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Jamonline / 2(4); 2012 / 312320 Research Article

E. J. Ukpong & I. A. Udoetok

Journal of Atoms and Molecules


An International Online Journal
ISSN 2277 1247

CYCLIC VOLTAMMETRY OF COPPER (II) IONS AT VARIOUS PH VALUES. MONONUCLEAR COPPER (II)-DIETHYLENETRIAMINE COMPLEXES E. J. Ukpong* and I. A. Udoetok Department of Chemistry, Faculty of Science, Akwa Ibom State University, Ikot Akpaden, Nigeria Received on: 09-08-2012 Abstract: The electrochemical behaviour of copper(II) diethylenetriamine complex species 1:1, 1:2, 1:10, 1:100 molar ratios at a various pH values was studied in aqueous solution of 110 -3M Cu(ClO4)2.6H2O containing 0.2M NaClO4 supporting electrolyte by means of cyclic voltammetry. The cyclic parameters were calculated. The first couple Cu2+/+ showed a diffusion controlled, quasireversible, one electron charge transfer at glassy carbon electrode (GCE). It was observed that the cathodic peak potential at a given [Cu (II)]: [dien] molar ratio and at a given pH value shifted cathodically with increasing ligand concentration. The effects of scan rate, pH and ligand concentration were examined. A linear relationship was obtained between the cathodic peak Revised on: 19-08-2012 Accepted on: 29-08-2012

current( Ipc1) and square root of scan rate in the range of 10 to 250mV/s with a correlation coefficient of 0.9971 .Key Words: Cyclic Voltammetry, Copper (II) complexes, Diethlenetriamine, Aqueous solution

* Corresponding author E. J. Ukpong, Email: jimmukpong@gmail.com Phone: +2348167731079

Introduction: Diethylenetriamine (DIEN) has been of a very important practical application in the removal of traces of transition metal ions in waste waters exchange
[1]

, determination of cation of clays


[2,3]

capacities

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Jamonline / 2(4); 2012 / 312320 Diethylenetriamine is often used in the complexes formation in aqueous solution [4,5]. Copper (II) complexes have
[6]

E. J. Ukpong & I. A. Udoetok coordination chemistry and favors metallic having an electrochemical cell with a three electrode system. The working electrode was a glassy carbon electrode (GCE). Platinum wire was used as an auxiliary electrode, while a saturated calomel electrode (SCE) as reference electrode with E0=0.242V vs NHE. The voltammograms were recorded on an X Y recorder. Diethylenetriamine was obtained from Aldrich (USA). The Copper

possible

medicinal use in the treatment of many diseases including cancer . Copper (II)

complexes are commonly air and moisture stable, having informative and easy to obtain UV-vis and EPR spectroscopic signatures
[7]

The stereochemical flexibility of copper (II) complexes also means that they adopt a wider range of coordination geometries shown for other transition metal ions
[8]

perchlorate and sodium perchlorate were of analytical reagent grade. Method All the experiments were done in an inert atmosphere achieved by purging the cell solutions with nitrogen gas for about 20 minutes and maintained over the cell solution during the recording of the voltammgrams. The nitrogen gas was purified by bubbling through alkaline vanadous sulphate solution and passing through a calcium sulphate drying tube before bubbling through the cell

. Dien is highly

caustic, soluble in ethylalcohol, in water and has almost the same physicochemical

properties like ammonia. Due to its high causticity, its electrochemical redox reaction is not too much investigated voltammetry, offers several
[4]

. Cyclic distinct

advantages over some methods of analysis because of ease and rapidity with samples preparation and analysis, ability to work outside pH range of glass electrodes and to use non-protic media [9]. In this work, the redox behaviour of copperdiethylenetriamine complexes has been

solution(s). The experiments were carried out at 25oC in aqueous solution 0.2M NaClO4 supporting electrolyte. Fresh solutions of copper (II) dien complexes were prepared by mixing the appropriate quantities of metal ion and ligand solutions. The pH of the working solutions were obtain with a digital pH meter model MD21 after calibration using pH 4.00, 7.00 and 10.00 commercial standard buffers. The pH of the solutions was adjusted by

studied under the conditions of pH and ligand concentration and the electrode process determined. EXPERIMENTAL Material The cyclic voltammetric data were obtained with a BAS Model CV-IB (Indiana, USA) cyclic voltammograph instrument

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Jamonline / 2(4); 2012 / 312320 controlled addition of sodium hydroxide or hydrochloric solutions as required. RESULTS AND DISCUSSION 1:1 Cu (II)-dien system At pH 7.10, the cyclic voltammogram (CV) scanned at 10mV/s cathodically from +0.40 to -0.75V shows a redox couple c1/a1 corresponding
, ,,

E. J. Ukpong & I. A. Udoetok peak current ratio Ipa1/Ipc1, remain almost similar over the pH range 7.10-11.05 and the potentials become more negative with rise in pH]
[12]

. However, Ipa1/Ipc1, decrease at pH

12.0. 1:2 Cu (II) dien system. The CV features at pH 7.10 scanned cathodically from +0.40 to -0.60V at 10 and 25mV/s are similar to that in 1:1 at 10mV/s (Figure 1). The anodic peaks a2 and a1, however indication disappear that the at V 50mV/s, electron-transfer
[10,11]

to

Cu2+/+

electron-transfer

reaction and three additional oxidation peaks a2, a1 and a1 (Figure 1). However, at scan rate 25 mV/s only the first couple c1/a1 remains with E0= -505mV. At pH 9.20 two small irreversible reduction peaks c1 and c1 appear at -360 and -410 and -460mV at pH 11.05 respectively with a formal electrode potential (E0) = -520 and -562mV at pH 9.20 and 11.05 respectively. This suggests that the electron-transfer at c1 is followed by chemical reaction (EC mechanism) [10]. On extending the negative potential limit to -1.15V, the reduction peak c2 attributable to Cu
+/0

an is

followed by chemical reaction

. The CV

features at pH 9.20 show a very small irreversible reduction peak c and a well define couple c1/a1. Further, it is noted that the peak currents are smaller in 1:2 ratio at a given pH (Table 1). This may be due to the formation of elongated tetragonal-octahedral complex
[15] [13,14]

, [Cu (dien)2] (ClO4)2 in 1:2

ratio as compared to square planer complex , [Cu (dien)(H2O)(ClO4)2] in 1:1 ratio at pH

electron transfer reaction

7.10. 1:10 and 1: 100 Cu (II) dien system The CV features at pH 7.10 and 9.20 show a single couple (c1/a1) as scanned from +0.20V to -0.80V at V = 25mV/s. However, in 1:100 ratio at pH 9.20, the cathodic peak c1is broad (Figure 3) which may be due to the presence processes of
[16]

is observed in the forward scan followed by a complicated oxidation process a1,a2,a1, a2 (Figure 2) in the reverse scan. At the second cycle a new reduction peak c1 appear at 150mV (pH 7.10), -130mV (pH 9.20), 330mV
[11]

(pH

11.05)

and

-330mV

(pH

12.0).This cathodic peak c1 may be assigned to electro-reduction of electrochemically Cu(II) species to Cu(o). The

two

very close

reduction

formed

. At pH 11.05, the CV of 1:10

magnitudes of Ipc1 and Ipa1 as well as the All rights reserved 2011

Cu(II) dien system shows two irreversible www.jamonline.in 314

Jamonline / 2(4); 2012 / 312320 reduction peaks c1 and c1 and one quasireversible couple c1/a1 in the forward scan followed by a relatively large stripping oxidation peak a2 at -0.30V at 25mV/s (Figure 4) which can be attributed
[17]

E. J. Ukpong & I. A. Udoetok to 250 mV/s. It was found that the cathodic peak current increases linearly with square root of scan rate for all molar ratios and all pH values. The best fit was obtained for the plot of square root of scan vs the cathodic peak for 1:10 molar ratio at pH 11.05 with a correlation coefficient of 0.9971, slope of 2.670 and intercept of+01245 (Figure 5). This indicates that the electrode process is not fully diffusion controlled chemical reaction[10] Effect of Ligand Concentration: The effect of variation of
[10,20,21]

to the electro-

oxidation of Cu(o) to Cu(1) species. The deposition of Cu(o) to the surface of the working electrode results due to chemical decomposition complex species of
[18]

Cu(I)-dien-hydroxo

. The peak current of a2


[10]

and also the

decrease markedly with increasing scan rate indicating an EC mechanism . At pH 11.05,

electron-transfer is followed by a preceding

the CV for 1:100 ratio shows similar features with that of 1: 10 at the same pH, except that in addition to the c1/a1 couple, only one irreversible reduction peak c1appears. However, three complicated oxidation peaks a1 a2 and a2 appear in the reverse cycle at V = 25mV/s (Table 1) Effect Of pH: The influence of solution pH on the reduction of copper(II)dien complex has been investigated at GCE. It shows that the value of Epc1 at a given [Cu(II)]:[dien] molar ratio shifts cathodically with increasing pH

concentration of dien at each pH was studied. A typical plot of cathodic current vs square root of dien concentration at pH 7.10 ( Figure 6) shows that cathodic peak current decreases linearly probably due to the fact that the Cudien complex formed is much larger size and hence there is the low value of diffusion current with increased ligand concentration[
22]

. However, the value of Epc1 at a given [

Cu(II)]:[dien] molar ratio at a given pH value shifts more negatively, indicating that the reduction becomes more difficult with
[12]

value(Table1), indicating that protons take part in these electrode reactions[19]. Effect of Scan Rate: The effect of scan rates on the

increasing ligand concentration and pH

. It

may therefore be concluded that higher order complex species are formed at higher pH values and increased ligand concentration[23]. The cyclic voltammetric results for 1:1, 1:2, 1:10 and 1:100 Cu(II) dien systems show the

electrochemical response of 1:1, 1:2, 1:10, and 1:100 Cu(II)dien system at pH7.10, 9.20, 11.05 has been studied between the range 10 All rights reserved 2011

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Jamonline / 2(4); 2012 / 312320 following features for c1/a1 couple (i) Ipa/Ipc, is less than unity indicating that Cu(I) dien complex is unstable, the electrode process is not chemically reversible. (ii) Ep (Epa1 Epc1) increases with increasing scan rate, demonstrating a quasi-reversible electrode process. CONCLUSIONS The electrochemical behaviour of copper(II)-dien complex species was

E. J. Ukpong & I. A. Udoetok mechanical and chemical pretreatment. Clay Minerals, 57(4),(2009), pp. 486-493. 4. Quattara, T. D. And Bokra. Influence of water on the anodic oxidation mechanism of diethylenetriamine on platinum electrode. Bull. Of Chem. Soc. Ethiopia.20(20),( 2006),pp.269-277. 5. Patel, R. N., Singh, N., Patel,D. K., and Gundla, V. L. N. Synthesis, characterization and superoxide dismutase studies of square pyramidal copper(II)complexes with bi and tridentate polyamine ligands. Indian Journal of chemistry.vol. 46A(2007), pp.422-427. 6. Gouch, R. K., Kensler, T. W., Oberly, L. W., and Sorenson L. W. In: Biochemical and Inorganic copper chemistry,(ed) K. D. Kalin and J. Zubieta, Vol 1. (adinine, New York) 1980,139. 7. Lever,A.B. P. Inorganic Electronic Spectroscopy 2nd Edition ( Elsevier, Amsterdam),1986, chapter 6. 8. Hathaway B. J. Structural Bond (Berlin), 57,1984,55. 9. Crouch,A. M.,Khosteng, L. E., Polhuis, M., Williams, D. R. Comparative study of cyclic voltammetry with potentiometric analysis for determining formation constant for polyaminocarboxylate-metal ion complexes. Analytica chimica Acta . 448, ( 2001), pp.231-237. 10. R.S. Nicholson, I. Shain. Theory of Stationary Polarography: Single Scan and Cyclic Methods Applied to Reversible and kinetic Systems. Anal. Chem. 36, (1964),pp.706-723. J. Prasad, K. Srivastava, D. Khare, K. B. Pandey. Unusual cyclic voltammetric behavior of oxovanadium(IV) chelates of www.jamonline.in 316

investigated by cyclic voltammetry. The electrode process for c1/a1 couple involves a one electron charge results transfer . The voltammetric show that a higher

order complex species are formed at higher pH values and increased ligand concentration. However, characterize Cu(II)/Cu(I) it would the exact be interesting to

nature of these the help of

species

with

coulometric and spectroscopic techniques. REFERENCES 1. A.Cremers, P. Peigneur, A. Maes, Weikwijze voor het Verwiijden van metalen uit oplossingen, Belgisch Patent 0839637, (1979) in press. 2. L. Ammann, F. Bergaya, G. Lagaalyi. Determination of the cation exchange capacity of clays with copper complexes revisited.Clay Minerals, 4,(4),(2005), pp. 441-453. 3. A. Stendell, P. G. Weidler, R. Schuhmann, K. Emmerich. Cation exchange reactions of vermiculite with Cu-triethylenetetramine as affected by All rights reserved 2011

11.

Jamonline / 2(4); 2012 / 312320 some Schiff bases. Microchem. Journal, 50, (1994),pp.136-140. 12. M. P. Sanchez, M. Barrera, S. Gonzalez, R. M. Souto, R. C. Salvarezza, A. J. Avrvia. Electrochemical behavior of copper in aqueous moderate alkaline media containing sodium carbonate. Electrochemica Acta.35,(9),(1990),p.1337. 13. F. S. Stephens. The structures of diethylenetriamine copper(II) cations. Part 1. Crystal structure of bis(diethylenetriamine)copper(II) nitrate. J. Chem. Soc. A.(1969) pp. 883-890. 14. F. S. Stephen. The structures of diethylenetriamine copper(II) cations. Part II Crystal structure of bis(diethylenetriamine) copper(II) bromide monohydrate. J. Chem. Soc. A. (1969), pp. 2233-2240. 15. M. J. Bew, B. J. Hathaway, R. J. Fereday. Electrochemical properties and stereochemistry of the copper(II) ion. Part VII. Mono(diethylenetriamine) copper(II)complexes. J. Chem. Soc. Dalton trans. (1972), pp. 1229-1237. 16. 16. A. J. Bard, R. L. Faulkner. Electrochemical methods, John Wiley and sons, New York, 1980, pp. 229-235. 17. L. Casella, M. Gulotti, A. Pintar, F. Pinciroli, R. Vigano, P. Zanello. Blue

E. J. Ukpong & I. A. Udoetok copper systems containing sulphur and nitrogen donor atoms. J. Chem. Soc., Dalton Trans. (1989), pp.1161-1169. 18. J. W. Allison, R. J. Angelici. Stability constants of N- methyl and N-ethylsubstituted diethylenetriamine complexes of copper(II). Inorg. Chem.(1971), 10,(10), pp.2233-2238. 19. M. B. Deepa, G. P. Mamatha, B. S. Sherigara, Y. Arthobanaik. Electrochemical studies of Ceftriaxone on Erichrome Black- T. Polymer Film Modified Glassy Carbon Electrode. International Journal of Research in Chemistry lalaand Environment. Vol.2(1),(2012). Pp.153-159. 20. D. K. Gosser.,(Ed), Cyclic Voltammetry VHC New York (1994). 21. G. Ongera, S. Kumara, U. Chandra, and B. S. Sherigara. Oxidation of Dopamine and Ascorbic Acid at Poly(Erichrome Bkack T) Modified Carbon Paste Electrode. Int. J. of Electro. Chem. Sci.,4,(2009), pp. 582-591. 22. Y. Kumar, A. Garg and R. Pandey.Polarographic study of Ni2tCurcumin complex. International Journal of Analytical and Bioanalytical Chemistry. 1(3) (2011). Pp. 110-115. 23. D. R. Crow. Polarography of metal complexes, Academic: London, 1969.

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Jamonline / 2(4); 2012 / 312320 FIQURE LEGEND.

E. J. Ukpong & I. A. Udoetok

Figure 1: CV of 1:1 Cu(II)-dien system at 10mV/s and pH 7.10

Fiqure 2: CV of 1:1 Cu(II)-dien system at 25mV/s and pH 7.10.

Fiqure 3: CV of 1:100 Cu(II)-Dien system at 100 mV/s and pH 9.10.

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Jamonline / 2(4); 2012 / 312320

E. J. Ukpong & I. A. Udoetok

Figure 4: CV of 1:10 Cu(II)-dien system at 10mV/s and pH 11.05

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Jamonline / 2(4); 2012 / 312320

E. J. Ukpong & I. A. Udoetok

Table 1: Cyclic Voltammetric Parameters for different Cu(II)-dien systems. at 25mV/s, (T= 25oc). [Cu(II)]:[dien] pH Epc1 Epc2 (pc1) Epa1 Epa2 Epa1 Epa1 Ep Ipa1/Ipc1 (Ipc2) (Ipa1) (Ipa2) (Ipa1) (Ipa1) -250 +10 +245 (13.0) (N/M) (13.0) 60 -270 +100 +210 (10.0) (31.5) (N/M) 100 -350 -50 (17.5) (N/M) N/A -450 -110 (N/M) (1.5) -180 (6.5) 0.61

7.10 -535 -875 -475 (13.0) (10.0) (8.0) 1:1 9.20 -570 -980 -470 (13.0) (9.0) (8.0) 11.05 -600 -1070 -525 (13.5) (9.5) (8.0) 12.0 -625 -1110 -550 (16.0) (7.0) (6.0) -515 (9.5) 1:2 9.20 -565 (8.5) 7.10 -536 (8.5) 1:10 9.20 -600 -475 (6.5) -455 (6.5) -530 (7.0) -450

0.61

75

0.59

N/A

75

0.43

7.10

+25 (0.70) (1.6)

N/A

65

0.68

N/A N/A

N/A N/A

N/A N/A

90 80

0.76 0.76

N/A -300 (4.5)

N/A

N/A

70

0.82

11.05 -650 -1070 -580 (12.5) (8.0) (8.0) 7.10 -565 (7.0) 1:100 9.20 -655 (7.0) 11.05 -685 (11.0) -465 (5.2) -545 (5.0) -605 (7.5)

N/A

N/A

70

0.64

N/A

N/A

N/A

100

0.74

N/A -330 (3.5)

N/A

N/A

110

0.71

N/A

N/A

80

0.68

N/A, not appear; N/M, not measurable; all potentials measure in mV from base line; all currents measured in A.

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