Synthesis of Copper Oxide Nanoparticle as an … of Copper Oxide Nanoparticle as an ... nickel and...
Transcript of Synthesis of Copper Oxide Nanoparticle as an … of Copper Oxide Nanoparticle as an ... nickel and...
International Journal of Applied Environmental Sciences
ISSN 0973-6077 Volume 12, Number 11 (2017), pp. 1841-1861
© Research India Publications
http://www.ripublication.com
Synthesis of Copper Oxide Nanoparticle as an
Adsorbent for Removal of Cd (II) and Ni (II) Ions
from Binary System
Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
Department of Chemistry, College of Science, University of Diyala, Diyala, Iraq.
Abstract
This study involves the preparation of copper oxide nanoparticles using
modified sol-gel method. Different techniques such as XRD, SEM, TEM, and
AFM were used to characterize and surface studies of it. From XRD analysis,
all the reflection peak with relative intensities of different planes, specify the
presence of CuO and spectrum revealed that particle size obtained was around
(21.11 nm), which agreed fairly well with those estimated from SEM and
TEM. SEM, TEM, and AFM analysis of the CuO showed that the diameters of
the particles is in a nanometer range. These oxide were used to separate Cd
(II) and Ni (II) ions from its aqueous solutions (binary system) via adsorption
batch method. The effect of contact time, adsorbent dosage, initial
concentration, pH, and temperature have been studied and finally the
thermodynamic parameters for the influence of temperature were calculated.
Keywords: Binary System, Removal, Copper (II) Oxide, Nanoparticle
1. INTRODUCTION
At least 20 metals are classified as toxic; the development of modern industry causes
an increasing serious pollution in the environment because half of these toxic metals
are emitted into the environment in the quantities that pose risk to human health
including cancer, reduced growth and development, organ and nervous system
damage and in extreme cases death[1,2]. Consequently, removal of heavy metals
from wastewater and industrial waste has become paramount environmental
issue[3,4].
1842 Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
Various treatments of technologies have been advanced successfully for refining of
water and wastewater impure by heavy metals[5]. The most commonly used methods
for the removal of metal ions from industrial effluents include chemical precipitation,
solvent extraction, reverse osmosis, membrane filtration, electro deposition, ion
exchange and adsorption on low-cost materials[6-9]. Among these techniques
adsorption is one of the best methods for removal of heavy metals from water because
it is simple to operate, highly efficient and low-cost[10].
The utilized of CuO nanoparticle to remove heavy metals from polluted water has
greater interest by research cause copper oxide nanoparticle has important properties
is high efficiency and low cost. Nanoparticle appears good and sorption efficiency
and greater active sites[11]. There are many methods for the synthesis of copper oxide
nanoparticle such as: sonochemical, vapor deposition, electrochemical method,
combustion, colloid thermal synthesis process, microwave irradiation, thermal
oxidation, pulsed wire explosion methods, precipitation, and sol-gel[12-14]. The sol-
gel technique is considered as one of the most important and famous technique to
synthesis nanoparticle[15].
The aim of the present work is to prepare and characterize CuO nanoparticle and
study the feasibility of using sol gel procedure, SGP to prepare copper oxide, CuO
nanoparticles, NP designed as, SGP.CuO.NP as an adsorbent for the removal of Cd
(II) and Ni (II) ions from its aqueous solution (binary system).
2. MATERIALS and METHODS
2.1. Adsorbate
A standard stock solutions of Ni(II) and Cd(II) ions (1000 mg/L) were prepared from
Ni(NO3)2.6H2O and CdCl2.H2O in deionized water. Several concentrations (20, 40,
60,80 and 100 mg/L) were prepared from this standard stock of each metal ions.
Absorbance of these solutions were measured at a wavelength (λ max) 232 nm for
nickel and 228.8 nm for cadmium in order to determine the concentrations of metals
by atomic absorption.
2.2. Adsorbent, (SGP.CuO.NP)
A stoichiometric amount of (CuCl2.2H2O) and citric acid were dissolved in distilled
water so that the mole ratio of copper chloride dihydrate to citric acid is equal to one.
These two solutions were mixed together using a magnetic stirrer at room temperature
until solution becomes smooth a slimy blue colored. Sodium hydroxide (8M) was
slowly added in drop wise into the mixed solutions to control it pH until reach the
Synthesis of Copper Oxide Nanoparticle as an Adsorbent for Removal of Cd… 1843
value of (7) with continuous stirring so the solution become dark blue color. Then
subsequently raise the temperature of the solution to (60 °C) for period of one hour
and then increase the temperature to (80 °C) for an o t h e r two hours. After that the
size of the solution in the glass beaker is reduced and viscosity increased with the gel
formation on the solution surface, particularly in the middle and then all the solution
turn to gel. After the completion of the solution turned to gel, reduce the temperature
of the gel to room temperature.
The gel placed in an oven a temperature of (120 °C) for 3 hours for drying and then
by raising the temperature of the drying to (200 °C ), for (30 minutes ) and finally
calcined at (450°C) for 2 hours to produce copper oxide nanoparticle.
2.3. Study of the adsorption
Many volumetric flasks containing 50 ml (25 ml of Ni (II) ion solution and 25 ml of
Cd(II) ion solution with (𝐶ₒ) of 100 mg/L for each one, pH of 6, then 0.1 g of
(SGP.CuO.NP) was added into each flask and placed in ( water bath shaker device )
at speed 150 rpm and room temperature (298 K) at different time intervals 15; 30; 45;
60; 75; 90; 105 and 120 min. Then samples filtered before analysis to prevent
nanoparticles interference with analysis. The concentrations of metals solution were
determined using atomic absorption. Studied for factors influencing the adsorption of
the two metals onto (SGP.CuO.NP) are; contact time, initial concentration , adsorbent
quantity, pH, temperature. The two metals removal percentage was calculated using
equation below[16,17]:
𝐑 % = ( Co−Ce)∗100
Co …….. (1)
Where: (R%) is percentage removal of the two metals, (Co) is initial concentration
(in binary system) of metals ions (mg/L), (Ce) is concentration of [cadmium and
nickel ions] after removal (mg/L).
2.4. Experiment of adsorption isotherm
The adsorption isotherm for nickel and cadmium ions removal in binary systems on
(SGP.CuO.NP) at temperature of 298 K, pH of 6, 0.1g adsorbents and stirring speed
150 rpm, contact time of (30 minutes) for two metals ions on prepared surface. In
binary systems (50 ml), 25 ml of cadmium (II) and 25 ml of nickel (II) ions with
initial concentration for (Cd (II) solution), varied from (20-100 mg/L) with presence
of nickel ions, and concentration of nickel (II) was varied in the range (20-100 mg/L)
with presence cadmium ions . In all experiment the equilibrium metal concentration
was measured using (AAS) .The adsorption quantity of adsorbent nanoparticles was
1844 Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
calculated using the equation(2) [16,17] :
Qe = (𝑪ₒ−𝑪𝒆 )∗ 𝒗
𝒎 …………….. (2)
Where:( 𝐐𝐞) ,The adsorption quantity of the surface nanoparticles at equilibrium (
mg/g),( 𝐂ₒ) means the initial adsorbent concentration (mg/L). (𝐂𝐞), equilibrium
concentration of metals after adsorption has occurred (mg/L), (V) ,volume of aqueous
solution (L), (m), weight of metal oxide nanoparticles (g).
3. RESULTS and DISCUSSION
3.1. Characterization of (SGP.CuO.NP)
3.1.1. X-ray diffraction
The X-ray diffraction pattern of the prepared oxide was recorded using XRD-6000
with Cukα (λ=1.5406A°) that have an accelerating voltage of 220/50 HZ which is
produce by SHIMADZU company. The XRD technique was used also to determine
and confirm the crystal structure of the nanoparticle with pattern of as prepared
copper (II) oxide nanoparticle using chemical method (sol-gel) is shown in Fig. (1),
and the data of strongest three peaks shown in Table (1). The peaks position of the
sample exhibited the monoclinic structure and single phase and it is with agreements
with those reported in JCPDS file (NO.48-1548), no other impurity peak was
observed in the XRD patterns. The broadening of the diffraction peaks indicates that
the crystal size is small. The particle sizes were calculated from Deby-Sherrer formula
given below[18]:
𝐷 = 0.9 𝜆
𝛽 cos 𝜃 ................... (3)
Where: (D) is the crystallite size, (λ) is the wave length of radiation, (θ) is the Bragg’s
angle, (β) is the full width at half maximum (FWHM).
The found particle size of the (SGP.CuO.NP) is (21.11 nm). The presence of sharp
peaks in XRD samples and particle size of less than 100 nm refers to the nano-
crystalline nature of the surface.
Synthesis of Copper Oxide Nanoparticle as an Adsorbent for Removal of Cd… 1845
Table 1: The strongest three peaks in XRD of (SGP.CuO.NP)
No 2θ (deg) d (Å) FWHM (deg) Intensity (counts)
1 35.5758 2.52149 0.35150 955
2 38.8073 2.31864 0.44450 864
3 48.8334 1.86346 0.42270 231
Fig. 1: XRD of copper (II) oxide nanoparticles (SGP.CuO.NP).
3.1.2. Scanning electron Microscope
The scanning electron microscope (SEM) used in imaging the nanoparticles was a
scanning electron microscope AIS2300C. (SEM) was utilized to check
morphology[19,20] . Fig. (2) show the SEM image of (SGP.CuO.NP) where copper
oxide nanoparticle appear clearly and indicated the formation irregular particles and
spherical with various size ranges (20-50) nm.
𝟐𝜽
1846 Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
Fig. 2: SEM image of copper (II) oxide nanoparticles (SGP.CuO.NP).
3.1.3. Transmission electron microscope.
The transmission electron microscope (TEM) images were recorded using a JEOL
2100Plus instrument operated at 200kV. TEM was used to characterize adsorbent
morphology too[21,22]. The TEM images of copper (II) oxide was shown in Fig. (3),
these images clearly indicate that spherical morphology, and the particle size is found
to be in the range (10-40) nm.
Synthesis of Copper Oxide Nanoparticle as an Adsorbent for Removal of Cd… 1847
Fig. 3: TEM image of copper (II) oxide nanoparticles (SGP.CuO.NP).
3.1.4. Atomic force microscope
Atomic force microscopy used to study surface of the samples was AFM model
AA3000 SPM 220 V- angstrom Advanced INC, USA where the average grain size of
surface nanoparticles was measured [23]. Fig. (4) show typical surface AFM images
(in three and two dimensional), and Table (2) show the granularity cumulating
distribution and the average diameter data of (SGP.CuO.NP). The average diameter
was (89.16) nm.
Fig. 4: AFM images for copper (II) oxide nanoparticles (SGP.CuO.NP).
1848 Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
Table 2: Granularity cumulating distribution & average diameter of (SGP.CuO.NP).
Avg. Diameter :89.16 nm
Dia
met
er
(nm
)<
Volu
me
(%)
Cum
ula
tion
(%)
Dia
met
er
(nm
)<
Volu
me
(%)
Cum
ula
tion
(%)
Dia
met
er
(nm
)<
Volu
me
(%)
Cum
ula
tion
(%)
35.00
40.00
45.00
50.00
55.00
60.00
65.00
70.00
75.00
0.69
1.38
2.08
2.42
2.42
2.77
8.30
7.61
5.88
0.69
2.08
4.15
6.57
9.00
11.76
20.07
27.68
33.56
80.00
85.00
90.00
95.00
100.00
105.00
110.00
115.00
120.00
6.92
7.61
6.57
5.88
7.61
4.15
5.19
4.15
4.50
40.48
48.10
54.67
60.55
68.17
72.32
77.51
81.66
86.16
125.00
130.00
135.00
140.00
145.00
150.00
155.00
165.00
170.00
2.08
3.11
2.42
0.69
1.04
2.42
1.38
0.35
0.35
88.24
91.35
93.77
94.46
95.50
97.92
99.31
99.65
100.00
3.2. Removal of cadmium (II) and nickel (II) ions in binary system on the
(SGP.CuO.NP) surface.
3.2.1. The Effect of contact time on adsorption
The effect of the contact time on the removal of [Cd (II) and Ni (II) ions] in binary
system on the (SGP.CuO.NP) was studied with contact time of (15, 30, 45, 60, 75,
90,105 and 120) min at 298 K, concentration 100 mg/L of each metal ions, and pH=6.
Fig. (5) explain the change of the percentage removal with contact time. As seen the
equilibrium time required for the adsorption of ions is almost (30 min). The effect of
contact time on the removal of ions using (SGP.CuO.NP) explain that increasing in
the percent removal at the beginning of contact time with both cadmium (II) and
nickel (II) ions, then there was a gradual decline in the percentage removal of ions ,
the rapid initial rate increase followed by a slow rate at later stages could be due to
availability of excess adsorption sites on the adsorbent[24]. The initial high adsorption
rate might possibly be due to ion exchange followed by a slow chemical reaction of
the metal ions active groups on the sample[25], and the remaining vacant surface sites
are difficult to be occupied cause to repulsive force. The metal ions have to traverse
farther and deeper into the pores encountering much larger resistance[26].
Synthesis of Copper Oxide Nanoparticle as an Adsorbent for Removal of Cd… 1849
3.2.2. Effect of adsorbent quantity on adsorption
Effect of the quantity adsorbent on Cd (II) and Ni(II) ions adsorption (binary system)
on the (SGP.CuO.NP) was studied using different quantity (0.01, 0.05, 0.1, 0.15 and
0.2 g) at 298 K, fixed concentration of nickel and cadmium ions (100 mg/L), pH of 6
with contact time 30 min. The influence of adsorbent quantity on the removal of the
binary metals ions is shown in Fig. (6). It can be observed that with increasing the
quantity of copper oxide nanoparticle, the metals ions removal will increases too, the
increase in the percentage removal can be explained by the increasing surface area
where the adsorption take place, and the optimum adsorbent quantity that can be used
in cadmium (II) and nickel (II) ions removal are (0.1 g) and after 0.1g , the
percentage removal will be increased slightly[27-29].
3.2.3. Effect of pH on Adsorption
The effect of pH on the percentage removal of the binary heavy metals ions on the
copper oxide nanoparticle surface was tested at pH (2, 4, 6 and 8) at temperature 298
K, contact time of 30 min, and the dose of adsorbent (0.1 g). Fig (7) show results
obtained for the effect of pH on Ni (II) and Cd (II) removal. It can be observed that
the removal of these metals ions was maximum at pH of 6. The uptake of heavy metal
ions is found to increase with an increase in the pH from 2 to 6. For the low pH a
significant electrostatic repulsion exists between the positively charged surface of the
copper oxide nanoparticles and the cationic metals. Besides, the higher concentration
of H+ in the solution competes with two metals [Ni (II) and Cd(II)] for the adsorption
sites. For the reduced adsorptive of Ni (II) and Cd (II), at pH of the binary system of
6, the number of positively charged site decrease and the number of negatively
charged sites increase on the surfaces. The copper oxide of the negatively charged
surface site on the (SGP.CuO.NP) the adsorption of Ni (II) and Cd (II) due to
electrostatic attraction, at pH values higher than (6) binary metals precipitated out
because of the rise concentration of (OH-) ions in the aqueous solution[30,31].
3.2.4. Effect of temperature on adsorption
In this section we explained the effect of temperature on the extent adsorption of the
two metals ions in binary solution at four different temperatures (298, 308, 318 and
333) K and pH 6, initial concentration 100 mg/L of each of Cd (II) and Ni (II) ions,
quantity of adsorbent (0.1 g) and contact time was of constant at 30 min. The general
shape of the adsorption of cadmium (II) and nickel (II) ions on the (SGP.CuO.NP) is
given in Fig (8) which show that the percentage removal decrease with increase in
temperature, these prove that removal of binary metals (Cd and Ni) ions on the
(SGP.CuO.NP) surface is exothermic, the reduction in the rate of adsorption with
1850 Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
increase in temperature may be back weakening of interaction force between the
active sites of the adsorption surface and the binary metals ions[32].
3.2.5. The effect of initial concentration
The adsorption of the binary metals from an aqueous solution onto (SGP.CuO.NP)
was studied first at optimum conditions, using different initial concentration of
aqueous solution of (20, 40, 60, 80 and 100) mg/L for each metal ions. The results
shown in Fig. (9) that the impact of the initial concentration indicate little decrease in
the removal with increasing of initial concentration of Cd (II) and Ni (II) ions on
surface (SGP.CuO.NP). The small decreasing in the percentage of the removal at
higher concentration could be attributed to the limited number of active sites of the
copper oxide nanoparticles adsorbent, which become more saturated with an increases
in the concentration of metal ions, and removal of cadmium (II) and nickel (II) ions
on the (SGP.CuO.NP) is high because of the small nanoparticle size and the high
surface area that contains a lot of active adsorption sites which will be available[33].
Fig. 5: Effect of contact time on adsorption of ions on the (SGP.CuO.NP) surface
Fig. 6: Effect of adsorbent quantity on adsorption of ions on the (SGP.CuO.NP)
surface
97
98
99
100
10 30 50 70 90 110 130
Re
mo
val (
%)
Contact time (min)
(Cd on SGP.CuO.NP)
(Ni on SGP.CuO.NP)
96
97
98
99
100
0 0.05 0.1 0.15 0.2 0.25
Re
mo
val (
%)
Adsrbent quantity (g)
(Cd on SGP.CuO.NP)
(Ni on SGP.CuO.NP)
Synthesis of Copper Oxide Nanoparticle as an Adsorbent for Removal of Cd… 1851
Fig. 7: Effect of pH on adsorption of ions on the (SGP.CuO.NP) surface
Fig. 8: Effect of temperature on adsorption of ions on the (SGP.CuO.NP) surface
Fig. 9: Effect of initial concentration on adsorption of ions on the (SGP.CuO.NP)
surface
3.2.6. The adsorption isotherm of binary metals ions systems
The adsorption isotherm studied for a binary system containing two metals Ni and Cd
ions by using copper oxide nanoparticles at 298 K and pH of 6. The results are
represented by initial ions concentration, and equilibrium concentration measured at
equilibrium state and adsorption capacity values are calculated from the experimental
data by using equation (2). The adsorption capacity are plotted versus equilibrium
concentration to obtain general adsorption isotherm for Cd (II) ions removal by using
92
94
96
98
100
1 3 5 7 9
Re
mo
val (
%)
pH
(Cd on SGP.CuO.NP)
(Ni on SGP.CuO.NP)
92
94
96
98
100
290 300 310 320 330 340
Re
mo
val (
%)
Temperture (K)
(Cd on SGP.CuO.NP)
(Ni on SGP.CuO.NP)
92
94
96
98
100
10 30 50 70 90 110
Rem
ova
l (%
)
Initial concentration (mg/L)
(Cd on SGP.CuO.NP)
(Ni on SGP.CuO.NP)
1852 Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
(SGP.CuO.NP), when its initial concentration varies from (20, 40, 60, 80 and 100)
mg/L in presence Ni (II) with a constant initial concentration in each experimental
ranges (20, 40, 60, 80, and 100) mg/L, as shown in Fig.(10). Also the general
adsorption isotherm of Ni (II) ions removal by using (SGP.CuO.NP), when its initial
concentration varies from (20, 40, 60, 80 and 100 mg/L) at presence Cd (II) with a
constant initial concentration in each experimental (20, 40, 60, 80, and 100), as shown
in Fig. (11)
Fig. 10: Adsorption isotherm of Cd(II) ions Co( 20–100) mg/L in the presence of
increasing concentration of Ni+2 ions on (SGP.CuO.NP) surface at ideal condition
Fig. 11: Adsorption isotherm of Ni (II) ions Co ( 20–100) mg/L in the presence of
increasing concentration of Cd+2 ions on (SGP.CuO.NP) surface at ideal condition
The results showed increase in adsorption capacities of the (SGP.CuO.NP) with
equilibrium concentration of solution, the general shape of adsorption isotherm is of
(L) type on Giles Classification[34]. It is observe that the equilibrium Cd+2 removal
increases with increasing of initial cadmium concentration up to 100 mg/L at all
Ni+2ion concentration and also the observed equilibrium of Ni+2 (II) uptake increases
with increasing of initial Ni+2 concentration up to100 mg/L at all concentration of
metal Cd+2 ion by using CuO nanoparticle. The increase in the initial Ni+2 has non-
effect on the capacity o f adsorption of Cd+2 and the total capacity adsorption yields
for each experiment and also increase in the initial Cd+2 has no effect on the
adsorption of Ni+2 and the total extent adsorption for experiment[35].
0
10
20
30
40
50
0 2 4 6
Qe
(mg/g
)
Ce (mg/L)
[Ni]= 20 mg/L
[Ni]= 40 mg/L
[Ni]= 60 mg/L
[Ni]= 80 mg/L
[Ni]= 100 mg/L
0
10
20
30
40
50
0 0.5 1 1.5 2 2.5 3
Qe
(mg
/g)
Ce (mg/L)
[Cd]= 20 mg/L[Cd]= 40 mg/L[Cd] = 60 mg/L[Cd]= 80 mg/L[Cd]= 100 mg/L
Synthesis of Copper Oxide Nanoparticle as an Adsorbent for Removal of Cd… 1853
Freundlich and Langmuir models are applied for adsorption equilibrium of [Cd+2 and
Ni+2] ions binary systems with CuO nanoparticle at different initial concentration of
each metal ions. Langmuir and Freundlich model equations[36,37] are (4) and (5),
respectively were applied for removal equilibrium for CuO nanoparticles at various
initial concentration to show the best model that explain the adsorption processes
𝑪𝒆
𝑸𝒆=
𝟏
𝒂𝒃+
𝑪𝒆
𝒂 …… (4)
Log Qe = Log kf + 1/n Log Ce ……… (5)
Where; (Ce) means the equilibrium adsorbate concentration “binary heavy metals”
after removal (mg/L), (Qe) the amount of adsorbed at equilibrium per unit weight of
surface(mg/g), (a) Langmuir constant which is a measure of adsorption
capacity(mg/g), and (b) is also Laungmuir constant which is a measure of energy of
removal, (L/mg), (n) and (Kf ) are the Freundlich constants. The values of the
Langmuir isotherm constant a is the monolayer adsorption capacity and b which is a
constant related to the energy of adsorption are calculated from the slope and intercept
of the plots Ce/Qe versus Ce, as shown in Fig.(12 ,13) and Table(3). If log (Qe) is
plotted against log (Ce) a straight line should be obtained, and the Freundlich constant
(Kf ) which is the adsorption capacity of the adsorbent, and (n) is the adsorption
intensity being calculated from the slope and intercept and the results are shown in
Fig.(14 ,15) and the Table (3).
Fig.12: Langmuir isotherm of Cd+2 ions Co ( 20–100) mg/L in the presence of
increasing concentration of Ni+2 ions on (SGP.CuO.NP) surface at ideal condition
Fig.13: Langmuir isotherm of Ni+2 ions Co ( 20–100) mg/L in the presence of
increasing concentration of Cd+2 ions on (SGP.CuO.NP) surface at ideal condition
0
0.05
0.1
0.15
0 2 4 6 8
Ce/Q
e (g
/L)
Ce (mg/L)
[Ni]= 20 mg/L[Ni]= 40 mg/L[Ni]= 60 mg/L[Ni]= 80 mg/L[Ni] = 100 mg/L
0.01
0.02
0.03
0.04
0.05
0.06
0 1 2 3
Ce/Q
e (g
/L)
Ce (mg/L)
[Cd]= 20 mg/L[Cd]= 40 mg/L[Cd]= 60 mg/L[Cd]= 80 mg/L[Cd]=100 mg/L
1854 Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
Fig. 14: Freundlich isotherm of Cd+2 ions Co( 20-100) mg/L in the presence of
increasing concentration of Ni (II) ions on (SGP.CuO.NP) surface at ideal condition.
Fig. 15: Freundlich isotherm of Ni+2 ions Co( 20-100) mg/L in the presence of
increasing concentration of Cd (II) ions on (SGP.CuO.NP) surface at ideal condition.
Table 3: Langmuir and Freundlich constants and the correlation coefficients for the
adsorption of cadmium ions in presence of variable initial nickel ions concentration
and the constants, correlation coefficient for adsorption of nickel ions in presence of
variable initial cadmium ions concentration by (SGP.CuO.NP) surfaces.
Metal ions Cₒ [Ni] Langmuir Freundlich
a (mg/g) b (L/g) R2 n Kf (mg/g) R2
Cd (II)
20 60.444 1.0511 0.9985 1.6515 33.174 0.9662
40 61.728 0.8141 0.9922 1.8570 24.694 0.9801
60 61.349 0.7836 0.9948 1.8639 24.004 0.9750
80 61.880 0.5422 0.9934 1.9025 19.451 0.9924
100 64.935 0.3930 0.9964 1.7460 17.382 0.9664
Ni (II)
Cₒ [Cd] a (mg/g) b (L/g) R2 n Kf (mg/g) R2
20 79.365 0.8873 0.9974 1.5174 35.612 0.9910
40 92.592 0.6067 0.9976 1.3966 33.481 0.9933
60 106.38 0.4607 0.9915 1.2665 31.560 0.9895
80 169.49 0.1446 0.9987 1.1626 20.878 0.9962
100 322.50 0.0605 0.9939 1.0796 18.543 0.9931
0.9
1.1
1.3
1.5
1.7
1.9
-1 -0.5 0 0.5 1
log
Qe
log Ce
[Ni]= 20 mg/L[Ni]= 40 mg/L[Ni]= 60 mg/L[Ni]= 80 mg/L[Ni]= 100 mg/L
0.8
1.1
1.4
1.7
-1 -0.5 0 0.5 1
log
Qe
log Ce
[Cd]= 20 mg/L
[Cd]= 40 mg/L
[Cd]= 60 mg/L
[Cd]= 80 mg/L
[Cd]= 100 mg/L
Synthesis of Copper Oxide Nanoparticle as an Adsorbent for Removal of Cd… 1855
From Table (3), one observed the correlation coefficients for the Laungmuir
regression fits are larger than that for the Freundlich models at removal of Cd (II) ions
in presence of initial nickel (II) ions concentration and at removal of nickel (II) ions in
presence of different initial concentration of cadmium (II) ions, which means that
adsorption occurs at homogenous sites and forms a monolayer. The values of (n) is
higher than unity show the physical nature of the adsorption process on adsorbent[38].
3.2.7. Thermodynamic study of binary metals ion systems
The Effect of temperature on removal of metals ions in binary system on adsorbent
nanoparticle at various temperature (298, 308, 318 and 333) K was investigated .This
study will help in evaluation the basic thermodynamic function (∆G), (∆H), and (∆S)
of adsorption processes, equilibrium of adsorption constant, K is explains
thermodynamically by Gibbs-Heimholtz equation below:
……….. (6)
The equilibrium constant, K were calculated at any different temperature by below
equation[39].
K=𝑄𝑒∗𝑊𝑔
𝐶𝑒∗𝑉 (L) …….. (7)
Where: Qe (mg/g) is the capacity of adsorption of metals ion, W (g) the quantity of
metal oxide nanoparticles, Ce (mg/L) the concentration of equilibrium after removal
metals in binary system, V (L) Volume of aqueous solution contains binary metals
ions.
Table (4) illustrates K values for adsorption ions in binary system on
(SGP.CuO.NP) at various temperatures.
Gibes free energy change can be calculated from relationship[40].
…….. (8)
Where: (∆G) means the free energy change (kJ/mole), (K) constant of thermodynamic
equilibrium, (R) the universal gas constant (8.314×10-3 kJ/mol.K), (T) is temperature
(K).
Values (∆S) and (∆H) can be calculated from (the slope = - ∆H/R and intercept = ∆S
/R) by drawing (ln k) versus (1000/T), as shown in Fig. 16.
Table (5) display the thermodynamic values of two heavy metals (Ni and Cd) ions
removal on adsorbent.
R
S
TR
HK
)
1(ln
∆G= - RT ln K
1856 Karim H. Hassan, Arrej A. Jarullah and Sally K. Saadi
Table 4: Impact of temperature on the thermodynamic equilibrium constant for the
removal of ions in binary system by adsorbent surface.
Metal ions Temperature
K
1000/T
K-1
Ce
mg/L
Qe
mg/g
K lnK
Cd(II)
298 3.355 4.367 47.816 21.897 3.086
308 3.246 6.113 46.943 15.360 2.731
318 3.144 7.110 46.444 13.064 2.569
333 3.003 7.553 46.223 12.241 2.504
Ni(II)
298 3.355 2.909 48.545 33.387 3.508
308 3.246 2.954 47.941 32.852 3.492
318 3.144 4.117 47.361 23.294 3.148
333 3.003 5.277 49.869 17.952 2.887
Table 5: Values of thermodynamic function for the adsorption of ions in binary
system on adsorbent surface at different temperatures
Metal ions T
K
ΔG
kJ/mol
ΔH
kJ/mol
ΔS
J/mol.K
Cd (II)
298 -7.645
- 0.0156 - 27.403 308 - 6.993
318 - 6.792
333 - 6.932
Ni (II)
298 - 8.691
- 0.0158 - 23.533 308 - 8.942
318 - 8.322
333 - 7.992
Fig. 16: The Van ᾽t Hoff Plot for removal of Cd (II) and Ni (II) ions in binary system
by (SGP.CuO.NP) surface
2
2.4
2.8
3.2
3.6
4
2.9 3 3.1 3.2 3.3 3.4
ln k
1000/K
Cd on SGP.CuO.NP
Ni on SGP.CuO.NP
Synthesis of Copper Oxide Nanoparticle as an Adsorbent for Removal of Cd… 1857
The ∆G values of the metals ions removal on adsorbent is negative, so the process is
indicated too to be favorable of adsorption. The rate increases as ∆G increases and the
values of ΔH being negative, indicating that the adsorption process was exothermic in
nature, and ΔS negative indicates a decreases and indicated that the adsorption
processes was spontaneous and ∆G values also determine the rate and type of the
adsorption reaction, ∆G < 0 indicates physisorption with randomness at (solid-
solution) interface through adsorption of ions on adsorbent[41].
4. CONCLUSION
In this investigation, the copper oxide nanoparticles can be prepared well by
reasonably practical method. XRD, AFM, TEM , and SEM results explain that the
particle size is less than100 nm. The (SGP.CuO.NP) have a high capacity for
removing the Cd+2 and Ni+2 ions from aqueous solution in binary system. Isotherm of
metals removal observed that removal of Cd+2 ions in presence different initial
concentration of Ni+2 ions in all experiments and Ni+2 ions in presence different initial
concentration of Cd+2 on (SGP.CuO.NP) follows Laungmiur model as R2 for the
Laungmiur regression are larger than that for the Freundlich one. The negative values
of the thermodynamic Functions ΔG, ΔH and ΔS for the adsorption of Cd+2 and Ni+2
ions in binary system on adsorbents indicates that the adsorption processes is
spontaneous, exothermic and less randomness at (solid– solution) interface.
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