In the Laboratory
A Cyclic Voltammetry Experiment Illustrating Redox W
Potentials, Equilibrium Constants and Substitution
Reactions in Coordination Chemistry
Henrique E. Toma,* Koiti Araki, and Sergio Dovidauskas
Instituto de Química, Universidade de São Paulo, C. Postal 26077, CEP 05599-970 São Paulo, SP, Brazil;
*henetoma@iq.usp.br
Cyclic voltammetry (CV) is a versatile electrochemical
technique, particularly useful in the study of coordination
compounds, whose redox potentials are sensitive to the nature
of the coordinated ligands. Consequently, ligand substitution
or linkage isomerization reactions can readily be monitored
by the shift of the oxidation–reduction waves as well as by the
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change in the current intensities associated with each species.
In this work we report an experiment illustrating the
dramatic change in the bond properties of the Ru(EDTA)
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ion as a function of the oxidation state and the fast equi-
librium dynamics in the [RuIII(EDTA)(H2O)]
/dimethyl
sulfoxide (DMSO) system in aqueous solution. The starting
[RuIII(EDTA)(H2O)]
complex is unusually labile and under-
goes substitution reactions via an associative mechanism (1).
On the other hand, DMSO is a typical ambidentate ligand
that binds Ru(II) ions preferentially via the S atom, as a
consequence of strong dπ–pπ back-bonding interactions (2).
However, DMSO can coordinate to Ru(III) ions through
either the S or the O atoms, allowing the occurrence of
linkage isomers (2–4). In this way, this system is particularly
rich for teaching purposes illustrating important topics such
as redox potentials, free-energy cycles, substitution reactions,
and determination of equilibrium constants by a simple cyclic
voltammetry experiment. The theoretical background of this
technique has been omitted because it has already been
published in this Journal (5–7).
Experimental Section
Reagents
The [RuIII(HEDTA)(H2O)]3H2O complex was pre-
pared by a modification of the published procedure (8), by
treating 16 g (50 mmol) of ruthenium trichloride hydrate
(Aldrich) with 8 mL of hydrochloric acid (6 mol dm
3), in a
hood, and evaporating the mixture almost to dryness on a
water bath. Then about 10 mL of deionized water was added
and the procedure was repeated. The resulting brown sticky
residue was dissolved in 30 mL of water, and 17 g (53 mmol)
of H4EDTA suspended in water was carefully added. The
mixture was heated almost to dryness on a water bath and the
residue was dissolved in water. This procedure was repeated
seven more times to get a satisfactory yield of the desired
EDTA complex from the inert starting Ru(III)(chloro) complex.
The final residue was dissolved in 70 mL of 6 mol dm
3 HCl
and kept overnight in the refrigerator. The yellow precipitate of
H[RuCl2(H2EDTA)]5H2O was collected on a filter and
washed first with cold 1:1 ethanol–water and finally with 1:1
ethanol–diethyl ether mixture. The solid was dissolved in
20 mL of water and the pH was adjusted to 1.6 with NaOH.
Ethanol (10 mL) was carefully added and the solution was
refrigerated. The product, [RuIII(HEDTA)(H2O)]3H2O,
JChemEd.chem.wisc.edu • Vol. 77 No. 10 October 2000 • Journal of Chemical Education
crystallized as fine yellow needles; it was collected on a filter
and dried under vacuum overnight. Yield 9.2 g (33%).
Sodium trifluoroacetate, NaTFA, was purchased from
Aldrich or prepared in situ by the neutralization of
CF 3COOH with NaOH solution. Dimethyl sulfoxide
(HPLC grade) was purchased from Aldrich.
Apparatus
The cyclic voltammograms were obtained with an
EG&G/PAR model 283 potentiostat, using a conventional
three-electrode cell (5–7) consisting of a glassy carbon
working electrode (A = 0.23 cm2), Ag/AgCl (KCl 1.0 mol
dm
3) reference electrode, and a coiled platinum wire as
auxiliary electrode. The measurements were carried out in
an aqueous 0.25 mol dm
3 NaTFA solution containing 0.05
mol dm
3 acetate buffer (pH 4.5), at room temperature. The
stock 5.0 × 10
3 mol dm
3 [RuIII(EDTA)H2O]
solution was
prepared by dissolving the solid in this electrolyte solution.
Notice that the pendant carboxylic acid group in the solid
ruthenium complex dissociates when dissolved in pH 4.5
acetate buffer (1).
Procedure
Cyclic Voltammetry of [RuIII(EDTA)H2O]

After bubbling argon or nitrogen gas for five minutes
into 1.0 mL of the electrolyte solution, a cyclic voltammo-
gram is registered (v = 50 mV s
1 is suggested) in the 1.00 to

0.70 V (vs SHE) range, starting at 1.00 V. Then 0.25, 0.40,
and 0.80 mL of a 5 × 10
3 mol dm
3 [RuIII(EDTA)(H2O)]

solution are sequentially added and the corresponding cyclic
voltammograms are recorded, to evaluate the effect of the
concentration on the electrochemical response. The effect of
the scan rate can be evaluated by recording the cyclic
voltammograms at v = 100, 50, and 20 mV s
1.
Cyclic Voltammetry of [RuIII/II(EDTA)(DMSO)]
/2

Five microliters of DMSO is then added to the
[RuIII(EDTA)(H2O)]
solution obtained above and a voltam-
mogram is recorded at v = 200 mV s
1, in the 1.00 to
0.70 V
range, starting at 1.00 V. This procedure is repeated after
successive addition of 65 and 320 µL of DMSO into the
above solution.
Hazards
No chemicals or procedures used by the students present
any significant hazards, but protective gloves should be worn
when handling DMSO because it is absorbed rapidly through
the skin, causes skin irritation, and can carry solutes through
the skin. The synthesis of [RuIII(HEDTA)(H2O)]3H2O in-
volves corrosive substances; it must be carried out in a fume
hood and the appropriate protective garments must be worn.
1351
 In the Laboratory

reverse scan is quite different. The anodic wave corresponding

to the oxidation of the [RuII(EDTA)(H2O)]2
(0.02 V) almost
vanishes (wave “b”) and a new oxidation wave appears at EPA =
0.56 V (wave “c”). This wave can be assigned to the
[RuII(EDTA)(κS-DMSO)]2
complex, since this species is
strongly stabilized by π-backbonding interactions (2). There-
fore, in the reverse scan, the concentration of the
[RuII(EDTA)(H2O)]2
species is depleted by its rapid con-
version into [RuII(EDTA)(κS-DMSO)]2
.
By increasing the concentration of DMSO, it is possible
to detect the formation of the [RuIII(EDTA)(κS-DMSO)]

species by the rise of a cathodic wave at 0.49 V (wave “d”), in
parallel to the decay of the waves “a” and “b”. The electrochemi-
cal response remains practically the same in the reverse scan,
indicating that the [RuII(EDTA)(κS-DMSO)]2
complex is
almost quantitatively formed even in the presence of a small
stoichiometric excess of DMSO.
From the voltammograms obtained in the presence of
DMSO, it is possible to determine the formation constant
of the [RuIII(EDTA)(κS-DMSO)]
complex:
K III
[RuIII(EDTA)(H2O)]
+ DMSO [RuIII(EDTA)(κS-DMSO)]

RuIII EDTA κS
DMSO

K III =


RuIII EDTA H2O DMSO
since
Figure 1. Cyclic voltammograms of [Ru(EDTA)(H2O)]
(50 mV/s). [Rutotal] = [RuII(EDTA)(κS-DMSO)
] =
A: At three concentrations. B: After addition of 5 µL (0.029 mol
dm
3), 65 µL (0.39 mol dm
3) and 320 µL (1.94 mol dm
3) of DMSO.
[RuIII(EDTA)(κS-DMSO)
] + [RuIII(EDTA)(H2O)
]
Curves a and b and curves d and c represent the reduction and Considering that the wave at E 0 = 0.53 V is typically revers-
oxidation waves of [RuIII/II(EDTA)(H2O)] and [RuIII/II(EDTA)(κS-DMSO)] ible, we have
redox pairs, respectively.
[RuII(EDTA)(κS-DMSO)
] ∝ i PA
[RuIII(EDTA)(κS-DMSO)
] ∝ i PC
Results and Discussion
[RuIII(EDTA)(H2O)
] ∝ (i PA – i PC)
Figure 1A shows some typically reversible cyclic volt-
ammograms obtained for the starting [RuIII(EDTA)(H2O)]
Therefore
complex. They can be used to illustrate the measurements of i PA
some important parameters such as ∆EP, E 0′, i PA, and i PC , as K III =
well as to calculate the i PA/iPC ratio (2–4) and to obtain the i PA – i PC DMSO
i P vs C and i PC vs v 1/2 plots. Such information and plots are
The equilibrium constant K III = 2.0 ± 0.2 can be cal-
normally used as reversibility parameters and to evaluate the
culated from the CV at the intermediate concentration
number of electrons transferred per molecule and the diffu-
[DMSO] = 0.39 mol dm
3. The determination can be improved
sion coefficient using the Randles–Sevcik equation (eq 1) (5–
by repeating the experiment for a larger number of DMSO
7 ). In this case, the area of the electrode should be known:
concentrations.
i P = (2.69 × 105)n3/2A D1/2v 1/2C (1) From the values of K III and E 0 of the aquo, EA0, and
[Ru(EDTA)(κS-DMSO)] complexes, ES0, one can calculate the
where i P is the peak current (A), n is the number of electrons
formation constant K II = 2.7 × 109 mol
1 dm3 by solving the
involved, A is the electrode area (cm2), D is the diffusion
thermodynamic cycle below (3); that is, K II = K III e nF (∆E )/RT,
coefficient (cm2 s
1), v is the scan rate (V s
1), and C is the
where ∆E = ES0 – EA0.
concentration (mol cm
3).
In Figure 1B one can see the dramatic changes in the volt- E 0A =
0.01 V

ammograms after the addition of 5 µL of DMSO ([DMSO] = [RuΙΙΙ(EDTA)(H2O)] − + e− [RuΙΙ(EDTA)(H2O)] 2−

0.029 mol dm
3). The profile of the voltammogram obtained

DMSO
in the cathodic scan is similar (wave “a”) to that obtained in the DMSO
KΙΙΙ KΙΙ
absence of DMSO, suggesting that the formation constant
of the [RuIII(EDTA)(DMSO)]
complex is relatively small. E 0S = +0.53 V

However, the profile of the voltammogram obtained in the [RuΙΙΙ(EDTA)(κS-DMSO)] − + e− [RuΙΙ(EDTA)(κS-DMSO)] 2−

1352 Journal of Chemical Education • Vol. 77 No. 10 October 2000 • JChemEd.chem.wisc.edu


Conclusions
This experiment illustrates the ligand substitution dynam-
ics associated with the electrochemistry of quite labile species
in which the stability constants differ widely as a function of
the oxidation state of the ruthenium complex. Although the
[RuII(EDTA)(κS-DMSO)]
complex is quite stable, the forma-
tion of the corresponding [RuIII(EDTA)(κS-DMSO)]
species
from [RuIII(EDTA)(H2O)]
requires a very large excess of
DMSO. The higher stability of the [RuII(EDTA)(κS-DMSO)]

and its more positive redox potential can be interpreted in terms
of the strong backbonding interactions in that species. Because
of the large difference between the formation constants of the
[Ru(EDTA)(DMSO)] complex in the Ru(II) and Ru(III) oxi-
dation states and the fast ligand substitution reactions involving
the Ru(II) and Ru(III) species, one can consider the Ru(EDTA)
species as a shuttle for the DMSO ligand in which the control
for loading or releasing is carried out electrochemically.
The cyclic voltammogram obtained in the presence of a
high excess of DMSO (Fig. 1B, [DMSO] = 1.94 mol dm
3),
indicates that the [RuIII(EDTA)(κS-DMSO)]
isomer is the
dominant species. The O-bound isomer [RuIII(EDTA)(κO-
DMSO)]
should have a redox potential similar to that of the
[RuIII(EDTA)(H2O)]
species. This assertion is based on the
comparison of the redox potentials of the analogous O- and
S-bound [Ru(NH3)5(DMSO)] complexes (3) and the ligand
electrochemical parameters EL (9, 10) for the S- and O-bound
DMSO (0.47 and 0.14 V, respectively) and water (0.04 V)
ligands. The CV in a concentrated DMSO solution (2), for
example 9 M, does not differ appreciably from that shown
in Figure 1B, obtained at 1.94 mol dm
3 of DMSO. In this
case, the estimated value for the S→O linkage isomerization
constant in the [RuIII(EDTA)(DMSO)]
complex, based
on the cathodic peak currents at
0.04 and 0.49 V, was only
0.03 mol
1 dm3. For this reason, in aqueous solution, the
[RuIII(EDTA)(κO-DMSO)]
complex is completely converted
into the [RuIII(EDTA)(H2O)]
species.
JChemEd.chem.wisc.edu • Vol. 77 No. 10 October 2000 • Journal of Chemical Education
In the Laboratory
This experiment has been carried out successfully in a
Coordination Chemistry course, by 60 undergraduate students
working in groups of two or three, with the instructor supply-
ing the [Ru(HEDTA)(H2O)]3H2O complex. The experiment
must be preceded by an explanation of the principles of cyclic
voltammetry, so that the students can properly interpret the
results. A discussion of about 1.5 h just after the experimental
section is recommended to help the students understand the
relationships between the electrochemical results and the ther-
modynamic parameters that have been sought.
Acknowledgments
We thank the Brazilian agencies FAPESP, CNPq, and
CAPES for their financial support.
W
Supplemental Material
Supplemental material for this article is available in this
issue of JCE Online.
Literature Cited
1. Matsubara, T.; Creutz, C. Inorg. Chem. 1979, 18, 1956.
2. Toma, H. E.; Araki, K. J. Coord. Chem. 1991, 24, 1.
3. Yeh, A.; Scott, N.; Taube, H. Inorg. Chem. 1982, 21, 2542.
4. Toma, H. E.; Alexiou, A. D. P. Electrochim. Acta 1993, 38, 975.
5. Evans, D. H.; O’Connell, K. M.; Petersen, R. A.; Kelly, M. J.
J. Chem. Educ. 1983, 60, 290.
6. Mabbott, G. A. J. Chem. Educ. 1983, 60, 697.
7. Kissinger, P. T.; Heineman, W. R. J. Chem. Educ. 1983, 60,
702.
8. Mukaida, M.; Okuno, H.; Ishimori, T. Nippon Kagaku Zasshi
1965, 86, 589.
9. Lever, A. B. P. Inorg. Chem. 1990, 29, 1271.
10. Alexiou, A. D. P.; Toma, H. E. J. Chem. Res. (Synop.) 1993,
464.
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