Analytica Chimica Acta 431 (2001) 8187

Adsorption voltammetry of the mix-polynuclear complex of zirconiumcalciumalizarin red S at a carbon paste electrode
Ju-Nan Li , Jun Zhang, Pei-Hong Deng, Ya-Qing Peng
College of Chemistry and Chemical Engineering, Xiangtan University, Xiangtan 411105, Hunan, PR China Received 27 January 2000; received in revised form 13 September 2000; accepted 13 September 2000

Abstract A novel new method is described for the determination of zirconium based on the cathodic adsorptive stripping of the mix-polynuclear complex of zirconiumcalciumalizarin red S (ARS) at a carbon paste electrode (CPE). The second-order derivative linear scan voltammograms of the adsorbed mix-polynuclear complex of zirconiumcalciumARS are recorded by model JP-303 polarographic analyzer from +0.20 to 0.80 V (versus SCE). Optimal conditions are found to be: a glycine (0.096 M)potassium biphthalate (0.036 M) buffer solution (pH 4.0) containing 8.0 104 M Ca2+ and 2.0 105 M ARS; accumulation potential, +0.20 V; accumulation time, 90 s; rest time, 10 s; scan rate, 500 mV s1 . The results show that the complex can be adsorbed on the surface of the CPE, yielding one peak at 0.50 V, corresponding to reduction of ARS in the complex at the electrode. The detection limit is found to be 4.0 1011 M with 4 min of accumulation time. The linear range is from 1.0 1010 to 2.0 107 M. Application of the procedure to the determination of zirconium in the ore samples gives good results. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Adsorption voltammetry; Carbon paste electrode; Zirconium; Mix-polynuclear complex

1. Introduction Zirconium, like aluminium or many other reactive elements such as thorium, alkaline earth and rare earth metals, cannot be easily determined by conventional voltammetry because of the difculty in reducing them at the electrode in aqueous solutions [1]. Advancing of the polarographic complex adsorption wave and complex adsorption voltammetry sets up a new way for determination of these elements. The complexes of zirconium with organic ligands such as pyridylazo resorcinol [2], almond acid [3] eriochrome black T [4], cupferron [5,6], ARS [7,8], 1,2,5,8-tetrahydroxyanthra-quinone
Corresponding author. E-mail address: doc@xtu.edu.cn (J.-N. Li).

[9], rsenazo III [10], nitrosulphophenol M [11], salicyl-uorene [12], calconcarboxylic acid [13], 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (PMBP) [14], chrome blueblack R [15], nitrosulphophenol C [16] were applied in the polarographic determination of zirconium. The trace measurement of zirconium by adsorptive voltammetry at a hanging mercury drop electrode was also reported [17,18]. Its limit of detection is as low as 0.23 nM. Recently, a polarographic adsorptive wave of the mix-polynuclear complex of zirconiumcalciumalizarin red S [8] was described. The limit of detection is 2 108 M. The adsorptive stripping voltammetry has become a sensitive and effective means for trace measurements of important species that cannot be accumulated by electrolysis. Wang [19] has summarized

0003-2670/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 0 0 3 - 2 6 7 0 ( 0 0 ) 0 1 2 0 0 - 9

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Scheme 1.

the method. CPE is used extensively in voltammetry [20,21], because of its many advantages, such as easy manufacture, nonpoisonous, cheap price, wider potential window and longer using life. No paper, however, has appeared for the determination of zirconium and other reactive metal ions using complex adsorptive voltammetry at a CPE. A new sensitive adsorptive stripping voltammetry for the determination of zirconium at a CPE in the presence of Ca2+ and ARS is described in this paper for the rst time. ARS is an anthraquinone dye having good complex function with the structure shown (see Scheme 1). The nonpoisonous, cheap CPE is used instead of the severe toxic, expensive mercury electrode in this method. Thus, it has excellent environmental and economical benet. By use of model JP-303 polarographic analyzer, 4 1011 M of zirconium can be detected when the second-order derivative linear sweep technique is used, and the linear range is 11010 to 2107 M. The method has been applied to the determination of zirconium in the ore samples with quite satisfactory results. The adsorptive and voltammetric characteristics of the mix-polynuclear complex of zirconiumcalciumARS at a CPE are investigated.

in 1 M hydrochloric acid and diluting to 100 ml with 1 M hydrochloric acid; a 1.0 103 M stock standard solution of ARS (Adrich) was prepared by dissolving an appropriate amount of ARS in water; a 1.0 102 M Ca2+ solution was prepared by dissolving an appropriate amount of CaCO3 in a little hydrochloric acid and diluting with water; a mixed buffer was a solution containing 0.4 M glycine and 0.15 M potassium biphthalate, this solution was adjusted to pH 4.0 with sodium hydroxide solution; Spectrally pure carbon powder and chromatographically pure ethylbenzenesilicon oil was used to prepare the CPE. 2.2. Apparatus JP-303 polarographic analyzer (Chendu Instrument Factory) was used for voltammetry, with a three electrode system consisting of a CPE as the working electrode, a Hg/Hg2 Cl2 ,(saturated KCl) reference electrode and platinum counter electrode pH measurements were performed with a pH-3c Model pH meter (Shanghai Leichi Instrument Factory) using a combined glass electrode. 2.3. Preparation of electrode The mixture containing carbon powder and silicon oil (7:3) was plunged in a 4 mm glass tube, in which a copper wire was inserted. The electrode was burnished on a piece of rubber paper. 2.4. Procedure The sample solution (25 ml), containing 2.0 105 M ARS, 8.0 104 M Ca2+ , and 0.096 M acetic acid0.036 M potassium biphthalate buffer was pipetted into the voltammetric cell. The stirrer was switched on. The accumulation potential (+0.2 V) was applied to a CPE for 90 s. Following the accumulation period, the stirrer was stopped, and after 10 s the second-order derivative voltammogram was recorded by applying a negative-going potential scan at 500 mV/s rate from +0.2 to 0.8 V and the second derivative peak current of the mix polynuclear complex was obtained at 0.50 V (Fig. 1).

2. Experimental 2.1. Reagents and solutions All reagents were of suprapure or analytical grade from Shanghai the rst chemical factory (China) except ARS. All solutions were prepared with doubly distilled water. A 1.0 102 M stock standard of Zr(IV) solution was prepared by dissolving 0.3223 g of ZrOCl2 8H2 O

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Fig. 2. Effect of accumulation time on the peak current: ( ) Zr(IV), 6.0 108 M; ( ) Zr(IV), 6.0 109 M (conditions as in Fig. 1).

Fig. 1. The second derivative voltammetric curves: 0.096 M acetic acid and 0.036 M potassium biphthalate buffer, accumulation time: 90 s, scan rate: 500 mV/s. (1) 2.0 105 M ARS; (2) 1 + 8.0 104 M Ca2+ ; (3) 2 + 6.0 108 M Zr(IV).

3. Result and discussion 3.1. Adsorptive and voltammetric characteristics of the Zr(IV)Ca2+ ARS complex No peak was found on the linear potential scan voltammogram in a solution containing 0.096 M glycine and 0.036 M potassium biphthalate buffer (pH 4.0), 8.0 104 M Ca2+ and 6.0 108 M Zr(IV). In Fig. 1, the adsorption voltammograms of the solutions of ARS without Zr(IV) (curve 1), with Ca2+ (curve 2) and with Ca2+ and Zr(IV) (curve 3) were reproduced. The peak potential of the reduction of adsorbed ARS in the mixed buffer (pH 4.0) is 0.35 V. When an amount of Ca2+ is added to the solution, a new peak appears at a more negative potential than the reduction of ARS. The peak potential is 0.45 V. The peak current of the reduction of adsorbed ARS decreases and that of the new peak increases with increasing concentration of Ca2+ . When a micro-amount of Zr(IV) was added to the

solution containing 8.0 104 M Ca2+ , a new even more sensitive peak appears at a more negative potential than that of the reduction of the Ca2+ ARS complex. The peak potential is 0.50 V, then the peak at 0.45 V disappears. It seems clear that the new peak results from the mix-polynuclear complex of Zr(IV)Ca2+ ARS. Li and coworkers [8,22] have studied the formation of the mix-polynuclear by polarography and spectrophotometry. Fig. 2 shows the plots of the peak current of the complex changing with accumulation time plots for 6.0 108 M (a) and 6.0 109 M (b) Zr(IV). At rst, the peak current increased with accumulation time, indicating that before adsorption equilibrium is reached, the longer the accumulation time, the more Zr(IV)Ca(II)ARS was adsorbed and the peak current became larger. However, after a specic accumulation period, the peak current tended to level off, illustrating that adsorption equilibrium is achieved. An accumulation time of 90 s is used for further studies in order to keep the linear relation under more concentration of zirconium condition. It was found that the peak current, Ip , of the complex varies with potential scan rate . There is linear relation between log Ip and log in range from 50 to 500 mV/s, and log Ip /log = 0.67. The above features are characteristic of a reaction in which the reactant is adsorbed on the surface of the CPE [23,24]. The peak current of the complex is not affected by a small amount of an anion surfactant (dodecyl benzene sulfonic acid sodium), but it is suppressed in the presence of a small amount of a cation

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Fig. 3. Cyclic voltammogram. Scan rate: 100mV/s, Start potential: 0.0 V. (a) 4.0 105 M ARS; (b) a + 8.0 104 M Ca2+ ; (c) b + 1.0 106 M Zr(IV) (other conditions as in Fig. 1).

(associated with the lower concentration of the free ligand and the competition of the complex and ligand for adsorption sites). In order to obtain some information on the reactants and products, electrolysis was used. The working electrode was large area CPE ( 6 mm) and an electrolysis potential of 0.55 V was applied. After 2 h the peak corresponding to the reduction of the Zr(IV)Ca2+ ARS complex dropped clearly. The CPE was taken out of the cell and ARS was added to the cell. By using linear scan voltammetry, the peak corresponding to the reduction of the complex was obtained again with a peak value that was the same as that before electrolysis. It is obvious that the electroactive component in the complex is ARS. The peak potential of ARS and the complex change linearly more negative with pH value increasing and the slope is equal to 55 mV/pH (Fig. 5). It indicates that protons also take part in the electrode reaction. This is in accord with Nernst equation of the reduction of the anthraquinongyl. 3.3. Effect of operational parameters 3.3.1. Selection of the adhesive in the electrode The liquid parafn, solid parafn, mineral butter and various silicon oil, etc. are used as the adhesive of the CPE. The experiments indicate that silicon oil is the best choice for the highest sensitivity (Table 1). Fig. 4 shows that adhesive ratio must be carefully optimized to make the best of peak shape and the highest sensitivity; the ratio in testing is 7:3 (w/w). If the surface of the CPE is renewed after testing, R.S.D. of 2.6% is obtained for eight determinations. 3.3.2. Effect of pH The inuence of pH on the stripping peak current is studied in the range pH 3.44.4 (Fig. 5). It is found that the most peak current is in the range pH 3.74.2. When the pH value is lower than 3.4, there is no peak

(hexadecyltrimethylammonium bromide) or neutral surfactants (TritonX-100). The complex can be charged positively. 3.2. Reversibility and reactant Fig. 3 shows the cyclic voltammograms recorded for 4.0 105 M ARS at the CPE in the absence (a) and presence (b) of 8.0 104 M Ca2+ and in presence (c) of 1.0106 M Zr(IV) and 8.0104 M Ca2+ , after 60 s stirring at 0.0 V. The cathodic peak potential of the ligand is at 0.35 V and the anodic peak potential corresponding to the cathodic peak is at 0.28 V (Fig. 3a). So the redox reaction of ARS is quasi-reversible at the CPE. The Ca2+ ARS complex is reduced at 0.45 V (Fig. 3b), and the complex of Zr(IV)Ca2+ ARS is reduced at 0.50 V (Fig. 3c). Note also the simultaneous decrease of the ARS peak
Table 1 Effect of the adhesives (conditions as in Fig. 1) Adhesive Ep (mV) Ip (106 A) Silicon oil 502 11.30 Parafn oil 500 9.74 Parafn 500 9.88

Mineral butter

Epoxy resin

Glass carbon 500 7.13

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Fig. 4. Effect of the concentration adhesive on the peak current. Conditions as in Fig. 1.

and when the pH value exceeds 4.2, the peak current begins to decrease.c 3.3.3. Effect of ARS concentration Fig. 6 shows the effect of variation of ARS concentration on the peak current. The peak current increases with increasing ARS concentration up to 8.0106 M, at higher concentration the peak current decreases with increasing concentration of ARS probably due to the competition of ARS with Zr(IV)Ca(II)ARS. 3.3.4. Effect of calcium concentration Fig. 7 shows that the sensitivity is highest when the concentration of Ca2+ is more than 1.6 104 M. To improve the reaction selectivity, 8.0 104 M Ca2+ was selected for further experiments. 3.3.5. Effect of medium We investigated the use of formate buffer, BrittonRobinson buffer, Walpole buffer, Kolthoff buffer, Michaelis buffer, ClarkLubs buffer and Srensen buffer. The highest peak current is in acetic

Fig. 6. Effect of ARS concentration on the peak current. Other conditions as in Fig. 1.

acid with potassium biphthalate and the optimum concentration of potassium biphthalate is in the range 2.4 102 to 5 102 M and the concentration of acetic acid has little effect on the peak current. 3.3.6. Effect of accumulation potential Fig. 8 shows the effect of accumulation potential on the stripping peak current of the Zr(IV)Ca(II)ARS complex over the range 0.3 to 0.3 V. The peak current increases with changing potential from 0.3 to 0.2 V. Beyond 0.20 V, the peak current is decreased. 3.4. Figures of merit 3.4.1. Linear range, detection limit of the method The linear range for zirconium determination was evaluated at 90 s accumulation time. The peak current increases linearly with Zr(IV).

Fig. 5. Effect of pH on the peak current. Other conditions as in Fig. 1.

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J.-N. Li et al. / Analytica Chimica Acta 431 (2001) 8187 Table 2 Results of determination of zirconium ore in mineral samples Sample GSD-1 GSD-3 GSD-5 GSD-7 Found (n = 5, %) 0.0314 0.0217 0.0213 0.0169 Recommended values (%) 0.0309 0.0211 0.0200 0.0162 R.S.D. +1.62 +2.84 +6.50 +4.32

Fig. 7. Effect of Ca(II) concentration on the peak current. Other conditions as in Fig. 1.

The linear range for zirconium determination was evaluated at 90 s accumulation time. The peak current increases linearly with Zr(IV) concentration over the range 1.01010 to 1.0109 M (accumulation time 180 s), 1.0109 to 1.0108 M (accumulation time 90 s), 1.0 108 to 2.0 107 M (accumulation time 60 s). A detection limit (3 ) of 4.0 1011 M (accumulation time 240 s) is obtained. 3.4.2. Interference studies The effect of co-existing ions on the determination of Zr(IV) was investigated. Experimental results showed that a 1000-fold excess of Al3+ , Ba2+ , Mg2+ , Zn2+ , Mn2+ , Ni3+ , Te4+ and Ag1+ ; a 500-fold excess of Sb3+ , Ti4+ and Hg2+ ; a 200-fold excess of Se4+ ; a 100-fold excess of Cu2+ , Pb2+ , Bi3+ , Fe3+ , and Fe2+ ; a 10-fold excess of rare earth ions do not interfere in the determination of 1.0 108 M Zr(IV) with an error of 5.0%. Scandium and thorium produce serious

disturbance. The interference of Sc3+ , Th(IV) and rare earth ions can be overcome by extraction. Because of the effect of lanthanide contraction zirconium and hafnium have very similar properties, the peak current of Hf(IV)Ca(II)ARS mix-polynuclecar complex adsorption have similar sensitivity in the same condition of the experiment. 3.4.3. Real sample analysis The samples are treated according to the reference [7]. The ore samples are melted with Na2 O2 . The solution is stripped with triotylaminebenzene, then counter-stripped with HClO4 (0.1 M)HCl (1 M)HNO3 (2 M) mixed solution. The proposed method was successfully applied to the determination of zirconium in the ore samples (Table 2).

Acknowledgements This research work was assisted by the Human Education Committee (98B007). References
[1] I.M. Kolthoff, J. Lingane, Polarography, Interscience, New York, 1959. [2] G.K. Budnikov, V.N. Maistrenko, V.F. Toropova, Zavod. Lab. 42 (1976) 512. [3] A. Tserkovnitskaya, N.S. Bborovaya, Vestn. Lenigr. Univ. Fiz. Khim. 16 (1977) 144. [4] V.F. Dorofeeva, S.L. Rogatinskaya, A.P. Kreshkov, Zh. Anal. Khem. 34 (1979) 913. [5] X.R. Yao, J.X. Zhou, M. Yin, Fenxi Huaxue 9 (1981) 22. [6] H.L. Ye, Y. He, Talanta 31 (1984) 638. [7] J.N. Li, A.J. Lo, Xiangtan Daxue Ziran Kexue Xuebao 5 (1983) 64. [8] J.N. Li, Y.F. Zhang, X.J. Zhao, Gaodeng Xuexiao Huaxue Xuebao 18 (1997) 372. [9] L. Kang, Y.X. Zhang, Yingyong Huaxue 2 (1985) 6.

Fig. 8. Effect of accumulation potential on the current. Other conditions as in Fig. 1.

J.-N. Li et al. / Analytica Chimica Acta 431 (2001) 8187 [10] W. Deng, X.R. Yao, L.Z. Li, Fenxi Huaxue 14 (1986) 192. [11] H.M. Li, X.Z. Lu, Yankuang Ceshi 6 (1987) 54. [12] X.J. Wang, S.Y. Lu, K. Sui, Fenxi Huaxue 16 (1988) 1037. [13] H.P. Huang, W.H. Shi, D.P. Xia, Yejin Fenxi 10 (1990) 26. [14] S.Q. An, X.Z. Lu, Fenxi Huaxue 18 (1990) 223. [15] Q.H. Zhou, M.Z. Fu, Y.X. Yin, Guangdong Gong Xueyuan Xuebao Ziran Kexue Ban 10 (1993) 59. [16] L.J. Zhang, X.Z. Lu, Yankuang Ceshi 17 (1998) 185. [17] Y.L. Chen, X.L. Zhang, S.Y. Shong, Fenxi Shiyanshi 6 (1987) 37.

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[18] J. Wang, T. Peng, Talanta 34 (1987) 561. [19] J. Bard, Electroanalytical Chemistry, Vol. 16, New York, 1989, pp. 188. [20] K. Kalcher, J.-M. Kallffmann, J. Wang, I. Svancara, K. Vgtras, C. Neuhold, Z. Yang, Electroanalysis 7 (1995) 5. [21] Z.Q. Zhang, H. Liu, Y.F. Li, Fenxi Kexue Xuebao 14 (1998) 80. [22] J.N. Li, M.L. Zhang, Y.S. Wang, Xiangtan Daxue Ziran Kexue Xuebao 19 (1997). [23] E. Laviron, J. Electronal. Chem. 52 (1974) 355. [24] A.P. Brown, F.C. Anson, Anal. Chem. 49 (1977) 1589.