Accepted Manuscript

Title: Design, characterization and evaluation of

hydroxyethylcellulose based novel regenerable supersorbent
for heavy metal ions uptake and competitive adsorption

Authors: Azhar Abbas, Muhammad Ajaz Hussain,

Muhammad Sher, Muhammad Imran Irfan, Muhammad
Nawaz Tahir, Wolfgang Tremel, Syed Zajif Hussain, Irshad
Hussain

PII: S0141-8130(16)32535-1
DOI: http://dx.doi.org/doi:10.1016/j.ijbiomac.2017.04.024
Reference: BIOMAC 7388

To appear in: International Journal of Biological Macromolecules

Received date: 20-11-2016

Revised date: 30-3-2017
Accepted date: 5-4-2017

Please cite this article as: Azhar Abbas, Muhammad Ajaz Hussain, Muhammad
Sher, Muhammad Imran Irfan, Muhammad Nawaz Tahir, Wolfgang Tremel,
Syed Zajif Hussain, Irshad Hussain, Design, characterization and evaluation
of hydroxyethylcellulose based novel regenerable supersorbent for heavy metal
ions uptake and competitive adsorption, International Journal of Biological
Macromoleculeshttp://dx.doi.org/10.1016/j.ijbiomac.2017.04.024

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Design, characterization and evaluation of hydroxyethylcellulose based novel

regenerable supersorbent for heavy metal ions uptake and competitive

adsorption

Azhar Abbasa, Muhammad Ajaz Hussaina,*, Muhammad Shera, Muhammad Imran Irfana,

Muhammad Nawaz Tahirb, Wolfgang Tremelb, Syed Zajif Hussainc, Irshad Hussainc

a
Department of Chemistry, University of Sargodha, Sargodha 40100, Pakistan

b
Institute of Inorganic and Analytical Chemistry, Johannes Guttenberg University,

Duesbergweg 10-14, 55128 Mainz, Germany

c
Department of Chemistry, SBA School of Science & Engineering (SSE), Lahore University

of Management Sciences (LUMS), DHA, Lahore Cantt. 54792, Pakistan

* Corresponding author.

Tel.: +923468614959; Fax: +92483222121.

E-mail address: majaz172@yahoo.com (M.A. Hussain)

1
Highlights

 Synthesis of Na-succinate bonded hydroxyethylcellulose (HEC-Suc-Na)

 Evaluation of HEC-Suc-Na as a supersorbent for heavy metal ions uptake

 Kinetic and isothermal modelling

 Competitive metal uptake

ABSTRACT

Hydroxyethylcellulose succinate-Na (HEC-Suc-Na) was designed and evaluated for removal

of some heavy metal ions from aqueous solution. Pristine sorbent HEC-Suc-Na was thoroughly

characterized by FTIR and solid-state CP/MAS 13C NMR spectroscopy, SEM-EDS and zero

point charge analyses. Langmuir isotherm, pseudo second order kinetic and ion exchange

models provided best fit to the experimental data of sorption of metal ions. Maximum sorption

capacities of supersorbent HEC-Suc-Na for sorption of heavy metal ions from aqueous solution

as calculated by Langmuir isotherm model were found to be 1000, 909.09, 666.6, 588 and 500

mg g-1 for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II), respectively. Competitive sorption of these

heavy metal ions was carried out from galvanic and nuclear waste water simulated

environment. The negative values of ∆G° and ∆H° indicated spontaneity and exothermic nature

of sorption. The sorbent was efficiently regenerated with no significant decrease in sorption

capacity after five cycles.

Keywords:

Cellulose

Metal uptake

Hydroxyethylcellulose
2
Succinylation

Competitive adsorption

1. Introduction

Heavy metal ions contaminated water may cause serious and irreversible damage to the

body vital organs such as lungs, kidneys, heart and liver [1-4]. Therefore, removal of toxic

metal ions from wastewater is utmost important. Sources of heavy metal ions in aqueous bodies

are unplanned industrialization and improper disposal of industrial wastewater [5]. Heavy

metals are removed from contaminated water using different techniques, i.e., precipitation,

adsorption, ion-exchange, filtration, electrochemistry, chelation and reverse osmosis, etc [6,7].

Among above mentioned methods, the ion exchange is of particular interest because it is rapid

and reversible process. In ion exchange, ions held in a porous and essentially insoluble solid

matrix allow the exchange of ions in solution. Further advantages of ion exchange materials

are selective removal of metal ions, high efficiency and regenerability [8].

Almost all of the renewable, abundant and low cost heavy metal sorbents such as fruit peels,

agricultural waste and plant barks, etc., consist of cellulosic materials. These un-modified

cellulosic sorbents showed low to moderate sorption capacity to remove heavy metals and dyes

from water [5-9]. Few recent reports suggested that after chemical modification of cellulosic

materials, their sorption capacity increases many fold and followed ion exchange mechanism

[10].
3
 Succinylated polysaccharaides are gaining more attraction for the removal of metal ions

due to their high sorption capacity, low cost, commercial availability and environment friendly

nature. Chemically cross-linked succinylated lignocellulose exhibited strong attraction with Pb

and Cd ions [10,11]. Succinylated corn starch showed high potential for heavy metal ions

uptake [12]. Similarly, succinylated chitosan makes the water clean by attracting copper ion

and dyes [13,14].

Commonly used lignocellulosic materials like agriculture waste contain different types of

functionalities which renders difficulty to assess the type of functionality responsible for metal

ion uptake. As well as, sorption capacity of agriculture waste (cellulosic materials) is also not

appreciable. Therefore, it is desirable to find chemically modifiable, efficient and selective

polysaccharide based supersorbents with single kind of functional groups, like in HEC, to get

tailored derivatives for defined and higher sorption capacity. Based on the above mentioned

literature, among polysaccharides, a commercially available cellulose ether derivative, HEC,

could be a potential choice for metal ion uptake after its chemical modification.

Herein, we report design and characterization of a novel supersorbent HEC-Suc-Na. It was

aimed to evaluate Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) uptake capacity of the newly

engineered supersorbent from aqueous solution. Present investigation also dealt with metal ions

uptake under equilibrium conditions using HEC-Suc-Na and their kinetic evaluation to

establish the mechanism of metal ion uptake. Besides kinetics, our interests were also focused

to estimate thermodynamics parameters, such as, ∆G°, ∆H° and entropy ∆S° which are used to

predict feasibility and spontaneity of sorption. We also dealt with reproducible performance of

regenerated sorbent. Comparative thermal studies of acidic and sodic form of the sorbent were

also aim of the present work.

4
2. Materials and methods

2.1. Materials

Natrosol hydroxyethylcellulose (HE10K, Belgium) was obtained from local market. Before

use HEC was dried at 110 °C for 2 h. All solvents and reagents used were of analytical grade

and provided by Fluka.

2.2. Spectroscopic characterization

IR Prestige-21 (Shimadzu, Japan) spectrophotometer was used to obtain FTIR (KBr)

spectra of the sorbent. The solid-state CP/MAS 13C NMR spectrum of solid sorbent (HEC-Suc-

Na) was attained at ambient temperature (100 MHz, NS 5000, acquisition time 0.032 s, delay

time 2 s, proton 90°, pulse time 4.85 μs) using Bruker DRX-400 machine. Flame atomic

absorption spectrophotometer (FAAS, AA 6300, Shimadzu, Japan) was used to determine

concentration of heavy metal ions in solution using air-acetylene flame.

2.3. Synthesis of HEC-Suc-Na conjugate

An optically clear solution of pre-dried HEC (10.0 g, 36 mmol) was obtained by dissolving

it in DMAc (150 mL) and heated at 80 °C for 2 h with continuous stirring. To pre-dissolved

HEC, succinic anhydride (21.74 g, 217 mmol) was added followed by the addition of

dimethylaminopyridine (DMAP, 500 mg) as a catalyst and reaction mixture was kept under

stirring at 80 °C for 24 h. Reaction mixture was precipitated in diethyl ether (500 mL) to obtain

HEC-Suc. Any unreacted reagent was removed by washing the precipitates with diethyl ether

(250 mL) three times. The precipitates were kept for drying under vacuum at 50 °C overnight.

In order to synthesize HEC-Suc-Na, HEC-Suc was suspended in saturated solution of

NaHCO3 and stirred at room temperature for 2 h. After filtration the product (HEC-Suc-Na)

was washed with distilled water (DW) several times until the filtrate turned neutral.

5
2.4. Determination of degree of substitution (DS)

Acid base titration was also used to calculate DS after saponification. For this purpose

HEC-Suc (100 mg) was put in 0.02 M NaHCO3 solution (100 mL) and stirred for 2 h at room

temperature. A known volume of the NaHCO3 solution was taken after filtration of above

mixture and titrated against 0.02 M HCl. Methyl orange was used as indicator. Following

relations (Eqs. (1) and (2)) were used to calculate DS of free carboxylic acid moieties of HEC-

Suc from the volume of HCl used to neutralize the NaHCO3 solution.

nsuc  VNaHCO3  M NaHCO3  VHCl  M HCl (1)

276.14  nSuc
DS  (2)
m polymer  Suc  100  nSuc

where mpolymer-suc is mass of conjugate HEC-Suc and nsuc is number of moles of carboxylic

acid moieties on to HEC-Suc.

2.5. Calculation of yield

Following relation (Eq. (3)) was used to calculate theoretical yield of the products.

 m polymer  Suc 
Theoretical yeild  mpolymer    DS  M Suc  (3)
 M polymer  Suc 
 

where mpolymer is mass of HEC used, Mpolymer-suc molar mass of HEC-Suc, mpolymer-suc is mass of

HEC-Suc, Msuc is molecular mass of succinate portion and DS is degree of substitution.

2.6. Scanning electron and energy dispersive spectroscopies (SEM-EDS)

SEM images and EDS analyses of the sorbent HEC-Suc-Na before and after metal uptake

were recorded using scanning electron microscope (Nova, NanoSEM 450) equipped with a low

energy Everhart-Thornley detector (ETD) and Oxford Energy Dispersive X-ray (EDX). For

this purpose, the samples were prepared by dispersing the sorbent, as such and after metal (Cr,

6
Co, Ni, Pb and Cu) ions uptake, in deionized water followed by drying their 20 µL volume on

separate aluminum stubs.

2.7. Determination of the zero point charge pH (pHZPC)

Solid addition method was used to determine the pH corresponding to the point of zero

charge (ZPC) for the HEC-Suc-Na [15]. The surface of sorbent will be neutral when pH =

pHpzc. For pH values greater than pHZPC surface of the sorbent become negatively charged and

there will be a positive charge on the surface of the sorbent at pH values lower than pHpzc.

2.8. Sorption studies

Salts of heavy metal ions, i.e., Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) were dissolved in

deionized water (DW) to prepare their stock solutions (1000 ppm). The stock solutions of each

metal ion was then diluted to a required concentration to perform sorption experiments.

Batch experiments were performed by stirring 100 mL of metal ion solutions of known

concentration and 20 mg of the sorbent. The flasks were closed using glass stoppers. These

solutions were then shaken using a shaking thermostat machine (Orbital Shaking Incubator,

PA-42/250R, PAMICO Equipments, Faisalabad, Pakistan) for desired time at a fixed

temperature. The sorbent was then separated from the solution first by decantation and later by

filtration and metal ion concentration in supernatant layer was determined using FAAS.

The wavelengths used to study the remaining concentration of metal ion were 283.3, 357.9,

240.7, 324.5 and 232nm for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II), respectively. The amount

of metal ions removed by the sorbent qe (mg g-1) was calculated by Eqs. (1) and (2) as follows:

Ci  Ce
qe  V (4)
m

Ci  Ce
Percentageuptake  100 (5)
Ci

7
where Ci and Ce are the initial and equilibrium metal ion concentration in mg/L, respectively.

V (L) and m (g) are volume of solution and mass of adsorbent, respectively.

Effect of initial metal ion concentration was studied by stirring the sorbent (20 mg) with

metal ion solution (100 mL) for 30 min at a speed of 150 rpm and 298 K. Initial metal ion

concentration were varied in the range Cr(VI) (110-290 mg L-1 ), Co(II) (70-230 mg L-1), Pb(II)

(120-300 mg L-1), Cu(II) (60-200 mg L-1 ) and Ni(II) (40-220 mg L-1 ). To determine minimum

amount of sorbent which gives maximum sorption capacity, the sorbent, i.e., HEC-Suc-Na (50

mg) was continuously stirred for 30 min with solutions (100 mL) containing optimized metal

ion concentration Pb(II) (180 mg L-1), Cu(II) (120 mg L-1), Cr(VI) (170 mg L-1), Ni(II) (100

mg L-1) and Co(II) (130 mg L-1) at a speed of 130 rpm at 298 K. Effect of shaking time was

observed by agitating the sorbent with metal ion solution under optimal conditions at room

temperature for different time periods between 5-120 min. The sorbent was then allowed to

settle, filtered and the filtrate obtained was analyzed with FAAS. The effect of pH on sorption

capacity of the sorbent was investigated by adjusting the pH of metal ion solution using 1M

HNO3 and 1M NaOH in the range 2.0 to 7.0 followed by treatment with the sorbent at optimal

conditions. FAAS measurements of the filtrate were then conducted. To study the effect of

temperature on sorption, temperature range chosen was 298-343 K. An optimized amount of

the sorbent (20 mg) was added in DW (100 mL) containing Cu(II) (120 mg L-1), Pb(II) (180

mg L-1), Ni(II) (100 mg L-1), Cr(VI) (170 mg L-1) and Co(II) (130 mg L-1) and stirred for 30

min at a speed of 130 rpm at optimal pH. Adsorption isotherm studies were performed by

stirring 20 mg of the sorbent with various concentrations of different metal ions under the above

mentioned optimum parameters. Kinetics studies were carried out by analyzing samples

withdrawn from the reaction mixture before the system has reached equilibrium.

Regeneration studies were also carried out. For the regeneration of HEC-Suc-Na (20 mg),

it was first stirred with metal ions Pb(II) (180 mg L-1), Cu(II) (120 mg L-1), Cr(VI) (170 mg L-

8
1
), Ni(II) (100 mg L-1) and Co(II) (130 mg L-1) each for 30 min. The recovered material was

agitated with freshly prepared brine solution (100 mL) overnight, filtered, completely washed

with DW until negative AgNO3 test and then air-dried. Regenerated sorbent was again used for

metal uptake. These sorption-desorption studies were carried out over five successive cycles.

Sorption experiments were also conducted for acidic form of sorbent, i.e., HEC-Suc by

agitating its 20 mg with optimal metal ion concentration for all the five metal ions (100 mL) to

test the uptake of Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) ions at specific pH and 298 K.

2.9. Competitive metal uptake

Sorption of a metal ion from binary metal solution was carried out to study potential of the

sorbent for competitive metal uptake. This was done by agitating HEC-Suc-Na (20 mg ) with

solution (100 mL each) containing i) Ni(II) (100 mg L-1) and Cr(VI) (170 mg L-1) ii) Ni(II)

(100 mg L-1) and Cu(VI) (120 mg L-1) iii) Cu(II) (120 mg L-1) and Pb(II) (180 mg L-1) at 298

K and pH 6 for 30 min. The reason for selection of this pH for competitive metal uptake was

that most of the metal ions have maximum sorption capacities around this pH in single metal

system. For each metal ion, metal ion uptake in the supernatant was determined by using FAAS

in the presence of other metal ion.

Competitive adsorption of heavy metal ions from tertiary mixtures {Ni(II), Cu(II), Cr(VI)

and Ni(II), Cu(II), Cr(VI)} by HEC-Suc-Na was studied using aforesaid optimal conditions.

Likewise, competitive adsorption from mixture of all the five metal ions {Ni(II), Cu(II), Co(II),

Pb(II), Cr(VI)} by HEC-Suc-Na was also studied at optimal conditions.

3. Results and discussion

3.1. Synthesis and characterization of HEC-Suc and HEC-Suc-Na

9
3.1.1. Synthesis of HEC-Suc and HEC-Suc-Na

Synthesis of HEC-Suc conjugate was carried out under homogeneous reaction conditions

in DMAc using succinic anhydride as a reagent and 4-dimethylaminopyridine (DMAP) as a

catalyst. HEC-Suc was then converted into its sodic form (HEC-Suc-Na) by treating it with

saturated NaHCO3 solution to enhance its ion exchange capacity. Fig. 1 is the schematic

illustration of fabrication of novel HEC-Suc and HEC-Suc-Na. HEC is a well-known water

soluble biopolymer and its succinylation resulted in derivative HEC-Suc (yield: 17.2 g; DS

2.78) which found insoluble in hot and cold water, ethanol and methanol and provided the basis

for its use in the removal of metal ions from aqueous solution. Reason for insolubility of HEC-

Suc-Na may be correlated with phenomenon of cross-linking of HEC-Suc chains that occurs

to some extent via OH and COOH groups under the given reaction conditions [16].

3.1.2. Determination of the zero point charge pH (pHZPC)

Charge on the surface of the sorbent HEC-Suc-Na was monitored by calculating pHZPC.

The pHZPC for the sorbent was found to be 4.2 (Fig. 2). The value of pHZPC also suggests

presence of carboxylic acid groups indicating the weak acid character of the sorbent.

3.1.3. FTIR spectroscopic analysis

The Fig. 3 shows overlay FTIR (KBr) spectra of HEC-Suc and HEC-Suc-Na for

comparison. Successful succinylation of HEC is evidenced from the FTIR spectrum of HEC-

Suc, which shows a distinct ester carbonyl signals at 1728 cm-1. The other signals of HEC-Suc

appeared at 3443 (O-H), 2924 (C-H) and 1053 (C-O-C) cm-1. Moreover, formation of sodium

salt was confirmed by appearance of characteristic carboxylate anion peak [11] at 1587 cm-1 in

the spectrum of HEC-Suc-Na. The other absorptions of HEC-Suc-Na appeared at 3420 (O-H),

2895 (C-H), 1728 (C=OEster) and 1045 (C-O-C) cm-1.

3.1.4. Solid-state CP/MAS 13C NMR spectroscopic analysis

10
 Solid-state CP/MAS 13C NMR spectra of unmodified HEC and HEC-Suc-Na are shown in

Fig. 4a and 4b, respectively. The spectrum of HEC-Suc-Na showed that the ester carbonyl (C-

11) appeared at 175.39 ppm while the carbonyl of COONa (C-14) of HEC-Suc-Na was noted

at 180.56 ppm indicating successful succinylation and sodium salt formation. The CH2 signals

of succinyl moieties in HEC-Suc-Na were appeared at 32.84 ppm. Methylene protons of

hydroxyethyl moieties of HEC were found overlapped with polymer backbone signals. Signals

at 103.70 and 61.78 ppm are of C-1 and C-6 of HEC-Suc-Na, respectively. However, signals

in the range 66.80-90.90 ppm show carbon of HEC backbone (C-2-5 and C-7-10).

3.1.5. SEM-EDS analyses

The surface morphology of the HEC-Suc (Fig. 5a) and sorbent HEC-Suc-Na (Fig. 5b)

before and after metal ions uptake (Fig. 5c-g) investigated by SEM and was observed to be

rough and inhomogeneous. EDS analyses confirmed the presence of Na ions on the sorbent

(Fig. 5i). Likewise, displacement of the Na ions on HEC-Suc-Na by Cr(VI), Co(II), Ni(II),

Pb(II) and Cu(II) ions confirmed their adsorption on the sorbent (Fig. 5 j-n).

3.2. Sorption studies

3.2.1. Effect of initial metal concentration

The effect of initial metal ion concentration on sorption was studied and saturated sorption

capacities were reached at 180, 170, 130, 120 and 100 mg L-1 for Pb(II), Cr(VI), Co(II), Cu(II)

and Ni(II), respectively. This is due to the reason that as the metal ion concentration increases,

availability of ions for exchange with the sorption sites of the sorbent also increase thus

increasing sorption capacity of the sorbent (Fig. 6a).

3.2.2. Effect of sorbent dosage

Amount of sorbent is optimized to find maximum sorption capacity of a given sorbent. It

was observed that the adsorption capacity decreases with increase in sorbent dosage after

11
an optimum value. This is due to the fact that some sites remain unsaturated during the

adsorption process after the optimum value. Due to greater affinities of Pb(II) and Cr(VI)

for binding sites, these have greater sorption capacities than Co(II), Cu(II) and Ni(II) (Fig. 6b).

It is revealed from the results that a sorbent dosage of 20 mg correspond to maximum sorption

capacity for all the five metal ions under study.

3.2.3. Effect of pH on metal-uptake

The pH of adsorption medium affects the charge on surface of sorbent and solution

chemistry. The pH range selected to study the effect of pH on sorption was 2.0-7.0 for all the

metal ions and results are shown in Fig. 6c. Results reveal that at low pH, metal uptake is

negligible. This low sorption is attributed to the fact that at lower pH, protonation of HEC-Suc-

Na takes place which results in the formation of HEC-Suc which has low ion exchange

capacity. Plots showed that as the pH value is increased from 4.0-7.0, metal removal increases

sharply. Results also show that pH value for maximum metal uptake were 6.0, 6.5, 4.5, 5.0

and 5.5 for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II), respectively. This is due to the reason that

at pH values greater than pHZPC (4.2 for HEC-Suc-Na), functional groups on sorbent surface

become deprotonated which results in an increase in negative charge density on the sorbent

surface thereby facilitating the binding of heavy metal ions. Formation of precipitate in the

form of metal hydroxides, i.e, M (OH) m occurs as the pH is increased beyond the value

corresponding to maximum metal uptake for a given metal ion. This causes a decrease in metal

ion concentration in solution which results in a decrease of sorption capacity.

3.2.4. Effect of temperature

Fig. 6d shows the effect of temperature on the sorption capacity of sorbent. Metal uptake

decreases as the temperature increased from 298 to 338 K. This is due the fact that at lower

temperature, metal ions present in the solution could interact more with the binding sites. As

12
the temperature increases, mobility of ions increases and forces of attraction between sorbent

and metal ions decrease thus decreasing sorption efficiency of the sorbent.

3.2.5. Effect of contact time

Time of contact between exchange sites of sorbent and sorbate ions affects the sorption

capacity of a given sorbent. To study the effect of contact time on sorption capacity of the

sorbent (HEC-Suc-Na), solutions containing metal ions are interacted with HEC-Suc-Na (20

mg) at contact time of 5, 10, 15, 25, 30, 45, 60, 90 and 120 min. The results showed that the

metal removal take place in two stages. The first rapid phase, during which more than 95 %

Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) are removed within first 10, 15, 30, 15 and 30 min,

respectively (Fig. 6e). While the second stage exhibited a gradual pattern of metal uptake by

the sorbent until equilibrium was reached. Equilibrium time was reached after 15 min for

Pb(II), Cr(VI) and Cu(II) and after 30 min for Co(II) and Ni(II). The first rapid phase during

the sorption process was due to the availability of large number of exchange sites on the

sorbent surface and there was a gradual decrease in sorption rate because exchange sites were

gradually occupied.

3.2.6. Kinetic modeling

Experimental data obtained from contact time experiments was fitted to different kinetics

models to establish whether the sorption process follow physio-sorption or chemisorption.

Two kinetics models, i.e., pseudo-first order and the pseudo-second order models were used in

this regard. Linear form of pseudo-first order kinetic model is given by relation (Eq. (6)):

k1
log  qe  qt   logqe  t (6)
2.303

where qe and qt are amounts of metal sorbed at equilibrium and time t, respectively and k1 (g

mg-1 min-1) is the rate constant. Table 1 show the values of k1, qe and R2 and graphs are depicted

in Fig. 7a. The results have indicated that this model did not provide the best fit for

13
experimental data. Therefore, pseudo-second order model [17] was fitted to experimental data

(Eq. (7)):

t 1 t
 2
 (7)
qt kqe qe

where qe and qt are amounts of metal sorbed at equilibrium and time t and k is rate constant (g

mg-1 min-1). Values of t/qt were plotted against t. A straight line with high correlation

coefficients was obtained (Fig. 7b). Slope and intercept of this straight line gave the values of

qe and k, respectively (See Table 1).

Greater values of correlation coefficient (> 0.99) and a good agreement of calculated qe

with experimental values for all the five metal ions suggest that the pseudo-second order model

provided the best fit to experimental data and gave a better prediction of kinetic behavior for

the whole range of contact time studied. Fitting of experimental data to pseudo second order

kinetic model suggested that sorption process occurred through chemisorption.

3.2.7. Sorption isotherm

Sorption isotherm shows, how sorbed molecules distribute themselves between the sorbate

(liquid phase) and the sorbent (solid phase) at the equilibrium stage. So the experimental data

obtained for the sorption of Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) was fitted to Freundlich

and Langmuir isotherm. Linear form of Freundlich isotherm is given below (Eq. (8)):

1
logqe  logk F  logCe (8)
n

where qe (mg g-1) and Ce (mg L-1) are equilibrium sorption capacity and equilibrium metal ions

concentration, respectively. kF and n represent the Frendlich constant and sorption intensity,

respectively. To fit the experimental data to Freundlich isotherm, the values of logqe were

plotted against logCe (Fig. 7c). Table 1 also shows the values of Freundlich isotherm

parameters kF, R2 and n. Straight lines obtained from the Frendlich isotherm had low

14
values of R2 which indicate inadequacy of this model. Therefore, Langmuir isotherm model

[18] was used to fit experimental data which is given as (Eq. (9)):

Ce Ce 1
  (9)
qe Qmax Qmax  b

where Ce (mg L-1) and qe (mg g-1) are metal ions concentration at equilibrium and equilibrium

sorption capacity, respectively. b and Qmax (mg g-1) are Langmuir constant and maximum

sorption capacity/g of sorbent, respectively. On plotting the values of Ce/qe against Ce, straight

lines with high correlation coefficients were obtained. Values of Qmax (maximum sorption

capacity) and b (Langmuir constant) were calculated from slope and intercept of these straight

line, respectively (See Table 1). This suggests that Langmuir model provided the best fit to the

experimental isotherm data (Fig. 7d).

Values of Qmax calculated from Langmuir model were 1000, 909.09, 666.6, 588 and 500

mg g-1 for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II), respectively. The reason for such high

values of Qmax was high DS value of HEC-Suc which is an evidence of presence of larger

concentration of succinate moieties (DS 2.78) on the sorbent HEC-Suc-Na. The separation

factor (RL) values can be used to envisage whether the adsorption is favorable or unfavorable

and is given by relation below (Eq. (10)):

1
RL  (10)
1  bCi

RL values ranging from 0 and 1 indicate favorable adsorption. Values of RL>1, RL= 1, 0

<RL< 1 and RL= 0 show unfavorable, linear, favorable and irreversible adsorption, respectively.

In the present case RL had value 0 <RL< 1 which indicated favorable adsorption for all the five

metal ions (see Table 1).

3.2.8. Ion exchange mechanism

To check the role of ion exchange mechanism during sorption, potential of both HEC-Suc

and HEC-Suc-Na for metal uptake was investigated. HEC-Suc-Na showed reasonably high
15
uptake (98.3, 98.8, 96.1, 95.4 and 97%) while HEC-Suc showed negligible uptake of (17.3,

16.4, 11.7, 11.7 and 9.2%) for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II), respectively. This is

due to the fact that an ion exchange takes place between metal ions and Na+ present in the sodic

form of sorbent (Fig. 7e).

Boyd [19] derived a rate equation which considered rates of ion exchange sorption of a

metal ion from aqueous solution through ion exchange mechanism which is given as (Eq. 11):

S
log 1  F    t (11)
2.303

where F=qt/qe, qe and qt are amounts of metal sorbed at equilibrium and time t, respectively

and S (min-1) is a constant. Moreover, involvement of ion exchange mechanism can also be

evidenced from high values of correlation coefficient of straight lines obtained from plot of

log(1-F) against t (Fig 7e, see Table 1).

Values of sorption capacity were also calculated theoretically from stoichiometric ratios of

incoming and outgoing cations and it was found that experimental sorption capacity values

were higher than the theoretical values for all the five metal ions. This might be due to

involvement of precipitation of metal ions [20] on the surface of sorbent along with ion-

exchange mechanism due to high metal concentration and pH for all the five metal ions.

3.2.9. Thermodynamic parameters determination

Thermodynamic parameters (∆G°, ∆S° and ∆H°) can be estimated by using the following

relations (Eq. (12-14)):

Cads
Kc  (12)
Ce

16
G   RTlnKc (13)

S  H 
lnK c   (14)
R RT

where Kc is the sorption equilibrium constant, Cads is the amount of metal sorbed and Ce is the

equilibrium concentration of metal ion. Values of these thermodynamics parameters ∆G°, ∆S°

and ∆H° for the sorption process were estimated from the effect of temperature on sorption of

Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) from aqueous solution by the sorbent (see Table 1).

The value of Gibbs free energy was calculated by Eq. (13). A plot between lnKc and 1/T (K-1)

gives values of ∆H° and ∆S° as slope and intercept, respectively (Fig. 7f). The negative values

of ∆G°, ∆S° and ∆H° show that the sorption process was spontaneous, chemically governed

and exothermic in nature. Similar trends in thermodynamics parameters were also observed

during sorption process by some other researchers as well.

It is important to mention the place of present sorbent with the already known

polysaccharidal sorbents. Literature showed that HEC-Suc-Na sorbent has highest place

amongst polysaccharidal sorbents for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) uptake (Table

2).

3.2.10. Sorption and desorption (Regenerability)

These sorption-desorption studies of the metal ions were carried out over five successive

cycles (Fig. 8a-e). Decrease in sorption capacities were 23.4, 26.35, 11.7, 16.2 and 19 mg g-1

for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II), respectively after five cycles. Fig. 8f shows the

percentage metal-uptake as a function of number of cycles. Results show that total decrease in

term of percentage uptake was 3.5, 3.1, 1.8, 2.4 and 2.6% for Pb(II), Cr(VI), Co(II), Cu(II) and

Ni(II), respectively after five cycles. These results suggest the repeated use of sorbent before

need to be replaced.

17
3.2.11. Competitive adsorption of multi-metal ions system by HEC-Suc-Na

3.2.11.1. Competitive adsorption from binary system by HEC-Suc-Na

Competitive uptake of metal ions by HEC-Suc-Na from different binary mixtures was

evaluated to simulate systems containing multiple heavy metal ions, e.g., electroplating

effluent, galvanic waste water [33], etc. Binary mixtures studied were i) Ni(II) + Cr(VI) ii)

Ni(II) + Cu(VI) iii) Cu(II) + Pb(II) and results are summarized in Table 3. Sorption capacity

value of a metal ion in binary system was less than its value in single metal ion solution. This

is due to the fact that in single metal system there is no competition between different metal

ions for sorption sites on the surface of sorbent. The results show that Cr(VI), Ni(II) and Pb(II)

have higher sorption capacities (410.7, 242.8 and 426.2 mg g-1) over their competing ions

Ni(II), Cu(II) and Cu(II) (244.8, 102.35 and 56.1) in their above mentioned binary systems,

respectively. Reason behind might be greater ion exchange capability of Cr(VI), Ni(II) and

Pb(II) over their competing ions Ni(II), Cu(II) and Cu(II), in proposed binary mixtures,

respectively. This preferential sorption of one metal ion over the other from the binary mixtures

might be due to difference in their redox potentials [34].

Ratio of sorption capacity for a metal ion along with other ion (qmix) to the sorption

capacity of that metal ion when present alone (q°) in the aqueous system gives the effect

of ionic concentrations on the adsorption process [35]. The value of qmix /q° was less than 1

for all the binary systems under study except Pb(II)+ Cu(II). This shows decrease in the

sorption capacity of both ions in presence of each other. For Pb(II)+ Cu(II) system the value of

qmix/q°> 1 which shows increase in sorption capacity of Cu(II)in presence of Pb(II). Difference

in ionic radii, ionic charge and electrode potential of these metal ions is the reason for decrease

in sorption capacity for metal uptake from binary systems [36,37].

3.2.11.2. Competitive adsorption of Ni(II), Cu(II) and Cr(VI) by HEC-Suc-Na

18
 Ni(II), Cu(II) and Cr(VI) are present in galvanic waste water which is commonly used to

test the efficiency of sorbent materials for galvanic waste management procedures [38]. So, the

present sorbent was tested for its competitive adsorption of these metal ions. It was noticed that

sorption capacity values for Cr(VI), Ni(II) and Cu(II) were 272.5, 163.8 and 140.2 mg g-1,

respectively. It was revealed that HEC-Suc-Na had ability to sorb Cr(VI) preferentially over

Ni(II) and Cu(II).

3.2.11.3. Competitive adsorption of Ni(II), Co(II) and Cr(VI) by HEC-Suc-Na

Large amounts of Co(II), Cr(III) and Ni(II) are present in synthetic nuclear power plant

coolant water. In order to simulate real conditions, i.e., to study removal of these metals from

nuclear wastewater by HEC-Suc-Na, competitive adsorption of Co(II), Cr(III) and Ni(II) was

performed from aqueous solution containing these ion [39]. It was noticed that Co(II), Cr(III)

and Ni(II) showed sorption capacity values in the order Cr(VI) ˃ Co(II) ˃ Ni(II) and the values

were 265.5, 156.8 and 150.2 mg g-1, respectively. The results indicated that Cr(VI) had greater

ion exchange capability than Ni(II) and Co(II) which may be due to differences in ionic charge

and electrode potential of these metals.

3.2.11.4. Competitive adsorption of Ni(II), Cu(II), Co(II), Pb(II) and Cr(VI) by HEC-Suc-Na

A solution containing Pb(II), Cr(VI), Ni(II) Co(VI) and Cu(VI) was agitated with HEC-

Suc-Na to study competitive removal of metal ions by HEC-Suc-Na under optimal conditions

and these ions showed sorption capacities of 174, 163.64, 102.3, 97.6, 82.6 and 68.0 mg g-1,

respectively. Difference in ionic charge and redox potential of these metal ions was the main

reason for difference in sorption capacity. These results of competitive removal of metal ions

suggest that HEC-Suc-Na can be used as a potential and selective sorbent for industrial waste

water treatment procedures and for heavy metal ions removal from nuclear power plant coolant,

galvanic waste water, etc. The reason for difference in sorption capacity of different metal ions

19
during competitive sorption of metal ions is, sorption of favoured specie lead to desorption of

those metals ions having less sorption capacity.

4. Conclusions

Developing interest has been seen in past ten years for the preparation of adsorbents as

alternatives to activated carbons in water and wastewater treatment processes. A pristine

supersorbent succinylated hydroxyethylcellulose in its sodic form appeared highly efficient for

the removal of Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) from aqueous solution. Effectiveness

of the supersorbent had shown maximum sorption capacity amongst polysaccharides based

sorbents in the literature reported to date. Accelerated metal ions uptake within first 5 min by

the sorbent suggested ion exchange mechanism during sorption process. The negative values

of ∆G° indicated feasibility and spontaneity of sorption. Furthermore, presence of single kind

of functionalities, i.e., Na-succinate on HEC backbone makes it superior sorbent over

unmodifiable/less modifiable multi-functionalized agricultural waste materials. Concluding, it

can be stated that HEC-Suc-Na is highly efficient and re-generable supersorbent.

Acknowledgments

A. Abbas gratefully acknowledges the financial support of the Higher Education

Commission (HEC) of Pakistan under the “HEC Indigenous 5000 PhD fellowships program”.

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25
List of Figure Legends

Fig. 1. Synthesis of HEC-Suc under homogeneous conditions and its conversion to HEC-Suc-

Na.

Fig. 2. Zero point charge pH (pHZPC) of HEC-Suc-Na sorbent.

Fig. 3. FTIR (KBr) spectra of HEC-Suc and HEC-Suc-Na. Shaded areas are showing

significant changes after salt formation.

Fig. 4. Solid-state CP/MAS 13C NMR spectra of HEC (a) and HEC-Suc-Na (b).

Fig. 5. SEM (a-g) images and EDS (h-n) spectra of HEC-Suc, HEC-Suc-Na and HEC-Suc-

Na where, Na ions are displaced with Cr(VI), Co(II), Ni(II), Pb(II) and Cu(II) ions,

respectively.

Fig. 6. Effect of initial concentration of metal ions (a), sorbent dosage (b), pH (c), temperature

(d) and contact time (e) on sorption capacity of HEC-Suc-Na.

Fig. 7. Fitting of pseudo-first order model (a), pseudo-second order model (b), Freundlich

sorption isotherms (c), Langmuir sorption isotherms (d), ion exchange model (e) and effect of

temperature on equilibrium constant for heavy metal ion removal from aqueous solution by

HEC-Suc-Na (f).

Fig. 8. Adsorption-desorption values for (a) Pb(II), (b) Cr(VI), (c) Co(II), (d) Cu(II) and (e)

Ni (II) ions by HEC-Suc-Na from aqueous solution, (f) percentage metal-uptake by the acidic

(HEC-Suc), sodic form of sorbent (HEC-Suc-Na, 1st cycle) and regenerated HEC-Suc-Na (2nd-

5th cycles

26
 7 9
O
O OH
6 7 8
4
5 O
3 2 O
1
HO
O OH
HEC O

Succinic anhydride
DMAP 80°C, 24 h

O
7 9 11
O OH
O O
7 8 10
6 O
4
5 O
3 2 O R = H or
1
RO Succinic acid
Succinate moieties
O OR
HEC-Suc O

NaHCO3
RT, 2 h
O
7 9 11
O ONa
O O
7 8 10
6 O
4
5 O
3 2 O
1
RO
O OR
O
HEC-Suc-Na

Fig. 1.

3.5

2.5
(pHi-pHf)

1.5

0.5

-0.5 1 2 3 4 5 6 7 8

-1.5
pHi

Fig. 2.

27
 HEC Succinate
3443

2924

1728

1408

1053
3420

2895

HEC Succinate
(sodic form)

1728

1587

1406

1045
COO-

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

Fig. 3.

28
 O OR
R = H or O
Succinic acid
H1 (a)

ppm

C-5 & 7-10

C-6
78 91 0
OCH
C
2HO
2CHC
2HO
2H
6
4
5 O
2 C-2
H
OH
CHCO
3 1O C-1
2 2
OCHC
2HO
2CHC
2HO
2H
H
EC
(a)
(b)

150
150 125
125 100
100 75
75 50
50

O C-2-5 & C-7-10

7 10 12 14
O ONa
O O 11 13
6 8 9 O
4 5 O
O 2
O O 1 O
O
O 3 O 7 12 14 ONa
NaO
8 O 11 13
H E C -S u c -N a O

C-14 C-11 C-1 C-6

C-12,13
(b)
(c)

ppm (t1) 175 150 125 100 75 50 25

Fig. 4.

29
 a h

10 mm

b i

10 mm

c j

10 mm

d k

10 mm

e l

10 mm

f m

10 mm

g n

10 mm

Fig. 5.

30
 (a) 900 (b) Cr
880 800 Co
Sorption capacity, mg g-1

Sorption capacity, mg g-1

780 Ni
700
680 Pb
Cr 600 Cu
580 500
Co
480 Ni 400
380 Pb 300
280 Cu 200
180 100
30 60 90 120 150 180 210 240 270 300 0 20 40 60 80
Initial concentration, mg L-1 Sorbent dosage, mg
1000 (c) 900 (d)
Cr

Sorption capacity, mg g-1

800
Sorption capacity, mg g-1

800
Co
Ni 700
600
Pb
600
400 Cu
500
200 400
Cr Co Ni Pb Cu
0 300
1.5 2.5 3.5 4.5 5.5 6.5 290 300 310 320 330 340
pH T, K
1000 (e)
900
Sorption capacity, mg g-1

800
700
600
500
400
300
200
Cr Co Ni Pb Cu
100
0
0 40 80 120
t, min

Fig. 6.

31
 2.5 0.3
Cr Co Ni Pb Cu Cr Co Ni Pb Cu
2 0.25

0.2
log (qe-qt)

t/qt, min/mg g-1

1.5
0.15
1
0.1
0.5
(a) (b)
0.05

0 0
0 20 40 60 0 40 80 120
t, min t, min
3 Cr Co Ni Pb Cu 0.48
Cr Co Ni Pb Cu
2.95 0.43

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

2.9
0.38
2.85
log qe

0.33
2.8
0.28
2.75
(c) (d)
2.7 0.23

2.65 0.18
1.95 2.15 2.35 80 130 180 230 280
log Ce Ce, mg L-1
t, min 4.5
0 20 40 60 80
0 (f)
Cr Co Ni Pb Cu 3.5
-0.5

-1 2.5
log(1-F)

ln Kc

-1.5
1.5
-2
Cr Co Ni Pb Cu
-2.5 (e) 0.5
0.0029 0.003 0.0031 0.0032 0.0033 0.0034
-3
1/T, K-1

Fig. 7.

32
 Sorption capacity, mg g-1 900 Sorption Desorption 900 Sorption Desorption

Sorption capacity, mg g-1

850 800
800 700
750 600
700 500
650 (a) 400 (b)
600 300
1 2 3 4 5 1 2 3 4 5
Number of cycles Number of cycles
600
650 Sorption Desorption Sorption Desorption

Sorption capacity, mg g-1

Sorption capacity, mg g-1

600 550

550
500
500
450
450
(c) (d)
400 400
1 2 3 4 5 1 2 3 4 5
Number of cycles Number of cycles

500 Sorption Desorption 100

Sorption capacity, mg g-1

Cr
80
Metal uptake, %

450 Co
60 Ni
400 Pb
40
Cu
350 20
(f)
(e) 0
300
1st cycle

3rd cycle
HEC-Suc

2nd cycle

4th cycle

1 2 3 4 5 5th cycle
Number of cycles

Fig. 8.

33
Table 1

Freundlich, Langmuir, pseudo-first order, pseudo-second order, ion exchange model and

thermodynamic parameters for heavy metal ions removal from aqueous solution using HEC-

Suc-Na.

Parameters Pb(II) Cr(VI) Co(II) Cu(II) Ni(II)

Experimental qe(mg g-1) 885 840 625 572 485

Qmax(mg g-1) 1000.0 909.09 666.66 588.0 500.0

Langmuir Qmax(mmol g-1) 4.8309 17.482 11.300 7.0622 8.5193

parameters b (mg L-1) 0.0477 0.1209 0.0968 0.1326 0.2062

b (mmol L-1) 9.8571 6.2857 5.7032 7.8230 12.101

R2 0.9983 0.9986 0.9978 0.9973 0.9980

RL 0.1735 0.0464 0.0736 0.0861 0.0462

Freundlich n 11.79 34.01 18.05 16.42 30.12

parameters kF 566.7 720.4 477.4 436.2 414.5

R2 0.89 0.44 0.66 0.39 0.37

Pseudo second qe(mg g-1) 909.09 833.33 625.0 572.0 485.0

order k 0.0020 0.0018 0.0009 0.0013 0.0004

R2 1 0.99 0.99 1 0.99

Pseudo first qe(mg g-1) 71.20 57.46 171.1 109.9 209.2

order k1 0.0606 0.0451 0.0645 0.0613 0.0532

R2 0.8965 0.2950 0.8865 0.8778 0.6767

Ion Exchange S (min-1) 0.0458 0.05573 0.05020 0.04675 0.04398

parameters R2 0.9971 0.9973 0.9987 0.9937 0.9997

Thermodynamic ∆S° (J mol-1K-1) -103.59 -62.651 -37.217 -109.13 -41.179

parameters ∆H°(kJ mol-1) -40.79 -29.71 -19.16 -40.12 -20.88

∆G°(kJ mol-1) -10.10 -4.431 -3.319 -7.50 -3.476

R2 0.993 0.975 0.985 0.990 0.993

34
Table 2

Comparison of HEC-Suc-Na with other related polysaccharidal sorbents for Pb(II), Cr(VI),

Co(II), Cu(II) and Ni(II) removal.

Sorbent (treatment) Metal ion Sorption capacity (mg.g-1)

Sodium carboxymethyl cellulose stabilized Fe Cr(VI) 225

nanoparticles [21]

Sugarcane bagasse (1,3-diisopropilcarbodiimide, Cu(II), Pb(II) 133, 313

triethylenetetramine) [22]

Modified cashew nut shell [23] Cu(II), Ni(II) 406.6, 456.3

Mercerized cellulose [24] Cu(II), Pb(II) 69.4, 192.3

Modified wheat straw [25] Cu(II) 397

Brown seaweed Co(II), Ni(II) 20.63, 18.58

(Sargassum wightii) [26]

Mercerized cellulose (succinic anhydride) [27] Cu(II), Pb(II) 185.2, 500

Chitosan/graphene oxide [28] Pb(II), Cu(II), 461.3, 423.8, 310.4

Cr(VI)

Poly(vinyl alcohol)/chitosan [29] Pb(II), Cu(II) 166, 238

Chitosan (epichlorohydrin, triethylenetetramine) Pb(II) 559.4

[30]

Cellulosic okra fibers (Acrylonitrile/methacrylic Pb(II) 268.32

Cu(II) 76.82
acid) [31]

35
Poly(itaconic acid) grafted cross-linked starch Pb(II) 1320

nanoparticles (PIACS) [32]

Hydroxyethylcellulose (succinic anhydride, sodic) Pb(II), 1000,909.09, 588, 666.6,

Cr(VI), 500 Present work

Cu(II), Co(II),

Ni(II)

36
Table 3

Sorption capacities for Pb(II), Cr(VI), Co(II), Cu(II) and Ni(II) for single metal system and

binary system by HEC-Suc-Na.

Metal ion System qe (mg g-1) qmix/q°

Ni(II) Ni(II) alone 500

Cr(VI) Cr(II) alone 909.1

Ni(II) Ni(II)+Cr(VI) 244.8 0.7627

Cr(VI) Ni(II)+Cr(VI) 410.7 0.7210

Ni(II) Ni(II) alone 500

Cu(II) Cu(II) alone 416.6

Ni(II) Ni(II)+Cu(II) 242.8 0.6903

Cu(II) Ni(II)+Cu(II) 102.35 0.8284

Cu(II) Cu(II) alone 416.6

Pb(II) Pb(II) alone 1000

Cu(II) Cu(II)+Pb(II) 56.1 1.1512

Pb(II) Cu(II)+Pb(II) 426.2 0.4823

37