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Adsorptive square wave voltammetry of metal complexes.
Effect of ligand concentration
Part I. Theory
Fernando Garay *
INFIQC, Departamento de F sico Qu mica, Facultad de Ciencias Qu micas, Uni6ersidad Nacional de Cordoba, Pabellon Argentina, Ala 1, 2
piso, Ciudad Uni6ersitaria, 5000 Cordoba, Argentina
Received 8 December 2000; received in revised form 19 February 2001; accepted 1 March 2001
Abstract
The electrochemical behaviour of non-labile metallic complexes under square wave voltammetry (SWV) conditions is analysed
theoretically, considering the inuence of ligand adsorptiondesorption processes as well as the ligand concentration on the
quasi-reversible redox reaction mechanism. The dependence of current and peak potentials on the transfer reaction rate and on
complex stoichiometry is considered. Voltammetric responses for processes in which the ligand is desorbed or remains adsorbed
after the electroreduction process are compared. Diagnosis criteria for the selection of optimum SWV parameters in view of
analytical applications are presented for each case. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Adsorptive square wave voltammetry; Mechanistic studies; Mathematical models
1. Introduction
The adsorption of electroactive analytes on the elec-
trode surface is used commonly as a preconcentration
step in electroanalytic procedures. This step improves
the sensitivity of the analytical technique, allowing
trace level determinations [16]. Square wave voltam-
metry (SWV) is one of the electrochemical techniques
more widely applied in quantitative analysis, due to its
high sensitivity, which is mainly the consequence of the
rejection of most of the capacitive currents [7]. The
alternating application of oxidation and reduction
pulses, characteristic of SWV, allows the concentration
gradients of reagents and products close to the surface
to be rebuilt in each wave. This fact allows the determi-
nation of both species almost simultaneously. The dif-
ferential peak current (Dc
p
) and the peak potential (E
p
)
are the most useful parameters of SWV from the ana-
lytical point of view. Nevertheless, Dc
p
values also
have been employed in some kinetic analyses, since a
plot of Dc
p
versus the charge transfer rate constant (k
s
)
depicts a maximum for quasi-reversible redox reactions
with adsorbed species; this quasi-reversible maximum
can be employed to obtain k
s
[810].
One of the modeling advantages is the optimisation
of the experimental conditions for quantitative determi-
nations of metallic complexes at trace levels. Many
studies in the literature take into account adsorbed
species involved in charge transfers of different rates
and examine also the effect of irreversible chemical
reactions coupled to the electrochemical step [922].
Models that simulate the voltammetric response for the
adsorptive accumulation of metallic cations have also
been developed. In all cases, the strong and labile
complexation forms of the metallic cations by organic
and inorganic ligands have been considered, respec-
tively, under conditions where the ligand is in great
excess with regard to the metal concentration [1216].
Simulation of mechanisms involving adsorbed species
requires the relationship between bulk concentrations
of soluble species and their surface excesses at a given
temperature. One of the simplest models considers a
linear relationship between bulk and surface concentra-
tions. This type of isotherm is applicable at low surface
coverages, which are found frequently in trace analysis
* Tel.: +54-351-4334169; fax: +54-351-4334188.
E-mail address: fgaray@squim.fcq.unc.edu.ar (F. Garay).
0022-0728/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S0022- 0728( 01) 00459- 4
F. Garay / Journal of Electroanalytical Chemistry 505 (2001) 100108 101
[12]. Nevertheless, a great excess of organic ligand is
usually added to the analytical solution in the adsorp-
tive quantication of metallic cations. This excess does
not necessarily increase the sensitivity of the response,
but it invalidates the applicability of the linear
isotherm.
In the present work, a theoretical model for a reac-
tion mechanism considering diffusion effects and the
adsorption of reagents is proposed. The model assumes
inert complexes with stability constants high enough to
consider that no free metal will be detected after the
formation of the complex. The concentration and ad-
sorption effects of the ligand on the voltammometric
response are analysed. This concentration was always
kept above the assumed trace amounts of metal. The
ligand excess range with regard to the total metallic ion
concentration was studied from 10
5
to 10
4
. In this
way, the evaluation of experimental cases under linear
adsorption conditions can be accomplished.
2. Mathematical model
The formation in the bulk solution of only one
chemically stable complex species is assumed:
M
+
(sol)
+uL
(sol)
Yk
K
st,o
ML
u(sol)
(1)
Here, the u value can be 1 or 2, depending on the
complex stoichiometry. For simplicity, the charge on
the oxidised complex is omitted, all M
n+
are symbol-
ised by M
+
and the sufx u in the stability (K
st,o
) and
adsorption (K
ad
) constants are also omitted; c* stands
for bulk concentrations. It is considered that c
L
* .c
M
+
*
and the distribution of these ionic species is dened
according to:
c
M
+
(ini)
* =c
ML
u
(eq)
* (2)
c
L (eq)
* =c
L (ini)
* uc
M
+
(ini)
* (3)
where the subscripts (ini) and (eq) indicate the species
concentration before the ligand is added and after the
complexing equilibrium is reached, respectively. The
ligandcomplex concentration ratio is dened as:
R
LM
=c
L
*(c
ML
u
* )
1
(4)
Considering the above conditions, two reaction
schemes were analysed. The rst one assumes that the
product of the adsorbed complex reduction is the lig-
and in solution, Eq. (5), while in the second scheme the
adsorbed ligand remains at equilibrium with its soluble
fraction, Eq. (6).
ML
u(sol)
Yk
K
ad,ML
ML
u(ad)
Yk
k
s
ne
M(Hg)
(sol)
+uL
(sol)
(5)
ML
u(sol)
Yk
K
ad,ML
ML
u(ad)
Yk
k
s
ne
M(Hg)
(sol)
+uL
(ad)
Yk
K
ad,L
uL
(sol)
(6)
where K
ad,ML
and K
ad,L
are the adsorption constants for
the oxidised metal complex and the free ligand, respec-
tively. As the adsorption constants are dened for the
forward reactions of Eqs. (5) and (6) their dimensions
are in centimetres. A complete list of symbols is sum-
marised in the nomenclature.
As stated before, adsorption isotherms for the metal-
lic complex and for the free ligand are assumed to be
linear. Also, no redox reactions involving the ligand are
supposed to occur within the working potential range.
Considering one-dimensional diffusion, Eqs. (5) and (6)
can be evaluated mathematically with the following
differential equations:
#c
ML
u
/#t =D(#
2
c
ML
u
/#x
2
) (7)
#c
M(Hg)
/#t =D(#
2
c
M(Hg)
/#x
2
) (8)
#c
L
/#t =D(#
2
c
L
/#x
2
) (9)
For simplicity, a common value of the diffusion coef-
cient, D=110
5
cm
2
s
1
was assumed for all diffus-
ing species. The following initial and boundary
conditions are considered.
t =0, x0:
c
ML
u
=c
ML
u
* ; Y
ML
u
ini
=K
ad,ML
c
ML
u
* (10)
c
M(Hg)
=0; c
L
=c
L
* (11)
Y
L
ini
=K
ad,L
c
L
* (12)
t .0, x:
c
ML
u
c
ML
u
* ; c
L
c
L
*; c
M(Hg)
0 (13)
x=0:
Y
ML
u
=K
ad,ML
c
ML
u
(14)
D(#c
ML
u
/#x)
x=0
=#Y
ML
u
/#t +I/nFA (15)
D(#c
M(Hg)
/#x)
x=0
=I/nFA (16)
D(#c
L
/#x)
x=0
=I/nFA (17)
Y
L
=K
ad,L
c
L
(18)
D(#c
L
/#x)
x=0
=#Y
L
/#t I/nFA (19)
Boundary conditions (12), (18) and (19) are applied
only to Eq. (6) whereas condition (17) is operative only
for Eq. (5). All the other conditions apply to both
reaction schemes. Provided that the rate of the electro-
chemical step is considerably faster than the complex
dissociation, the reduced complex species could be as-
sumed to be an intermediate species in equilibrium with
the dissociated products:
K
st, r
=Y
ML
u
(c
M(Hg)
c
L
u
)
1
(20)
F. Garay / Journal of Electroanalytical Chemistry 505 (2001) 100108 102
where K
st,r
describes the chemical equilibrium between
the adsorbed reduced complex and its dissociated spe-
cies, M (in the amalgam) and L (in solution, close to
the electrode surface). The rate of the charge transfer
reaction is given by the well-known equation:
I(t)/nFA=k
s
exp[ h(t)]{Y
ML
u
Y
ML
u
exp[(t)]}
(21)
where the symbols have their usual meaning and (t) is
a function of the reaction scheme considered, according
to the following expressions [11,13]:
(t)
Eq. (5)
=nF[E(t) E]/RT+ln(K
ad,ML
)
+ln(K
st,o
/K
st,r
) (22)
(t)
Eq. (6)
=nF[E(t) E]/RT+ln(K
ad,ML
/K
ad,L
)
+ln(K
st,o
/K
st, r
) (23)
where E(t) is the square wave (SW) potential function
and E is the standard potential for the simple redox
reaction involving soluble free metal species.
In order to simulate the reactions described in Eqs.
(5) and (6), the current is normalised according to
c(t) =I(t)/(nFAfY
ML
u
ini
) where f is the SW frequency. A
numerical integration method is employed in the resolu-
tion of differential equations (7), (8) and (9) under the
relevant boundary conditions, Eqs. (10)(19) [23]. The
following results were obtained.
Reaction scheme of Eq. (5), assuming u=1:
0=c
(m)
2
+c
(m)
{Z
a
[T
(m)
(m)
+1] +2]
a(m)
}
+Z
a
T
(m)
[]
b(m)
f
1
] +]
a(m)
[Z
a
+]
a(m)
] (24)
Reaction scheme of Eq. (5), assuming u=2:
0=c
(m)
3
+c
(m)
2
{Z
a
+3]
a(m)
}
+c
(m)
{(Z
a
/2)
2
[T
(m)
(m)
+1]
+]
a(m)
(2Z
a
+3]
a(m)
)}
+(Z
a
/2)
2
[T
(m)
(]
b(m)
f
1
) +]
a(m)
]
+(]
a(m)
)
2
[Z
a
+]
a(m)
] (25)
Reaction scheme of Eq. (6), assuming u=1:
0=c
(m)
2
+c
(m)
{Z
b
[T
(m)
(m)
+1] +]
a(m)
+]
c(m)
}
+Z
b
T
(m)
[]
b(m)
f
1
] +]
a(m)
[Z
b
+]
c(m)
] (26)
Reaction scheme of Eq. (6), assuming u=2:
0=c
(m)
3
+c
(m)
2
{Z
b
+2]
c(m)
+]
a(m)
}
+c
(m)
{(Z
b
/2)
2
[T
(m)
(m)
+1] +]
c(m)
(Z
b
+]
c(m)
)
+]
a(m)
(Z
b
+2]
c(m)
)}
+(Z
b
/2)
2
[T
(m)
(]
b(m)
f
1
) +]
a(m)
]
+]
c(m)
]
a(m)
[Z
b
+]
c(m)
] (27)
where ]
a(m)=
m1
j =1
c
( j )
S
(i )
; ]
b(m)
=
m1
j =1
c
( j )
Q
(i )
;
]
c(m)
P
(1)
=
m1
j =1
c
( j )
P
(i )
;
(m)
=exp[h
(m)
]k
s
1
+Q
(1)
;
S
(i )
=(i )
1/2
(i 1)
1/2
; i =mj +1; Q
(i )
={uS
(i )
+
Y
1(i )
}a
1
1
; P
(i )
={uS
(i )
+Y
2(i )
}a
2
1
; Y
y(i )
=
{exp[a
y
2
(li )] erfc[a
y
(li )
1/2
] exp[a
y
2
(l(i 1))] erfc[a
y
(l-
(i 1))
1/2
]}a
y
1
. In this latter equation, y subscripts can
be either 1 or 2 for the complex or ligand parameters,
respectively. Accordingly, a
1
=D
ML
1/2
K
ad,ML
1
; a
2
=D
L
1/2
-
K
ad,L
1
; Z
a
=R
LM
K
ad,ML
D
L
1/2
[ fu]
1
; Z
b
=R
LM
-
K
ad,ML
[K
ad,L
fP
(1)
]
1
; T
(m)
=D
M(Hg)
1/2
{ur
s
exp[
(m)
]}
1
.
The constant r
s
=1 cm determines the surface and bulk
standard concentration relationship [22]. The parameter
u=2(l/p)
1/2
depends upon the period l=(qf )
1
in-
volved in each numerical integration step, where q
stands for the number of subintervals considered in
each wave and a value of q=40 was employed.
3. Results and discussion
Fig. 1 shows the theoretical voltammograms for both
reaction schemes, Eqs. (5) and (6). Direct (c
f
) and
reverse (c
b
) normalised currents as a function of poten-
tial at 100 Hz are presented for different values of k
s
(curves af). The rst scheme, Eq. (5), is analysed for
u=1 and 2, whereas Eq. (6) is analysed for u=2. The
normalised currents present asymmetric bell-shaped
proles, with marked differences, depending on k
s
. The
sweeps start at the positive potential limit and the
reducing current, c
f
, is considered to be negative.
Curves calculated with Eqs. (24), (25) and (27) using
R
LM
=10 are arranged in Fig. 1A, B and C, respec-
tively. Almost identical cE proles were obtained for
the lowest k
s
value irrespective of the reaction scheme
and the complex stoichiometry, as is shown in curves a,
Fig. 1A, B and C. This is a clear indication that neither
the chemical state of the reduced products nor the
stoichiometry of the complex has any inuence on the
current potential proles, since k
s
is the only parame-
ter controlling the oxidation step. As k
s
is increased, the
quasi-reversible (curves be), and the reversible voltam-
metric responses (curves f) are sensitive to the chemical
properties of the complex, depending on both the u
value and the nal state of the ligand. The voltammet-
ric proles presented in Fig. 1C are independent of R
LM
values for R
LM
0.1. This indicates that ((c
L
/(x)
x=0
c
L
near the electrode surface (mol cm
3
)
D diffusion coefcient (cm
2
s
1
)
dE SW step amplitude (V)
DE
p/2
half-peak width (V)
E
(t)
SW potential program (V)
E standard potential for a simple redox
reaction of free soluble species (V)
E
p
peak potential (for the net current)
(V)
E
sw
half peak-to-peak SW potential ampli-
tude (V)
f SW frequency (Hz)
Faraday constant (C) F
i =mj+1
current (A) I
(t)
K
ad,L
; K
ad,ML
ligand and complex adsorption con-
stants (cm)
k
s
standard reaction rate constant (s
1
)
the value of k
s
at the quasi-reversible k
s,max
maximum (s
1
)
K
st,o
stability constant of oxidised species
(cm
3
mol
1
)
stability constant of reduced species K
st,r
(cm
4
mol
1
) or (cm
7
mol
2
)
n number of electrons
P
(i )
={uS
(i )
+Y
2(i )
}a
2
1
(s)
=40; number of time increments in q
each SW period
Consequently, a SW amplitude of 100 mV is preferred
for reversible reactions in which R
LM
10
1
.
In the case of irreversible charge transfer reactions, a
suitable Dc
p
DE
p/2
1
value was obtained for E
sw
=100
mV, regardless of the R
LM
value (not shown).
4. Conclusions
A description of the SW voltammetric behaviour
considering the ligand concentration effect over non-
labile metallic complexes has been formulated. The
theoretical voltammograms obtained according to the
proposed schemes permit the morphology of the re-
sponse for a wide range of experimental parameters to
be examined. These schemes can be found for broad
categories of reactions, especially for the case of SW
stripping analysis of adsorbed metallic complexes.
The schemes in this study provide a means to charac-
terise the electrochemical properties of adsorbed metal-
lic complexes without employing a great ligand excess.
Low ligand concentrations can be adjusted to discern
the complex stoichiometry as well as to determine the
ligand chemical state. In contrast, high ligandcomplex
ratios emphasise features concerning the rate process.
Thus, the quasi-reversible maximum is increased and
the effect of k
s
is stronger.
F. Garay / Journal of Electroanalytical Chemistry 505 (2001) 100108 108
={uS
(i )
+Y
1(i )
}a
1
1
(s) Q
(i )
gas constant (J mol
1
K
1
) R
R
LM
ligandcomplex concentration ratio
=1 cm r
s
=(i )
1/2
(i1)
1/2
S
(i )
T temperature (K)
=D
M(Hg)
1/2
{ur
s
exp[
(m)
]}
1
T
(m)
complex stoichiometry u
(m)
=exp[h
(m)
]k
s
1
+Q
(1)
(s)
={exp[a
y
2
(li )] erfc[a
y
(li )
1/2
] Y
y(i )
exp[a
y
2
(l(i1))] erfc[a
y
(l(i1))
1/2
]}
a
y
1
(s
1/2
)
Z
a
=R
LM
K
ad,ML
D
L
1/2
[ fu]
1
Z
b
=R
LM
K
ad,ML
[K
ad,L
fP
(1)
]
1
=
m1
j =1
c
( j )
S
(i )
]
a(m)
=
m1
j =1
c
( j )
Q
(i )
(s) ]
b(m)
=P
(1)
1
m1
j =1
c
( j )
P
(i )
]
c(m)
charge transfer coefcient h
time increments in each SW period (s) l
dimensionless SW potential program (t)
initial ligand and complex surface con- Y
L
ini
; Y
ML
u
ini
centrations (mol cm
2
)
ligand and complex surface concentra- YL; Y
ML
u
tions (mol cm
2
)
u =2(l/p)
1/2
(s
1/2
)
=I
(t)
/(nFAfY
ML
u
ini
) dimensionless c(t)
current function
forward and backward normalised cur- c
f
, c
b
rents
=c
f
c
b
; normalised net current Dc
normalised net peak current Dc
p
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