165

J. Electroanal. Chem., 221 (1987) 165-174

Elsevier Sequoia S.A., Latmume - Printed in The Netherlands

TImJ!ILEcrRocHEMI STRY OF FJZRROCENE IN NON-AQUEOUS

SOLVENTS

ALFRED0 J. ZARA, SERGIO S. MACHADO and LUIS OTAVIO S. BULH&.S

Departamento de Qulmica, Universidade Feakral de S& Carlos, Caixa Post4 67613.560~Scio Carlos,
&io Paul0 (Brazil)
ASSIS VICENTE BENEDETTI
Institute de Quimica de Araraquara, UNESP, Caixa Postal, I74-148W-Araraquara, S& Paul0 (Brazil)

TIBOR RABOCICAI

Institute de Qulmica & Universihde de MO Paulo, Caixa Postal, 20780-O.I498&io Paulo,

SZo Paul0 (Brazil)

(Received 7th June 1985; in revised form 1st October 1986)

ABSTRACT

The electrochemical oxidation of ferrocene on Pt in dimethylfo rmamide, ethanol, propylene carbonate

and their aqueous solutions was studied at 25O C. The concentration of the supporting electrolyte,
NaClO,, was varied from 0.1 to 0.5 M. The results show that the electrode process may be described as a
quasi-reversible one-electron charge transfer, followed by slow decomposition of the oxidized species.

INT’RODUCTION

The electrochemical behaviour of ferrocene has been investigated in several

media [l-5] and chemically modified platinum-ferrocene electrodes have been
employed in acetonitrile [6] and in sulpholane [7]. Little is known, however, about
the electrochemical oxidation of ferrocene in propylene carbonate (PC), or even in
ethanol (EtOH), while several authors disagree on the interpretation of the overall
electrode process when the solvent is dimethylformamide (DMF).
There is also disagreement on how the oxidation product behaves: whether or not
it decomposes in different media. The influence of adding water, on the oxidation of
ferrocene was investigated in methanol only by Duschek and Gutmann [S], who
observed a shift of approximately 40 mV in the El,* values, when the water content
was increased from 1 to 5%. Recently [9], it was observed that the E” of ferrocene
decreases by 100 mV as the water content of an acetone + water mixture is
increased from 60 to 95 wt%.

0022-0728/87/$03.50 8 1987 Elsevier Sequoia S.A.

166

The present paper deals with the potentiodynamic behaviour of ferrocene in pure
DMF, EtOH and PC and in their aqueous solutions, containing sodium perchlorate
as the supporting electrolyte. A platinum electrode was used as the working
electrode and the temperature was maintained at 25 o C.

Ferrocene (FeCb) (Fhtka) was purified by sublimation at llO°C and low

pressure. Sodium perchlorate (Merck, p.a.), recrystallized in ethanol (p.a.) and dried
at 110 o C for 24 h, was used as the supporting electrolyte. Silver nitrate (Carlo Erba,
p.a.) was used without any purification. DMF was purified following Brummer’s
procedure [lo]. Technical grade EtOH was treated as described elsewhere [II].
Purification of PC (Merck) has been described previously [12]. The water content of
the purified solvent (DMF: 0.06% v/v; EtOH: 1.9% v/v and PC: 0.08% v/v) was
determined by the Karl Fischer method.
The cyclic voltammetric investigations were performed by means of a PAR model
173 ~t~tios~t/~v~~~t, plug-in model 376 and model 175 universal pro-
grammer. A PAR model 4102 signal recorder was used to record the cyclic
voltammograms for potential scan rates higher than 0.2 V s-t. A three-compartment
electrochemical cell was employed with a flat commercial platinum disk (Beckmann;
surface area 0.18 cd) working electrode and a platinum wire auxiliary electrode.
The working electrode was pretreated by successive triangular potential sweeps in
the solvent containing sodium perchlorate. Ag/AgNQ, (10 mM), 0.5 M NaClO,,
DMF; Ag/AgNO, (5 mM), 0.1 M NaGlO,, EtOH and Ag/AgClO, (20 mM), 0.1
M NaC10,, PC electrodes were employed as the reference in DMF, EtOH and PC,
respectively. They were prepared as described in refs. 11-13. The ohmic drop was
compensated following the procedure of Martin et al. 1141.
The temperature of the cell was maintained at 25 *C using a MLW-U15 thermo-
stat. Ah the solutions were deaerated by bubb~g with high purity nitrogen,
pre-saturated with the blank solution at 25O C. The cyclic voltammograms were
recorded in the ranges -0.30 to 0.50 V vs. Ag/Ag” (DMF); -0.70 to 0.09 V vs.
Ag/Ag+ (EtOH) and -0.65 to 0.12 V vs. Ag/Ag’ (PC) for DMF, EtOH and PC
solutions, respectively. No anodic or cathodic peaks were observed in the absence of
ferrocene in these Potential ranges.
In calculating the ratio between the cathodic current peak and the anodic current
peak a correction was made for the capacitative current. The concentration of the
complex was corrected for the addition of water. After each addition of water, the
cyclic voltammograms were recorded when the temperature returned to 25 0 C.

RESULTS

The results obtained for the oxidation of ferrocene in pure DMF, EtOH and PC
and in their aqueous solutions are assembled in Table 1. The table shows the values
 167

of the anodic current peak (i;), the ii/ii ratio, the current function i~u”-“2c-’
(where c is the molar concentration of ferrocene) as a function of the potential
sweep rate (u) the anodic peak potential ( J?Z;),the cathodic peak potential (E,C) and
the difference AEp between E; and Ei, for different potential sweep rates.

DISCUSSION

Table 1 shows that the peak current ratio, ii/i;, is close to unity, never being
lower than 0.91, under all the experimental conditions, when the solvent is DMF. A
slight increase in the peak current ratio and a slight decrease in the current function
i~v-‘/2c-’ with increasing potential scan rate is observed for solutions with a water
content lower than 2% (v/v). For higher water concentrations, both the current ratio
and the current function remain constant within experimental error.
The ii/i; ratio increases slightly with u for ethanolic solutions, mainly with the
higher water content, approaching unity. The current function tends to decrease
with the potential scan rate.
In propylene carbonate and its aqueous solutions, iE/i: is close to unity and
tends to decrease with increasing u. The current function remains constant within
experimental error.
The anodic peak current varies linearly with the ferrocene concentration for all
the solvents studied.
These results, considering the time scale of the experiments and taking into
account the criteria of Nicholson and Shain [15], suggest that very slow decomposi-
tion of the oxidized species (FeCpz) occurs in all the ethanolic solutions. In these
solutions, a second oxidation peak was observed at a positive potential. After
controlled potential electrolysis at -0.065 V vs. Ag/AgNO, (5 mM), NaClO, (0.1
M), EtOH, 2% H,O (v/v), a green product was obtained. The melting point of this
product was higher than that of ferrocene. Probably, the second oxidation peak is
associated with a ligand oxidation reaction in the FeCp: complex, generating a
product that decomposes rapidly. In Fig. 1 the cyclic voltammogram of ferrocene in
ethanol containing 22% (v/v) of water is shown.
Very slow decomposition of ferrocene also occurs in DMF solutions containing
up to 2% of water (v/v), as may be inferred from the current function increase with
potential scan rate. In the other DMF solutions and in the PC solutions, no
evidence was found of chemical reactions. There are several reports in the literature
of a very slow decomposition reaction of the oxidized species in CH,CN, EtOH,
DMSO and DMF [l], in water at pH > 4 and in proton acceptor aprotic solvents
such as acetone and DMF [16] and in methanol [17]. The idea of the instability of
the FeCpl ion in several media is reinforced by the ESR studies of Prins et al. [18].
These authors observed decomposition of the cation, for example, in the presence of
Cl- and Br-, producing ferrocene and FeX;, and in the presence of strong donor
solvents (S) such as DMSO and DMF following the equation:
2FeCp:+6S+FeCp2+Fe$++2Cp
TABLE 1

Electrochemistry of ferrwene on platinum at 25 ’ C

(A) Dimethylformamide [ E( f 2 mV) vs. Ag/AgNO,(lO mM), 0.5 M NaGlO.,, DMF]

c/mM % H,O u/v s-1 lo6 +‘A i;/ii p”-‘&-‘/ - E,P/mV - Ei/mV AE,/mV
c/M
NaClO, Fecp, (VP) A s V-’ mole1 1

0.500 2.00 0.06 0.020 47 0.91 0.166 -7 52 59

0.050 72 0.92 0.161 -9 52 61
0.075 90 0.91 0.163 -9 52 61
0.100 101 0.93 0.160 -10 51 61
0.200 143 0.94 0.160 -10 51 61
0.300 170 0.97 0.155 -11 51 62
0.500 221 0.95 0.156 -16 53 69
0.750 270 0.97 0.156 -17 55 72
1.000 312 0.96 0.156 -20 55 75
2.00 428 0.99 0.151 -22 60 82
5.00 680 0.98 0.152 -25 65 90
0.492 1.97 1.70 0.020 48 0.93 0.154 -11 52 63
0.050 71 0.95 0.160 -11 52 63
0.075 80 0.93 0.148 -10 52 62
0.100 100 0.96 0.160 -11 53 64
0.200 137 0.95 0.155 -10 54 64
0.300 166 0.98 0.154 -9 54 63
0.500 214 0.98 0.153 -12 58 70
0.750 260 0.98 0.152 -12 59 71
l.OOO 301 1.00 0.153 -11 60 73
2.000 415 1.00 0.149 -17 64 81
0.476 1.90 4.82 0.020 40 0.99 0.147 3 -64 61
0.050 63 0.96 0.148 1 -64 63
0.075 75 0.98 0.144 0 -64 64
0.100 87 0.98 0.144 1 -62 61
0.200 125 0.98 0.147 1 -66 65
0.300 153 0.99 0.147 2 -66 64
0.500 197 0.98 0.146 0 -66 66
0.750 238 0.99 0.144 0 -70 70
1.00 267 1.02 0.141 0 -72 72
2.00 383 1.00 0.142 -4 -75 79
5.00 615 0.98 0.145 -10 -76 86
0.462 1.85 7.75 0.050 58 0.96 0.140 12 -72 60
0.075 72 0.96 0.141 11 -73 62
 0.100 84 0.95 0.142 13 -75 62
0.200 116 0.97 0.140 13 -77 64
0.300 137 0.99 0.135 12 -78 66
0.500 180 0.98 0.138 12 -80 68
0.750 224 0.97 0.140 11 -80 69
1.00 256 0.97 0.138 10 -81 71
2.00 353 1.00 0.135 6 -85 79
5.00 551 1.00 0.133 0 -94 94
0.448 1.79 10.50 0.020 32 0.95 0.128 21 80 59
0.050 50 0.97 0.124 19 80 61
0.075 62 0.95 0.126 20 81 61
0.100 75 0.98 0.133 26 89 63
0.200 107 0.99 0.134 25 88 63
0.300 131 0.98 0.133 22 87 65
0.500 169 0.99 0.133 22 87 65
0.75 206 0.98 0.133 22 90 68
1.0 230 1.00 0.128 20 92 72
2.0 338 0.96 0.133 17 92 75
5.0 548 0.92 0.137 9 97 89
0.429 1.71 14.34 0.050 48 0.98 0.125 33 92 59
0.075 58 0.97 0.124 33 93 60
0.100 67 0.98 0.124 31 92 61
0.200 96 0.99 0.125 36 100 64
0.300 117 0.98 0.125 37 98 61
0.500 152 0.98 0.126 34 100 66
0.750 186 0.97 0.126 34 101 67
1.00 211 1.01 0.123 34 102 68
2.00 297 0.98 0.123 27 103 76
5.00 472 0.98 0.123 24 112 88
0.395 1.58 21.1 0.020 26 0.98 0.114 53 111 58
0.050 41 0.98 0.115 51 112 61
0.075 50 0.98 0.116 50 111 61
0.100 59 0.98 0.118 55 116 61
0.200 83 0.98 0.117 56 117 61
0.300 100 0.99 0.116 55 117 62
0.500 132 0.96 0.118 52 119 67
0.750 161 0.98 0.117 51 118 67
1.00 181 0.99 0.115 50 121 71
2.00 262 0.99 0.117 45 122 77 s
5.00 421 0.94 0.119 39 128 89

(to be continued)
TABLE 1 (continued)

(B) Ethanol [E f 2 mV vs. Ag/AgNO, (5 mM), 0.1 M NaClO,, EtOH]3

c/M c/mM I H,O v/v s-1 lo6 ii/A ii/i; i’v-“2c-‘/ - E,^/mV - Ei/mV AEJmV
NaC10, Fecp2 (v/v) A’s V-’ mol-’ 1

0.200 3.00 2.0 0.020 17 0.94 0.182 78 136 58

0.050 112 0.95 0.167 79 137 58
0.100 157 0.96 0.165 77 136 59
0.200 213 0.97 0.159 77 137 60
0.500 337 0.97 0.159 75 135 60
0.198 2.91 3.0 0.020 73 0.95 0.174 85 144 59
0.050 110 0.97 0.164 81 147 60
0.100 154 0.98 0.164 87 147 60
0.200 209 0.98 0.157 88 148 60
0.500 336 0.98 0.157 89 150 61
0.1% 2.94 4.0 0.020 72 0.94 0.173 89 147 58
0.050 106 0.95 0.161 92 149 58
0.100 150 0.95 0.161 92 152 60
0.200 206 0.96 0.157 94 154 60
0.500 322 0.97 0.155 94 154 60
0.194 2.86 7.0 0.020 68 0.90 0.168 107 165 58
0.050 98 0.91 0.153 109 167 58
0.100 138 0.95 0.153 109 168 59
0.200 1% 0.96 0.153 110 168 58
0.500 307 0.96 0.152 110 169 59
0.192 2.73 12.0 0.020 58 0.88 0.150 125 184 59
0.050 83 0.90 0.136 126 185 59
0.100 119 0.91 0.138 128 187 59
0.200 168 0.94 0.138 128 188 60
0.500 265 0.96 0.137 128 188 60
(C) Propylene carbonate [E i2 mV vs. Ag/AgClO, (20 mM), 0.1 M NaCIO,, PC]

c/mM X H,O U/V s-1 lo6 ii/A i’,/iG ,a “-l&-l/ - E,B/mV - Ec/mV AE,/mV
c/M
NaCIO, ‘+-CP, (v/v) APsVmol-’ 1

0.500 1.43 0.2 0.020 17 0.96 0.084 0.177 0.243 66

0.030 21 0.96 0.085 0.177 0.243 66
0.050 27 0.96 0.084 0.177 0.243 66
0.075 32 0.95 0.082 0.177 0.243 66
0.100 37 0.95 0.082 0.177 0.243 66
0.150 45 0.96 0.081 0.177 0.245 68
0.200 52 0.95 0.081 0.177 0.245 68
0.300 64 0.94 0.082 0.176 0.248 72
0.4% 1.42 1.0 0.020 17 0.96 0.085 0.183 0.244 61
0.030 21 0.98 0.085 0.183 0.245 62
0.050 27 0.96 0.085 0.183 0.248 65
0.075 33 0.97 0.085 0.183 0.248 65
0.100 38 0.95 0.085 0.183 0.248 65
0.150 46 0.96 0.084 0.180 0.248 68
0.200 53 0.95 0.083 0.180 0.248 68
0.300 66 0.95 0.085 0.180 0.249 69
0.491 1.40 2.0 0.020 17 0.99 0.086 0.183 0.244 61
0.030 21 0.98 0.087 0.183 0.245 62
0.050 26 0.97 0.083 0.183 0.245 62
0.075 33 0.94 0.086 0.183 0.245 62
0.100 38 1.00 0.086 0.183 0.245 62
0.150 47 0.96 0.087 0.183 0.248 65
0.200 54 0.94 0.086 0.180 0.248 68
0.300 65 0.96 0.085 0.180 0.248 68
0.477 1.36 5.0 0.020 17 1.00 0.088 0.189 0.251 62
0.030 21 1.00 0.089 0.189 0.251 62
0.050 27 0.98 0.089 0.189 0.251 62
0.075 34 0.96 0.091 0.189 0.251 62
0.100 39 0.97 0.091 0.189 0.251 62
0.150 47 0.96 0.089 0.189 0.254 65
0.200 54 0.96 0.089 0.187 0.254 67
0.300 66 0.96 0.089 0.187 0.254 67 z
172

,
-0.70 -0.20 + 0.30 l 0.80
E/V(vs. Ag/Ag+)

Fig. 1. Cyclic voltammogram of 3.0 mM fexrocene in ethanol (22% H,O (v/v)). Scan rate = 0.1 V s-l.

The same authors verified that in weak donor solvents such as acetone, acetonitrile
and nitromethane, the FeC$ cation is stable.
Table 1 also shows that for potential scan rates up to 0.3 V s-l in DMF
solutions, the AEp values are about 60 mV, suggesting a reversible electrode process
and a one-electron charge transfer. For higher scan rates, the separation between the
anodic and cathodic peaks increases, and the electrode process is described better as
a quasi-reversible one. The value of k O, calculated following Nicholson’s procedure
[19], is equal to (0.063 f 0.006) cm s-l for potential sweep rates between 0.5 and 5.0
V s-l, in DMF with 0.06% (v/v) of water. This result is somewhat different from
the value obtained by Diggle and Parker [l] (k o = 0.033 cm s-l at 1 V s-l). The k o
values are approximately constant for all the DMF + H,O mixtures studied (k o =
(0.062 f 0.005) cm s-l).
In ethanolic solutions, AEr has a value of about 59 f 2 mV, constant within
experimental error, under the conditions studied (u values up to 0.5 V s-l).
Therefore the charge transfer is reversible. Our results in ethanol disagree with those
obtained by Diggle and Parker [l], who suggest that the charge transfer is quasi-re-
versible (k’ = 0.016 cm s-l). The high values of AEp obtained by those authors are
probably associated with ohmic drop.
In propylene carbonate solutions containing 0.2% (v/v) of water, AEr is equal to
66 mV for potential scan rates up to 0.1 V s-i and increase for u > 0.1 V s-l. With
a 1% (v/v) water content, AEr is approximately 60 mV for u < 0.03 V s-l.
Increasing values were observed for higher scan rates. In the case of the other
PC + H,O mixtures, the AEr value remains almost 60 mV for potential scan rates
up to 0.01 v s-l. Under conditions in which AEr is higher than 60 mV and
increases with u, the electrode process is described better as quasi-reversible and the
 173

values of k” can be estimated. For example, the value of (0.023 f 0.005) cm s-l is
found for the rate constant when the solution contains 0.2% (v/v) of water. The
value of k o increases slightly as the water content in PC increases. For solutions
with 5% (v/v) of water, k” = (0.039 f 0.005) cm s-l was obtained.
Cabon et al. [2] observed an 88 mV difference between the anodic and cathodic
peak potentials for the FeCpJFeCp: couple in ethylene carbonate, with 0.1 M
LiClO, as the supporting electrolyte at 40°C. Courtot-Coupez and L’Her [20]
report a difference of 100 mV in PC and 0.1 M LiClO,. Andruzzi and Trazza [3],
using ac and dc polarography, found that the redox reaction for the FeCp,/FeCpG
couple is a reversible process in acetonitrile and DMF + 0.1 M TFXP. The
deviation of i, vs. I_?/’ and bEi,/ at high frequencies from the values correspond-
ing to a reversible process was attributed, by those authors, to an uncompensated
ohmic drop or, alternatively, to a deviation from reversible behaviour. Chronopo-
tentiometric studies of the oxidation of ferrocene in acetonitrile +0.2 M LiClO,
suggest that the electrode process is described better as approximately reversible. In
the AlCl, + ethylpyridinum bromide (2 : 1) fused salt system, the oxidation of
ferrocene is reversible at sweep rates from 0.1 to 100 V s-l, without any kinetic
complications [5].
It may be concluded, therefore, that the addition of water does not give rise to
great changes of the electrode process of ferrocene in the three solvents studied. In
general, AEr does not vary with the water content if the sweep rate is maintained
constant.
The addition of water affects mainly the peak potentials. As Table 1 shows, the
anodic peak potentials shift to less positive values in all of the solvents, with
increasing water content. In DMF, the shift is about 60 mV for a change of
= O.l-21% (v/v) in water concentration; in EtOH, the anodic peak potential shifts
to 50 mV when water increases from 2 to 12% (v/v). In PC, a 12 mV shift is
observed when the concentration of water increases from 0.2 to 5% (v/v). Similar
results are reported in the literature for the addition of water to organic solvents
[8,9]. It is observed that the oxidation of ferrocene is easier when water is added to
the solution. Double-layer effects may also occur when the solvent is changed, and
this effect is probably responsible for the potential shift when the water content is
increased.
The diffusion coefficient of ferrocene (Dn) (estimated considering a reversible
charge transfer without kinetic complications) diminishes when water is added to
DMF and EtOH and increases when water is added to PC, as expected, since the
viscosity of the solvent + water mixture, in the absence of the supporting electrolyte,
becomes greater with the water content for DMF and EtOH, and diminishes for PC,
in the concentration ranges studied [21-231. Thus the diffusion coefficient of
ferrocene in DMF + 0.5 M NaClO, is equal to 1.1 X 10e5 cm2 s-l and with 21%
(v/v) of water it decreases to 5.7 X low6 cm2 SK’; in ethanol + 0.2 M NaClO,,
D, = 1.1 x low5 cm2 s-l and with 12% Hz0 (v/v), D, = 8.0 X lO-‘j cm2 s-‘; in
PC + 0.5 M NaClO, with 0.2% (v/v) of water, DR = 3.0 X 10e6 cm2 s-l and for 5%
of H,O, D, increases to 3.4 X 10e6 cm2 s-l.
174

ACKNOWLEDGEMENTS

The authors acknowledge Funda@o de Amparo A Pesquisa do Estado de S5o

Paul0 (A.J.Z., proc. 80/1266-9), CNPq (S.S.M., TR proc. 30.1426/79-QU.07, proc.
30.0967/83) and FINEP for financial support.

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