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


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.


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


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.


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).


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].


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


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)


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)


(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


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


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


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


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


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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