Analytica Chimica Acta 448 (2001) 231237

Comparative study of cyclic voltammetry with potentiometric analysis for determining formation constants for polyaminocarboxylatemetal ion complexes
A.M. Crouch a, , L.E. Khotseng a , M. Polhuis a , D.R. Williams b
a

Department of Chemistry, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa b Department of Chemistry, Cardiff University, P.O. Box 912, Cardiff CF10 3TB, Wales, UK Received 24 December 1999; received in revised form 19 July 2001; accepted 25 July 2001

Abstract Cyclic voltammetry offers a convenient route towards the determination of ligand protonation/deprotonation constants and also for metalligand complex stability constants in aqueous media. The utility of voltammetry is exemplied by a comparison of the metalligand stability constants of complexes of ethylenediamine (ED), ethylenediamine-N,N,N ,N -tetra-acetic acid (H4 EDTA) and diethylenetriamine-N,N,N ,N ,N -penta-acetic acid (H5 DTPA) with transition metals, with these stability constants being in good agreement with those obtained using potentiometric analysis. Further support for the usefulness of voltammetry as an analytical tool is the good correlation of the protonation constants for (S,S)-ethylenediamine-N,N -disuccinic acid with those determined potentiometrically. 2001 Published by Elsevier Science B.V.
Keywords: Cyclic voltammetry; Potentiometry; Complex stability constant; Protonation constant; Polyaminocarboxylate; Speciation

1. Introduction Potentiometric analysis is often the mode of choice for determining complex stabilities in aqueous media, which leads on to insight into the speciation of these compounds [1,2], as the equipment required for potentiometric determination is relatively inexpensive and glass and reference electrodes are so reliable. Such determinations account for a large proportion of formation constant data. However, the use of voltammetric methods of analysis offers several distinct advantages over potentiometric evaluation of constants, notably the ease and rapidity with which samples can be prepared and analysed, the ability to work outside the
Corresponding author. Tel.: +27-21-808-3535; fax: +27-21-808-3964. E-mail address: amc@land.sun.ac.za (A.M. Crouch).

pH range of glass electrodes, and to use non-protic media. We have recently performed a semi-empirical MO study on (S,S)-ethylenediamine-N,N-disuccinic acid (H4 EDDS) (1) at the ZINDO/1 level of approximation and ethylenediamine-N,N,N ,N-tetra-acetic acid (H4 EDTA) (2) [3], and derivatives thereof (Fig. 1), to evaluate the inuence of conformational effects upon the stabilities of complexes between ligands formed by deprotonation of these agents and various transition metal ions, as our interest currently lies in assessing the viability of H4 EDDS as a successor ligand to H4 EDTA on environmental grounds, as the former agent and its complexes with transition metal ions are readily-biodegradable whereas H4 EDTA and its complexes are not [46]. Voltammetry offers a convenient route for analysis of ligandmetal stability constants [710], but before

0003-2670/01/$ see front matter 2001 Published by Elsevier Science B.V. PII: S 0 0 0 3 - 2 6 7 0 ( 0 1 ) 0 1 3 3 4 - 4

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Fig. 1. H4 EDDS (1) and H4 EDTA (2).

gaining widespread acceptability the reliability of this procedure ought to be re-established by re-measuring the complex constants for hexadentate polyaminocarboxylate ligandmetal ion complexes, and analogues thereof, and comparing these data with corresponding data obtained using the long-established potentiometric titration approach. Thence, characterisation of the H4 EDDSmetal ion complexes would be easier and faster. We report here on our results from the cyclic voltammetric analysis of complexes between H4 EDTA, ethylenediamine (ED) and diethylenetriamine-N,N, N ,N ,N -penta-acetic acid (H5 DTPA), and the heavy metal ions Cd2+ , Cu2+ , Pb2+ and Zn2+ , and compare these values with those obtained using potentiometric methods of titration, as these values are readily available in the literature and, will thus, provide a reliable means for ascertaining the efciency and precision of cyclic voltammetry for determining complex stability constants; the precision of cyclic voltammetric methods of analysis should allow for a great degree of reproducibility, as the ligands and their complexes all exhibit distinct reduction peaks in the cyclic voltammograms and are highly reproducible. In addition, the speciation of H4 EDDS was determined in an analogous manner and compared with values previously presented in the literature.

H4 EDDS (Associated Octel Co. Ltd., UK) were used as supplied. 2.2. Standard preparations 2.2.1. 0.1 M KNO3 stock solution in pH 10 buffer KNO3 (10.11 g, 0.10 mol) was weighed into a 1000 cm3 volumetric ask together with 100 cm3 pH 10 NH3 buffer solution and the solution made up to the mark with distilled water. 2.2.2. 1 mM H4 EDDS stock solution in pH10 buffer H4 EDDS (0.38 g, 0.99 mmol) was weighed into a 1000 cm3 volumetric ask and the solution made up to the mark by the addition of 0.1 M KNO3 stock solution in pH 10 buffer. 2.2.3. 1.53 mM zinc standard solution A volume of 10.00 cm3 of a 1000 ppm zinc stock solution were diluted to the mark with 0.1 M NH3 solution in a 100 cm3 volumetric ask. 2.2.4. 4.83 mM lead standard solution A volume of 20.70 cm3 of a 1000 ppm lead stock solution were diluted to the mark with 0.1 M NH3 solution in a 100 cm3 volumetric ask. 2.2.5. 8.90 mM cadmium standard solution A volume of 11.24 cm3 of a 1000 ppm cadmium stock solution were diluted to the mark with 0.1 M NH3 solution in a 100 cm3 volumetric ask. 2.2.6. 4.83 mM zinc standard solution A volume of 6.54 cm3 of a 1000 ppm zinc stock solution were diluted to the mark with 0.1 M NH3 solution in a 100 cm3 volumetric ask.

2. Experimental 2.1. Chemicals The 1000 ppm metal standard solutions (Merck), pH 4.00 and 7.02 buffer solutions, pH 10 buffer solution (Riedel-de Haen), distilled water (Milli-Q) and

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2.2.7. 0.01 M H4 EDTA solution H4 EDTA (0.372 g, 1.00 mmol) was weighed into a 100 cm3 volumetric ask and made up to the mark with 0.1 M NH3 solution. 2.2.8. 0.01 M ED solution ED (0.060 g, 1.00 mmol) was weighed into a 100 cm3 volumetric ask and made up to the mark with 0.1 M NH3 solution. 2.2.9. 0.01 M H5 DTPA solution H5 DTPA (0.393 g, 1.04 mmol) was weighed into a 100 cm3 volumetric ask and made up to the mark with 0.1 M NH3 solution. 2.3. Equipment A controlled growth mercury dropping electrode, platinum wire and Ag/AgCl electrode were used as working, auxiliary and reference electrodes, respectively. The pH measurements were recorded using a Beckman 71 pH meter or a Crison micro pH 2000 pH meter, which were calibrated using Crison pH 7.02 and 4.00 buffers. 2.4. Voltammetric analyses of H4 EDTA, ED and H5 DTPA Background voltammograms were obtained rst for the 0.1 M NH3 buffer solution, and then for the 0.01 M solutions of H4 EDTA, ED and H5 DTPA. Metalligand complexation was then examined as follows: 10.00 cm3 of Zn2+ , Pb2+ , Cu2+ and Cd2+ stock solutions each were used, to which were added aliquots of the appropriate ligand standard solutions

to ensure a 1:1 ratio of metal:ligand. The pH values of the solutions were then adjusted by the addition of aliquots of HCl and the voltammograms recorded for the corresponding pH values of the solutions at a scan rate of 50 mV/s on an AMEL Model 433 Polarographic Analyzer. 2.5. Voltammetric analysis of the pH prole (speciation) of H4 EDDS The pH of 5.00 cm3 of 1 mM H4 EDDS stock solution in pH 10 buffer was adjusted by the addition of HNO3 and the voltammograms recorded for the corresponding pH values of the solution at a scan rate of 100 mV/s on a BAS Controlled Growth Mercury Electrode linked to a BAS100B system tower stand.

3. Results and discussion 3.1. H4 EDTA, ED and H5 DTPA Metal complexation was investigated for the hexadentate polyaminocarboxylate agents H4 EDTA, ED and H5 DTPA, and Cd2+ , Cu2+ , Pb2+ and Zn2+ . The logarithms of the overall formation constants (log Kf ) for these species are given in Table 1. These complex stability constants were determined by plotting the change in the reduction potential ( E) against solution pH. The plot follows directly from the modication of the Lingane equation: E= RT [ML] 2.303x ln pH + nF [M][LHx ] n

Table 1 The log Kf values for H4 EDTA, ED and H5 DTPA with Cu2+ , Pb2+ , Zn2+ and Cd2+a M+ H4 EDTA Observed Cu Pb Cd Zn
a b

ED Reportedb 18.80 17.90 16.50 16.50 [11] [11] [11] [11] Observed 20.10 8.60 12.16 12.45 Reportedb 20.03 5.05 12.09 13.52 [11] [12] [11] [11]

H5 DTPA Observed 20.38 18.90 17.85 18.61 Reportedb 21.00 18.60 19.00 18.60 [11] [11] [11] [11]

18.76 18.01 16.42 16.52 T = 25 C, I = 0.1 M. Observed by potentiometry.

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Fig. 2. Cyclic voltammogram of Cu2+ H4 EDTA at pH 10.3 (0.1 M, 25 C, 50 mV/s).

Fig. 3. Cyclic voltammogram of Cu2+ H4 EDTA at pH 9.3 (0.1 M, 25 C, 50 mV/s).

On rearranging the following equation is obtained: ln K = nF 2.303x pH RT n E

where K = [ML]/[M][LHx ]. Changes in the gradient of such plots correspond to a log K value for the complex and can be read directly off the graph. A similar approach relating to a modied Lingane equation has been followed by Cukrowski et al. in the polarographic determination of formation curves for complexes between N,N,N ,N -tetremethylethylenediamine and Pb(II) [13] and Cd(II) [14] at a xed ligand to metal ratio and varied pH, and complexation of Pb(II) by ED [12]. Shown in Figs. 2 and 3 are the cyclic voltammograms of the Cu2+ H4 EDTA complex at pH 10.3 and 9.3, respectively. The shift towards a more positive potential with decreasing pH is clearly evident when comparing the gures (544 mV for Cu2+ H4 EDTA at pH 10.3 and 300 mV at pH 9.3), and provides the basis for our complex stability determinations. An example plot of E against pH is shown later in the speciation of H4 EDDS. Clearly, voltammetric analysis of the formation of complexes between H4 EDTA and the selected transition metals results in formation constants similar to those obtained using potentiometric analysis methods, indicating the viability of voltammetric determination of complex formation constants. Similar agreement occurs for the formation constants for complexes

between these metal ions and ED and H5 DTPA, with the exception of the Pb(II)ED complex. The anomalous behaviour of the Pb(II)ED complex is ascribed to the possible formation of Pb(OH)2 at higher solution pH, due in part to the relatively large ionic radius as well as the electronegativity of the Pb2+ ion. A value of log K1 = 5.04 at T = 25 C and I = 0.1 M has been reported for the Pb(II)ED complex at a glass electrode using potentiometric analysis [15], where some of the difculties in studying Pb(II) complexes with amines were highlighted and as such will not be discussed here. 3.2. H4 EDDS Figs. 4 and 5 show the cyclic voltammograms of H4 EDDS at pH 10.04 and 9.30, respectively. According to modelled speciation data (Fig. 6) 1 at pH 10 the predominant form of H4 EDDS is EDDS4 . Thus, in Fig. 4, the peaks observed at 98.75 and 42.50 mV may be assigned to HEDDS3 and EDDS4 , respectively. It is also evident from Figs. 4 and 5 that as the pH is decreased the proportion of EDDS4 gives way to produce HEDDS3 . Also, as
1 The speciation data for H EDDS was obtained using the Joint 4 Expert Speciation System (JESS) speciation program, and predicts the percentage distribution of the various forms of the ligands at different pH values based upon input stability constants contained in a thermodynamic database [1618].

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Fig. 4. Cyclic voltammogram of H4 EDDS at pH 10.04 (0.1 M, 20 C, 100 mV/s).

Fig. 5. Cyclic voltammogram of H4 EDDS at pH 9.30 (0.1 M, 20 C, 100 mV/s).

the pH decreases, so too do the reduction potentials of the species; this is exemplied by the shift in the reduction potential of EDDS4 from 42.5 mV at pH 10.04 to 32.9 mV at pH 9.30. The ratio of the reduction currents of EDDS4 and HEDDS3 at pH 10.04 should reect the speciation of these two species, where the ratio EDDS4 :HEDDS3 is calculated to be 63 and 37% for EDDS4 and HEDDS3 , respectively. Speciation data modelled using JESS predicts that, at pH 10, EDDS4 and HEDDS3 are present in 62 and 38%, respectively, which is a very good approximation of the values determined experimentally by cyclic voltammetry. The ligand protonation constants (log Kp ) were calculated by plotting the change in potential ( Ep ) against pH, with the log Kp values for H4 EDDS corresponding to the pH values where changes in the gradient of the graph are observed (a similar approach was used to evaluate the complex stability constants for the metalligand complexes displayed in Table 1). For log Kp1 , which corresponds to the protonation of EDDS4 , i.e. EDDS4 + H+ HEDDS3 , the pH was adjusted from an initial value of 10.10 down to 9.20 by the addition of dilute HNO3 solution to a 1 mM EDDS solution prepared with pH 10 ammonia buffer solution (Fig. 7). The remaining log Kp values for H4 EDDS, viz. log Kp2 , log Kp3 and log Kp4 , which correspond to protonation of HEDDS3 , H2 EDDS2 , H3 EDDS , respectively, were determined in an analogous fashion, by further decreasing the pH of the solution by addition of dilute HNO3 and recording the corresponding cyclic voltammograms. From the data plotted the following log Kp values are obtained for H4 EDDS (log Kp values obtained by potentiometry at T = 20 C and ionic strength, I = 0.1 M are shown in parentheses) [19]: log Kp1 = 9.70(10.13), log Kp3 = 3.92(3.85), and log Kp2 = 7.01(6.93), log Kp4 = 3.03(3.00) (i = 14)

log Kpi = 23.80(23.91)

Fig. 6. Speciation prole of H4 EDDS.

As was the case with the comparison between H4 EDTA, ED and H5 DTPA using voltammetry versus potentiometry, the log Kp values for H4 EDDS as found using voltammetry are in good agreement with those obtained potentiometrically, further high-

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Fig. 7. Plot of

Ep vs. pH for determination of log Kp1 in pH 10 buffer (I = 0.1 M and T = 20 C).

lighting the utility of cyclic voltammetry as a means for collecting stability data. In the case of log Kp1 , it might seem that there is a signicant deviation between the protonation constants determined potentiometrically and those determined using cyclic voltammetry. However, the value for log Kp1 still compares extremely well with the value of 9.82 obtained by potentiometry at T = 25 C and I = 0.1 M, and which is included as a constant in the JESS thermodynamic database for determining the speciation of H4 EDDS.

ions, as well as other metalligand complexes in the future.

Acknowledgements The authors would like to thank the National Research Foundation (NRF), the Electricity Supply Commision (ESCOM) (for LEK) and the United Masonic Education Fund for Central South Africa (for MP) for nancial support, and also S. Woolley and M. Brewer of Associated Octel Co. Ltd. (UK) for providing (S,S)-ethylenediamine-N,N -disuccinic acid. A special thanks must also go to Paul Winston Jones of the University of Wales, Cardiff, for generation of speciation diagrams. References
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4. Conclusion A comparison of voltammetry with potentiometry reveals that very similar formation constants are obtained in both cases with complexes between H4 EDTA, ED and H5 DTPA, and the metal ions studied, although an exception is noted for the Pb(II)ED complex. Similarly, speciation of H4 EDDS using voltammetric analysis corresponds very well with the analogous values obtained using potentiometric methods of analysis, thereby showing that cyclic voltammetry does indeed afford a facile, reliable and convenient route towards the determination of complex stability constants. Having, thus, re-established the viability of cyclic voltammetry for determining complex stability constants we will now utilise this approach to measure the stability constants of complexes between H4 EDDS and selected transition- and heavy-metal

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