-
tion. A graph was plotted between logðqe
qt Þ against t
(Fig. 7a). Time range chosen was 5–30 min because it was
found in different cases that experimental data fitted well for
the initial rapid phase to this model.
Values of qe and k1 were calculated from the intercept of
the straight line and its slop, respectively. The values of differ-
ent constant (qe, R2 and k1) are given in the Table 1. Low value
of correlation constant (R2) and deviation of experimental
data indicate that pseudo-first order model didn’t fit well for
both GW and DW. So pseudo-second order kinetic model
was applied, which is given by the following linear relation
(Eq. (7)).
¼ þ ð7Þ
qt kqe 2 qe
where qe and qt denote the amount of metal adsorbed at equi-
librium and time t, k (g mg
1 min
1) is rate constant. Pseudo-
second order model was applied to the whole time range of
experimental data of the sorption process. A graph was plotted
between t/qt against t. A straight line was obtained with higher
value of correlation coefficient (Fig. 7b, Table 1). The values of
qe and k were calculated from the slope and intercept of the
straight line, respectively (Table 1). The qe calculated from
the pseudo-second-order kinetic model matched with the
experimental values. Therefore, it was inferred that pseudo sec-
ond order is best model to evaluate the dynamic sorption of Cd
(II) ions by HEC-Adip-Na (sorbent). Fitting of pseudo second
order kinetic model is also an evidence for involvement of
chemisorption as the rate determining step.
3.4.2. Sorption isotherms
At equilibrium stage, studies of sorption isotherms provide
useful information about the mechanism of sorption process.
A sorption isotherm exhibits the distribution of adsorbed
Sodium hyroxyethylcellulose adipate: An efficient and reusable sorbent 2773

2.5
(a) DW 4.77 (c)
DW
GW
2 4.76 GW
Log (qe-qt)

1.5 4.75

Log qe
4.74
1
4.73
0.5
4.72

0 4.71
0 5 10 15 20 25 30 4 4.2 4.4 4.6 4.8 5
t, min
Log Ce
1.2
1.4
(b) (d)
1
1.2

Ce/qe, mg L-1 /mg g-1

t/qt, min/mg g-1

0.8
1
0.6
0.8
0.4
DW DW
0.6 GW
0.2 GW

0 0.4
0 20 40 60 80 100 120 50 70 90 110 130 150
t, min Ce, mg L-1

Fig. 7 Pseudo-first order (a), pseudo-second order (b) kinetic models, Freundlich (c) and Langmuir sorption isotherm (d) for Cd(II)
uptake by HEC-Adip-Na sorbent from GW and DW solutions.

Table 1 Pseudo-second order, pseudo-first order, Langmuir, molecules between the sorbent (solid phase) and the adsorbate
Freundlich, ion-exchange models and thermodynamic param- (liquid phase) of any sorbate-sorbent system. The experimental
eters for for Cd(II) uptake by HEC-Adip-Na from GW and data obtained from the sorption of Cd(II) ions by the prepared
DW solutions. sorbent (HEC-Adip-Na) from both GW and DW solutions
Models Parameters DW GW was fitted to both Langmuir and Freundlich isotherms. Fre-

1 undlich isotherm model can be written in the form of following
Pseudo second order qe (mg g ) 120.48 120.48
linear equation (Eq. (8));
k2 (g mg
1 0.0040 0.0018
min
1) 1
R2 0.9997 0.9990 logqe ¼ logkF þ logCe ð8Þ
n
Pseudo first order qe (mg g
1) 8.770 10.93 where Ce (mg L
1) is equilibrium metal ion concentration, qe
k1 (g mg
1 0.0878 0.0747 (mg g
1) is equilibrium sorption capacity, kF and n are the Fre-
min
1)
undlich constant and sorption intensity, respectively. The val-
R2 0.9188 0.9456
ues of sorption parameters for Freundlich isotherm (R2, kF and

1
Experimental qe (mg g ) 114.94 112.35 n) are obtained by plotting a graph (Fig. 7c) between log qe
Langmuir parameters Qmax (mg g )
1
112.37 1.0019 and Ce and there values are given in the Table 1.
b (mg L
1) 1.2428 1.8937 It is evident from the plot that it has low value of correla-
R2 0.9998 0.9999 tion coefficient (R2) which indicates that Freundlich isotherm
RL 0.0132 0.0087 model is not valid for this sorption process. So the data was
Freundlich parameters n
170.7
488 fitted to Langmuir isotherm model, which is represented by lin-
kF 119.43 113.27 ear equation given as (Eq. (9));
R2 0.3228 0.0147 Ce Ce 1
¼ þ ð9Þ
Ion Exchange model S (min
1) 0.08070 0.5488 qe Qmax Qmax  b
R2 0.9977 0.9978
where Ce (mg L
1) and qe (mg g
1) are Cd(II) ions concentra-
Thermodynamic DS° (J mol
1
101.90
80.351 tion at equilibrium and equilibrium sorption capacity, respec-
parameters K
1)
tively. Qmax (mg g
1) and b are maximum sorption capacity of
DH° (kJ mol
1)
38.632
30.595
sorbent and Langmuir constant, respectively. When the graph
R2 0.9862 0.9844
DG° (kJ mol
1)
8.73
6.50 was plotted between Ce/qe and Ce, a straight was obtained with
high correlation coefficient for both GW and DW (Fig. 7d).
2774 M.A. Hussain et al.

The values of Qmax and b were calculated from the slop and
intercept of the straight line, respectively (Table 1).
Maximum sorption capacities for Cd(II) ions uptake by the
sorbent (HEC-Adip-Na) were calculated to be 112.35 and
114.94 mg g
1 for GW and DW solutions. Validation of this
model by the experimental data confirms the formation of
monolayer, i.e., chemisorption.
The value of separation factor (RL) is also used to investi-
gate whether the process of sorption is favorable or not, if
its value is between 0 and 1. It is given by the following equa-
tion (Eq. (10));
1 Cads
RL ¼
1 þ bCi
Table 1 shows that RL has values between 0 and 1 indicat-
ing that uptake of Cd(II) by the sorbent is a favorable process
(Table 1).
3.5. Effect of temperature
In order to predict the thermodynamic nature of sorption pro-
cess, effect of temperature on the sorption capacity of HEC-
Adip-Na was also examined under optimized conditions by
changing temperature between the range 298–338 K
(Fig. 8a). It was observed that the sorption capacity reduced
by 22.9 and 19.2 mg g
1 for GW and DW solutions, respec-
tively. Hence, it was inferred that the process of sorption
was exothermic in nature. The reason behind this decrease in
sorption capacity can be explained on the basis of mobility
of Cd(II) ions which increases as the temperature is increased
which results in decreased adsorbent-adsorbate interaction.
3.6. Determination of thermodynamic parameters
Thermodynamic parameters (DG°, DS° and DH°) were also
estimated to predict the spontaneity of sorption process by
using the data obtained from the effect of temperature on
the sorption capacity of HEC-Adip-Na for uptake of Cd(II)
ions from GW and DW solutions. These parameters can be
measured by using the following relations (Eqs. (11)–(13);
ð10Þ Kc ¼ ð11Þ
Ce
DGo ¼
RlnKc ð12Þ
DSo DHo
lnKc ¼
ð13Þ
R RT
In Eq. (11), Kc represents equilibrium sorption constant,
Cads shows amount of adsorbed metal and Ce is the concen-
tration of metal ions at equilibrium stage. When a graph
was plotted between lnKc and 1/T (K
1), a straight line
was obtained ((Fig. 8b) with slop and intercept giving the
value of entropy change (DS°) and enthalpy change (DH°),
respectively. Negative values of entropy (DS°) shows spon-
taneity of the sorption while negative values of DG° and
DH° demonstrate the exothermic nature and feasibility of
the process (Table 1).

130 DW 4
DW
GW 3.5
120 GW
Sorption capacity, mg g-1

3
110 2.5
100 2
Ln Kc

1.5
90
1
80 (a) 0.5 (b)
70 0
295 305 315 325 335 345 0.00285 0.00295 0.00305 0.00315 0.00325 0.00335
1/T, K-1
T, K
t, min
0 10 20 30 40 50 60 70 80 90
0
-0.5
-1
log(1-F)

DW
-1.5
GW
-2
-2.5
-3 (c)
-3.5

Fig. 8 Sorption capacity of HEC-Adip-Na as a function of temperature (sorption conditions: sorbent dose = 50 mg in 100 mL Cd(II)
solution, Cd(II) concentration both in DW and GW = 60 mg L
1, temperature = 298–343 K, contact time = 30 min, pH was kept at 6.0
for both DW and GW) (a), effect of temperature on equilibrium constant (Kc) (b) and fitting of ion exchange model for Cd(II) uptake by
HEC-Adip-Na from GW and DW solutions (c).
Sodium hyroxyethylcellulose adipate: An efficient and reusable sorbent 2775

3.7. Mechanism of sorption form (HEC-Adip-Na) has very enhanced activity of Cd(II)
uptake (93.3 and 96.6% from GW and DW, respectively)
High rate of Cd(II) uptake during initial phase of sorption because it has sufficient Na ions on its surface which can be
indicates that ion-exchange mechanism is involved in the sorp- exchanged with Cd(II) ions. Application of pseudo-second
tion process. It can also be observed that the sorbent has neg- order model and Langmuir isotherm model also confirms the
ligible property of Cd(II) uptake (9% and 13% from GW and involvement of ion-exchange mechanism. Moreover, Fig. 4f
DW, respectively) in its acidic form (HEC-Adip) while its sodic shows no signal for Na ions which might be an evidence that

Table 2 Comparison of HEC-Adip-Na for Cd (II) uptake from GW and DW solutions with other reported sorbents.
Sorbent (treatment) Sorption capacity (mg g
1) References
Spent green (modified with sodium hydroxide, pH 5.3–5.6, 298 K, 2 h) 17.3 Low et al. (2000)
Bagasse pith (SO2 and H2S, heat) 149.9 Krishnan and Anirudhan (2003)
Corncob (modified with citric acid and nitric acid pH 6.0, 298 K) 32.3 and 19.3, respectively Leyva-Ramos et al. (2005)
Mercerized cellulose (modified with succinic anhydride, 10 min) 250 Gurgel et al. (2008)
Mercerized sugarcane bagasse (functionalized with ethylenetetramine, 20 min) 86 and 106.4 Gurgel and Gil (2009)
Filter aid cellulose (modified with succinic anhydride, sodic) 178.6 from GW Belhalfaoui et al. (2009)
COOH/TUD-1 mesoporous solid 72.34 Bensacia et al. (2014)
Hydroxyethylcellulose (modified with succinic anhydride, 15 min) 454.5 from GW Abbas et al. (2015)
Hydroxyethylcellulose (modified with adipic anhydride) 114.94 from DW Present study
112.35 from GW
Note: All values of sorption capacities given in table are calculated by Langmuir model.

118 (a) 115 (b)

Sorption Sorption
Desorption
Sorption capacity, mg g-1

114 Dsorption 110

Sorption capacity, mg g-1

110 105

106 100

102 95

98 90

94
85
1 2 3 4 5
1 2 3 4 5
Number of cycles Number of cycles

100 DW
90 (c) GW

80
Metal uptake, %age

70

60

50

40

30

20

10

0
HEC-Adip HEC-Adip-Na Regenerated Regenerated Regenerated Regenerated
(1st cycle) HEC-Adip-Na HEC-Adip-Na HEC-Adip-Na HEC-Adip-Na
(2nd cycle) (3rd cycle) (4th cycle) (5th cycle)

Fig. 9 Adsorption–desorption values for Cd(II) ions by HEC-Adip-Na (sorption conditions: sorbent dosage = 50 mg/100 mL for both
DW and GW, Cd(II) concentration = 60 mg L
1, temperature = 298 K, pH = 6.0 for both DW and GW solutions. Desorption
conditions: 50 mg Cd(II)-loaded HEC-Adip-Na/100 mL of saturated solution of M NaCl contact time = 24 h at a temperature = 298 K)
DW(a), GW (b) solutions and percentage of Cd(II) ions uptake by the acidic (HEC-Adip), and its sodic form (HEC-Adip-Na) and
regenerated sodic forms of the sorbent from GW and DW solutions over five cycles (c).
2776
all the Na ions in the sorbent are exchanged with Cd(II) ions
and ion exchange is the main phenomenon involved in sorp-
tion of Cd(II) ions by the sorbent.
Boyd et al in 1947 (Boyd et al., 1947) derived an equation
for ion-exchange mechanism (Eq. (14));
S Abbas, A., Hussain, M.A., Amin, M., Sher, M., Tahir, M.N., Tremel,
logð1
FÞ ¼
t ð14Þ
2:303
q
F¼ t ð15Þ
qe
where qe and qt are amounts of metal adsorbed at equilibrium
and time t, respectively and S (min
1) is a constant. Values of
log(1-F) were plotted against t. A Straight line was obtained
with high values of correlation coefficient which further veri-
fied the involvement of ion-exchange mechanism during sorp-
tion of Cd(II) ions from GW and DW solutions (Fig. 8c,
Table 1).
HEC-Adip-Na sorbent appeared highly valuable in term of
high sorption capacity for Cd(II) uptake and got reasonable
place in chemically modified polysaccharide based sorbents
(Table 2).
3.8. Sorption and desorption (Re-generability)
Regenerability studies are performed to check the efficiency
of prepared sorbent in real situations. For this purpose,
HEC-Adip-Na (sorbent) was first used for Cd(II) uptake
and then almost all sorbed Cd(II) were desorbed by treating
with brine and then washing with deionized water. This
regenerated sorbent was again used for Cd(II) uptake. Same
experiment was repeated up to five regeneration cycles for
both GW and DW solutions. The results of sorption–des-
orption experiments have been given in Fig. 9a and 9b,
respectively and these show that there is negligible decrease
in sorption capacity (10 mg g
1 for DW and 14 mg g
1 for
GW) of the sorbent after five cycles.
A graph was plotted between percentage values of sorption
and number of sorption–desorption cycles for Cd(II) ions
removal (Fig. 9c). It indicated a slight decrease in the percent-
age of Cd(II) ions uptake (11.4 and 8.3% from GW and DW
solutions, respectively) after five regeneration cycles.
4. Conclusions
Present study illustrates synthesis, characterization and use of
a novel material (HEC-Adip-Na) as a sorbent for the removal
of Cd(II) ions from spiked high-hardness ground water (GW)
and distilled water (DW). The experimental sorption data was
best fitted to Langmuir isotherm and pseudo-second order
kinetic model. Negative values of thermodynamic parameters
(DG°, DS° and DH°) showed spontaneity and feasibility of
the sorption process. The sodic form of sorbent (HEC-Adip-
Na) proved a better choice for the adsorption of Cd(II) ions
as their sorption capacity is calculated to be 112.35 and
114.94 mg g
1 form GW and DW solutions, respectively. It
is also concluded that HEC-Adip-Na have high selectivity
for Cd(II) ions in the presence of other bivalent (Ca+2 and
Mg+2) metal ions which are generally found in GW. Regener-
ation studies confirm that the prepared sorbent (HEC-Adip-
Na) has negligible decrease in sorption capacity over five
regeneration cycles for the uptake of Cd(II) ions which
M.A. Hussain et al.
suggests that it can serve as an economical sorbent for GW
purification because it can be recycled many times.
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