International Journal on Recent and Innovation Trends in Computing and Communication ISSN: 2321-8169

Volume: 4 Issue: 7 190 - 196

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A Comparative Study of Adsorption of Cyanide onto Dried Peels of Plantain and
Banana
Nwoko Christopher Ikpe Amadi1, Mbonu Petrolina Ihuoma2, Okoji Josephine Nkechi3
1,2,3
Department of Chemistry, School of Physical Sciences, Federal University of Technology, Owerri, Nigeria.
nwokochristopher@yahoo.com, ihuomambonu01@yahoo.com, lajoe4real@yahoo

Abstract-- Dried plantain peels and dried banana peels were investigated for adsorption of cyanide from solution. Studies concerning the
adsorption equilibrium parameters were presented and discussed. The effect of cyanide concentration, temperature, adsorbent dose, pH and
contact time on cyanide adsorption were also investigated. The equilibrium data were modeled using Langmuir, Freundlich and Redlich Peterson
isotherms. The adsorption equilibrium data were well explained by Freundlich isotherm. The percentage removal was found to be 83.84 % and
76.36 % at contact time of 140 minutes for Dried Plantain Peel (DPP) and Dried Banana Peel (DBP) respectively. There was a rapid increase in
adsorption of cyanide from low pH of 2 to about pH of 8 and a maximum adsorption was observed at pH 10. Adsorption capacity of 53.90 mg/g
and 47.56 mg/g was achieved at initial concentration of 150 mg/L for DPP and DBP respectively. The specific surface area of 5.3 m2/g and 4.4
m2/g of the adsorbents were separately determined using the method of p-nitrophenol. The result of this investigation has shown the possibility
of using dried plantain peel to adsorb cyanide from waste water outweighs using dried banana peel.

Keywords- Dried Plantain Peels, Dried Banana Peels, Cyanide, Adsorption, Equilibrium Data, Isotherm.
__________________________________________________*****_________________________________________________

1. Introduction Numerous treatment methods such as: chemical and

Water pollution is one of the major concerns of
environmentalists worldwide. The pollution may be
attributed to various reasons such as industrial wastes,
natural contaminants or sewage discharge. Cyanide is
widely used in industry. Industrial discharge from coke
processing industry contains large quantities of toxicants
like phenol, cyanides, thiocyanides, thiosulphates,
ammonium and chlorides. Hydrocyanic acid, also known as
hydrogen cyanide or HCN, is a highly volatile liquid used to
prepare acrylonitrile which is used in the production of
acrylic fibers, synthetic rubber and plastics. Cyanides are
employed in a number of chemical processes including
fumigation, hardening of iron and steel, electroplating and
the concentration of ores which shows the importance of
cyanide to man.
Cyanide and their associated compounds have been listed as
priority pollutants by the Central Pollution Control Board,
India and Environmental Protection Agency (EPA), USA.
Cyanide, is a deadly poisonous substance which exists in
water as HCN, a weak acid with pKa of 6 X 10-10 In
addition, thiocyanate, which is metabolized from cyanide,
interferes with iodine uptake by the thyroid gland, causing
goiters and other long-term iodine deficiency diseases.
According to the recommendation of the United State
Environmental Protection Agency (USEPA), the threshold
concentration of cyanide in effluent discharge should be
within 0.2 mg L-1. All forms of cyanide are categorized as
toxic materials with chronic and acute features of poisonous
substance [6, 13].
Treatment of waste water bearing cyanide, prior to
discharge, is essential. The permissible limit of cyanide in
effluent according to United States (U.S.) health service is
0.2mg/L. For cyanide, Central Pollution Control Board
(CPCB), India has fixed a Minimal National Standard
(MINAS) limit in effluent as 0.2 mg/L and U.S.
Environmental Protection Agency (USEPA) standard for
drinking waters about total cyanide are 200 ppb [18].
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biological oxidation and precipitation have been used for the
removal of cyanide levels in effluents in acquiescence with
environmental guidelines advantages [14, 18]. Each of the
overhead treatment methods has their specific limitations.
Treatment of cyanide from waste waters by adsorption onto
granular activated carbon has established great consideration
[1, 7]. The important step to optimize and design an
adsorption process is finding a suitable isotherm for
demonstrating the equilibrium condition of an adsorption
process.
A number of chemical, physical and biological methods are
available for treatment of waste water. However the
presence of multiple contaminants poses certain hindrances
making no single treatment sufficient for complete
remediation of waste water. However, among available
waste water treatment technologies, adsorption, particularly
using granular activated carbon (GAC), has gained much
popularity owing to its efficiency and ease. Nevertheless,
high cost of GAC and its difficulty in regeneration, has led
to exploration of non-conventional adsorbents. Dry plantain
and banana peels which are agricultural waste products and
do not require much treatment would be used to adsorbed
cyanide from aqueous solution, owing to their availability
and low cost.
2. Materials and Method
2.1. Preparation of Dried Plantain Peel and Banana Peel
Fresh plantain peels and banana peels were collected from
fruit sellers in the streets of Owerri, Imo State, Nigeria. The
plantain peels and banana peels were first washed with bore-
hole water to remove dirt and mud and finally washed with
distilled water. After washing, they were sliced into small
bits and sun-dried for about two weeks, before grinding with
a ball mill. The ground dry plantain peels and banana peels
were sieved respectively with a sieve of mesh 125 m to
obtain the desired ultimate fineness. The precursor obtained
were washed with distilled water to remove surface bound
impurities and dried in the oven at 105 oC for 24 hours.
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2.2. Determination of Surface Chemistry (Microscopy)
10 g of dried plantain peel and banana peel was sent to
Ahmadu Bello University (ABU) Zaria respectively, in
order to study the morphology of the samples in a Scanning
Electron Microscope (SEM). Surface topographical
information was obtained by a surface morphological study
in Phenom Prox Scanning Electron Microscope and the
surface functional groups of the samples were equally
estimated by Fourier Transform Infra-red
Spectrophotometer (FTIR).
2.3. Determination of Surface Area
The surface areas of the two adsorbents were determined
respectively using solution adsorption of p-nitrophenol
method. 0.1 M solution of p-nitrophenol containing 13.90
g/dm3 was prepared. This was subsequently diluted to eight
different concentrations. About 0.2 g of DPP and DBP
samples was weighed into 10 mL of the eight solutions
respectively and then agitated for 30 minutes at temperature
of 29 oC filtered and then the absorbance was measured at
400 nm using spectrophotometer. A plot of equilibrium
concentration of p-nitrophenol against the various amount
adsorbed onto DPB and DPP were prepared [15].
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3. Results and Discussion
3.1. Surface Characterization of DPP and DBP
3.1.1. Determination of Specific Surface area by Solution
Adsorption of p-nitrophenol
The adsorption data were analyzed according to the
Langmuir equation:
1
= = (3)
/ . /
Where Ce is the equilibrium concentration of solute
remaining in the solution, x/m is the quantity of solute
adsorbed per unit weight of adsorbent; xm and k are
Langmuir constants. These constants are called adsorption
capacity (solute monolayer capacity) and bonding energy
constant, respectively.
Straight lines were fitted to the points by the method of least
squares, where the slope of the regression line is 1/xm and
the intercept is 1/k.xm. The linear regression lines obtained
for DPP and DBP had highly significant correlation
coefficients (r), indicating a good fit to the Langmuir
equation [10]. It is observed that DPP has a higher
correlation coefficient when compared to DBP.
The surface area was calculated from the Langmuir plot
using the equation below [9]

. .
2.4. Preparation of Cyanide Stock Solution Surface area (S.A) = (4)

2.503 g of KCN and 1 g of NaOH was dissolved in distilled Where
water and diluted to 1 liter. Different concentrations of 50, Xm is amount of solute adsorbed at monolayer per gram of
75, 100, 125 and 150 mg/L of cyanide were prepared from adsorbent (mg/g)
the stock solution. After preparation, the solution was stored Am is cross- sectional area occupied by the adsorbate (m2)
in a cool environment until required. L is Avogadro number
N is coverage factor
2.5. Batch adsorption of Cyanide DPP and DBP have S.A. of 5.3 m2/g and 4.4 m2/g
Batch experiments for optimization of operating parameters respectively. The adsorption isotherms and Langmuir lines
and equilibrium, kinetic and thermodynamic studies were are shown in Figures 1 and 2. Langmuir constants are given
carried out in 250 mL round bottom flasks with working in Table 1.
volume of 100 mL. All the experiments were carried out in
triplicates and average results were used.
The optimum pH and adsorbent dose were selected from a 5.0
range of pH 2-12 and 0.2-1 g L-1. The contact time was
4.5
carried out at 100 minutes at 30 oC temperature.
4.0
2.6. Direct Spectrophotometric Determination of
Cyanide 3.5
The cyanide concentration in solution was determined using
3.0
ce/qe (g/L)

picric acid method according to [11]. After equilibrium was

attained, the cyanide uptake capacity for each sample was
2.5
DPP
calculated according to equation 1: DBP
= (1) 2.0

Where m is the mass of adsorbent (g), V is the volume of 1.5
solution (L), is the initial concentration of cyanide
(mg/L), is the equilibrium cyanide concentration (mg/L) 1.0
and is the amount of cyanide adsorbed at equilibrium
(mg/g). The percent removal of cyanide from the solution 0.5
0.00 0.01 0.02 0.03 0.04 0.05 0.06
was calculated using equation 2.
ce (mg/L)
% = 100 (2)

Where is the initial cyanide concentration in (mg/L) and Fig.1. Calibration curve for p-nitrophenol at 400 nm for
is the final cyanide concentration in solution in (mg/L) DPP and DBP
and R% is the percentage removal of cyanide.

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International Journal on Recent and Innovation Trends in Computing and Communication ISSN: 2321-8169
Volume: 4 Issue: 7 190 - 196
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22
Amount of Baryte Adsorbed (moles X 10 )

20
3

18

16

14

12

10

8 DPP
DBP
6

0 Plate. 2. SEM picture of DBP at 500x magnification

0 10
Equilibrum concentration of PNP (M x 10 )
Fig.2. PNP adsorption isotherm for DPP and DBP.
Table 1. Langmuir constants for PNP
Sample DPP
Adsorption CN-
r 0.975
k 0.015
Xm 0.017
3.1.2. Scanning Electron Microscope (SEM)
The surface morphology of the DPP and DBP samples was
examined by Scanning Electron Microscope (SEM). It is
quite obvious from the obtained SEM images in Plates 1 and
2 that mechanical modification of the DPP and DBP
(adsorbent) significantly alters the porosity of the materials.
From the porous structure characteristic it was observed that
DPP has a pore structure which assists it in normal cyanide
adsorption as shown in plate 1. The obtained results indicate
that the surfaces of DPP samples possessed greater surface
area when compared to DBP adsorbent in plate 2.
20 30 40 50 60
3
3.1.3. FTIR Analysis of DPP and DBP
The FTIR spectrum of DPP is shown in figure 3. Several
peaks were observed in the spectra which indicated that the
DPP is composed of various functional groups which are
responsible for the binding of the cyanide anion. The broad
DBP peak observed at 3397 cm-1 is due to the presence of
CN- hydrogen bonded O-H band. The sharp peaks observed at
0.981 2926.04 cm-1 is due to C-H stretch in alkanes. The Band due
0.022 to the presence of P-H stretch in phosphines can be observed
0.015 in the range of 2363.74 cm-1. The Band at 1734.91 cm-1 is
due to the presence of C=O stretch in ester. The sharp peaks
at 1636.79 cm-1 is due to the C=O stretch as a result of
disubstituted tertiary amides. The sharp peaks at 1375.79
cm-1, 1312 cm-1 and 1156.48 cm-1are due to the presence of
S=O asymmetric stretch in sulfonates, sulfones and sulfonic
acids compounds. The band at 1079.95 cm-1 and 1022.97
cm-1 is attributed to the presence of R-O stretch in phosphate
esters. The bands in the range 785 cm-1 540 cm-1 are due to
the presence of C-CI stretch in aliphatic chloride.

Plate. 1. SEM picture of DPP at 500x Figure 3. FTIR Analysis of DPP

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International Journal on Recent and Innovation Trends in Computing and Communication ISSN: 2321-8169
Volume: 4 Issue: 7 190 - 196
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The FTIR spectrum of DBP is shown in figure 4. The peaks
appearing at 3423.81 cm-1 is due to the presence of hydrogen
bonded OH groups on the adsorbent surface. The peak
appearing at 2923.99 cm-1 can be attributed to C-H
stretching of alkanes. The Band at 1735.15 cm-1 is due to the
presence of C=O stretch in ester. The sharp peaks at 1637.06
cm-1 is due to the C=O stretch that may be attributed to
hemicelluloses and lignin aromatic group. Bands appearing
at 1442.8-1048.35 cm-1 are due to CH2 characteristic
bending and S=O in sulphoxides. The bands in the range
785 cm-1 540 cm-1 are due to the presence of C-CI stretch
in aliphatic chloride.

Fig.5. Effect of Temperature on the percentage removal of

cyanide by PP and BP

Fig.4. FTIR spectra of DBP
3.2. Effects of Operating Parameters
Effect of Temperature
The effect of temperature was carried out at 30, 40, 50, 60,
and 70 oC for DPP and DBP as shown in Fig 5. The rate of
uptake of cyanide onto two samples was observed to
increase with increase in temperature, thus demonstrating
the process to be endothermic in nature. Though, the
increase in removal percentage was maximum as
temperature changed from 30 OC to 50 OC and turned out to
be slower on further increase in the temperature. This may
be due to increase in temperature which leads to reduction in
viscosity of solution and therefore increase in rate of
diffusion of adsorbate inside the pores. The increase in
adsorption with temperature may be attributed to either
increase in the number of active surface sites available for
adsorption on the adsorbent or adsorbing species and the
decrease in the thickness of boundary layer surrounding the
adsorbate and the adsorbent. At higher temperature the
possibility of diffusion of solute within the pore of the
adsorbent may be enhanced leading to higher adsorption
density since diffusion is an endothermic process, greater
adsorption will be observed at high temperature. Thus the
diffusion rate of ion in the external mass transport process
increases with temperature. The observations of temperature
effect of DPP and DBP adsorptions on cyanide therefore
confirm that chemical reaction is dominant and this is as a
result of fast reaction kinetics of the adsorbate species.DPP
sample has the highest percentage removal of 90.93 % at
temperature of 70 oC [17].
Effect of pH
The effect of pH on removal of cyanide was calculated in
the pH range of 2.0-10.0 and results are demonstrated in
Fig.6. pH plays an important role in cyanide adsorption onto
biosorbent. Numerous researchers reported that biosorption
process is dependent on the functional groups on the
adsorbent, and the aqueous phase pH, and their ionic states
(at specific pH) [8,12]. In this study, the maximum
biosorption was detected at above pH 10, where the surface
charges on the adsorbent surface may be negative [7].
Maximum cyanide adsorption at pH 10 can be described by
seeing the fact that the pH of the solution affects both the
cyanide in the solution and the surface charge of the
adsorbent. According to results of this study, the pH of 10
was designated as the optimum pH when using PP as
adsorbents. The pKa of cyanide is 9.0 suggested that
cyanide is totally dissociated to CN at a solution pH of 10
[5]. Cyanide is a nucleophilic ion, when it comes in contact
with negatively charged adsorbent; it fixes with the anionic
functional groups existing on the adsorbent surface and thus
increases adsorption [7]. Furthermore, some removal may
occur through chemical reactions with surface sites and
surface precipitations, physical adsorption and complexation
of cyanide with functional groups. Some researchers have
correspondingly reported achieving maximum cyanide
adsorption onto dissimilar adsorbents in the pH range of 9
and 10.
Fig.6. Effect of pH on the percentage removal of cyanide by
PP and BP

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Volume: 4 Issue: 7
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Effect of Initial Concentration
Figure 7 indicate the relationship between cyanide
adsorption capacity at various initial cyanide concentrations
of 50-150 mg/L. The graph shows an increase in adsorption
capacity with increase in initial concentration of cyanide.
This is perhaps due to sufficient vacant sites existing and a
high concentration gradient occurring between the solid
phases and adsorbate in aqueous solution. The adsorbent
capacity gets exhausted with the increase in initial cyanide
concentration as shown in figure 7. This was also owing to
the fact that for a fixed adsorbent dose, the total existing
adsorption sites were limited, which became saturated at
higher cyanide concentration. The adsorption capacity of
cyanide is 53.90 for DPP sample and 47.56 for DBP sample
as cyanide initial concentrations increased from 50 mg/L to
150 mg/L. Thus, the adsorption of cyanide by DPP sample
is strongly dependent on the initial concentration.
55
50
45
40
qe (mg/g)
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adsorption process of CN- on prepared dried plantain and
banana at different conditions of process parameters.
The Langmuir isotherm is applicable to homogeneous
sorption where the sorption of each sorbate molecule on to
the surface has equal sorption activation energy and is
represented as follows [4].
= (5)
1+
Where qe is the solid phase sorbate concentration at
equilibrium, KL and aL are the Langmuir isotherm constants.
The linear form of Langmuir equation is given as
1
= + (6)
The adsorption data were analyzed according to the linear
form of equation 6. The plots of Ce/qe versus Ce are linear
which indicates that the adsorption data fitted reasonably to
the Langmuir isotherm (Figure 8). The constants were
evaluated from the slope aL/KL and intercept 1/KL, where
aL/KL gives the theoretical monolayer saturation capacity Qo.
The Langmuir constants obtained for all the two adsorbents
are summarized in Table 2. The adsorption data of the two
adsorbents (DPP and DBP) were well fitted to the Langmuir
equation with reasonably high regression coefficients. The
essential characteristics of Langmuir isotherm can be
explained in terms of a dimensionless constant, separation
factor (RL), is represented as
1
= (7)
1 +

35 Where Ci is the initial cyanide concentration and is the

DPP Langmuir equilibrium constant (L/mg). The value of the
30 DBP separation factor provides important information about the
nature of the adsorption process. The adsorption is said to be
25
favorable if RL is a positive number (0< <1), unfavorable
20
if ( >1) and linear if RL = 1. The value of RL ranges from
between 0.014 to 0.486.
15
40 60 80 100 120 140 160
Concentration (mg/L) 1.2

1.1
Fig.7. Effect of initial concentration on adsorption capacity
of cyanide onto DPP and DBP 1.0

0.9
3.3. Adsorption Equilibrium Study
The successful representation of the dynamic adsorptive 0.8
DPP
Ce/qe (g/L)

separation of solute from solution by an adsorbent depends

upon a good description of the equilibrium between the two 0.7 DBP
phases. Adsorption equilibrium is established when the
0.6
amount of solute being adsorbed onto the adsorbent is equal
to the amount being desorbed [4]. The equilibrium 0.5
adsorption isotherms were depicted by plotting solid phase
concentration (qe) against liquid phase concentration (Ce) of 0.4
solute.
0.3

Langmuir Isotherm 5 10 15 20 25 30 35 40 45 50 55 60
Adsorption isotherm explains the interaction between
Ce (mg/L)
adsorbate and adsorbent and is critical for design of
adsorption process. The Langmuir, Freundlich, and D-R
isotherms are the most frequently used models to describe Fig.8. Langmuir plot of cyanide onto DPP and DBP
the experimental data of adsorption. In the present study
these three isotherms were applied to investigate the Freundlich Isotherm
The most important multisite or multilayer adsorption
isotherm for heterogeneous surfaces is the Freundlich
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International Journal on Recent and Innovation Trends in Computing and Communication ISSN: 2321-8169
Volume: 4 Issue: 7 190 - 196
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isotherm which is characterized by the heterogeneity factor Redlich-Peterson Isotherm Model
1/n, and is represented by the equation: Redlich-Peterson [16], incorporated three parameters into an
= 1/ (9) empirical isotherm. The Redlich-Peterson isotherm model
Where, qe is the solid phase concentration in equilibrium, combines elements from both the Langmuir and Freundlich
Ce is the liquid phase sorbent concentration at equilibrium, equations, and the mechanism of adsorption is a hybrid
KF is the Freundlich constant and 1/n is the heterogeneity unique and does not follow ideal monolayer adsorption. The
factor. Redlich-Peterson equation is widely used as a compromise
The magnitude of n gives an indication on the feasibility of between Langmuir and Freundlich systems.
adsorption. It is generally stated that the values of n in the
range 2 10 represent good, 1 2 moderately good, and less The linear form of the model is given as:
than 1 poor adsorption characteristics [3]. The value of n for
ln 1 = + ln
( ) (11)

DPP and DBP is 2.02 and 1.39, which is an indication that
the adsorption was moderately good. The Freundlich
isotherm is an empirical equation based on an exponential Although a linear analysis is not possible for a three-
distribution of adsorption sites and energies. The linear form parameter isotherm, a trial and error procedure has
of Freundlich equation is: previously been applied to a pseudo-linear form of the
1 Redlich-Peterson isotherm to obtain values for the isotherm
= + (10) constants. This method involves varying the isotherm

Where, the intercept ln KF is a measure of adsorption parameter, KR, to obtain the maximum value of the
capacity, and the slope 1/n is the adsorption intensity.
correlation coefficient for the regression of ln 1
The values of KF and n were calculated from the intercept
and slope of the plots ln qe against ln Ce as shown in figure against . Figure 10 shows the coefficient of
9. The Freundlich isotherm describes reversible adsorption determination, R2, as a function of KR.
and is not restricted to the formation of monolayer. The
isotherms were found to be linear as evidenced from
correlation coefficients obtained in the range of 0.986
0.989. The Freundlich isotherm showed a better fit to the
adsorption data than Langmuir isotherm suggesting
heterogeneous nature of the DPP and DBP samples.
Freundlich sorption isotherm constants were determined for
all the DPP and DBP samples and are summarized in Table
4.3. The steepness and curvature of isotherms were obtained
from the values of KF and n [2]. The value of KF signifies
the adsorption intensity and higher KF value of DPP
confirmed the higher adsorption capacity for cyanide as
compared to DBP sample. The obtained KF and n values of
DPP samples are 8.413 and 2.02, respectively.

1.8
Fig. 10. Redlich-Peterson plot of cyanide onto DPP and
DBP
1.7
Error Function
The traditional methods of determining the isotherm
1.6
parameters by linear regression appear to give a good fit to
experimental data. However, the R2 is based on the linear
log qe

1.5 forms of the isotherm equations, but does not represent the
errors in the isotherm curves. To evaluate the fit of the
DPP isotherm equations to the experimental data, an error
1.4 DBP
function of non-linear regression was used here to determine
the constants model parameters, and they were compared
1.3 with those determined from the less accurate linearized data
fitting. The chi-square test was used. The equivalent
mathematical statement is given as
1.2
0.8 1.0 1.2 1.4 1.6 1.8
= (12)
log Ce
Where, is the equilibrium capacity (mg/g) from the
Fig. 9. Freundlich plot of cyanide onto DPP and DBP experimental data and is the equilibrium capacity
obtained by calculation from the model. If data from the
model were similar to the experimental data, x2 would be a
small number and vice versa. The values of x2 of each
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Volume: 4 Issue: 7 190 - 196
____________________________________________________________________________________________________________________
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Isotherm, Journal of Physical Chemistry. 63 (1959)
Freundlich equation. This study proved that dried plantain
1024-1024
peel appeared to be more stable adsorbent in cyanide [17] A.H. Sulaymon, A.A. Mohammed, and T.J. Al-Musawi,
solution than dried banana peel. Dried plantain peel has Competitive biosorption of lead, cadmium, copper, and
more pore spaces than dried banana peel which makes it a arsenic ions using algae, Environmental Science and
better adsorbent. Dried plantain peel is a waste material Pollution Research. (2013) 301
which has been converted to a useful resource as it is able to [18] C.A. Young, Remediation technologies for the
reduce cyanide concentration from solution through management of aqueous cyanide species. In: Young,
adsorption. It is easily prepared and very cheap, and thus a C.A. (Ed.) Cyanide: Social, Industrial and Economic
good substituent for expensive adsorbents. Aspects. TMS, Warrendale, PA. (2001) 175194.

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