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Copper and cadmium removal from synthetic industrial wastewater using

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Environ Sci Pollut Res
DOI 10.1007/s11356-012-0801-8
RESEARCH ARTICLE
Copper and cadmium removal from synthetic industrial
wastewater using chitosan and nylon 6
N. Prakash & P. N. Sudha & N. G. Renganathan
Received: 12 December 2011 / Accepted: 27 January 2012
# Springer-Verlag 2012
Abstract
Purpose Chitosan with nylon 6 membranes was evaluated
as adsorbents to remove copper and cadmium ions from
synthetic industrial wastewater.
Methods Chitosan and nylon 6 with glutaraldehyde blend
ratio with (1:1+Glu, 1:2+Glu, and 2:1+Glu) have been pre-
pared and these were used as membranes to remove copper
and cadmium ions from synthetic industrial wastewater.
Characterization of the synthesized membrane has been
done with FTIR, XRD, TGA/DTA, DSC, and SEM.
Chemical parameters for quantities of adsorption of heavy
metal contamination have been done and the kinetics of
adsorption has also been carried out.
Results The optimal pH for the removal of Cd(II) and Cu(II)
using chitosan with nylon 6. Maximum removal of the
metals was observed at pH 5 for both the metals. The effect
of adsorbent dose also has a pronounced effect on the
percentage of removal of the metals. Maximum removal of
both the metals was observed at 5 g/100 ml of the adsorbent.
Responsible editor: Vinod Kumar Gupta
N. Prakash (*)
Department of Chemistry, Sri Chandrasekharendra Saraswathi
Viswa Mahavidyalaya (SCSVMV) University,
Enathur, Kancheepuram, India
e-mail: k_nprakash1981@rediffmail.com
P. N. Sudha
P.G.and Research Department of Chemistry,
D.K.M. College for Women,
Vellore, India
N. G. Renganathan
Department of Chemistry,
Veltech Dr.RR & Dr.SR Technical University,
Chennai-62, India
Conclusion Copper and cadmium recovery is parallel at all
time. The percentage of removal of copper increased with
increase in the pH from 3 to 5. In the case of cadmium
containing wastewater, the maximum removal of metal
occurred at pH 5. The uptake amount of Cu2+ ions on
chitosan increased rapidly with increasing contact time
from 0 to 360 min and then reaches equilibrium after
360 min; the equilibrium constant for copper and cadmium
ions is more or less the same for the adsorption reaction.
Keywords Chitosan . Nylon 6 . Glutaraldehyde . Heavy
metals removal
1 Introduction
Electroplating wastewater led to the contaminations of heavy
metals, paddy soil, and rice samples which have been reported
by Gupta et al. (1999) and by Liu et al. (2011). The adsorption
behavior of Hg(II), Pd(II), and Cd(II) from aqueous solution
on duolite C-433, a synthetic resin, has been studied by Gupta
et al. (2004) at different temperature by batch process and they
have reported thermodynamic parameters to predict the nature
of sorption. Low cost fertilizer industry waste material carbon
slurry, product in generators of fuel oil-based industrial gen-
erators was converted into an effective adsorbent by the re-
moval of hexa valent Cr(VI) from aqueous solution by Gupta
et al. (2010). The maximum adsorption reported by the authors
was found to be at 70 min, pH 2, 4.0 g/L dose, at 303 K
temperature. The utility of waste material in adsorbing reactive
dyes like Vertigo Blue 49 and Orange DNA 13 from fuel oil-
based generators has been studied as a function of contact
time, temperature pH and initial dye concentration by batch
experiments by Gupta et al. (2007a). The optimum conditions
of biosorption of hexavalent chromium by raw and acid treated

green alga oedogonium hatei from aqueous solution were
reported as, a biomass dose of 0.8 g/L, contact time 110 min,
pH and temperature 2.0 and 318 K (Gupta and Rastogi 2009).
The biosorption of Cd(II) ions on oedogonium has been stud-
ied in a batch system with respect to initial pH, algal dose,
contact time and the temperature by Gupta and Rastogi
(2008a) and it is reported that oedogonium sp. appears to be
a good sorbent for remaining metal Cd(II) from aqueous
phase. A comparative study on the ability of two non-living
(dried) fresh water algal oedogonium and Nostoc sp. to remove
Pd(II) from aqueous solution has been done by Gupta and
Rastogi (2008b) and the optimum conditions for lead biosorp-
tion arrived at from this study are pH 5.0, contact time 90 and
70 min, biosorbent dose 0.5 g/L, and initial Pd(II) concentra-
tion 200 mg/L. The mass transfer kinetic approach has been
successfully attempted (Gupta et al. 2000) for the determina-
tion of various design parameters for the treatment of phenolic
wastes obtained from fertilizer waste management by carbon
columns. An expensive and effective adsorbent from bagasse
fly ash obtained from a sugar industry has been developed by
Gupta and Ali (2004) and Gupta et al. (1998) for the removal
of lead and chromium and it is reported through communica-
tion that removal of these to metal ions upto 93% by column
experiments. Cyanobacterial biomass Nostoc muscorum has
been used successfully by Gupta and Rastogi (2008c) to
demonstrate sorptions of chromium (VI) and it is reported that
the maximum adsorption capacity in this biomass is 22.92 mg/
g at 25°C and pH 3.0. Another inexpensive and efficient for
sugar industry bagasse fly ash adsorbant obtained has been
developed by Gupta and Sharma (2003) graph for removal of
zinc from aqueous solutions over a wide large of initial metal
ion concentration (10−4 to 10−3 m) contact time 24 h, ad-
sorbent dose (5.20 g/L), and pH (1.0 to 6.0).
Agricultural waste and the wheat husk have been used as
adsorbent for the adsorption of reactofix golden yellow 3
RFN from aqueous solution which has been reported by
Gupta et al. (2007b) and in this study, the equilibrium
adsorbtion level has been determined to be a function of
solution pH, adsorbent dosage, dye concentration, and con-
tact time. The blast furnace waste generated in steel plants
has been converted into low cost adsorbent for the removal
of lead and chromium by Gupta et al. (1997) and Srivastava
et al. (1997) and in this study, the effect of pH, sorbent
dosage, adsorbate concentrations pressure of other metal
ions temperature, and contact time on the sorptions of lead
and chromium have been reported. Bottom ash, a power
plant waste and de-oiled soya, by-product obtained during
the processing of soybean in soya oil extraction mills have
been used by Gupta et al. (2006) to remove and recover the
hazardous azo dye orange 7 and in this report, a fixed bed
column has been designed by the authors to assess the
practical utility of the adsorbents. Red mud from aluminum
industry has been converted into an inexpensive and
Environ Sci Pollut Res
efficient adsorbent by Gupta et al. (2001) and the authors
have used this adsorbent for the removal of lead and chro-
mium from aqueous solution and the authors have sought
various factors on the removal of their metal ions from
waste, e.g., pH, adsorbant dose, adsorbate concentration,
temperature, and particle size.
Photochemical degradation of the hazardous dye safranin-T
using TiO2 catalyst has been reported by Gupta et al. (2007c)
and in this the authors concentrated on the process which has
been carried out at different pH, amounts of catalyst, concen-
tration of the dye, and effects of the electron acceptor H2O2.
Gupta et al. (2009a) have reviewed critically the wastewater
treatment and in this the authors have discussed and highlight-
ed in brief the use of low cost alternative adsorbents. Ali and
Gupta (2006) have devised a protocol which describes the
development of inexpensive adsorbents from waste materials.
These adsorbents remove pollutants in 1-2 days and they
remove these pollutants by adsorption process in 15–
120 min. The authors have discussed batch and column pro-
cesses with a view to adopt this technology to industrial scale.
Srivastava et al. (1995a) determined lead using poly (vinyl
chloride) (PVC)-based crown ether membrane. The analytical
usefulness of the proposed electrode PVC-based membrane
has been evaluated by Jain et al. (1995b) during its application
in the determination of Molybdate ions in corrosion inhibitor
samples. Srivastava et al. (1995b) used a PVC-based mem-
brane of dibenzo-24-crown-8 for detecting Cs+ ion in a wide
concentration range (Jain et al. 1995a). Jain et al. (1997a) have
developed a new Cerium (IV) Vanadate-based solid membrane
for detecting Bi(III) and they have demonstrated the use of this
electrode as an indicator electrode to determine Bi3+ by poten-
tiometry. Srivastava et al. (1996a) described a PVC-based 2, 2,
2-Cryptand sensors for zinc ions and they have also demon-
strated that the response time of the sensor is <10 s and the
membrane can be used for more than 3 months without any
observed divergence in potentials. Srivastava et al. (1996b)
have successfully demonstrated the use of a plasticized PVC-
based membrane of benzo-l5-crown-5 for detecting Cd2+ in a
wide concentration range (Gupta et al 2009b). Gupta et al.
(2007d) have demonstrated the performance characteristics
of polymeric membrane electrodes based on two neutral
ionophores, N,N′-[bis(pyridin-2-yl)formylidene] butane-1,4-
diamine (S1) and N-(2-pyridinylmethylene)-1,2-benzenedi-
amine (S2) for quantification of cadmium ions. Gupta et
al. (2002) have used the membranes of 4-tert-butylcalix [4]
arene (I) as an electroactive material, sodium tetraphenyl
borate (NaTPB) as an anion excluder, and dibutyl phthalate
as solvent mediator in (PVC) matrix for lead-selective
sensor. Jain et al. (1997b) have constructed Poly(vinyl
chloride) and polystyrene based uranyl ion-selective electro-
des in the concentration range of ca. 10−5–10−1 M with a
response time as fast as 30 s and these electrodes perform
satisfactorily up to 20% (v/v) partially non-aqueous content.
Environ Sci Pollut Res
Gupta et al. (2009c) have used the membranes of Novel alizarin
sensor for the determination of Vanadium, Zirconium, and
Molybdenum.
Chitosan membranes as sorbents for trace elements deter-
mination in surface waters have been tried by Elisaveta et al.
(2011) and the authors have successfully used their membranes
as an efficient sorbents for the pre concentration and they have
recommended their membranes for solid phase extraction of
Cd(II), Eu(II), Ni(II), and Pd(II) from surface water. In the case
of bio-polymers chitin, chitosan and nylon 6 are widely
employed as bio polymers. As adsorbent for the removal of
heavy metals from water, biopolymer has been studied.
Chitosan is the one of them (Hasan et al. 2006; Navarro et al.
2003). Chitosan has the ability to form complexes with metals.
It has a better adsorption capacity for metal ion. It has severe
limitations in its use in acidic media because of its solubility in
acid (Llorens et al. 2004; Nomanbhay and Palanisamy 2005).
In this present study, chitosan is blended with nylon 6 mem-
brane and is used in removing copper and cadmium from
synthetic industrial wastewater.
2 Materials and methods
2.1 Experimental methods
2.1.1 Preparation of chitosan
Chitosan (90%) from DNP International (city and state) was
used to make all chitosan solutions. Chitosan solutions from 2
to 20 g/L were used for the experiments. Chitosan was pow-
dered, weighed, and dissolved in 0.05 M or 0.01 M acetic
acid; pH was then adjusted as per the requirement. Slight
adjustments in pH were made using 1 M acetic acid.
Standard heavy metal stock solutions (1,000 mg/L) were
prepared by dissolving 200 mg/L CuCl2 and 200 mg/L
CdCl2. pH adjustment of solutions was made using dilute or
concentrated NaOH (Sigma Chemicals Co.) and HCl (Sigma
Chemicals Co.) solutions using Orion 420 A pH meter.
Double distilled water was used to prepare all solutions. All
reagents were analytical grade and stored in polyethylene
polypropylene containers. Plastics were cleaned in dilute
HNO3 (10% v/v) and dried at 60°C after rinsing with deion-
ized water and acetone. Then these solutions were cast on
plastic weighing boats and dried in vacuum for 10 h to remove
the formic acid.
2.1.2 Nylon 6
Nylon 6 in pellet form was obtained from DuPont and had a
molecular weight of 19,000. Chitosan was obtained from
India sea foods, Cochin which is 92% deacetylated. All the
other materials such as formaldehyde and glutaraldehyde are
of analytical grade.
2.1.3 Characterization
Characterization of chitosan biopolymers was carried out by
IR spectroscopy, X-ray diffraction, thermal gravimetric
analysis (TGA/DTA), differential scanning calorimetry
(DSC), and scanning electron microscopy (SEM). Kinetic
analysis has also been made.
3 Results and discussion
3.1 FTIR spectra analysis
Figure 1 shows the effect of chitosan and nylon 6 with
glutaraldehyde as additive to improve the properties of chito-
san. As per Liang and Marchessault (1959), the peak at
1,628 cm −1 has been assigned to water. The peak at
1,087 cm−1 may be due to C–O–C stretching in the spectrum
of pure chitosan. Bands also appear at 3,454, 2,925, 2,857,
1,450, 1,383, 1,384, 1,087, and 898 cm−1. According to Xu et
al. (1996), the amide group band of chitosan will appear at
1,628 to 1,650 cm−1. The shift of the bands in these areas is
attributed to the molecular miscibility of the polymers. In the
present case of investigation, the band is even more shifted
and there is strong interaction between the compounds of the
polymers and this may be due to the presence of glutaralde-
hyde. Figure 1 depicts the effect of glutaraldehyde addition on
the FTIR spectra of chitosan and nylon 6.
Inter hydrogen bonds are formed between chitosan and
nylon 6. For pure chitosan and nylon 6, the displacement
number was about 25 cm−1 (from 1,650 to 1,628 cm−1) and
this is not further affected when chitosan content is increased.
This indicates the strong interaction between chitosan and
nylon 6. This may be due to chelation effect caused by the
coordination interaction between NH2 groups (Li and Bai
2005) of the chitosan and nylon 6. This is the reason for the
shift of the above peaks. From the above data, it is suggested
that the coordination interaction between chitosan and nylon 6
becomes stronger with an increase in chitosan content.
3.2 X-ray diffraction analysis
Figure 2 shows the X-ray diffraction analysis pattern of
chitosan, nylon 6 and glutaraldehyde, as it is there is sharp-
ness at two places. They are 13.166° and 19.69°. This is in
good agreement with the results reported by (Ritthidej et al.
2002). In the case of glutaraldehyde the peak at 2θ019.69°
(d04.505) decreases and as the chitosan content increases.
Two peaks emerge in the presence of excess nylon 6 and
this approaches crystalline nature, whereas in the case of

Fig. 1 FTIR spectra of
chitosan, nylon 6 and
glutaraldehyde blend
(1:1+Glu), (1:2+Glu)
and (2:1+Glu) ratio
(2:1+Glu), again crystalline nature is approached. The dif-
fractograms, as indicated in Fig. 2, are the blend of chitosan,
nylon 6, and glutaraldehyde blend (1:1+Glu), (1:2+Glu),
and (2:1+Glu) ratio. From the diffractograms of blend with
nylon 6 (1:1+Glu), (1:2+Glu), and (2:1+Glu) of chitosan
indicate the presence of chitosan in general and miscibility
of the polymer with blended polymer in particular.
3.3 Thermo gravimetric analysis
Thermo gravimetric data are shown in Fig. 3. From this, it is
seen that chitosan with glutaraldehyde of (1:1+Glu) ratio is
stable up to 300°C and also indicates that the decomposition
the blend polymer (2:1+Glu) involves 2 events. These may be
due to decomposition of adsorbed water, whereas at 335°C a
sharp peak with shoulder appears and this may be due to
decomposition due to de-methoxylation.
In these figures, there are two peaks, and in some cases,
there is only one peak. The first peak may be due to removal
Fig. 2 XRD pattern of chitosan, nylon 6 and glutaraldehyde blend (1:1+Glu), (1:2+Glu) and (2:1+Glu) ratio
Environ Sci Pollut Res
of water either in the bound or unbound state. Second
thermal event for pure chitosan and blend with nylon 6 is
observed at about 300°C with the maximal rate at 355–356°
C and is related to degradation. The peaks are due to
dehydration and de-methoxylation. The degradation profile
of chitosan is in good agreement with similar results and
reports (Khutoryanskiy et al. 2003; Mucha and Pawlak
2005. The absence of the event typical for pure chitosan at
250–350°C in this blend indicates on some interactions
between the polymers and may be considered as a proof of
their partial miscibility.
3.4 Differential scanning calorimetry
DSC studies have been undertaken and the resulting curve
(first scan) of the prepared membranes is shown in Fig. 4, a
broad endothermic peak is around 76.55°C for the chitosan
and nylon 6 (1:2+Glu). Similar endothermic peak is reported
to be observed at 225°C and corresponding peak in the
Environ Sci Pollut Res
Fig. 3 TG/DTG of chitosan, nylon6 and glutaraldehyde blend (1:1+Glu), (1:2+Glu) and (2:1+Glu) ratio
present case is 215°C for chitosan and nylon 6 (1:1+Glu)
ratios. This shows that there is interaction between chitosan
and nylon 6. This interaction is due to the formation of inter
hydrogen bonds, as evidenced and discussed under FTIR.
DSC scan of chitosan indicates an endothermic peak centered
on 100°C. This is assigned to the adsorbed water which gets
evaporated. There is a strong endothermic peak at 270°C. This
is due to the oxidation degradation of chitosan.
In the present study, only one endothermic peak is observed.
The temperature of the endothermic peak corresponds to Tm
(melting point) of nylon 6. The temperature of the endothermic
peak is shifted towards low temperature whether increasing of
chitosan content. From these it is clear that chitosan interferes in
the crystallization of nylon 6 both in reducing the crystal size
and broadening the distribution of crystals which leads to amor-
phous nature. The hydrogen bond formed between molecular
chains in the two compositions prevents the crystallization of
Fig. 4 DSC of chitosan, nylon6 and glutaraldehyde blend (1:1+Glu),
(1:2+Glu) and (2:1+Glu) ratio
nylon 6. In addition to this hindrance occur due to the molecular
chains of chitosan and this cause the difficulties in crystalliza-
tion. But the hydrogen bond plays an active role in the misci-
bility between chitosan and nylon 6 exits.
3.5 Scanning electron microscope analysis
SEM micrographs of chitosan with nylon 6 are shown in
Figs. 5 and 6. It is seen from Fig. 5 that there is uniform
morphology the blend of chitosan and nylon 6. It is very clear
from Fig. 5 that there is a three-dimensional porous structure
of chitosan which is cross-linked with nylon 6. Surface mor-
phology changes can be easily seen from Fig. 5 and this
happens when chitosan and nylon 6 forms a uniform layer
as reported by (Kim et al. 2000). This is due to diffusion of
chitosan molecules into synthetic polymer directly and forms
a blend. This is also seen from the cross-section image of SEM
shown in Fig. 6. From Fig. 6, it is clearly seen that there is
flushy nature and this has come so nicely because of chitosan.
4 Adsorption experiments
4.1 Percentage of metal removal as a function of time
Percentage of removal of copper and cadmium using
chitosan and nylon 6 at different time intervals is depicted
in Fig. 7.
It is seen from Fig. 7 that recovery of copper and cadmi-
um at all times is parallel. However, copper recovery is
higher compared to cadmium recovery at all times. It is seen

Fig. 5 SEM images of the
chitosan and nylon 6 beads with
(2:1+Glu) ratio
from the graph that the complexes of Cd2+ and Cu2+ behave
in the same manner as the cadmium and copper complexes
are stable. Percentage of recovery is almost parallel and this
is going to be so as they do not differ very much in the
molecular weight (Cu2+ 063.55 g/mol and Cd2+ 0112.41 g/
mol) and Pauling electro negativity values are the same
(Cu2+ 01.9 and Cd2+ 01.69). And the radius of hydrated
ion values is also same. (Rehydrated ion of Cu2+ 02.07Ǻ
and Rehydrated ion of Cd2+ 02.28Ǻ). Cadmium recovery is
slightly higher at all times than copper and this is under-
standable from the fact that polarizability for copper is
slightly higher than for cadmium (Cu2+ 06.8×10−24 and
Cd2+ 07.2×10−24) whereas co-valency of copper is higher
than cadmium (R co-valency Cd2+ 01.48Ǻ; R co-valency of
Cu2+ 01.31Ǻ). Figure 7 also shows the effect of contact time
on the removal of copper and cadmium metals in the artifi-
cial wastewater. The results indicate that the percentage of
copper removal increases from 17.00%, 32.00% and
49.00% during 30, 60 and 90 min of shaking with chitosan
and nylon 6, respectively. From 270 to 300 min, the per-
centage of removal of copper remains constant (89.00%),
which shows that equilibrium is reached at 30 min itself. In
the case of cadmium, the percentage of removal of cadmium
increased from 14.00%, 25.00%, 32.00%, and 79.00% dur-
ing 30 to 270 min, respectively. From 300 to 360 min, the
Fig. 6 SEM images of the
chitosan, nylon 6 beads with
(2:1+Glu) ratio
Environ Sci Pollut Res
percentage of removal of cadmium remained constant
(81.00%) indicating that 300 min of contact time is enough
for the maximum of removal of cadmium from wastewater.
4.2 Percentage of metal removal as a function
of time at different pH
It is seen from Fig. 8 that copper and cadmium recovery
increases from pH 3 to pH 5 or 6 and then decreases from 5
or 6 to 8. This is understandable from the fact that in these
ranges the stable species is Cu2+ or Cd2+ and even here Cd2+
recovery is more compared to Cu2+. The pH of aqueous
solutions and hence wastewater effluents affect a number of
reactions that takes place in these solutions as reported by
Hodi et al. (1995), Okieimen et al. (1988), Sadiq et al.
(1983), and Igwe and Abia (2003). The effect of pH on
heavy metal adsorption from aqueous solutions has been
reported by Okieimen et al. (1988), Namasivayam and
Senthilkumar (1998), Igwe and Abia (2003), Gang and
Weixing (1998), and Zouboulis et al. (1992). It is found
from graph that the removal of heavy metal ions was pH
dependent each result presents a characteristic variation of
pH with amount adsorbed depending on the adsorbent type,
metal ion concentration. In the present investigation, when
the adsorption study was conducted in a pH range of 3 to 8,
Environ Sci Pollut Res

Copper
Cadmium understandable from the fact that the stability of copper or
% of Cu+2 & Cd+2 from indusrial waste water
100
cadmium (2+) complex maximum at this pH range. This is
80 clearly depicted in Fig. 8. The PZC in the case of chitosan
with nylon 6 may be shifted to lesser values, viz (pH value)
60 4.5 to 5.5 unlike in pure chitosan where the value is 6.7.

40
4.3 Percentage of removal of copper and cadmium using
chitosan and nylon 6 with different adsorbent dosage
20

0 Various operational parameters are employed to determine

adsorption characteristics of chitosan biopolymers for heavy
0 100 200 300 400
Time in minutes
metal ions adsorption from aqueous solutions. These param-
% of Cu+2 & Cd+2 removal from industrial wastewater as function of time eters are solid/liquid ratio, pH, contact time, metal ion
concentration, and temperature.
Fig. 7 Percentage of copper and cadmium removed from industrial
waste water as function of time The effect of solid/liquid ratio for Cu2+ and Cd2+ ion
adsorption on chitosan biopolymer was examined. In these
experiments, operational parameters were kept constant, T0
it was observed that the percentage of removal of copper
298 K and Co 0100 mg/L; pH varied initially for various
increased with increase in the pH from pH 3 to pH 5, after
time. Figure 9 indicates that percentage of absorption of
which there is regular decrease in the percentage of removal
copper and cadmium increases steadily with solid to liquid
of copper with the increase in the pH up to 8. In the case of
ratio of 2% to 6% where as at 6% to 7% there is saturation.
cadmium containing wastewater, the maximum removal of
Increasing solid to liquid ratio for chitosan biopolymers
metal occurred at pH 5, after which there was regular
increases the number of active sites available for absorption.
decrease in the percentage of removal of the metal showing
that the removal of metals from wastewater depends on the
4.4 Effect of contact time
pH of the medium.
At low pH values, adsorption is low where surfaces have
Contact time is an important parameter because this factor
strong positive charge similar to that of the ions. Still ad-
determines the adsorption kinetics of an adsorbent at a given
sorption takes place at low pH values. This may be due to
initial concentration of the adsorbent. The effect of contact
limited contribution of chemical adsorption that is caused by
time on the heavy metal ions adsorption by chitosan was
the unpaired electrons of nitrogen at acetamide and amino
investigated for different time and it is shown in Fig. 7. It
functional groups of chitosan. The maximum adsorption
was observed that the uptake amount of Cu2+ and Cd2+ ions
occurs near to potential of zero charge (PZC) in the pH
on chitosan increases rapidly with increasing of the contact
range is 5 to 7 and this is what happens in the case of both
time 0 to 360 min and then reaches equilibrium after
Cu2+ and Cd2+ metal absorption. It is seen from Fig. 8 that
360 min. The initial rapid phase of adsorption with time
cadmium and copper recoveries are maximum in the pH
range 4.5 to 5.5 whereas it decreases after that. This is
Copper
Cadmium
% of Cu+2 & Cd+2 recovery by chitosan and ntlon 6

90
Copper
80 Cadmium
% of Cu+2 & Cd+2 removal

80
75
70 70
65
60 60
55
50 50

45
40
40
35
30
30 1 2 3 4 5 6 7 8
3 4 5 6 7 8 9 Dosage g/100 ml
pH % of removal of Cu+2 & Cd+2 using chitosan and nylon 6
% of Cu+2 & Cd+2 recovery by chitosan and nylon 6 at different pH with different adsorbent dosage

Fig. 8 Percentage of copper and cadmium recovery by chitosan and Fig. 9 Percentage of removal of copper and cadmium using chitosan
nylon 6 at different pH and nylon 6 with different adsorbent dosage
 Environ Sci Pollut Res

indicates that there are a large number of vacant sites and as a Fig. 10, the slope is 0.013 and k1 value is calculated to be
result there exists a concentration gradient between adsorbate 0.00022 min−1 and this is or the value of k1 at 298 K.
in solution and adsorbate in the adsorbent surface. As time
precedes, this concentration is reduced due to the accumulation 5.2 Pseudo second order kinetics
of Cu2+ ions on the vacant sites and this causes a decrease in
gradient in the adsorption rate after 240 to 360 min. The adsorption kinetic data can be further analyzed using
In all these cases, mass transfer limitations have been Ho’s pseudo second order kinetics. This is represented by
overcome by the use of nylon 6. This is evident from the Ho (2003).
results that without nylon 6 it is reported (Schmuhl et al.
2001; Hasan et al. 2006) that the authors have used rotation t 1 t
to overcome the mass transfer limitation. This is achieved ¼ þ ð3Þ
q k2 q2e qe
without rotation by the use of nylon 6.

Where q is the amount of metal adsorbed at any time mg/g

5 Kinetics of adsorption or mol/g. And qe is the amount of metal adsorbed at equilib-
rium time mg/g or mol/g. k2 is pseudo second order rate
5.1 Pseudo first order kinetics for copper and cadmium constant 9 g/mg/min or g/mol/min. Separating the vari-
able and integrating the equation for the boundary con-
The pseudo first order kinetic model has been widely used ditions at t00 to t0t and q0qe gives. A plot between qt
to predict the metal adsorption kinetics. The metal adsorp- versus t gives the value of the constants k2 (g/mgH) and
tion kinetics following the pseudo first order model is given (g/mol h) and qe (mg/g) and (mol/g) can be calculated.
by Ho and Mckay (1998) and Sivaraj et al. (2001) is The constant k2 is used to calculate the initial adsorp-
tion rate h, at t→0, as follows:
dq
¼ k1 ðqe  qÞ ð1Þ From Fig. 11 qt versus time for the pseudo second order
dt
kinetics the value of k2 is obtained. So Initial absorption rate
Where q is the amount of metal adsorbed at any time mg/g of copper is h074.7 mg/g and pseudo second order value of
or mol/g. qe is the amount of metal adsorbed at equilibrium the rate constant k2 is 0.0036 g/mg.h
time mg/g or mol/g k1 Pseudo first order rate constant Figure 11 also depicts the variation of qt versus time and
(min−1). Integrating equation with respect to boundary con- from this initial absorption rate of cadmium. Pseudo second
ditions q00 at t00 and q0q at t0t then the equation becomes order value of the rate constant for Cd is 0.00196 g/mg.
  h and the value of h051.39 mg/g which is initial absorption
qe
ln ¼ k1 T ð2Þ rate of cadmium. This gives clearly why cadmium recovery
qe  q
is high even though initial absorption rate of cadmium is
Thus the rate constant k1 (min−1) can be calculated from the low. The kinetic analysis of heavy metal ions adsorption on
 
plot of ln qeqq
e
versus time. biopolymer chitosan indicates that pseudo second order
kinetic model correlates better with the experimental data.
From Fig. 10 for copper, the slope is 0.014 and k1 value is
As indicated earlier, the initial rate of adsorption of
calculated and the value is found to be 0.00023 min−1 and
cadmium on chitosan is greater than copper and this
this is the value of k1 at 298 K. For cadmium from
Copper
Copper Cadmium
Cadmium Y=1.33718+0.00699x-Copper
Y =-0.22411+0.00605 X 4.5
1.6 Y =-0.25341+0.00571 X
Y=1.94592+0.00608x-Cadmium

1.4 4.0
1.2
3.5
1.0
ln(qe/(qe-q))

0.8 3.0
t/q

0.6
2.5
0.4
0.2 2.0
0.0
1.5
-0.2
-0.4 1.0
0 50 100 150 200 250 300 0 100 200 300 400
Time in miuntes Time in miuntes
 
qe t
Fig. 10 Plot of ln qe q versus time Fig. 11 Plot of q versus time
Environ Sci Pollut Res

indicates that the energetic barrier against chitosan for
cadmium is easier to overcome when compared to
copper.
5.3 Intra particle diffusion
The intra particle diffusion coefficient for the adsorption of
heavy metal ions in chitosan biopolymers is calculated from
the slope of the plot between qt versus t0.5. Figure 12 depicts
the amount of cadmium and copper removal versus square
root of time.
Figure 12 shows multi linearity. This is true for both
copper and cadmium. This suggests that there are two or
more steps involved in the adsorption process (Sun and
Yang 2003). The two graphs for copper and cadmium show
that there is an initial linear portion ended with a smooth
curve. The second curve may be considered as another
linear portion. Thus the two portions suggest clearly that
there are two mechanisms operating and they may be intra
particle diffusion and surface adsorption. The initial
curved portion of the plot indicates boundary layer effect
whereas the second linear portion suggests intra particle
diffusion or pore diffusion. The slope of second linear
portion of the plot is characterized as the intra particle
diffusion parameter k1 (mg/L h, 5). The slope is zero in
the present case as it is almost parallel to X axis as it is
evidenced from Fig. 12.
The slope for copper and cadmium for the first region is
17.00 and 14.00. They are almost parallel and the slope of
copper is slightly higher compared to cadmium. The inter-
cept of the plot reflects the boundary layer effect. The
intercept is larger in both the cases. This suggests that there
is greater contribution and this is due to surface adsorption
in the rate determining step.
2 3
Y =12.85774-5.48599 X+2.14268 X -0.07398 X
2 3
Y =73.92823-23.96846 X+3.42234 X -0.1009 X
180
q1the amount of recovered mg/L
6 Adsorption isotherm models
The analysis and design of the adsorption process requires the
relevant adsorption equilibrium. Adsorption equilibrium pro-
vides fundamental physicochemical data for evaluating the ap-
plicability of the process as a unit operation. The data obtained
are now analyzed using the Freundlich and Langmuir isotherms.
6.1 Freundlich isotherm
The logarithmic form of Freundlich model is given by the
following equation
1
logqe ¼ log KF þ ð4Þ
nlogce
Where qe is the amount adsorbed per unit weight of
adsorbent at equilibrium (mg/g, mol/g). And ce is the equi-
librium concentration of adsorbate in solution after absorp-
tion (mg/g, mol/L) and KF is empirical Freundlich constant
or capacity factor (mg/g, mol/g). And 1n is Freundlich
exponent (Figs. 13 and 14; Table 1),
The exponent 1n is less than 1 in these cases. Sorbets are
bound with weaker and weaker free energies. Between the
two copper and cadmium 1n value for cadmium is higher and
is approaching 1 much faster indicates that the cadmium
adsorption is better in chitosan with nylon 6 than copper.
And this is because there are more adsorption sites for
cadmium in presence of nylon 6 and mass transfer limitation
is avoided without resorting to rotation. There is a limit to
the amount adsorbed and there is no multilayer adsorption
as this is indicated by fitting the Freundlich isotherm.
6.2 Langmuir isotherm
Langmuir isotherm in its linear form is given by the equation
Ce Ce 1
¼ þ ð5Þ
qe Q 0 bQ0
Copper
Cadmium

1.50 Y =1.34413+0.08511 X Copper

160
1.48
140
1.46
120
1.44
log qe mg/g

100
1.42
80
1.40
60
1.38
40
1.36
20
1.34
0
2 4 6 8 10 12 14 16 18 20 22 1.32
Sqrt time -0.5 0.0 0.5 1.0 1.5 2.0
log Ce mg/L
Fig. 12 Plot of q versus square root of time for the amount of
cadmium removed Fig. 13 Plot of logqe versus log ce Freundlich isotherm
 Environ Sci Pollut Res

cadmium 0.44 Y =-0.11748+0.01809 X Copper

1.6
Y =-14.29228+9.96963 X 0.42
1.4 0.40
1.2 0.38

Ce/qe mg/L
0.36
1.0
log qe mg/g

0.34
0.8
0.32
0.6 0.30
0.4 0.28
0.26
0.2
20 22 24 26 28 30
0.0
Ce mg/L
-0.2
1.42 1.44 1.46 1.48 1.50 1.52 1.54 1.56 1.58 1.60
log ce mg/L Fig. 15 Plot of ce/qe versus ce

Fig. 14 Plot of logqe versus logce Freundlich isotherm

2. The extent of removal of the two metals in the above

Where Q0 represents the total number of surface sites per
mass of adsorbent
The Langmuir isotherm parameters are obtained by fit-
ting the data of adsorption by the elemental concentration in
solid and liquid are equilibrium at the end of the experi-
ments (4–7 h). The q0 represents the total number of surface
sites per mass of adsorbent (Finqueneisel et al. 1998). A plot
of Cqee versus ce will yield Q0 from the slope and from the
intercept KL can be obtained. This is provided in Figs. 15
and 16.
q0 for copper and cadmium are calculated and they are
74.7 and 51.39 and this reflects that the rate of adsorption
for cadmium is faster than copper as there are more sites for
cadmium adsorption than for copper.
KL for copper is 0.01809/0.11748 00.1539 and for
cadmium 00.02203/0.22992 00.0958 and this Langmuir
constant indicates that the process of adsorption of copper
and cadmium takes place in a similar fashion (Nelson and
Cosgrove 2004). This also indicates that the equilibrium
constant for cadmium and copper are more or less the same
for the adsorption reaction and adsorbate affinity of the
polymer is the same for both copper and cadmium and
depending on the adsorbable sites available the extraction
of copper and cadmium will take place.
conditions was found to be almost the same. With the
increase in the contact time, there is an increase in the
percentage of removal of the metals. The removal
became stagnant in 4 h.
3. The removal of heavy metals using chitosan and nylon
6 is pH dependent. The maximum removal of the
metals observed at pH 5 for both the metals.
4. The effect of adsorbent dose also has a pronounced
effect on the percentage removal of the metals.
Maximum removal of both the metals was observed
at 5 g/100 ml of the adsorbent.
5. From the present study, it is evident that chitosan and
nylon 6 is an efficient adsorbent for the removal of
heavy metal contaminated wastewater. Also the re-
moval of the metals is dependent on the contact time,
the pH, and adsorbent dose.
6. From the present study, it is seen that the process can
be easily scaled up as recovery of copper and cadmium
can be done without resorting to rotation to overcome
mass transfer limitations.
7. From the present study, it is seen that nylon 6 foam
provides enough absorbable sites to overcome mass
transfer limitations and thus this process can be easily
scaled up.

cadmium
7 Conclusions Y =-0.22992+0.02203 X
0.60

1. The present investigation is aimed in the use of a novel 0.55

indigenous adsorbent, chitosan, and nylon 6 for the
Ce/qe mg/L

0.50
removal of heavy metals copper and cadmium from the
wastewater. 0.45

0.40

Table 1 Freundlich 1 0.35

isotherm for copper and Metal KF n
cadmium 26 28 30 32 34 36 38
Copper 0.1603 0.3929 Ce mg/L

Cadmium 0.2418 0.4737

Fig. 16 Plot of ce/qe versus ce
Environ Sci Pollut Res
8. The number of absorbable sites for cadmium is more
compared to copper and thus the rate of recovery of
cadmium is faster than copper.
9. Recovery of copper and cadmium at all times is parallel
and it is concluded that cadmium recovery is higher
compared to copper recovery at all times.
10. In the present investigation, when the adsorption study
was conducted in a pH range of 3 to 8, it was observed
that the percentage removal of copper increased with
increase in the pH 3 to pH 5, after which there is
regular decrease in the percentage removal of copper
with the increase in the pH up to 8.
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