3

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9
Research Article
Received: 26 June 2009 Revised: 13 October 2009 Accepted: 29 October 2009 Published online in Wiley Interscience: 1 February 2010
(www.interscience.wiley.com) DOI 10.1002/pi.2774
Conformational energy fromthe oxidation
kinetics of poly(3,4-ethylenedioxythiophene)
lms
Toribio F Otero

and Mara Caballero Romero

Abstract
Electroactivepoly(3,4-ethylenedioxythiophene) perchloratelms shrinkandpackbyelectrochemical reductionat highcathodic
potentials. Any subsequent oxidation by potential step gives chronoamperograms showing a maximum. At the maxima the
electroactive oxidationreaction occurs under chemical kinetic control. Rate coefcients andactivationenergies for the reaction
can be obtained by applying chemical kinetics methodology. Both parameters present two ranges as a function of the cathodic
potential of pre-polarization that denes the initial oxidation state of conformational packing. The activation energy includes
two components: the constant chemical activation energy and the conformational packing energy that increases linearly after
reductionshrinkingpacking at risingcathodic overpotentials. This methodology opens a way to quantify the conformational
energy of polymer chains: the energy used by molecular motors constituting the actuator lms of conducting polymers.
c 2010 Society of Chemical Industry
Keywords: PEDOT; activation energy; conformational energy; kinetics; oxidation
INTRODUCTION
The electrochemistry of conducting polymers includes complex
reactions involving in particular electron and ion exchanges,
swelling/shrinking and conformational packing processes during
oxidationreduction reactions.
1,2
From that point of view the
electroactivity of conducting polymers is constituted of chemical
reactions, the polymer acting as a reactant. Devices such as
articial muscles or smart membranes are based on those
changes of lmvolume under electrochemical control.
37
Volume
changes linkedtoelectrochemical reactions indicate a progressive
and reverse variation of the intermolecular forces (polymer,
solvent, cation, anion) during the electrochemical reactions.
In a reduced poly(3,4-ethylenedioxythiophene) (PEDOT) lm,
polymerpolymer van der Waals attractive interactions between
neighbouring chains are present and give rise to a packed
structure of folded polymeric chains. At potentials more anodic
than the oxidation potential, electrons are extracted from
the chains, and positive charges (polarons) are stored at the
active centres along chains (PEDOT
n+
) with a progressive
transformation of the double bond distribution. Repulsion
forces between emerging positive charges on neighbouring
chains start to appear that provoke conformational movements
induced by double bond transformation, which generate free
volume between chains, thus allowing the entrance of balancing
counterions (A

) and solvent molecules from the solution.

815
This entrance of counterions and solvent promotes polymer
swelling (Fig. 1). During voltammetric reduction the polymer
shrinks, counterions and solvent are expelled towards the
solution and the structure closes (interchain distances become
shorter than counterion diameters) when the polymer is partially
reduced.
6,7,11,15
Polymeric reduction and conformational packing
go on at high cathodic potentials under slow conformational
kinetic control.
The electrochemical oxidationreduction of PEDOT lms in
acetonitrile (ACN) can be expressed by the reaction
[PEDOT
a+
(A

)
a
]
s
+n(A

)
org
reduced chains
+m(ACN)

[PEDOT
(n+a)+
(A

)
n+a
(ACN)
m
]
gel
oxidized chains
+(ne

)
metal
(1)
where s means solid, org means organic solution and a is the
number of positive charges on the partially reduced chain; a
is lower the higher the reduction potential or the longer the
reduction time. The main reactants are anions (A

) from the
solution and active centres (ACs) on the chains, understood as
those places along the chains able to store a positive charge
(PEDOT
+
) after oxidation.
Physical aspects of the reactionare includedinthe electrochem-
ically stimulatedconformational relaxation (ESCR) model
11,12,1416
in order to describe chronoamperometric or voltammetric re-
sponses. The model states that a PEDOT lm should shrink and
become packed on electrochemical reduction. The subsequent
oxidation by potential step starts by nucleation
11,16
of the ox-
idized material under conformational relaxation kinetic control
(increasing currents before the maximum). Once the entangled
and packed molecular structure is relaxed and open, the oxidation

Correspondence to: Toribio F Otero, Universidad Polit ecnica de Cartagena,

ETSII, Centrefor ElectrochemistryandIntelligent Materials(CEMI), PaseoAlfonso
XIII, Aulario II, 30203 Cartagena, Spain. E-mail: toribio.fotero@upct.es
Universidad Polit ecnica de Cartagena, ETSII, Centre for Electrochemistry and
Intelligent Materials (CEMI), Paseo Alfonso XIII, Aulario II, 30203 Cartagena,
Spain
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Figure 1. VoltammogramobtainedfromaPEDOTlmin0.1 mol L
1
LiClO
4
ACNsolutions, betweendifferent cathodicpotentials (as indicated), maintained
for 120 s (t
pol
is the polarization time) and the same anodic potential (800 mV) versus Ag/AgCl, at 0.1 V s
1
and 25

C, showing relaxation/swelling and

shrinking/packing processes.
of the lm is completed under diffusion kinetic control of the
counterions (decreasing currents after the maximum).
The electrochemical synthesis and electrochemical characteri-
zation of electroactive conducting polymers to produce tailored
materials include many unresolved issues.
5,9,1322
The question
here investigated is to determine whether the kinetics of the
chemical reactionof Eqn (1) is thelimitingratestepat intermediate
stages of potentiostatic oxidation, as occurs with polythiophene,
poly(3-methylthiophene) or polypyrrole.
2325
In that case the general electrochemical reaction, under kinetic
control of the chemical reaction, must t the general empirical
kinetic equations:
R = k

j
j
exp

zF
RT

= k[A

[PEDOT
+
]

(2)
where R is the reaction rate, which is a function of the product
of the reactant (j) concentrations (c),
j
being the concomitant
reaction orders, k

is the rate coefcient, is the electronic

transferencecoefcient, is theoxidationoverpotential, [A

] is the
salt concentration of the counterions in solution, is the reaction
order related to perchlorate, [PEDOT
+
] is the concentration of
active centres in the lm, is the reaction order related to the
active centres and k = k

exp(zF/RT) correlates the chemical

and electrochemical rate coefcients.
At the same time the applicability of the methodologies usedby
chemical kinetics must be checked when applied to these dense
and reactive polymers, which swell and shrink during reactions,
thus changing their structure in a reversible and continuous way
from a solid to a dense gel.
EXPERIMENTAL
ACN (Lab Scan) and anhydrous lithium perchlorate (LiClO
4
; Fluka)
were used as received, and 3,4-ethylenedioxythiophene (from
Merck) was distilled under vacuum before use. The working
electrode was a platinumsheet having a surface area of 1 cm
2
, the
counter electrode was a stainless steel sheet having a surface area
of 2 cm
2
and double-wall Ag/AgCl in 3 mol L
1
Cl

aqueous
solution/0.1 mol L
1
LiClO
4
ACN solution, supplied by Crison
Instruments, was the reference electrode. A one-compartment
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1.5 1.0 0.5 0.0 0.5
0.0032
0.0016
0.0000
0.0016
0.0032
0.0048
i

(
A
)
E (V)
0 50
35
36
37
38
39
40
41
42
43
Q

(
m
C
)
Sample number (PEDOT films)
10 20 30 40
A
B
Figure 2. (a) Cyclic voltammograms for the control of lm electroactivity,
after electropolymerization: potential sweep rate, 0.1 V s
1
; cathodic
potential limit, 1.6 V; anodic potential limit, 0.8 V; in 0.1 mol L
1
LiClO
4
ACN solution. (b) Voltammetric oxidation charge: average oxidation
charge (solid line) and standard deviation (dash lines). Each lm
was electrogenerated in 0.1 mol L
1
LiClO
4
and 10 mmol L
1
3,4-
ethylenedioxythiophene ACN solutions by consumption of 300 mC cm
2
,
under ow through a platinum working electrode of a constant current
density of 2 mA cm
2
.
electrochemical cell was used. The experiments were carried out
under nitrogen atmosphere. Electrochemical techniques were
applied using an Eco Chemistry Autolab potentiogalvanostat. The
temperature of the cell was maintained by means of a Julabo F25
cryostat.
PEDOT lms were electrogenerated from 0.1 mol L
1
LiClO
4
and 10 mmol L
1
3,4-ethylenedioxythiophene ACN solutions, by
ow of a constant current (2 mA) through the working platinum
electrode, consuming a total constant charge of 300 mC cm
2
.
After polymerizationthecoatedelectrodewas rinsedwithACNand
driedbefore use. The weight of the driedlms was 0.360.05 mg,
measured using a Sartorious SC2 balance.
Every electrogenerated lmwas checked by cyclic voltammetry
in 0.1 mol L
1
LiClO
4
ACN solution, using a potential sweep rate
of 0.1 V s
1
; 1.6 V was the cathodic potential limit and 0.8 V
was the anodic potential limit (Fig. 2(a)). The charge consumed
to oxidize every electrogenerated lm (the lm electroactivity)
allowedcontrol of the electrogenerationreproducibility (Fig. 2(b)).
Figure 2(b) shows thereproducibilityandthestandarddeviationof
the oxidation charges obtained from the control voltammograms
of the 30 electrogenerated lms used in this work.
The oxidation reaction kinetics, or the electroactivity kinetics,
was studied by reducing the lm at a cathodic potential for a
constant time to obtain the initial state for the oxidation, then
an anodic potential step promoted the lm oxidation followed
through the chronoamperometric response. The procedure was
applied for the same cathodic potential and the same reduction
time under various values of the experimental variables required
to check, through Eqn (2), the existence of a chemical kinetic
control: various concentrations of LiClO
4
in solution, various AC
concentrations, [AC], in the lm and various temperatures.
The procedure was repeated for different initial states for the
oxidation attained by reduction at different cathodic potentials.
That means that the kinetic study was repeated for different initial
states of conformational packing, in order to check the inuence
of the initial state on the kinetics.
After every experimental series a new control voltammogram
was performed on the lm. When the oxidation voltammetric
charge decreased by around 10%, compared to that of the
just electrogenerated lm, a new lm was electrogenerated and
checkedfor thekinetic study. Thevoltammetric electroactivity was
also used to check the polymeric degradation during the kinetic
studies and to decide when the used lmshould be discarded and
a new lm required to continue the study.
RESULTS ANDDISCUSSION
PEDOT oxidation: reaction kinetics having an induction time
After polymeric reduction (pre-polarization) of a PEDOT lm
for 30 s at increasing cathodic potentials in 0.1 mol L
1
LiClO
4
ACN solutions, the subsequent oxidation by potential steps
to 500 mV produces chronoamperometric responses (Fig. 3(a))
showing maxima with increasing oxidation times. The evolution
of the current for every experiment represents the oxidation
kinetics. The chronoamperometric kinetics gives, on integration,
chronocoulometric kinetics (Fig. 3(b)) showing the usual shapes of
reactionkinetics havinganinductiontime(Fig. 3(c)). Theinduction
time is the intersection between the slope and the abscissa. The
initial rate for every oxidation process can be obtained from the
slope at the inexion points of the chronocoulograms (dQ/dt = i):
this is the current of the chronoamperometric maximum.
The reaction of Eqn (1) occurs between ACs in the neutral
polymer chains, understood as those places along the polymeric
chains able to store a positive charge (PEDOT
+
) after oxidation,
and counterions (ClO
4

) coming from the solution. We consider,

as an initial hypothesis, the occurrence of a prevalent interchange
of anions between the solution and the lm during the oxidation
reaction (Eqn (1)). The empirical kinetics should be
R (in mol L
1
s
1
) =
d[PEDOT
+
]
dt
=
1
FV
dQ
ox
dt
=
i
FV
= k[ClO
4

[AC]

(3)
where dQ
ox
/dt (C s
1
)= i (mA), and are the reaction orders
relatedtocounterions andACs onthepolymer chains, respectively,
F = 96 500 C mol
1
, V is the lm volume obtained from the
experimental polymer weight, k is the rate constant or rate
coefcient and [ClO
4

] and [AC] are the electrolyte and AC

concentrations, respectively. Equations (3) and (2) are equivalent:
k = k

exp(zF/RT).
By using the polymerization charge (Q), the polymer weight
obtained and the oxidation charge, various parameters related to
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0
5
10
15
20
25
30
i

(
m
A
)
200
400
600
800
1000
1500
2000
2500
3000
0 4 8 10 12
0
5
10
15
20
25
30
Qox -3000mV
Qox -2500mV
Qox -2000mV
Qox -1500mV
Qox -1000mV
Q

(
m
C
)
t (s)

0
0
5
10
15
20
25
Qox -3000mV
Qox -2000mV
Qox -1000mV
Q

(
m
C
)
t (s)
Induction time
1 2 3 4 5 6
2 6
0 4 8 10
t (s)
2 6
A
B
C
Figure 3. (a) Chronoamperometric responses of a PEDOT-coatedplatinum
electrode in 0.1 mol L
1
LiClO
4
ACN solution, submitted to potential steps
from different cathodic potentials, as indicated, to 500 mV maintained for
30 s. (b) Chronocoulograms obtained by integration of the experimental
chronoamperograms. The conformational relaxation loop is obtained
by plotting the evolution of the reduction charge on a reverse time
scale. (c) Experimental chronocoulograms show reaction kinetics having
induction times.
the reaction can be obtained. By considering the polymer weight
(w) and the PEDOT density, = 1.49 g cm
3
,
26
the lm volume
(V) and its average thickness (h) can be obtained:
=
w
V
V =
w

=
0.3582 10
3
g
1.49 g cm
3
= 2.4040 10
4
cm
3
From V = Ah, where A = 1 cm
2
is the surface area of the working
platinum electrode, the lm thickness can be obtained:
h =
V
A
=
2.4040 10
4
cm
3
1 cm
2
= 2.4040 10
4
cm = 2.4 m
The concentration of active centres, [AC], considered (as dened
above) as those places along the chains that will store a positive
charge after electrochemical oxidation(PEDOT
+
), is obtainedfrom
the consumed oxidation (chronoamperometric) charge (Q
ox
, mC),
the polymer weight (0.36 0.05 mg) and the density of the
polymer ():
[PEDOT
+
] (in mol e

L
1
) = [AC] (in mol e

L
1
)
=
Q
ox
(in C)
96485 C mol
1

(in g L
1
)
w (in g)
(4)
Figure 3(b) also shows the reduction reaction, in reverse,
produced by a cathodic potential step back to the initial
potential: an electroactive relaxation loop is obtained. In contrast
to magnetic, mechanical or dielectric relaxation loops, the
electroactive relaxation width and the relaxation times are under
the control of the cathodic pre-polarization. This fact can open
new possibilities for relaxation memory. Both ways to show the
experimental results (Figs 3(a) and (b)) were historically named
anomalous electrochemical results, memory effect, relaxation
effect or asymmetric effect.
2732
Chemical kinetic control and reaction orders
Coming back to Eqn (3), taking logarithms is one way to obtain
the various parameters:
log R = log k + log[ClO

4
] + log[AC] (5)
This equationdescribes thechemical kinetic control of theprocess.
It will allow one to check if the oxidation occurs under chemical
kinetic control, and, in that case, to obtain the various kinetic
parameters.
Equation (5) states that k and can be obtained by potential
steps from the same cathodic potentials kept for the same polar-
ization time (the same reduced and conformational packed initial
states) tothesameanodic potential (whichmeans aconstant [AC]),
in solutions having different salt concentrations, [ClO
4

], under
constant temperature (constant k). Equation (5) also indicates that
k and can be obtained by potential steps to different anodic
potentials (which means different [AC]), from every initial packed
state, under constant [ClO
4

] and constant temperature.

From the current at the experimental chronoamperometric
maxima the reaction rates (R) were obtained using Eqn (3).
Figures 4(a) and (b) show the experimental double logarithmic
relationship expected from Eqn (5), corroborating the aim of this
work: the electrochemical oxidation of PEDOT occurs around the
chronoamperometric maximum under chemical kinetic control.
Slopes from Fig. 4(b) are the reaction order (0.3 0.6),
being independent of both the initial packing state and the
oxidation potential.
The increasing slopes in Fig. 4(a) indicate increasing reaction
orders (0.86, 1.10, 1.40, 1.41, 1.37, 1.44, 1.54, 1.88, 2.01, 2.09 and
2.14; Fig. 5) when the oxidation starts from increasingly packed
initial states. This variation could indicate, from a mechanistic
point of view, that the number of neighbouring polymeric chains
interacting with a counterion arriving from the solution can be
one or two. The interaction with the emerging positive charges
on the chains contributes to the generation of the required
free volume to accommodate the counterions at the end of the
oxidation. The relative weight of the elemental step involving
two neighbouring polymeric chains increases when the oxidation
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0.8 0.6 0.4 0.2 0.0 0.2 0.4
0.90
0.75
0.60
0.45
0.30
0.15
0.00
0.15
0.30
0.45
l
o
g

R

(
m
o
l

L

1
s

1
)
l
o
g

R

(
m
o
l

L

1
s

1
)
log (PEDOT
+
) (mol e

L
1
)
200mV
400mV
600mV
800mV
1000mV
1100mV
1200mV
1300mV
1400mV
1500mV
1600mV
1800mV
2000mV
2200mV
1.6 1.2 0.8 0.4 0.0
0.0
0.4
0.8
1.2
1.6
2.0
0.96
0.99
0.95
0.97
0.98
0.99
log (ClO

4
) (mol L
1
)
0 mV
200 mV
400 mV
600 mV
800 mV
1000 mV
B
A
Figure 4. Double logarithmic plots, from Eqn (5), of the oxidation rates
(R) obtained from the chronoamperometric maxima versus reactant con-
centrations. (a) Chronoamperometric results were obtained by potential
steps from a cathodic potential kept for 30 s to different anodic potentials
each time (0, 200, 400, 600, 800 and 1000 mV) in 0.1 mol L
1
LiClO
4
ACN
solutions. Each [PEDOT
+
] was obtained from the chronoamperometric
charge. The experimental procedure was repeated by reduction at a differ-
ent cathodic potential (as indicated) each time (correlation coefcients >
0.99). (b) Chronoamperometric results were obtained by potential steps
from 1000 mV, kept for 30 s, and an anodic potential, in a different
electrolyte concentration each time: 0.05, 0.1, 0.2, 0.4, 0.6 and 0.8 mol L
1
LiClO
4
ACN solutions. The procedure was repeated by oxidation at dif-
ferent anodic potentials as indicated. The correlation coefcients (r
2
) are
indicated.
starts after pre-polarization at higher cathodic overpotentials,
which means using as initial states more packed conformational
structures. Some more careful kinetic and mechanistic studies
are required using complementary techniques to corroborate this
hypothesis.
Rate coefcients
By using the values of obtained from Fig. 4(a), the experimental
concentrations of [ClO
4

] and R
0
, the origin ordinates from
Fig. 4(b), the rate coefcient k can be calculated using Eqn (5):
log R
0
= log k + log[ClO

4
] (6)
log k = log R
0
log[ClO

4
] (7)
Fig. 5 shows two ranges for the obtained rate coefcients.
Rate coefcients are independent of the initial state after
-2.0 -1.5 -1.0 -0.5 0.0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0.6
0.9
1.2
1.5
1.8
2.1
2.4
k

(
m
o
l

L
-
1

s
-
1
)
E
c
(V)
b
e
t
a
Figure 5. Evolution of k (triangles) and (squares), the rate coefcient
and the reaction order related to [PEDOT
+
] from Eqn (3), respectively, as a
function of the cathodic potential of pre-polarization for 30 s.
pre-polarizations at 0.2 and 0.4 V, and decrease after pre-
polarizations at higher cathodic potentials.
Electrochemical reductions by polarization at cathodic poten-
tials lower than 0.4 V give a partially swollen structure: the
subsequent oxidationswelling processes occur under fast coun-
terion diffusion kinetic control. The oxidation rate coefcient
is constant and independent of the cathodic potential of pre-
polarization, as expected for any chemical or electrochemical
reaction. This potential (0.4 V) is the closing potential (E
s
) of
the polymer under the experimental conditions studied. Af-
ter reduction at higher cathodic potential, the oxidation rate
coefcient is inuenced by the degree of compaction of the
reduced polymer structure. Any reduction at a cathodic po-
tential higher than the closing potential promotes fast reduc-
tionshrinkingclosingconformational packingprocesses. More
packed structures are attained by reduction at increasing cathodic
potentials. The subsequent oxidation rate is slower the more
packed the initial state, which means, as shown by Eqn (5), lower
rate coefcients (since the work is done under constant tem-
perature, electrolyte concentration or anodic potential constant
[AC]), in accordance with the experimental results (Fig. 5). This
means that the rate coefcients should include structural informa-
tion about the packed initial state of the chain conformations in
the polymer lm.
As a partial conclusion, the oxidation of PEDOT lms occurs
under chemical kinetic control (Fig. 4), and the rate coefcient
obtained changes as a function of the cathodic potential of pre-
polarization. In order to get a quantitative explanation for those
changes we come back to the ESCR model. The rate coefcient
of any electrochemical reaction of conducting polymers can be
written as k = k
0
exp(H/RT), where H = H

z
c

c
+ z
r
.
Therefore
k = k
0
exp

z
c

c
+z
r

RT

(8)
where H is the molar partial enthalpy of the reacting polymer,
H

is the molar partial enthalpy in the absence of any

electric eld, z
c
and z
r
are the charges required to compact
(by reduction/packing) or to relax (by oxidation/relaxation) one
mole of polymeric segments, respectively,
c
is the compaction
overpotential (related to the closing potential:
c
= E
s
E
c
,
where E
c
is the cathodic potential applied for 30 s) and is the
oxidationrelaxation overpotential.
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-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
k

(
m
o
l

L
-
1

s
-
1
)
E
c
(V)
k
exp
k
theo
Figure 6. Evolution of k, the rate coefcient, as a function of the cathodic
potential of pre-polarizationfor 30 s andtheoretical, k
theo
, results according
to Eqn (10), z
c
being obtained from experimental results.
Under constant oxidation potential (constant ) and con-
stant temperature, a semi-logarithmic dependence is predicted
between the rate coefcient and the cathodic potential of
pre-polarization:
ln k = ln k
0
+
H

+z
r

RT

z
c

c
RT
= ln k
1

z
c

c
RT
(9)
where ln k
1
= ln k
0
+ (H

+ z
r
)/RT. After pre-polarization at
any cathodic potential less than the closing potential (
c
= 0),
ln k = ln k
1
and
k = k
1
(10)
So the rate coefcient of the electrochemical oxidation of PEDOT
(under constant temperature, constant electrolyte concentration
and constant oxidation overpotential) has two different domains
as a functionof the cathodic potential of pre-polarization: it retains
a constant value when the cathodic potential of pre-polarization
and conformational packing,
c
, is zero (Eqn (10)); and it follows
an exponential decay for increasing cathodic potentials of pre-
polarization,
c
(Eqn (9)).
The limiting potential between both regions is the closing
potential of theshrinkingpolymer. Equation (9) includes structural
information, k being the number of moles of ACs on the relaxed
polymer chain, and oxidized per unit volume and per unit time.
An equivalent number of moles of counterions per unit volume
and per unit time must penetrate from the solution for charge
balance.
Fromtheaboveexperimental resultsobtainedbypotential steps
from different cathodic potentials by following the ESCR model
methodology,
12
a value of z
c
= 1388.52 C mol
1
was obtained.
By substituting this value in Eqn (9) and giving values to
c
, we
obtained the evolution of k (termed theoretical) which shows the
two evolution ranges as a function of the cathodic potential of
pre-polarization (Fig. 6).
The average evolution of k is well described by the theoretical
evolution. Nevertheless the experimental results show that four
main domains can be considered for the variation of k. Constant
kinetic coefcients are observed when the initial states for
oxidation are obtained by reduction at E
c
> 0.4 V. An initial
exponential decay of k is observed after initial reduction between
0.4 < E
c
< 1.0 V; thena secondexponential decay is observed
after initial reduction between 1.0 < E
c
< 2 V. Finally, k
increases after increasing cathodic reduction at E
c
< 2 V.
This nal increase is attributed to the simultaneous presence
of a new process related to the reduction of some electrolyte
contaminant (i.e. some water content (<0.3 wt%) givinghydrogen
at the polymermetal interface, pushing and expanding the
polymeric structure). The other three processes correlate with
voltammetric results (Fig. 2(a)): two oxidation processes (shoulder
and maximum) and two reduction processes (two maxima) are
present, each of them can be the rate-control step after reduction
in the two potential ranges of decreasing k. Voltammetric results
also indicate that by reduction at anodic potentials higher than
0.4 V, the material is not compacted.
All those aspects are now being separated, checked and
quantied in our laboratory. The results underline how powerful
the methodology used is in separating different rate-control
processes, giving a tool, the variation of k, to try now to quantify
each of them.
Activation energy and conformational energy
Following the usual kinetic methodology indicated by Eqn (5),
k = Aexp(E
a
/RT), the activation energy, E
a
, can be obtained
from experiments performed at various temperatures. Two
electrochemical cells were used containing the working solution.
One cell was maintained at 25

C, the temperature of the second

being adjusted (10, 5, 0, 5, 10, 15, 20, 25, 30, 35 and 40

C)
for each experimental series. The platinum coated electrode was
reduced and packed at 25

C each time by pre-polarization at

various cathodic potentials (200, 400, 600, 800, 1000,
1200, 1600 or 1800 mV), for 30 s, every time. Then it was
translated into the second cell at the working temperature. There,
it was submitted to the same pre-polarization potential for 1 s
and then the potential was stepped to the oxidation potential of
800 mV for 30 s.
The oxidation rate obtained from the chronoamperometric
maximum for every cathodic potential of pre-polarization and
packing then shift to higher values (Fig. 7). With increasing
temperature, conformational movements of polymer chains and
the linked oxidation reaction become faster. Linear evolutions of
ln R versus 1/T were obtained for every cathodic potential of pre-
polarization and packing and each slope represents the activation
energy (Fig. 8).
When the initial state is obtained by pre-polarization at
cathodic potentials lower than the closing potential (E
s
= 0.4 V),
the activation energy is constant, independent of the pre-
polarizationpotential. After pre-polarizationat increasingcathodic
potentials higher than E
s
, increasing activation energies are
obtained. Experimental results for PEDOT are more dispersed
than those obtained using polythiophene
24
or polypyrrole
25
lms.
The electrochemical models indicate the inuence of the anodic
overpotential on the activation energy through the rate constant
by Eqn (2), k = k

exp(zF/RT), not describing any inuence

of the cathodic potential of pre-polarization. Coming back to
thermochemistry, the activation energy, E
a
= RT + H, and
considering the relaxation model, H = H

z
c

c
+ z
r
, one
obtains
E
a
= RT +H = RT +H

z
c

c
+z
r
(11)
This equation states that the activation energy changes, for
potential steps to the same anodic potential (constant ), as a
www.interscience.wiley.com/journal/pi c 2010 Society of Chemical Industry PolymInt 2010; 59: 329336
3
3
5
Conformational energy from oxidation kinetics of PEDOT www.soci.org
0.0032 0.0034 0.0036 0.0038 0.0040
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2

l
n

R

(
m
o
l

L
-
1

s
-
1
)
T
-1
(K
-1
)
-200mV; r
2
= 0.98
-400mV; r
2
= 0.98
-600mV; r
2
= 0.98
-800mV; r
2
= 0.99
-1000mV; r
2
= 0.98
-1200mV; r
2
= 0.99
-1600mV; r
2
= 0.98
-1800mV; r
2
= 0.96
Figure 7. Inuence of temperature on the oxidation of PEDOT. The coated
electrode was reduced at the pre-polarization potential and 25

C for 30 s
in 0.1 mol L
1
LiCIO
4
ACN solution. The electrode was then switched off
and translated into a new cell at the working temperature and submitted
to a potential step from the pre-polarization potential, kept for 1 s, to
800 mV versus Ag/AgCl. The procedure was repeatedfor different cathodic
potentials of pre-polarization and for experimental temperatures of 10,
5, 0, 5, 10, 15, 20, 25, 30, 35 and 40

C.
-2200 -2000 -1800 -1600 -1400 -1200 -1000 -800 -600 -400 -200 0
2000
4000
6000
8000
10000
12000
14000
E
a
(
J

m
o
l

s
-
1
)
E
c
(V)
r
2
= -0.93
Figure 8. Evolution of the activation energy (E
a
) as a function of the
cathodic potential of polarization for 30 s.
function of the cathodic overpotential (
c
), kept for the same
polarization time, as
E
a
= B z
c

c
(12)
where B = RT + H

+ z
r
is a constant, the electrochemical
activation energy of the reaction, and z
c

c
is the molar energy of
conformational packing (conformational energy).
Equation (12) denes two ranges for activation energies. After
pre-polarization at anodic potentials higher than the closing
potential, E
c
> E
s
and
c
= 0, the activation energy is constant
E
a
= B, the electrochemical activation energy (E
a
)
elq
. After
pre-polarization at cathodic potentials higher than the closing
potential, E
c
< E
s
and
c
< 0, the activation energy increases for
the same oxidation potential as a linear function of the cathodic
potential of pre-polarization, tting experimental results.
The physical meaning is that increasing packed initial states
are attained by increasing cathodic pre-polarization, thus storing
conformational energy. The electrochemical oxidation can only
be initiated after the anodic potential step by generation of the
0 4 6 8 10
0
2
4
6
8
10
Rising
Packed
Conformations
Conformational
Activation
Energy
Final State
E
n
e
r
g
y
Reaction Coordinate
Activated State
Chemical
Activation Energy
2
Figure 9. Experimental activation energies for PEDOT oxidation by
potential steps from different cathodic pre-polarizations are constituted
of two components: the chemical activation energy, (E
a
)
elq
, and the
conformational activation energy, (E
a
)
conf
, required to relax the initial
packed conformations of folded chains. The conformational energy
of the initial state can be increased in a continuous way, obtaining
increasingly packed conformations, by pre-polarizations at increasing
cathodic potential for a constant polarization time.
required free volume between chains to accommodate incoming
counterions. In this way, the electrochemical activation energy,
(E
a
)
elq
, and the conformational energy, (E
a
)
conf
, required to relax
the packed polymeric conformations must be provided to the
system (Fig. 9). So, whatever the initial conformational state:
E
a
= (E
a
)
elq
+(E
a
)
conf
(13)
Considering that articial muscles are applications of the
electrochemomechanical properties of conducting polymers
based on volume changes associated with conformational
changes, a way is open nowto initiate an energetic quantication
of actuating, mechanical sensing and tactile
1,2,3337
properties.
CONCLUSIONS
This kinetic study conrms that the potentiostatic oxidation of
PEDOTlms, after partial electrochemical reductionbypolarization
at different cathodic potentials, held for a constant time, occurs
around the chronoamperometric maximum under chemical
kinetic control. Rate constants, reaction orders and activation
energies from the empirical kinetic equation can be obtained
followingtheusual procedures fromchemical andelectrochemical
kinetics principles.
The initial conformational packing state, obtained by cathodic
pre-polarization, has a strong inuence on the rate coefcient and
the activation energy of the subsequent polymeric oxidation. The
electrochemical reduction by cathodic pre-polarization produces
different states of a partially reduced polymer lm (small
differences) and different conformational packing states (large
differences) of polymeric chains. Initial states of increasingly
packed conformations (physical states) produce slower oxidation
kinetics, using as driving force the same anodic overpotential, at
the same temperature and at the same electrolyte concentration.
Lower rate constants and increasing activation energies are
obtained for polymeric oxidation for increasing pre-polarization
potentials.
PolymInt 2010; 59: 329336 c 2010 Society of Chemical Industry www.interscience.wiley.com/journal/pi
3
3
6
www.soci.org TF Otero, M Caballero Romero
The experimental activation energy has two linear ranges as a
function of the cathodic pre-polarization. Using as initial states for
the oxidation open structures attained by pre-polarization at low
cathodic potentials, constant activation energies are obtained:
namely the chemical activation energy. Using as initial states for
the oxidation closed and packed structures, the activation energy
includes two components: the constant chemical energy plus the
conformational energy required to relax the structure allowing
the entrance of counterions. The conformational energy increases
linearly as a function of the cathodic potential of pre-polarization
and conformational packing.
Obtainingthe conformational energy opens the way toquantify
new technical aspects of electrochemomechanical actuators.
ACKNOWLEDGEMENTS
The authors acknowledge nancial support fromthe Spanish Gov-
ernment (MCI) Project MAT2008-06702, the Seneca Foundation
Project 08684/PI/08 and the Consejera de Educaci on de Murcia,
Plan Regional de Ciencia y Tecnologa 2007-2010.
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