Document Type: Original Article

Authors

Chemistry Department, Faculty of Science, Mansoura University, 35516- Mansoura, Egypt

Abstract

The redox behavior for nano cadmium chloride (Ncc) was studied using cyclic voltammetry in the absence and presence of isatin (Isa.) on the use carbon glassy electrode (CGE) prepared in laboratory in 0.1M KCl electrolytic solution at two different temperatures . All cyclic voltamograms were carried at the selected temperatures in the absence and presence of isatin (Isa.). The redox reactions and reaction mechanism were suggested. All avialable cyclic voltammetry and thermodynamic data were calculated from cyclic voltammetry measurments and their values were explained .All the thermodynamic parameters necessary for the interaction of nano CdCl2 withisatin were calculate,explained and interapretatited.

Graphical Abstract

Keywords

Main Subjects

1. Introduction

 

      Heavy metal ions like cadmium ions are dangerous pollutants in environment [1-3].Some experimental methods for the removal of heavy elements  are used with a combination for different techniques such as membrane and electrolysis [3-5]. The extraction of heavy metal ions as pollutants from water pollution, using electrochemical methods, is important [6-9].Several metal ions in solutions can be recovered by reduction at the cathode.The recovery and extraction of metals from Ni-Cd batteries have been studied [10,11].Cadmium ion is highly toxic and responsible for poisoning the food. Binding Cd with organic compounds is a treatment for remediation of Cd in vivo and vitro [12,13]. In this work electrochemical cyclic Voltammetry behavior of nano cadmium ions in chloride form was studied.

Experimental

The used chemicals CdCl2, KCl, Isatin are of high purity 98% of the Sigma Aldrish Company. Pure water was used after distillation. The cell has three electrodes connected to potentiostat DY2000 . Ag/AgCl ,KCl sat was used as reference electrode, carbon glassy electrode (CGE) was used as working electrode, and platinum wire as auxiliary electrode. The electrochemical studies were done in a potentiostat of the type DY2000.Flow of purified N2 was done to ensure diffusion experiment. The carbon glassy electrode  (CGE) is locally prepared in our laboratory from pure carbon piece and polished with fine aluminium oxide on wool piece. Area of electrode is 0.502 cm2. All cyclic Voltammetry parameters  are measured at the selected two temperatures 27 and 40oC using ultra thermostat of the type Assistant 3193.

The nano cadmium chloride (Ncc) was prepared by ball milling method ,it is technically used for reducing material particle size.This  nano cadmium chloride (Ncc) was prepared by being shaken  in a ball-mill apparatus of type Retsch MM2000 swing mill for a period of two days. The mill contains 10 cm3 stainless steel tubes and Three stainless steel balls of 12 mm diameter were used. After the ball milling process which was performed at 20225 Hz at room temperature, the particles  have a nano size. The nanoparticles were investigated using JEM-2100  TEM, Transmission electron microscope in Mansoura University.

 

 3.Results and discussion

3.1.TEM Image for nano cadmium chloride (Ncc)

 

 

Fig. 1. The TEM image of nano cadmium chloride (Ncc) from JEM-2100 TEM, transmission electron microscope.

      From this image with 72,000 X , we conclude that the nano cadmium chloride is in the form of a nano scale and dimensions of particles lie between 15.86 and 30.46 nm.

3.2.Electrochemical behavior of nano cadmium chloride (Ncc) in absence of (Isatin)

    The electrochemical behavior of nano cadmium ions in carbon glassy electrode (CGE) was examined and hemi cycle waves were obtained. Cyclic Voltammetry of cadmium ions show charge transfer at the carbon glassy electrode(CGE) in 0.1 M KCl . Ag/AgCl was used as a reference electrode to follow the redox of Cd(II) ions in aqueous solution.One cathodic peak and one anodic peak were observed according to the suggested mechanism:

Cathodic reaction   Cd 2+ + 2e -àCd

Anodic reaction      Cdà Cd 2+ + 2e -

 

   3.2.1 Effect of metal ion concentrations

     Effect of cadmium ion concentrations  for nano cadmium  chloride (Ncc) was examined at two selected temperatures,26.5 and 40oC.Cyclic voltammograms for different concentrations from 3.3 × 10-4 till 1.96 × 10-3mol.L-1 in 0.1 M KCl were done . It was found that peak current gradually and linearly increases with increase in metal ion (salt) concentration due to the presence of ions active species at carbon glassy electrode(CGE) as shown in Figs. 2-4, at the two different temperatures.

                         

 

Fig. 2. Different cyclic voltammograms for different nano CdCl2 concentrations in 0.1M KCl at 26.5 ˚C.

 

 


Fig. 3. Different cyclic voltammograms for different nano CdCl2 concentrations in 0.1M KCl at 40 ˚C.

 

                

 

 

Fig. 4.  The effect of temp on redox behavior of nano CdCl2.

 

 

Fig.(4) illustrates the effect of raising the temperature on the redox behavior of nano CdCl2. It  was observed that increasing temperature increases the peak current for the two redox waves.

 

 3.2.2. Effect of different scan rates

      Effect of scan rate of the redox behavior of and nano CdCl2 (Ncc) in 0.1 M KCl was studied in the range 0.01,0.02,0.05 and 0.1(V.s-1) as given in Figs.(5) &(6). The different cyclic Voltammetry analysis data were calculated and the obtained data are Ipa (anodic current) , Ipc (cathodic current), ∆EP(difference in potentials), Da ( anodic Diffusion coefficient), Dc (cathodic diffusion coefficient), E 1/2 (half wave potential), Ks ( electron transfer rate constant ), Гa (anodic surface coverage), Гc (cathodic surface coverage), qa (anodic quantity of electricity) and qc (cathodic quantity of electricity) and 𝝰na (transfer coefficient). Quasireversible mechanism was observed for the redox behavior of bulk and nano CdCl(Ncc) in 0.1 M KCl  from all cyclic Voltammetry CV analysis data and specially Ipa/Ipc . Increase of scan rate is followed by increasing in the diffusion parameters, especially, Ksac ,qa and qc indicating the increased in the diffusion process by  an increase in scan rate as the data given in Tables 1&2.

 

 

Fig. 5. Different scan rates of 1.96×10-3 M nano CdCl2 at 26.5 ˚C.

 

Fig. 6. The relation between log Ipc and log𝜈 of 1.96×10-3 M nano CdCl2 at 26.5 ˚C.">

 

The relationship between log Ip and log 𝜈 giving straight lines indicate that the redox mechanisms are diffusion controlled for nano CdCl2  in 0.1M KCl. Randles Sevick equation was used for the relation between peak current (anodic and cathodic) and square root of scan rate which gives straight lines. In this sense, it indicates that the redox reaction is the diffusion process.

3.3. The electrochemical behavior of bulk and nano CdCl2 (Ncc) in presence of isatin in aqueous solution:

3.3. 1.Effect of different isatin concentrations

Figs.(7) and (8) represent the electrochemical behavior of complex interaction between nano CdCl2 (Ncc) and ketone (isatin) in 0.1M KCl at the two selected temperatures 26.5 and 40oC. As shown from the previous figures by increasing the isatin concentration, the peak current decreases due to decreasing of concentration of dissolved cadmium ions at the carbon glassy electrode (CGE). Also, peak potentionl shifts to more negative values in case of oxidation and more positive value shift in case of reduction indicate complex formation.

 

 

Fig.7. Cyclic voltammograms for interaction of 1.96×10-3 M nano CdCl2 and different concenterations of isatin at 26.5˚C.

 

Fig.8.  Cyclic voltammograms for interaction of 1.96×10-3 M nano CdCl2 and different concenterations of isatin at 40˚C.

 

Figs.(7) and (8) illustrates that temperature causes more decrease in peak current (anodic and cathodic) which means that the complex formation reaction became more accelerated by increasing temperature. It is also worth mentioning that the reaction was an endothermic one.

3.3.2. Effect of different scan rates

     Effect of scan rate on the interaction between bulk,nano CdCl2 and Ketone Isatin was studied in 0.1,0.05,0.02 and 0.01 V.s-1 Fig.(9).


 

Fig.9. Different scan rates of 1.96×10-3 M nano CdCl2 interacted with 1.63 × 10-3 M isatin at 26.5 ˚C.

 

Fig.10. The relation between log Ipc and log 𝜈 of 1.96×10-3 M CdCl2 interacted with 1.63×10-3 M isatin at 26.5 ˚C.


Fig. (11) illustrates the relation between log Ip and log 𝜈 for interaction between nano CdCl2(Ncc) in 0.1M KCl giving straight lines. Besides, it indicates the reversibility of the mechanisms and the redox mechanisms which are diffusion controlled. Randless Sevicek equation was used to apply the relation between peak current (anodic and cathodic) and square root of scan rate which gives straight lines.

 

 

 

Fig. 11. The relation between Ipc ,IPa and  𝜈1/2  of  1.96×10-3 M nano CdCl2 interacted with 1.63×10-3 M isatin at 26.5˚C.

 

 

Table 1. Effect of  different scan rates for interaction between 1.96×10-3 M nano CdCl2 (Ncc) and 1.63×10-3M isatin(ketone) at 26.5˚C on the diffusion parameters.

 

 


Scan rate

(V.S-1)

ml added (ml)

[L]

 (mol.L-1)

Ipa ×10-5

(A)

Ipc ×10-5

(A)

Ipa/Ipc

Epa (V)

Epc (V)

∆Ep (V)

E ½ (V)

0.1

6

0.00163

18.10

12.30

1.4722

-0.6722

-0.9965

0.3242

0.8343

0.05

6

0.00163

14.90

11.50

1.3036

-0.7017

-0.9521

0.2503

0.8269

0.02

6

0.00163

9.79

10.50

0.9343

-0.7383

-0.9304

0.1920

0.8343

0.01

6

0.00163

6.23

8.15

0.7638

-0.7461

-0.8930

0.1469

0.8195

 

 

Table 2. Cont. effect of  different scan rate for interation between 1.96×10-3 M nano CdCl2 (Ncc) and 12 "> 1.63×10-3 M isatin(ketone) at 26.5˚C on the diffusion parameters.


Scan rate

(V.S-1)

ml added (ml)

[L] (mol.L-1)

Da ×10 -14

(cm2.s-1)

Dc ×10-14

(cm2.s-1)

Ks ×10-6 (cm.s-1)

Гa ×10-10

( mol.cm-2)

Гc × 10-10

( mol.cm-2)

qa ×10-5

(C)

qc ×10-5

(C)

𝝰na

0.1

6

0.00163

59.27

27.34

3.13

9.68

6.57

9.34

6.34

0.3241

0.05

6

0.00163

40.46

23.81

2.74

7.99

6.13

7.71

5.92

0.4322

0.02

6

0.00163

17.34

19.87

2.12

5.23

5.60

5.05

5.40

0.5864

0.01

6

0.00163

7.02

12.03

1.49

3.33

4.36

3.21

4.20

0.8098

 

 


3.4.The equations used for the electrochemical cyclic Voltammetry calculations [15-25]

 

     Where ᵠ , charge transfer parameter taken as one for better approximation[13], 𝝰 charge transfer coefficient, Ks standard rate constant for electron transfer coefficient, 𝜈 scan rate, Da diffusion coefficient for the reduced species, Dc diffusion coefficient of the oxidized species, n electrons, F faraday constant, R gas constant and T is the absolute temperature for the experiment , 𝝰 = 0.5 which can be used for a good approximation for calculations, A is the area of the electrode used [25-31].

     The complex stability constant measuring the strength and power of the interaction between CdCl2 and isatin (Isa) is important. The complexation stability constant ( 12β"> ) nano CdCl2 (Ncc) complexes in 0.1 M KCl are calculated by applying equation(7).

[13,11-18]

                                                       (7)

   Where (EP)M is peak potential for metal in absence of ligand, (EP)C is peak potential of the complex, R gas constant, CL analytical concenteration of ligand (ketone) isatin (Isa). Gibbs free energies of interaction, solvation of nano  CdCl2 (Ncc) with ketone isatin (Isa) was calculated [19-26] using equation (8).

                  (8)

Enthalpy (∆H) of complex formation reaction between nano CdCl2 (Ncc) with isatin (Isa)  was calculated using equation (9) [29-31].

    (9)

Where  12β1">  is a complex stability constant at lower temperature T1 (26.5 oC), 12β2">  is the complex stability constant at higher temperature T2 (40oC).

The entropy (∆S) for bulk CdCl2 and nano CdCl2 (Ncc) at the two used temperatures is calculated by using equation (10)

∆G = ∆H - T∆S                              (10)

 

Table 3. Solvation parameters for the interaction between nano CdCl2 (Ncc) and isatin (ketone) at 26.5˚C

T 12℃">

T 12°K">

ml added

[L]

(mol.L-1)

E ½ C (V)

E ½ M (V)

∆E ½  (V)

12βj">

∆G(KJ)

26.5

299.5

1

0.00031

0.7900

0.7826

0.0073

5600.08

-21.49

26.5

299.5

2

0.00061

0.7900

0.7826

0.0073

2888.65

-19.84

26.5

299.5

3

0.00089

0.7935

0.7826

0.0108

2603.16

-19.58

26.5

299.5

4

0.00115

0.7974

0.7826

0.0147

2717.68

-19.69

26.5

299.5

5

0.00140

0.8195

0.7826

0.0369

12455.29

-23.48

26.5

299.5

6

0.00163

0.8343

0.7826

0.0517

33526.41

-25.95

 

Table 4. Solvation parameter for the interaction between nano CdCl2 (Ncc) and isatin (ketone)  at 40 ˚C

T 12℃">  

T 12°K">

ml added

[L]

E ½ c (V)

E ½ m (V)

∆E ½ (V)

12βj">

40

313

1

0.00031

0.7939

0.7826

0.0112

7287.88

40

313

2

0.00061

0.8087

0.7826

0.0260

11241.93

40

313

3

0.00089

0.8118

0.7826

0.0291

9727.69

40

313

4

0.00115

0.8304

0.7826

0.0478

29966.79

40

313

5

0.00140

0.8343

0.7826

0.0517

32912.29

40

313

6

0.00163

0.8674

0.7826

0.0847

326875.77

 

Table 5. Solvation parameter for the interaction between nano CdCl2 (Ncc) and isatin (ketone) at 40 ˚C

T 12°K">

T 12℃">

ml added

[L]

∆G(KJ)

∆H(KJ)

∆S(KJ)

40

313

1

0.00031

-23.1488

15.21

0.1225

40

313

2

0.00061

-24.2769

78.46

0.3282

40

313

3

0.00089

-23.9004

76.11

0.3195

40

313

4

0.00115

-26.8288

138.59

0.5285

40

313

5

0.00140

-27.0728

56.10

0.2657

40

313

6

0.00163

-33.048

131.49

0.5256

 

From data in  Tables 3,4,5 we deduce that interaction between nano CdCl2 and isatin (Isa) leads complex  is formed with high stability , cleared from the values of 12βj .">  Increasing temperature accelerate complex formation in case of nano salt because values of 12βj">  at higher temperature are higher than at lower temperature.Enthalpy change are positive which indicate endothermic reaction.All the thermodynamic data support the formation of a complex between nano CdCl2 (Ncc) and isatin (Isa).

Conclusion

  • As shown from all cyclic voltamograms for nano CdCl2 (Ncc), one cathodic peak and one anodic peak were observed at the carbon glassy electrode (CGE) with  a suggested reaction mechanism including two electrons

Cd 2+ + 2e -  Cd

  • The relationship between log Ip and log𝜈 which gives straight line indicates the reversibility and the diffusion controlled mechanism.
  • The redox reaction of nano salt was affected by temperature.
  • The complex formation reaction was accelerated by increasing the temperature.

 

How to cite this manuscript: Mohamed A. Morsi, Esam A. Gomaa * and Alaa S. Nageeb. Thermodynamic data (Voltammetrically)  Estimated for the Interaction of Nano Cadmium Chloride (Ncc) with Isatin Using Glassy Carbon Electrode. Asian Journal of Nanoscience and Materials, 2018, 1 (4), 282-293. 

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How to cite this manuscript: Mohamed A. Morsi, Esam A. Gomaa * and Alaa S. Nageeb. Thermodynamic data (Voltammetrically)  Estimated for the Interaction of Nano Cadmium Chloride (Ncc) with Isatin Using Glassy Carbon Electrode. Asian Journal of Nanoscience and Materials, 2018, 1 (4), 282-293.