Int. J.

2012,
Int. J. of GEOMATE, June, of GEOMATE,
Vol. 2, No.June,
2 (Sl.2012, Vol.
No. 4), pp.2,227-234
No. 2 (Sl. No. 4), pp. 227-234
Geotec., Const. Mat. and Env., ISSN:2186-2982(P), 2186-2990(O), Japan

Removal of Copper from Water by Adsorption onto Banana Peel as

Bioadsorbent
M. A. Hossain, H. Hao Ngo, W. S. Guo and T. V. Nguyen
School of Civil and Environmental Engineering, University of Technology Sydney, Australia

ABSTRACT: Banana peel, a fruit waste were used to produce bioadsorbent through environment friendly process. It
were cut, washed, dried, grounded into powder and used for copper removal. Copper adsorption onto banana peel was
depended upon the controlling parameters such as particle size, doses, pH, contact time, agitation speed and
temperature. Slightly acidic water (pH = 6) was found to be suitable for copper removal. Equilibrium data were well
fitted (R2 = 0.998) with the Langmuir and Freundlich isotherms. The monolayer adsorption capacity was 27.78 mg/g.
The calculated RL and ‘n’ values has proved the favorability of copper adsorption onto banana peel. Copper
adsorption was followed the second order kinetic properly rather than other models. The equilibrium adsorption
capacity was 1.439, 8.849, 18.182, 31.250 and 71.429 mg/g when initial copper concentrations were 10, 50, 100, 200,
and 400 mg/l respectively. Solvent 0.1N Sulphuric acid showed higher desorption of copper (94%) and
adsorption-desorption process can be continued till seven cycles efficiently.
Keywords: Banana peel, Adsorption, Biosorbents, Isotherm models


agro-wastes may act as a significant material for copper

1. INTRODUCTION adsorption. Banana peel, an agro wastes is discarded all
Eco-toxicity on living organism has become a prime over the world as useless material. It is causing waste
concern from the last few decades. Massive urbanization management problems though it has some compost,
are continuously releasing waste and wastewater to the cosmetics and adsorbent potentiality. It is an abandoned,
ecosystem and, causing pollution to environment and readily available, low cost and cheap, environment friendly
eventually toxicity to living being. The industrial effluents bio-material. Considering the above criteria, banana peel
which contain different derivatives of heavy metals such as was selected to prepare the biosorbent. A step was taken for
Cd, Pb, Ni, Cr, As, Cu, Fe etc. are continuously discharging preparing biosorbent and used for removal of copper from
to the ecosystem and producing a significant toxic impact water. The main aim of this research was to determine the
on aquatic environment. Among the heavy metals, copper is potentiality and adsorption capacity of banana peel as
the major available type of heavy metal in the aquatic bioadsorbent.
environment. Copper in the blood system may generate
reactive free oxygen species and damage the protein, lipids 2. MATERIALS AND METHODS
and DNA [1]. The excess copper compound in the body 2.1 Materials
may also affects on aging, schizophrenia, mental illness, The stock solution of copper (1000 mg/l) was prepared by
Indian childhood cirrhosis, Wilson’s and Alzheimer’s dissolving 3.929 g of copper sulphate (CuSO4.5H2O) in 1L
diseases [2-4]. Copper has damaged the marine ecosystem of milli-Q water and used for all experiments with required
and damaged the gills, liver, kidneys, the nervous system dilution. The banana peel were collected from kitchen and
and changing sexual life of fishes [5-6]. Recent awareness used for whole experiments.
of toxicity originated from water and wastewater are
attending the interest for environmental scientist and 2.2 Methods
researcher. 2.2.1 Preparation of adsorbent
The collected banana peel were cut into small pieces (< 5
The sustainable removal of heavy metals from water and mm), washed three times with tap water and three times
wastewater has become a major challenge for scientists. with distilled water to remove external dirt. The wetted
Besides the available methods for copper removal, banana peel were kept in air for removing the water from
bio-technological removal are shown some advantages as the surface and dried in oven at 105°C for 24 hours. The
they are cheap, readily available, low cost, simplicity to use dried banana peel were grounded into powder and kept in
and environment friendliness. Huge and abandoned an air tied bottle for experimental uses.
agro-wastes may be the potential sources for producing
bioadsorbents besides the high cost adsorbents for heavy 2.2.2 Study of adsorbent doses
metals removal. Different bioadsorbents are developed The effect of adsorbent doses on the equilibrium adsorption
from agro-wastes and used for heavy metals removal such of copper was investigated with banana peel of 0.05, 0.1,
as rice straw [7], seaweed [8], wood and bark [9], tea-waste 0.2, 0.5, 1, 2, 5 and 10 g in five set of 100 ml water which
[10], maize corn cob, jatropha oil cake, sugarcane bagasse contained 1, 2.5, 5, 10 and 15 mg/l of copper concentration
[11], tamarind hull [12], sawdust [13], rice husk [14], each. The Erlenmeyers were shaken for 24 hours with 120
saltbush [15], marine algal biomass [16], olive pomace [17], rpm at room temperature. The water samples were then
activated sludge [18], sugar beet pulp [19], wool, olive cake, filtered and analyzed in terms of Cu by AAS.
sawdust, pine needles, almond shells, cactus leaves, and
charcoal [20], seafood processing waste sludge [21] and 2.2.3 Study of pH
pine bark [22]. Bioadsorbents which produced from The effect of pH for copper adsorption onto banana peel
was investigated with 0.5g of banana peel in 100 ml water
containing 10mg/l of copper and each sample were adjusted

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to pH between 1.18 to 13.5 using either 1N H2SO4 or NaOH and the percent removal (%) of copper was calculated using
solution. The Erlenmeyers were shaken for 24 hours with the following equation:
120 rpm at room temperature. (C  Ce ) (2)
%removal  i  100
Ci
2.2.4 Study of particle sizes where, V is the volume of solution (l), m is the amount of
The grounded banana peel were graded with standard adsorbent (g), and Ci and Ce (mg/l) are the initial and
sieves to six particles sizes of 600, 420, 300, 150, 75 and < equilibrium metal concentrations in the water, respectively.
75 µm. Banana peel (0.5g) from each graded sizes were The percent deviation was calculated as follows:
added to six Erlenmeyer with 100 ml water containing 10 (q  q e.cal ) (3)
mg/l copper concentration and shaken for 24 hrs at 120 %deviation  e.exp 100
q e.cal
rpm.
where, qe.exp and qe.cal are experimental and calculated
2.2.5 Study of temperature, contact time and shaking values of amount of copper adsorption onto banana peel.
speed
3. RESULTS AND DISCUSSION
The effect of temperature, contact time and shaking speed
3.1 Environment friendly preparation
(rpm) on adsorption of copper were examined with
The preparation methods are the key factor for any type of
different temperature (30-70C), time (3h) and speed bioadsorbent, because morphological properties such as
(30-200 rpm) for 10 mg/l copper concentration with 0.5 g particle size and shape, binding surface area, and overall
banana peel in 100 ml water. removal capacity depend on it. Simple, easy to prepare and
use, hazard free and environment friendly treatments are
2.2.6 Equilibrium study
the requirement for sustainable preparation of bioadsorbent.
Equilibrium adsorption experiments (triplicate) were
Considering the above this research is used simple and
conducted with 16 Erlenmeyer of 100 ml water containing
non-treated preparation methods rather than the expensive
1 to 500 mg/l of copper concentration. Grounded banana
and high-tech pyrolysis and non-environment friendly
peel of 0.05, 0.1 and 0.5 g were added in each sets of
acid/base pre-treatment methods [7-22]. This is the novelty
experiments and shaken for 24 hours with 120 rpm at room
of this study. The SEM micrograph (Fig.1) revealed that
temperature without pH adjustment. The equilibrium data
microporous structures, heterogeneous, rough surface with
were fitted with Langmuir, Freundlich and Temkin
crater-like pores were existed in banana peel. The electron
isotherm models.
micrographs also revealed that the particles are of irregular
2.2.7 Kinetics study shape and its surface exhibits a micro-rough texture, which
Kinetics experiments were conducted with 10, 50, 100 and can promote the adherence of copper.
200 mg/l copper concentration in 1L water and with 5 g of
banana peel at room temperature (20oC) without pH
adjustment. Water was agitated at 120 rpm for 2 hours. At
different intervals 5ml of water samples were withdrawn
and filtered for analysis. The kinetics data were evaluated
with pseudo-first-order, pseudo-second-order, Elovich and
Reichenberg kinetics equation.

2.2.8 Desorption study

Desorption of banana peel was studied using 8 types of
solvent medium including tape water, milli-Q water,
distilled water, 0.1N H2SO4, 0.1N HCl, 0.1N HNO3, 0.1N
NaOH and 0.1 N CH3COOH. For this purpose, 0.5 g of
saturated (with Cu) banana peel was taken in 100 ml of Fig.1 SEM micrograph (1k) of banana peel
above mentioned medium and shaken at 120 rpm for 24 hr.
3.2 Effect of doses
2.3 Analysis The effect of doses was investigated with five copper
The collected water samples from different experiments concentration-sets (1-15 mg/l) in 100 ml water by adding
were filtered with filter paper (Whatmann 5) and prepared eight doses for each set (Fig.2). The percent removal of
for AAS analysis. The samples were analyzed in term of Cu copper was found to increase with an increase in the mass
by Atomic Absorption Spectrometer (AAS 932 plus, GBC, of adsorbent. Highest copper removals were 85 and 88 %
Australia). The pH was measured by Hanna HI 9025 for the initial copper concentration of 5 and 10 mg/l,
(HANNA Instrument, Romania) pH meter. respectively at the adsorbent dose of 5 g/l. Thereafter, the
2.4 Calculation removal of copper started to decline with increasing in mass
The amount of copper adsorbed by adsorbent (q) in the of adsorbent for all five sets and then remained leveled. The
adsorption systems were calculated by the following mass partial aggregation among the available active binding sites
balance equation: may acts for less removal of copper at high doses [23]. Also,
V.(Ci  Ce ) due to lack of active binding site, the lower removals were
q (1) obtained at low adsorbent doses [24]. Thus, 5g (0.5
m

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g/100ml) of banana peel and 10 mg/l of copper room temperature and pH of 6-6.5 (without adjustment).
concentration were chosen to use for other experiments. Fig.4 indicates that the removal of copper was increased by
100 decreasing the particle sizes. The percent removal of copper
increased from 74 to 96% when decreasing particle sizes
%removal of copper

80
from 600µm to <75µm. This behavior can be attributed to
60 the effective surface area increased as the particle size
decreased and as a consequence, the copper adsorption
40 Cu: 1 mg/l
Cu: 2.5 mg/l increased [28].
Cu: 5 mg/l
20 Cu: 10 mg/l
Cu: 15 mg/l 3.5 Effect of contact time
0
0 20 40 60 80 100
Experiments for contact time were conducted with five
Adsorbent doses g/l initial copper concentrations (Co:10, 20, 50, 100 and 200
Fig.2 Effect of adsorbent doses on removal of copper (t: mg/l) with a dose of 5 g/l banana peel at 120 rpm and room
24h; rpm: 120; pH: 6-6.5; T: 20°C) temperature for 2 hours. Fig.5 shows the effect of contact
time on adsorption of copper ions by banana peel.
3.3 Effect of pH
Adsorption rate of copper on banana peel was found to be
pH is a controlling factor for any kind of metal adsorption
relatively much faster than those reported for some other
process from aqueous solution. The surface properties of
bio-adsorbents [24]. The rate of copper removal was very
adsorbents, ionic state of functional groups and species of
rapid during the first 30 min, and thereafter, the rate of
metals are dependent on pH condition. pH dependent
copper removal remained constant. There was no
experiments were conducted and the result are shown in
significant increase in adsorption after about 60 min. The
Fig.3. The copper adsorption was found to increase with an
experiment with high Co showed the higher amount of
increase in pH from 2 to 6 and attained a maximum value
copper removal. The copper ion adsorption on banana peel
(1.76 mg/g) at pH 6 (which was slightly acidic). Latter the
was reached at equilibrium after 1h. Initially, there were
copper adsorption capacity was declined. The speciation
large number of vacant active binding sites in banana peel
diagram [25] has confirmed that Cu2+ is the dominant free
and consequently large amount of copper ions were bound
species below pH 6 which involved in true adsorption. The
rapidly onto banana peel. The binding site was shortly
H3O+ ions compete with Cu2+ for binding on adsorbent sites
become limited and the remaining vacant surface sites are
and it may be responsible for lower adsorption capacity at
difficult to be occupied by copper ions due to the formation
low pH [24, 26]. At higher pH, the removal was also low
of repulsive forces between the copper on the solid surface
compared to the optimum condition. This can be explained
and the liquid phase [29-30]. Besides, the meso-pores
as the binding site may not activate in basic condition [27].
become saturated at the initial stage of adsorption where the
Above pH 6, the copper started precipitating as Cu(OH)2+,
metal ions are adsorbed. As a result, the driving force of
therefore the removal was not completely by adsorption [25,
mass transfer between liquid and solid phase in an aqueous
26].
adsorption system decreases with time elapse. Further, the
2.5
metal ions have to pass through the deeper surface of the
2 pores for binding and encounter much larger resistance
qe (mg/l)

1.5 which slowing down the adsorption during the later phase
of adsorption [29].
1
35
0.5 30 Co: 10 mg/l
Co: 20 mg/l
0 25
Co: 50 mg/l
qe (mg/g)

0 2 4 6 pH 8 10 12 14 20 Co:100 mg/l
Co:200 mg/l
Fig.3 Effect of pH of copper adsorption (t: 24h; Co: 10 mg/l; 15
d: 5 g/l; rpm: 120; T: 20°C) 10
5
3.4 Effect of particles sizes of adsorbent 0
100 0 50 100 150 200
Contact time (mins)
Fig.5 Effect of contact time on removal of copper (Co: 10
% removal

90
mg/l; d: 5 g/l; rpm: 120; T: 20°C; pH: 6-6.5)
80
3.6 Effect of shaking speed
70
The effect of shaking speed on adsorption of copper was
60 studied over the range of 30-200 rpm for 2h with 100 ml
600µm 420µm 300µm 150µm 75µm <75µm water containing 10 mg/l copper and 0.5 g of banana peel.
Particle Sizes Fig.6 indicates that the percent adsorption increased with an
Fig.4 Effect of particle size on removal of copper (t: 24h; increased of shaking speed and obtained a maximum 88%
Co: 10 mg/l; d: 5 g/l; rpm: 120; T: 20°C; pH: 6-6.5) adsorption at near 120 rpm. This shaking speed was
employed for other experiment. At low and high speeds, the
Batch experiments for the effects of particles on adsorption copper removal was lower than optimum. Low speed could
were conducted for six particle sizes (600µm to <75 µm) at not spread the particles properly in the water for providing

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active binding sites for adsorption of copper. It is resulted affinity of the banana peel for copper ions and suggests
an accumulation of banana peel in the bottom of water and some structural changes in copper ions and banana peel
buried the active binding sites. On the other hand, the high fiber [31]. In addition, the negative value of ∆S (for both
speed vigorously spreading the particles of banana peel in isotherms) also suggests that the adsorption was enthalpy
the water and did not allow sufficient time to bind with driven and spontaneous in nature [27].
copper ions [23]. 4
90 2

Gibs free energy, ∆G°

%removal of copper

80 y = 0.0111x - 1.32 Langmuir Isotherm

0 2
R = 0.7677
70
-2 Temkin Isotherm
60
-4
50 y = 0.0579x - 24.4
-6
40 2
R = 0.9844
-8
30
300 310 320 330 340 350
0 30 60 90 120 150 180 210
T (°K)
Shaking speed (rev/min) Fig.7. Relationship between Gibbs free energy change, ∆G
Fig.6 Effect of shaking speed on removal of copper (t: 24h;
and temperature, T (K) of adsorption reaction
Co: 10 mg/l; d: 5 g/l; T: 20°C; pH: 6-6.5)
Table 1 Calculated values of thermodynamic parameters
3.7 Thermodynamics properties for the equilibrium adsorption of copper onto banana peel
To determine the thermodynamic properties and thermal T qm ΔG° ΔH° ΔS°
effects on the adsorption, the temperature variation (°C) (mg/g) (kJ/mol) (kJ/mol) (kJ/mol K)
experiments were conducted at 30, 40, 50 and 70°C, with an Lang Tem Lang Tem Lang Tem
initial copper concentration between 1-200 mg/l and 0.5g 30 4.082 -6.945 1.950 0.057 0.011 -24.4 -1.32
banana peel. The experimental data show that the 40 2.203 -6.268 2.224
equilibrium adsorptions were decreased with an increase of 50 0.710 -5.521 2.391
temperature (Table1). It seems to be that higher 70 0.884 -4.626 2.425
temperature has negative impact on copper adsorption. The * Lang : Langmuir ; Tem : Temkin
thermodynamic parameters such as Gibbs free energy
(ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) 3.8 Adsorption isotherms
were calculated to evaluate the nature of the adsorption Adsorption isotherms describe the equilibrium
process. For a given temperature, a phenomenon is relationships between adsorbent and adsorbate. Three
considered to be spontaneous if the ΔG° has a negative adsorption isotherms (6)-(8) were used to fit the
value. Moreover, if ΔH° is positive, the process is equilibrium data namely, Langmuir [32], Freundlich [33]
endothermic and if it is negative, the process is exothermic. and Temkin [34]. Its applicability was judged with the
The magnitude of ΔG° (kJ/mol) was calculated using the correlation coefficients (R2). Langmuir equation can be
following equation: linearized by the following form:
G o   RTlnK a (4) 1

1

1 (6)
where, R is universal gas constant, 0.008314 kJ/mol K; T is qe bq m C e qm
absolute temperature (°K) and Ka the adsorption where, Ce is the equilibrium concentration in liquid phase
equilibrium constant from Langmuir and Temkin isotherm (mg/l), qm is the monolayer adsorption capacity (mg/l) and
and ΔH° (kJ/mol) was calculated by the following equation: b is the Langmuir constant related to the free adsorption
ΔH o  ΔG o  TSo (5) energy (l/mg).
7
A plot of ∆G versus T was found to be linear (Fig.7) and 6
the values of ∆H and ∆S, were calculated from the slope Dose: 5 g/l
5 Dose: 0.5 g/l
and intercept of the plots. The thermodynamic parameters 4 Dose: 1 g/l
1/qe

calculated from both Langmuir and Temkin isotherm are 3

shown in Table 1. The negative values of ∆G for Langmuir 2
isotherm have confirmed the feasibility of process and the 1
spontaneous nature of adsorption. However, the positive 0
values from Temkin isotherm showed the opposite of 0 2 4 1/Ce 6 8 10
nature of adsorption. The values of ∆G were decreased Fig.8 Langmuir isotherm for copper adsorption onto banana
from -6.95 to -4.63kJ/mol for Langmuir isotherm and peel (Co: 1-500 mg/l; t: 24h; rpm: 120; pH: 6-6.5; T: 20°C).
increased from 1.95 to 2.43 kJ/mol for Temkin isotherm as Freundlich equation can be linearized by the following
the temperature increases from 30 to 70C. The values of form: 1
lnq e  lnK F  lnC e (7)
∆H and ∆S calculated from Fig.6, using Langmuir n
constant, Ka and Temkin constant KT are given as 0.057 where, KF is a constant indicative of the adsorption capacity
kJ/mol and -24.4 kJ/mol K and 0.011kJ/mol and -1.32 of the adsorbent (mg/ g) and the constant 1/n indicates the
J/mol K, respectively. The positive value of ∆H indicates intensity of the adsorption. The linearized form of Temkin
that the adsorption reaction was endothermic and strong isotherm is as follows:

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q e  B1lnK T  B1lnCe (8) Fig.10 and Table 2 shows Temkin isotherm and calculated
constant related to heat of adsorption (bT). Its’ were 0.083,
where, B1 = RT/bT, KT (l/g) and bT (kJ/mol) are the Temkin 0.228 and 0.474 kJ/ mol for copper adsorption on banana
constants. peel for the doses of 0.5, 1 and 5 g/l respectively. The lower
values of bT (<8) indicate that the interaction between metal
The linear plot of Langmuir isotherm for copper adsorption and banana peel was weak. The adsorption process of
and the calculated parameters along with regression copper onto banana peel can be expressed as physiosorption
coefficients are shown in Fig.8 and Table 2, respectively. as indicated by the value of bT.
Maximum adsorption capacity, qm, for complete monolayer
coverage are found 125, 35.714 and 28.571 mg/g for 0.5, 1 Table 2 Langmuir, Freundlich and Temkin isotherm
and 5 g/l doses, respectively. R2 values approaching to one, parameters and correlation coefficients for the adsorption
clearly suggest that Langmuir isotherm follows a good of copper onto banana peel at different adsorbent doses.
relation of copper adsorption with banana peel. The Doses Langmuir Freundlich Temkin
adsorption capacity for banana peel was found higher than qm b R2 KF n R2 bT KT R2
the previously reported methods of metal adsorption [27]. (g/l) (mg/g) (l/mg) (mg/g) (kJ/mol) (l/mg)
‘b’ is the adsorption constant related to the affinity of 0.5 125 0.36 0.975 14.60 2.05 0.992 0.08 3.07 0.858
binding sites(l/g) and lower value of ‘b’ (0.364, 0.191 and 1 35.71 0.19 0.993 4.44 2.05 0.983 0.23 1.21 0.942
0.024 l/g for three doses) indicate that the particles radius of 5 28.57 0.03 0.998 1.51 1.29 0.989 0.47 1.22 0.806
banana peel were small toward adsorption [23]. Separation
factor (RL), an essential characteristic of Langmuir 3.9 Adsorption kinetics
isotherm model was calculated as the following equation: Kinetic studies are significant for any kind of biosorption
RL = 1/(1 + bCi) (9) processes. Adsorption kinetics not only describes the
where, Ci is the initial concentration of metal ions. The adsorption mechanism of metals on adsorbents but also
values of RL (0.9-0.07) revealed that copper adsorption on describe the metal adsorption rate which controls the
banana peel is favourable as the values lies between 0 and 1 contact time of metals at the solid-liquid interface [35]. The
[32] adsorption mechanism depends on the physical and
. 6 chemical characteristics of adsorbent and adsorbate, pH of
medium, temperature, contact time and aids and mass
4 transport process [30]. Kinetics studies were conducted at
lnqe

non adjusted pH condition with four initial copper

2 concentrations. The data were fitted with different kinetics
Dose: 5 g/l equation namely First Order, Second Order, Elovich and
0 Dose: 0.5 g/l
Dose: 1 g/l
Reichenberg kinetics models.
-2
3.9.1 The pseudo-first-order and pseudo-second-order
-3 -1 1 3 5 7
lnCe kinetics equation
Fig.9 Freundlich isotherm for copper adsorption onto 0 50 t (min) 100 150 200
banana peel (Co: 1-500 mg/l; t: 24h; rpm: 120; pH: 6-6.5; T: 4
20°C) 2
0
The linear plot of Freundlich equation for copper
ln(qe-qt)

-2
adsorption and the calculated parameters are shown in Fig.9 -4
and Table 2, respectively. The Freundlich isotherm model -6 Co: 10 mg/l
was found best fitted with experimental data as its poses -8 Co: 50 mg/l
Co: 100 mg/l
higher R2 value (0.992, 0.982 and 0.989). KF is a Freundlich -10 Co: 200 mg/l
-12
constant that shows adsorption capacity on heterogeneous
sites with non-uniform distribution of energy level and n Fig.11 Linear plot of pseudo-first-order equations for
shows the intensity between adsorbate and adsorbent. The copper adsorption onto banana peel
calculated values of ‘n’ (Table 2) prove that the adsorption
The linear form of pseudo first-order kinetic model [44] is
of copper onto banana peel is favourable as the magnitude
as follows:
lies between 1 and 3 [30].
ln(qe  q t )  lnqe  k ad t (10)
300
250
Dose: 5 g/l The adsorption rate (kad) are calculated from linear
Dose: 0.5 g/l
200 regression analysis from the slope of linear plot of
qe (mg/g)

Dose: 1 g/l

150
experimental data (ln(qe - qt) vs t). The linear plot of the
experimental data and the calculated parameters are shown
100
in Fig.11 and Table 3, respectively. The experimental data
50
is not well fitted for pseudo-first-order kinetic equation as
0
the R2 were low. The kinetics data were also analyzed by
-50
pseudo-second order equation and the linear form as [37]:
-3 0 3 6 9 12 15 18
lnCe t 1 1 (11)
  t
Fig.10 Temkin isotherm for copper adsorption onto banana q t k 2q e2 q e
peel (Co: 1-500 mg/l; t: 24h; rpm: 120; pH: 6-6.5; T: 20°C)

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where, k2 is the constant of pseudo-second-order rate; qe is yielded a linear relationship with a slope of (1/β) and an
the biosorption capacity at equilibrium; and qt is the intercept of (1/β) ln(αβ).
biosorption capacity at time t. If the initial adsorption rate,
as h = qt/t when t approach to 0, h, (mg/g min) [35], is: Table 4 Calculated kinetic parameters of Elovich equation
(12) for copper adsorption onto banana peel at different Co
h  kq 2 e Parameter Elovich kinetics model
Table 3 Calculated parameters of pseudo-first-order and Co qe.exp qe.cal α β R2 %deviation
pseudo-second-order kinetics (mg/l) (mg/g) (mg/g) (mg/g.min) (g/mg)
Kinetics Parameters 10 50 100 200 10 1.288 1.217 1.863 5.236 0.991 5.8
50 8.692 8.582 1.45x10+22 6.623 0.951 1.28
models mg/l mg/l mg/l mg/l 100 17.732 17.526 7.69x10+18 2.762 0.914 1.17
Pseudo-first-order 200 29.752 29.140 36796.5 0.469 0.866 2.10
qe.exp (mg/g) 1.288 8.692 17.732 29.752 35
qe.cal (mg/g) 1.148 1.811 1.198 6.488 30
Co: 10 mg/l
Co: 50 mg/l
kad (min-1) 0.056 0.034 0.024 0.068 Co: 100 mg/l
Co: 200 mg/l
R2 25

qt (mg/g)
0.903 0.951 0.915 0.881
Pseudo-2nd-order 20
qe.cal (mg/g) 1.439 8.849 18.182 31.250 15
k2 (g/mg.min) 0.097 0.156 0.078 0.027 10
h (mg/g.min) 0.200 12.195 25.641 26.316 5
R2 0.997 0.999 0.999 0.999
0
60 0 1 2 ln(t) 3 4 5 6
50 Co: 10 mg/l Fig.13 Linear plot of Elovich model for copper adsorption
t/qt (min.g/mg)

Co: 50 mg/l
40 Co: 100 mg/l onto banana peel at various Co
Co: 200 mg/l
30 The Elovich model is used to explain the copper adsorption
20 mechanism onto banana peel. The two parameters (α and β)
10 were calculated from the slope and intercept of the linear
plot of qt vs ln(t) (Fig.13) and tabulated in Table 4. A good
0
range of R2 values (0.914 to 0.991) were found except when
0 50 t (min) 100 150 200
initial copper concentration was 200 mg/l. The calculated
Fig.12 Linear plot of pseudo-2nd-order equation for copper values of α and β (Table 4) showed a general trend of
adsorption onto banana peel at various Co changes with an increase in the initial copper concentration.
The values of α increased from 1.863 to 36796.5 with
The equilibrium adsorption capacity and the second-order
increased Co (10 to 200 mg/l), suggesting that the process
rate constant were calculated from the slope and the
was chemisorptions corresponding to the heterogeneity in
intercept of the plot t/qt against t. The graphical
nature of active sites [39]. On the other hand, with
interpretation of the data for second-order-kinetic model
increased of Co, the β-values showed a reduction trend
and calculated parameters are shown in Fig.12 and Table 4,
(45.236 to 2.762 g/mg). Thus, 1/β (which is apparently
respectively. A good fitted (R2>0.999) linear plots are
indicative of the number of sites available for adsorption, as
obtained from experimental data (Table 3) while the
per the second assumption) showed a distinct increase with
calculated values of qe also agreed with the experimental
an increase in concentration, again reinforcing the
values. This finding revealed that the copper adsorption
occurrence of chemisorptions [40].
onto banana peel follows the pseudo-second-order
mechanism and the chemical adsorption process controls 3.9.3 Reichenberg equation
the adsorption rate. It was found that equilibrium Reichenberg [41] stated that the radius of adsorbent’s
adsorption capacity (qe) increased with an increase in initial particles (r) controls the effective diffusion of exchanging
copper ion concentration (Co). The adsorption capacity ions and film diffusion in adsorption may be reduced from
increased from 1.288 to 70.304 mg/g when Co was the linear fit:
increased from 10 to 400 mg/l. The calculated values of 6e  Bt
Q 1 (14)
equilibrium adsorption capacities (qe.cal) were well agreed π2
with the experimental values (qe.exp) for the second-order where, Q is the ratio of adsorbed concentration at time ‘t’
kinetic model and the lower ‘% deviation’ confirmed the and the maximum adsorption capacity of the adsorbent
process (Table 4). The qe increased with increasing Co, (=qt/qm), Bt =π2Di/r2 and Di is the coefficient of effective
while the k decreases and the h increases with increasing diffusion of ions exchanging inside the adsorbent particles.
Co. The value of Bt can be calculated mathematically for each
3.9.2 The Elovich kinetics value of Q, using the following equation:
The simplified and linearized form of Elovich kinetics Bt  0.4977  ln(1 Q) (15)
model [38] can be expressed as:
1 1
The linear plot of ‘Bt’ versus contact time‘t’ is shown in
q  ln( α  )  ln(t) (13)
t
β β
Fig.14. The linear plot revealed that the data was not quite
fitted with model for 2 h time period as produce low R2
where, α is the initial adsorption rate (mg/g.min) and β is values (0.962, 0.855, 0.931 and 0.900) for the initial copper
the desorption constant (g/mg). A plot of qt versus ln(t) concentration of 10, 50, 100 and 200 mg/l, respectively.

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 Int. J. of GEOMATE, June, 2012, Vol. 2, No. 2 (Sl. No. 4), pp. 227-234

However, it was linear between 0 to 60 min with a higher R2 4 ACKNOWLEDGMENTS

values (>0.98). The regression lines did not pass through
the origin which indicated that a thin film of copper was This research was supported by the Centre for Technology
formed on the surface of banana peel. in Water and Wastewater (CTWW), School of Civil and
8 Environmental Engineering, University of Technology,
Co: 10 mg/l

6
Co: 50 mg/l
Co: 100 mg/l
Sydney (UTS) and UTS International Postgraduate
Co: 200 mg/l Research Scholarship.
Bt

4
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