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10 2116@analsci 18 997
10 2116@analsci 18 997
18 997
2002 © The Japan Society for Analytical Chemistry
*Ankara University, Faculty of Science, Department of Chemistry, Tandoğan, 06100 Ankara, Turkey
**Ondokuz Mayıs University, Faculty of Science and Arts, Department of Chemistry,
55139 Kurupelit-Samsun, Turkey
Fig. 1 Cyclic voltammograms of 1.67 × 10–5 M 2′-I-N,N-dimethyl- Fig. 3 Change in the limiting current of 1.67 × 10–5 M 2′-halogeno-
4-aminoazobenzene in (a) acidic (pH 2.00), (b) basic media (pH 6.83) N,N-dimethyl-4-aminoazobenzene with the pH [EtOH:BR = 1:5 ν/ν,
[EtOH:BR = 1:5 ν/ν, scan rate = 100 mV/s, with HMDE and scan rate = 10 mV/s, drop time = 1 s with SMDE and Ag/AgCl
Ag/AgCl reference electrode)]. reference electrode].
DPP CV
C/10–7 mol L–1
Ep/mV ip/10–7 A Ep,c/mV ip,c/10–7 A
Table 2 Diffusion coefficients, amount of reactant adsorbed on the mercury surface (Γ , mol cm–2), standard rate constants (ks) values
in 1:5 ν/ν EtOH:BR buffer, C = 1.67 × 10–5 M 2′-halogeno-N,N-dimethyl-4-aminoazobenzene derivatives in acidic media (pH 5.08)
2′-Cl-4-N,N 2.10 × 10–5 ± 7.76 × 10–6 ± 10.41 × 10–3 ± 2.5 × 10–1 ± 1.31 × 10–11 ±
5.25 × 10–6 5.02 × 10–7 2.18 × 10–3 1.5 × 10–2 3.28 × 10–12
2′-Br-4-N,N 1.77 × 10–5 ± 1.83 × 10–6 ± 6.50 × 10–3 ± 2.3 × 10–1 ± 1.79 × 10–11 ±
4.43 × 10–6 1.28 × 10–7 1.37 × 10–3 1.4 × 10–2 4.48 × 10–12
2′-I-4-N,N 1.73 × 10–5 ± 7.92 × 10–6 ± 2.97 × 10–3 ± 1.8 × 10–1 ± 2.40 × 10–12 ±
4.33 × 10–6 5.13 × 10–7 6.24 × 10–4 1.1 × 10–2 6.01 × 10–13
EtOH:BR = 1:5 ν/ν, and Ag/AgCl reference electrode. a. Calculated from Cottrell slope (Eq. (2)), the data were determined by the use of
i–t–1/2 plots in the diffusion region (pulse amplitude 250 ms, E1 = –400 mV and E2 = –900 mV). b. Calculated from Eq. (3), considering
adsorption (tp = 15 s). c. Calculated from Eq. (4), ignoring adsorption. d. C = 1.67 × 10–7 M, calculated from Eq. (5), considering
adsorption (for confidence interval of 95%, mean α value for the cathodic peak is 0.30). e. Qdl = 3.3 × 10–9C (Eq. (1)), (pulse amplitude
250 ms, E1 = –400 mV and E2 = –900 mV).
Laviron method
Since the adsorption phenomenon was found to have an
effect, the rate constants were determined using a method
developed by Laviron, which takes the effect of adsorption into
account.15 The ks values were calculated using
nF∆EP
RT – α (1– α) —
logks = α log(1– α)+(1– α)log α –log — ———,
nF—
ν 2.3RT
(5)
The α value was determined from the slope of the Ep,c vs. log ν
graph, which is equal to 2.53RT/αnF for the cases ∆Ep,c > 200/n
mV. The number of electrons (n) transferred was taken as two
for a basic medium and four for an acidic medium, as Scheme 1
mentioned above. The ks values, determined by these two
different methods, are tabulated in Table 2. The standard rate
constant determined by the Nicholson method was found to be basic media with two-electron transfer.9,12,23,25,28 A TLC analysis
different from those determined by the Laviron method, which of the bulk electrolysis products gave similar results to the
indicates the presence of adsorption (Table 2). The halogene literature.23,25 The polarographic reduction products of azo
atoms are easily deformed and can act as electron bridges in compounds have also been analyzed by TLC23 and HPLC.29
some electrode reactions, resulting in a change in the values of
the charge-transfer coefficients.
All of these methods were used under the conditions to which Acknowledgements
they respectively apply. In other words, the standard rate
constants for the Nicholson methods were determined at high The authors are grateful to Ankara University Research Fund
concentrations where adsorption had no effect, while the rate for its financial support of this work under Grant No: CHE 95-
constants determined by the use of the Laviron method were 25-00-04. The authors thank Dr. Mehmet Toy for the supplying
those obtained under the conditions where the adsorption the azo compounds.
phenomenon was operative (i.e. at low concentrations).
Brillas, J. Electroanal. Chem., 1992, 324, 19. Collect. Czech. Chem. Commun., 1990, 55, 2636.
17. R. S. Nicholson, Anal. Chem., 1965, 37, 1351. 24. A. J. Bard and L. R. Faulkner, “Electrochemical Methods:
18. S. Yamamoto, N. Nishimura, and S. Hasegawa, Bull. Fundamentals and Applications”, 1980, John Wiley and
Chem. Soc. Jpn., 1971, 44, 2018. Sons, New York, Chichester, Brisbane, Toronto, 213.
19. S. Yıldırır and M. Toy, “The synthesis of some azobenzene 25. M. Uçar, Ph.D. Thesis, Ankara University, Ankara, 1998.
derivatives and investigation of ultraviolet spectra”, 26. F. C. Anson, Anal. Chem., 1966, 38, 54.
Marmara University Fen Bilimleri Dergisi, 1989, 6, 213. 27. M. L. Foresti, F. Pergola, and R. Guidelli, J. Chem. Soc.
20. L. Holleck, S. Vavricka, and M. Heyrovsky, Electrochim. Faraday Trans. I, 1979, 75, 155.
Acta, 1970, 15, 45. 28. J. Barek, H. Halodova-Blahova, and J. Zima, Collect.
21. I. M. Issa, R. M. Issa, Y. M. Temerk, and M. R. Mahmoud, Czech. Chem. Commun., 1989, 54, 1549.
Electrochim. Acta, 1973, 18, 139. 29. A. Burcinova, K. Stulik, and V. Pacakova, J. Chromatogr.,
22. N. Menek, O. Çakır, and H. Kocaokutgen, Mikrochim. 1987, 389, 397.
Acta, 1996, 122, 203.
23. J. Barek, J. Kubickova, V. Mejstrik, O. Petira, and J. Zima,