216804

Talanta 51 (2000) 645665
Polarographic and voltammetric behavior of selenious acid

and its use in analysis
P. Zuman
a,
*, G. Somer
b
a
Department of Chemistry, Clarkson Uni6ersity, Potsdam, NY 13699-5810, USA
b
Department of Chemistry, Faculty of Science, Gazi Uni6ersity, Ankara 06500, Turkey
Received 24 August 1999; received in revised form 25 October 1999; accepted 26 October 1999
Abstract
Solution chemistry of Se(IV), in particular the acidbase properties, salt and complex formation, chemical
reduction and reaction of Se(IV) with organic and inorganic sulfur compounds are briey summarized. The
electrochemical reduction of Se(IV) on dropping and stationary mercury electrodes is dealt with in some detail. The
effects of antecedent acidbase equilibria and of consecutive reactions of the reduction product, Se
2
, adsorption of
their products, and effects of added metal ions are discussed. The principles and applications of stripping analyses for
determination of ultratraces of Se(IV) are summarized. The behavior on unreactive (Au, Pt, carbon) and reactive (Hg,
Ag, Cu) electrodes are compared. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Acidbase; Sulfur; Metal ions
www.elsevier.com/locate/talanta
1. Introduction
Selenium is present in the earth crust as the
seventeenth most common element and occurs in
volcanic eruptions, some minerals, soil and waters
in variable quantities. In trace amounts it is a
biologically essential element for vertebrates, but
can be toxic when introduced in larger quantities.
It is usually present as Se(VI) or Se(IV) and in
organoselenium compounds.
In this review, attention will be paid to electro-
chemical properties of selenious(IV) acid and its
anions as well as practical applications of electro-
analytical techniques. As the electrochemical be-
havior of Se(IV) is accompanied by chemical
reactions, such reactions will be briey mentioned
rst.
2. General properties of Se(IV)
2.1. Acidbase properties
Selenious acid can undergo in aqueous solu-
tions the following equilibria:
H
3
SeO
3
+
X
K
1
H
2
SeO
3
+H
+
(1)
H
2
SeO
3
X
K
2
HSeO
3
+H
+
(2)
HSeO
3
X
K
3
SeO
3
2
+H
+
(3)
* Corresponding author. Fax.: +1-315-2686610.
0039-9140/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S0039- 9140( 99) 00323- 9
P. Zuman, G. Somer / Talanta 51 (2000) 645665 646
For the individual dissociation steps the follow-
ing pK
a
-values have been reported:
pK
3
pK
1
pK
2
8.33 [1] 2.72 [1] 3.3 [1]
8.32 [2] 2.62 [2]
The pK
1
-value has been determined [1] spec-
trophotometrically using values of Hammett acid-
ity functions Ho as a rst approximation for
log a
H+
. The existence of the protonated form
of Se(IV) in solutions of sulfuric acid has been
conrmed by cryoscopic and conductometric
measurements and by
77
Se NMR data [3].
2.2. Salt and complex formation
Solutions of selenious acid react with numerous
metal cations to form slightly soluble, white pre-
cipitates [4]. In unbuffered solutions formation of
slightly soluble salt (K
3
=3.810
9
) of Cu
2+
with selenite has been conrmed using polarogra-
phy [5]. On the other hand, Pb
2+
forms under the
same conditions a 1:1 complex (K
f
=1.410
4
),
which is relatively soluble [5]. Shifts of half-wave
potentials of the polarographic wave of cadmiu-
m(II) ions with increasing concentration of selen-
ite indicates formation of soluble complexes
between Cd
2+
and SeO
3
2
in ratio 1:1 with K
f
=
210
4
([6]).
For electrochemical studies involving mercury
electrodes, the formation of salts of Se(IV) species
with mercury ions is of particular interest. For the
slightly soluble [7] mercury(I) (K
s
=2.310
15
)
and mercury(II) (K
s
=1.410
14
) compounds
were proposed structures HgSeO
3
([8]) and Hg
3
(HSeO
3
)
2
(SeO
3
)
2
([9,10]). It has been suggested [4]
that in the presence of calomel occurs a dispro-
portionation of Se(IV) into Se(VI) and Se(0) to-
gether with an oxidation of Hg(I) to Hg(II).
2.3. Chemical reductions
Most common metals(0), with the exception of
Au, Pt and Pd, reduce Se(IV) in acidic media, as
the cation H
3
SeO
3
+
(similarly as for example
H
3
CrO
4
+
) is a strong oxidizing agent. Reductions
with Mg, Al and Zn yield both Se(0) and Se( 2),
whereas Raneynickel and Cu yield Se
2
([4]).
The reaction with Fe
2+
yields Se(0) ([11]).
Se(IV) can be reduced quantitatively to Se(0) by
iodide[4,12] following reaction (4):
H
2
SeO
3
(l) +4H
+
+4I
XSe(0) +I
2
(s) +3H
2
O
(4)
For the equilibrium constant K=[H
2
SeO
3
][H
+
]
4
[I
]
4
v
2
was reported [13] the value 1.4
10
14
. In order for the reaction between Se(IV)
and I
to be quantitative, pH should be smaller

than 1.0 ([12]).
This reaction can be used as a basis of titrimet-
ric determination of Se(IV) using a thiosulfate
solution [12] or an amperometric titration with
two polarized electrodes [14] or potentiometric
titration at constant current [14] using a Pt anode
and C cathode. Iodide ions can be also generated
electrochemically on a carbon electrode and this
can be used for a coulometric titration with two
platinum electrodes (DE=0.1 V) for amperomet-
ric end point detection [15,16]. Similarly, the cou-
lometric titration can be carried out using
electrogenerated titanium(III) [17].
Both the hydrazinium ion and its aryl deriva-
tives [4,18,19] yield predominantly Se(0), but un-
der optimal conditions it is possible to reduce
Se(IV) to Se
2
([18]). Se(0) is also obtained in the
reduction of Se(IV) by protonated forms of hy-
droxylamine and semicarbazide [4,20], together
with a smaller amount [21] of H
2
Se. Reductions
with sodium borohydride [22] and a mixture of
H
3
PO
2
and HI [20] yields H
2
Se.
Aldehydes reduce Se(IV) to Se(0) and do not
form addition compound as with sultes [4].
Ascorbic acid reduces also Se(IV) to red form of
Se(0); the reaction can be utilized for titrimetric
determinations of Se(IV) [23].
The complex reactions of Se(IV) with sulfur
compounds will be discussed in Section 2.4.
2.4. Reactions with sulfur compounds
Among inorganic sulfur containing species con-
siderable attention has been paid to the reaction
of Se(IV) with sulte. This reaction has been used
in some analytical procedures to separate Se from
other components of the analyzed sample. In this
procedure elemental Se (obtained by reduction of
Se(IV) with iodide) is extracted from the sample
quantitatively at pH 89 by an excess of sodium
sulte. The reaction is chemically reversible, as
upon acidication with hydrochloric acid the ele-
mental selenium is again formed [12].
There is a strong indication that the composi-
tion of the reaction product may vary with a
stoichiometric ratio of Se(IV) to S(IV). Unfortu-
nately, the reaction between Se(IV) and S(IV) has
been often carried out in unbuffered solutions.
When SeO
2
was mixed with solutions of H
2
SO
3
,
NaHSO
3
and Na
2
SO
3
complex acidbase and
hydration-dehydration equilibria are established
and the nature of the reacting species is difcult to
identify.
Under conditions used in the most recent study
[24] the predominant product has been proved to
be selenotrithionate, with selenium as central
atom to which two SO
3
2
groups are linked, either
by SeO or by SeS bonds. Based on an analogy
of the reaction of Se(IV) with thiolates, the follow-
ing reaction scheme (5) (8) has been proposed:
HSO
3
+H
2
SeO
3
HSeSO
5
+H
2
O (5)
HSeSO
5
+HSO
3
OSe(OSO
2
)
2
2
+H
2
O (6)
OSe(OSO
2
)
2
2
+HSO
3
Se(OSO
2
)
2
2
+H
+
+SO
4
2
(7)
Se(OSO
2
)
2
2
slow
Se(SO
3
)
2
2
(8)
Reactions (5) to (7) are supposed to be fast so that
reaction (8) is the rate determining step. Neverthe-
less, no evidence has been offered for the kinetics
or intermediates involved in these processes.
Similarly, the reaction of Se(IV) with thiosulfate
[25] has also been carried out in unbuffered solu-
tions. In a reaction mixture consisting of 0.5 M
SeO
2
, 2 M Na
2
S
2
O
3
and 2 M HCl selenopen-
tathionate is formed (9):
H
2
SeO
3
+4S
2
O
3
2
+4H
+
Se(S
2
O
3
)
2
2
+S
4
O
9
2
+3H
2
O (9)
As selenopentathionate is formed [26] in reaction
of selenotrithionate with thiosulfate, it is probable
that selenotrithionate is an intermediate in the
formation of selenopentathionate.
In selenopentathionate, the central Se can be
bound either to two sulfurs (
O
3
S-S-Se-S-SO
3
),
to one sulfur and one oxygen atom (
O
3
S-S-Se-
O-SSO
2
), or to two oxygens (
O
2
S-S-O-Se-O-
SSO
2
). At higher pH-values the selenopentathion-

ate is cleaved and yields Se(0):
Se(S
2
O
3
)
2
2
S
4
O
6
2
+Se(0) (10)
Finally, the reaction of Se(IV) with thiocyanate
yields a selenium dithiocyanate [27] (11):
H
2
SeO
3
+4HSCN
Se(SCN)
2
+NCSSCN+H
2
O (11)
For the reaction of thiolates with Se(IV) a 4:1
stoichiometry was established and the following
reaction scheme proposed [2831]:
RSH+H
2
SeO
3
RSSeO
2
H+H
2
O (12)
RSH+RSSeO
3
H(RS)
2
SeO+H
2
O (13)
(RS)
2
SeORSH+RSSeOSR (14)
RSH+RSSeOSR(RS)
2
Se+RSOH (15)
RSH+RSOH(RSSR) +H
2
O (16)
In a consecutive reaction Se(0) is formed (17):
(RS)
2
Se
RS
Se+RSSR (17)
This latter reaction is the basis of a spectropho-
tometric procedure [32] for determination of
Se(IV), in which elemental selenium is dissolved
by an excess of thiolate (18):
Se+nRS
(RS)
n
Se (18)
Formation of species of the type (RS)
2
SeO,
named selenotrisuldes or bis(thio)selenides, has
been reported as products of reactions of alkylthi-
ols [29], 2-mercaptoethanol [31], thiosalicylic
[33,34] and thioglycolic [35] acids, but particularly
(because of their physiological importance) for
cysteine [36,37] and glutathione [36,38]. The mix-
ture of Se(IV) and glutathione catalyzes genera-
tion of superoxide radicals [39] and reacts with
mercury compounds [40,41]. Se(IV) reacts also
with methionine [42], but the product of this
reaction was not identied. The reaction of Se(IV)
with 1, 2-dimercaptoethane yielded in a pH-de-
pendent reaction [43] the compound:
The electrochemical reduction of (RS)
2
Se and of
(RS)
n
Se is assumed to involve a two-electron re-
duction (19) followed by a reduction of RSSR by
Se
2
ions (20) [38]:
(RS)
n
Se
n
+2enRS
(19)
Se
2
+RSSR2RS
+Se (20)
Bis(alkylthio)selenides RSSeSR undergo also
readily nucleophilic attacks, either on S or Se
depending on substituent R [44]. For glutathione,
formation of GSSeSG predominates at pH 2 and
pHB4 at a ratio [GSH]:[Se(IV)] B4:1 and this
species is reduced [45] by glutathione reductase
(gl.r.) (21):
GSSeSG+TPNH+H
+
gl.r.
GSH+GSSeH
+TPN
+
(21)
3. Electrochemical reduction
3.1. Reductions on mercury electrodes
3.1.1. Reduction at the dropping mercury
electrode
In the rst observation of polarographic reduc-
tion of Se(IV) the indistinct waves in 1 M HCl
were attributed to consecutive reductions to +2,
0, and 2 oxidation states, the single wave in an
ammonia-ammonium buffer to the formation of
Se(0) [46]. All these attributions turned out to be
wrong. Lingane and Niedrach [47] in a communi-
cation well advanced for the time-period recog-
nized correctly that between pH 0 and 11 the
reduction of Se(IV) occurs in three different
waves, i
1
, i
2
and i
3
. These authors concluded
correctly that in each of these waves another
ionized form of selenious acid is reduced. Never-
theless, due to the less developed state of theory
of polarographic processes that involve an-
tecedent acidbase equilibria at that time, their
attribution of i
1
to the reduction of H
2
SeO
3
, i
2
to
that of HSeO
3
and i
3
to that of SeO
3
2
was
incorrect. These authors [47] proved that electrode
processes in waves i
3
and i
1
(the latter followed by
a reaction of Se
2
formed with mercury ions)
correspond to a six-electron process, but their
attribution of wave i
2
to a four-electron reduction
was incorrect. In the following group of studies
[4853], the role of interaction of Se
2
ions
formed by electrolysis with mercury ions was mis-
understood and a process involving four-electron
reduction of Se(IV) and a formation of elemental
Se was erroneously proposed. Further studies of
the reduction of Se(IV) in various buffers [5459]
did not offer substantial new mechanistic
information.
The sharp-edged portion of wave
i
, in acidic
media was correctly attributed to a formation of a
mercury selenide [60] formed in an anodic process
[61]. The selenide ions, formed in a six-electron
reduction of Se(IV), react with mercury ions,
formed by anodic dissolution of mercury. Result-
ing selenide is slightly soluble and adsorbed at the
mercury surface. Similarly as sulde ions, selenide
ions are manifested on polarographic current
voltage curves by at least two anodic waves
[47,62]: the wave with the characteristic sharp
upper edge at about 0.6 V is formed at low
concentrations of selenide rst. At concentrations
of selenide higher than about 1210
4
M an-
other anodic wave increases with increasing con-
centration of selenide at about 0.2 V (actual
potentials depend on pH). The two anodic pro-
cesses result in different adsorbed layers, but it is
questionable, if these two adsorbates differ in the
oxidation state of mercury, in the stoichiometry of
the mercury selenide formed or just in the struc-
ture of the adsorbate (e.g. surface orientation).
The two adsorbates certainly occupy different ar-
eas at the electrode surface. Both these anodic
waves are superimposed on the cathodic wave of
the reduction Se(IV) Se(2). The description of
the process occurring at 0.7 V depends on the
direction of the voltage scan: When the potential
is scanned from negative (e.g. 1.0 V) to more
positive potentials (e.g. 0.0 V), the anodic current
corresponds to an oxidation of mercury and for-
mation of an adsorbate, as corresponds to Eqs.
(22) (24) from left to right. When the potential is
oppositely scanned from more positive to more
negative potentials, the increase in current at
about 0.7 V corresponds to a desorption of the
selenide and reduction of mercury ions, corre-
sponding to Eqs. (22) (24) from right to left:
nHg XHg
n
2+
+2e (n=1 or 2) (22)
Hg
n
2+
+2e
2
XHg
n
(23)
Hg
n
Se X(Hg
n
Se)
ads
(24)
In 3 M H
2
SO
4
the limiting current of Se(IV)
decreased over period of hours when standing in
the presence of metallic mercury. The decrease
was larger when a dropping mercury was im-
mersed into the standing solution than in the
presence of an unstirred mercury pool. The pas-
sage of drops of mercury through the solution
was hence more effective than the contact with the
mercury pool surface [61]. The white precipitate
formed was attributed to a formation of a mer-
cury selenite.
A formation of mercury selenide in the course
of reduction of Se(IV) in a perchloric acid solu-
tion has been conrmed [63] by controlled poten-
tial electrolysis at concentrations of Se(IV) lower
than about 510
4
M. At higher concentrations
of Se(IV) and vigorous stirring, Se(0) is formed,
possibly by reaction (25)
H
2
SeO
3
+2H
2
Se3Se+3H
2
O (25)
There is a competition between reactions (25)
and (23) involving Hg
2
2+
or Hg
2+
.
The overall shape of the part of wave i
1
more
positive than about 0.5 V is qualitatively simi-
lar for solutions of Se(IV) in HNO
3
, HClO
4
,
H
2
SO
4
and HCl at comparable acidities [60,64],
but quantitatively the current at a given potential
depends on the nature of the acid [65]. Changes in
the limiting current of wave i
3
observed in ammo-
niacal buffer pH 8.5 in wateralcoholic mixtures
[66] are either due to changes in viscosity or of
solvation of SeO
2
.
The decrease of current with increasing pH
corresponds to a decrease of the peak at about
0.6 V observed when DPP was used. The shape
of this peak and observed decrease of i
p1
with
increasing scan rate [67] indicates the role of
adsorption.
Based on a comparison of the shape of i =f
(pH) plots with equilibrium pK
a
values [1] (Sec-
tion 2.1) for H
3
SeO
3
+
, H
2
SeO
3
, and HSO
3
and on
the kinetic character of i
1
, i
2
, and i
3
when i B0.15
i
d
it was possible to show [68] that wave i
1
corre-
sponds to the reduction of H
3
SeO
3
+
, wave i
2
to
that of H
2
SeO
3
and wave i
3
to that of HSeO
3
.
The dianion SeO
3
2
is not reducible within the
accessible potential range, similarly as SO
3
2
is
not reduced. Limiting currents are controlled by
the rate of protonation, which can be accom-
plished by interactions with both the hydrogen
ions and acid buffer components [65,69]. The
shape of i
1
at pHB3 is complicated not only by
the additivity of the wave of reduction of H
3
SeO
3
+
to Se
2
and the two anodic waves mentioned
above, but also by current due to a nonfaradaic
oxidation of mercury(0) by H
3
SeO
3
+
and reduc-
tion of mercury ions formed [70].
A.C. polarography of acidic solutions of Se(IV)
shows a round, kinetic peak at 0.1 V and an
adsorption-desorption peak of HgSe at 0.65 V
[53,71]. Linear sweep and cyclic voltammograms
obtained on a single drop show three or more
cathodic peaks in acidic media resulting from
reduction of Se(IV) to selenide and reactions with
mercury. These peaks are replaced with increasing
pH rst by peak i
p2
and then by a small peak i
p3
.
Only the peak at about 0.65 V corresponding
to adsorptiondesorption of the mercury salt has
an anodic counterpeak [72].
3.1.1.1. Polarographic studies of Se(IV) in the pres-
ence of hea6y metal ions. Lingane and Niedrach
[47] observed that in ammoniacal buffer pH 8.4
polarographic waves of Cu
2+
and Se(IV) are not
additive. With increasing concentration of Cu
2+
the wave i
3
of Se(IV) decreased. They correctly
concluded that Se
2
ions formed at the electrode
surface react with Cu
2+
transported toward the
electrode. As the reduction in wave i
3
occurs at
negative potentials, where practically no mercury
ions are formed, the decrease of current in the
potential range where Se(IV) is reduced is actually
due to a decrease in Cu
2+
ions reduced caused by
formation of slightly soluble CuSe. This is an
early example of a system, called by Kemula [73]
latent limiting currents. In acidic media addition
of Cu
2+
ions resulted in a decrease of the more
negative portion of wave i
1
, due to a precipitation
of CuSe [61]. The reaction of Cu
2+
transported to
the electrode by diffusion with Se
2
generated at
the electrode has not recently been considered [5]
in the interpretation of the variation of the cur-
rent of Cu
2+
in the presence of excess of SeO
3
2
.
In acidic media, where any ZnSe formed is rela-
tively soluble, the addition of Zn
2+
ions does not
affect the wave i
1
of Se(IV). An addition of Hg
2+
ions decreases the wave at 0.6 V and its pre-
wave at about 0.4 V, but has little effect on
current of Se(IV) at potentials more positive than
about 0.3 V [56].
Measurements of limiting currents (as obtained
by d.c., sampled, or normal pulse polarography)
as a function of the composition of the reaction
mixture containing varying ratio of Se(IV) and
Me
n+
-ions is the simplest starting point for inves-
tigations of complex processes occurring in such
mixtures. Other techniques, such as a.c. polarog-
raphy (ACP), differential pulse polarography
(DPP) or square-wave polarography (SWP) are
less suitable for this task. This is due to (a) the
difculty to distinguish between cathodic and an-
odic processes, when these techniques are used.
This reects the fact that in these techniques
principally derivatives of the i E curve are
recorded. But more importantly these techniques
are less suitable, because for ACP, DPP and SWP
a theoretical treatment for the transport phenom-
ena has not yet been developed for systems where
electrolysis product may react with species trans-
ported from the bulk. In particular, such treat-
ment is needed for a situation where
electrogenerated selenide ions may be involved in
competing reactions with Hg
n
2+
(formed at the
electrode) and Me
n+
(transported from the bulk
of the solution). In the investigated potential
range, which is several hundred millivolts more
negative than the standard potential of the Hg
n
2+
+2e XHg couple, the surface concentration of
Hg
n
2+
will be several orders of magnitude smaller
than that of the Me
n+
ion transported from the
bulk of the solution. Moreover, interactions be-
tween Se
2
and metal cations in the vicinity of
the electrode will most probably be controlled by
kinetics rather than thermodynamics.
For these reasons various observations ob-
tained by ACP, DPP, and SWP in mixtures of
Se(IV) and Me
n+
are currently difcult to inter-
pret and thus only results will be reported here.
When ACP is used, Se(IV) yields in 0.03 M
HNO
3
, 0.08 M KNO
3
an adsorption-desorption
peak at 0.64 V. Addition of Pb
2+
results in a
decrease of this peak to practically zero at
[Se(IV)] =[Pb
2+
]. Simultaneously, an increase of
two new peaks at 0.68 and at 0.29 V is
observed. Both these peaks reach a limiting height
at [Se(IV)] =[Pb
2+
]. With a further increase in
[Pb
2+
] the peak at 0.29 V remains unchanged,
but the peak at 0.68 V shows a decrease with
increasing [Pb
2+
]; moreover, the peak of the re-
duction of free Pb
2+
ions at 0.47 V also in-
creases [71].
The ACP peak at 0.44 V in a solution of
Se(IV) (at concentration of the order of 10
7
M)
is a linear function of [Se(IV)], when 10
4
M
Cd(II) and Cu(II) are present. In a solution con-
taining 0.1 M HClO
4
, 0.1 M NaClO
4
, 0.043 M
EDTA and 10
5
M Pb
2+
, Se(IV) yielded a single
ACP peak at 0.62 V, the height of which is a
linear function of [Se(IV)]. In the same solution
DPP yielded two peaks at 0.53 and 0.62 V,
which both increased with increasing [Se(IV)] [74].
The addition of Hg
2+
to a solution of Se(IV) in
0.1 M HClO
4
results in a slight decrease of the
ACP peak at 0.6 V, but a marked decrease of
the peak at 0.0 V [63].
At low concentration of Se(IV) [6.310
7
M]
addition of excess Cu
2+
ions results in a decrease
of DPP i
p1
current, whereas at higher concentra-
tion of Se(IV) [1.310
6
M] addition of Cu
2+
results rst in a decrease in i
p1
, followed by an
increase at higher [Cu
2+
] [75].
In ammonical buffers the peak i
p3
is not af-
fected by the presence of Fe(III), Pb(II) and
Cu(II), which interfere with i
p1
when added in
acidic media [75]. Similarly in BrittonRobinson
buffer pH 4 addition of Cu(II), Cd(II) and Pb(II)
resulted in a decrease of the DPP Se(IV) peak at
0.6 V, but had no effect on i
p2
at 1.3 V [76].
The addition of Pb
2+
to a 310
5
M solution
of Se(IV) in 0.1 M HCl results in a decrease of the
adsorption-desorption peak at 0.54 V. In the
presence of 310
5
M Pb
2+
the adsorption
component of this peak is practically eliminated
and only a small, probably faradaic peak remains
at 0.54 V. Further increase in [Pb
2+
] results in
a small gradual decrease of the reduction peak at
0.54 V. In the absence of Pb
2+
, Se(IV) yields a
small peak at 0.33 V. The height of this peak
increases with increasing [Pb
2+
] as the peak at
0.54 V decreases. The maximum height is
reached when [Se(IV)] =[Pb
2+
]. This peak at
0.33 V is sharp and may be affected by adsorp-
tion. In the presence of excess [Pb
2+
], a peak of
free Pb
2+
ions appears at 0.41 V. At a twofold
excess of Pb
2+
, the peak at 0.41 V is smaller
than the peak at 0.33 V.
The addition of Se(IV) solutions to a solution
of 310
5
M Pb
2+
results in a replacement of
the peak of free Pb
2+
ions at 0.41 V by a peak
at 0.33 V and in an increase of the peak at
0.54 V. At an excess of Se(IV) the peak at
0.33 V does not increase with increasing
[Se(IV)]. This tendency to reach a limiting height
indicates effect of adsorption. This is further sup-
ported by the effect of temperature. An increase
of temperature from 25 to 45C results in an
elimination of the peak at 0.33 V. On cooling
to 25C the peak at 0.33 V reappears.
The addition of Se(IV) to a solution of Cd
2+
ions that are reduced at 0.62 V results in a
decrease of this peak and formation of a new
peak at 0.41 V. Addition of Cu
2+
ions has a
relatively small effect on the peak i
p1
at 0.54 V
[77].
In cyclic voltammetry carried out at a single
mercury drop [72] addition of Cu
2+
results at pH
1.5 in a shift of the adsorptive peak at 0.7 V to
more positive potentials, increase in the small
peak at 0.3 V and formation of a new peak at
about 0.0 V. When Cu
2+
was added at pH 6.0 the
sharp adsorptive peak at 0.8 V disappears and
new peaks at about 0.1 and 0.0 V are formed.
Addition of Hg
2+
resulted in a decrease of peaks
at 0.7 and 0.3 V.
3.1.1.2. Applications of polarographic methods for
determination of Se(IV). For analysis of relatively
pure samples, recording of current voltage curves
in ammoniacal buffers has been recommended
[47,78]. As selenates are not reduced at the DME,
determination of Se(IV) in the presence of Se(VI)
is straightforward [64]. After a conversion of
Se(VI) into Se(IV) in 3.6 M HCl the total amount
of Se can be determined. Simultaneous determina-
tion of Se(IV) and Te(IV) is possible in support-
ing electrolytes containing 1 M ammonium salts
of various organic acids [79].
The most common interference in the determi-
nation of Se(IV) are Cu(II) ions. To determine
Se(IV) in the presence of Cu
2+
ions the sum of
Se(IV) and Cu(II) was determined in solution of
perchloric acid at pH 23 and Cu
2+
had to be
determined separately in an ammoniacal buffer
pH 8.39. From the difference the concentration
of Se(IV) can be obtained [80]. Alternatively, it is
possible to use the reaction of 4-chloro-1, 2-
phenylpiazselenol [81]. In a formate buffer pH 2.5
this compound yields two peaks at 0.11 and
0.62 V, which depend on [Se(IV)]. In the ab-
sence of Se(IV) in the solution of the diamine
ligand two other peaks at 0.41 and 0.97 V
are present. The peak at 0.97 V may corre-
spond to a catalytic hydrogen evolution, that at
0.41 V to an oxidation of the phenylenediamine
(as DPP does not allow distinguishing between
cathodic and anodic processes). But even this
procedure shows interferences by Cu
2+
, Sn
2+
and Ni
2+
; these ions must be separated using a
Chelex-100 resin column.
Two main areas of applications of polaro-
graphic determination of Se(IV) are the analyses
of waters and soils. In a procedure using dc
polarography Se(IV) was chemically reduced to
Se(0), separated by ltration and dissolved in a
solution containing HBr and Br
2
. After removal
of excess of Br
2
by CO
2
Se(IV) was determined in
2 M HCl [82].
To determine Se(IV) in contaminated water,
adsorption-desorption DPP peak at 0.63 V in
0.1 M HNO
3
can be used after heavy metal ions
are removed on Chelex-100 resin [67]. When an
ammoniacal buffer containing Na
2
SO
3
is used [76]
the peaks at 0.6 and 0.8 V, attributed to the
reduction of the SeSO ion, are not affected by
heavy metal ions which need not to be removed
prior to recording of the DPP i E curve. This
procedure was used for analyses of Asian river-
waters. A similar approach was used for analyses
of waters from Chinese rivers [83]. When the
determination of Se(IV) was carried out in soil
using as a supporting electrolyte a buffer pH 8.0
consisting of 1.0 M ammonium acetate and 0.01
M EDTA, no serious inorganic interferences were
encountered [75].
Using a linear sweep voltammetry with a DME
for determination of Se(IV) in vegetables [84],
Se(0) obtained by reduction with ascorbic acid
was oxidized by bromine in hydrobromic acid.
After removal of excess bromine the peak at
0.35 V was measured.
In spite of the complex nature of the reaction
between Se(IV) and SO
2
(Section 2.4), such reac-
tion between Se(IV) and SO
2
in 3.04.0 M HCl
was reported to be fast and quantitative. From
the decrease in the DPP adsorption-desorption
peak at 0.5 V it was possible to determine SO
2
in air [85].
For the determination of Se(IV) in biological
material, a catalytic electrochemical processes
have recently been used. The sample is rst
treated with permanganate in a mixture of sulfuric
and perchloric acid and left to react for 20 min.
Then a mixture of sodium sulte, thiocyanate,
mandelic acid and potassium chlorate is added,
left to react for 1 h at 75C, some more thio-
cyanate is added and a peak at 0.2 V on DPP
current voltage curve measured [86]. It is as-
sumed that Se(IV) oxidizes mandelic acid to ben-
zaldehyde and Se(0) formed is reoxidized by
chlorate to Se(IV). Nevertheless, in the presence
of sulte and CNS
ions other reactions men-

tioned in Section 2.4 may be involved. In a
medium containing sodium sulte and potassium
periodate Se(IV) yields a catalytic wave which can
be used for analysis of hair [87]. A similar reac-
tion has been carried out in a mixture containing
HNO
3
, HClO
4
, HCl, citric acid, Na
2
SO
3
and
EDTA, which is added to a ammoniacal buffer
containing phenolphalein and potassium iodate
[88]. Peak currents obtained by LSV were mea-
sured at 0.8 V. Use of EDTA eliminates inter-
ferences by many metals. The linear dependence
on mercury pressure (h) indicates that the current
depends on the surface area and is most probably
controlled by adsorption. This conclusion is sup-
ported by the decrease of i
p
in the presence of
surfactants. It is assumed [88] that the reaction of
Se(0) with SO
3
2
yields SeSO
3
2
which is consid-
ered to be the reducible species (26). Selenide
formed is then reoxidized by iodate (27):
SeSO
3
2
+2eSe
2
+SO
3
2
(26)
Se
2
+IO
3
+12H
+
Se(0) +I
2
+6H
2
O (27)
Finally, a catalytic wave obtained by treatment of
the blood serum with a mixture of H
2
SO
4
, HClO
4
and ammonium molybdate has been used to de-
termine Se(IV) in blood serum [89].
3.1.2. Beha6ior of Se(lV) on static mercury
electrodes
The majority of electrochemical studies with
mercury electrodes, the surface of which is not
renewed, involved the use of a hanging mercury
drop electrode (HMDE) and the most common
technique was the linear sweep (LSV) or cyclic
voltammetry (CV). The current-voltage curves ob-
tained by CV using HMDE in acidic media are
characterized by a sharp peak at about 0.6 V,
the potential of which depends on pH and con-
centration of Se(IV) [53,63,72,9094]. This peak
corresponds to an adsorption-desorption process
involving one or more layers of mercury selenide
which is accompanied by an oxidation reduction
of the couple Hg
n
2+
/Hg(0), as was indicated in
Section 3.1.1 and Eqs. (22) (24). This peak ap-
pears in the same potential range where in dc
polarography the most negative, sharp-edged an-
odic wave is observed, which corresponds to an
anodic dissolution of mercury and formation of a
slightly soluble mercury selenide at the electrode
surface. A corresponding anodic peak is also ob-
served on cyclic voltammograms in solutions of
H
2
Se, which on reverse sweep yields a sharp ca-
thodic desorption-reduction (further des-red)
peak. Nevertheless, the ratio i
cath
:i
anod
which in
solutions of Se
2
is close to 1.0, is in solutions of
Se(IV) usually smaller than 0.1 [90,93]. This indi-
cates that during the scan from about 0.5 to
1.2 V and back to 0.5 V Se
2
ions can
undergo competitive processes. This is supported
also by the dependence of the ratio of i
cath
:i
anod
on
the rate of voltage scanning.
Depending on concentration of Se(IV) the
sharp cathodic des-red peak can be split into two
or even three peaks. The number of peaks ob-
served by individual authors differs: in 13
10
6
M Se(IV) were reported two peaks [90,93],
at 110
5
M Se(IV) two [93] or three [90] peaks,
in 110
4
M Se(IV) two [63,90,92] or three [93]
peaks and in 110
3
M Se(IV) one [93], two
[63], or three peaks [90]. The role of voltage scan
rate and drop-size cannot be excluded in explana-
tion of these differences.
At potentials more negative than about 0.8
V H
2
Se is the main reduction product and no
interaction with mercury takes place. The H
2
Se
formed at the electrode can react with Se(IV)
transported to the electrode and form Se(0) ac-
cording to reaction (25). This is demonstrated by
formation of a red, colloidal precipitate in the
vicinity of the electrode [47,50,72,90,92].
The i E curve at potentials more positive than
about 0.6 V has a peculiar shape [47,63,9094]
which indicates an overlap of several processes.
First indication that different processes play a role
in this potential range was the dependence of the
height of the stripping peak (Section 3.1.3.1) on
the accumulation potential [95], which indicated
different reactions occurring in three potential
ranges: (A) between :+0.2 and 0.15 V; (B)
between 0.15 and 0.35 V, and (C) between
0.35 and 0.5 V. Only the accumulation in the
(A) and (C) range yielded a single, well dened
cathodic des-red peak [63].
Repeated cyclic scans between 0.0 and 1.2 V
resulted in a marked decrease of current in the
range A and a small decrease in range C [92].
Increase in pH in acetate buffers at pH\3.8 (in
the presence of 0.01 M EDTA) resulted in a
decrease in current larger in range A than in C
[92]. Current in range A increases markedly with
decreasing temperature, but shows little change in
range C [92]. When the adsorbate was generated
at +0.2 V, then chronoamperometric reduction
at potentials in the range A indicated complex
kinetics, whereas at potentials in the range C the
decrease in current followed simple kinetics [93].
In range A also the formation of Se(0) has been
reported [50]. Whereas current in ranges B and C
was found to be independent of the nature of the
strong acid used, current in range A varied de-
pending on if 0.1 M HClO
4
, 0.1 M HNO
3
and
most markedly if 0.1 M H
2
SO
4
was used [90].
D.C. anodic waves of selenides with a sharp
edge [47], observed at about 0.6 V, are a linear
function of selenide concentration only below
about 110
4
M. At higher concentration of
Se
2
this wave reaches a limiting value and an-
other wave at more positive potentials increases.
The presence of two waves is attributed to a
formation of two different adsorbates. The pro-
cess occurring in the more positive wave may
correspond to one of the process in the potential
range B or A.
A microscopic observation of the surface of the
HMDE in the course of controlled potential elec-
trolysis of 110
3
M Se(IV) indicated different
appearances of deposits obtained at different po-
tentials [90]. Under above conditions multilayer
deposits are formed. On top of such deposits
formation of some Se(0) was assumed [93], but
experimental evidence based on photocurrent
measurement is not unequivocal. The surface of
these lms is namely black rather than red.
When the electrolysis of 110
3
M Se(IV)
was carried out with HMDE for 4 min at 0.34
V in an unstirred solution, deposit corresponding
to about 40 monolayers was formed [90]. When
now some mercury was drawn from the drop, a
wrinkled bag was formed. This demonstrates that
the slightly soluble deposit is strongly adsorbed at
the surface of the mercury drop. When the chosen
potential for electrolysis was more negative than
about 0.7 V, removal of some mercury from
HMDE resulted in a smaller perfect sphere rather
than in a bag. In this potentials range all of HgSe
is desorbed and no deposit is formed.
Thus at potentials more positive than about
0.6 V at least three different processes take
place. The process occurring at potentials more
positive than about 0.15 V is limited by the rate
of a chemical reaction. This is indicated mainly by
its dependence on pH and temperature. Our pre-
liminary results [70] suggest a reaction between
H
3
SeO
3
+
and metallic mercury. Other processes
involved result in a formation of several different
adsorbates of mercury selenides. The differences
between these adsorbates may be caused by for-
mation of mono- and multilayers, of adsorbates
forming islands rather than a monolayer instead
of growing larger these islands can grow higher by
forming multilayers. When islands are formed,
electrochemical reactions can occur between these
islands or through these islands. The adsorbates
can also differ in orientation of monomers and/or
chemical composition of monomers, for example
in the oxidation state of mercury and/or stoi-
chiometry of slightly soluble species. To make
decision between these alternatives can be further
complicated by aging of adsorbates, both in solu-
tion and by solid state reactions.
The adduct of Se(IV) and glutathione (Section
2.4) yields in 0.04 M NaOH, 0.1 M KCl an
irreversible cathodic peak at 0.89 V. To convert
all Se(IV) into the adduct a tenfold excess of
glutathione is needed [38].
Differential pulse linear sweep voltammetry of
Se(IV) in 0.2 M HCl yielded very large des-red
peak at 0.45 V, smaller sharp peak at 0.07 V
and a very small peak at 0.14 V 96. Square-
wave voltammetry on HMDE yielded in the range
A to C one or two peaks depending on the
frequency of the square wave [91].
Controlled potential electrolysis at a mercury
pool electrode in a 110
4
M solution of Se(IV)
at pH 4.2 yielded at potentials more positive than
0.6 V a black lm and at more negative poten-
tials a thin layer of colloidal Se(0) formed by
reaction (25).
3.1.3. Stripping analysis using mercury electrodes
To increase the sensitivity and possibly also
selectivity of electroanalytical determination of
Se(IV), selenium is accumulated at the mercury
electrode, usually as a mercury selenide, by elec-
trolysis at a constant potential. The accumulated
mercury compound is then dissolved using a po-
tential sweep, using either a dc voltage (in LSV or
CV), differential pulse, square wave or ac super-
imposed voltage.
3.1.3.1. Principles. In spite of the wide use of
stripping determination of Se(IV) in various mate-
rials (Section 3.1.3.3) only limited attention has
been paid to a systematic evaluation of factors, on
which this determination is based. In cathodic
stripping voltammetry of Se(IV) the number,
shape and height of reduction peaks depends on
deposition potential, time-period of accumulation,
and equilibration, the rate of stirring of the solu-
tion during the accumulation, composition of the
analyzed solution particularly on acidity, pres-
ence and concentration of complexing agents,
presence of other cations and the concentration
range of Se(IV) as well as on conditions of the
stripping, such as the shape of the voltage ramp,
potential range and direction of the voltage scan
and duration of the period between application of
the starting potential and beginning of the record-
ing of the current voltage curve. Rarely the
choice of working conditions has been based on
systematic optirnization of the above parameters.
Usually such conditions were selected empirically,
using trial and error approach and all conse-
quences of the choice made were not fully
understood.
Among the above factors perhaps the most
important is the choice of the deposition potential
(E
d
). The electrodeposition must be carried out at
a potential at which the mercury selenide is
formed, for example in 0.1 M HClO
4
at a poten-
tial more positive than about 0.6 V. In the
available scope of potentials it is possible to dis-
tinguish three ranges, as discussed in Section
3.1.2: (A) between +0.2 and 0.15 V; (B) be-
tween 0.15 and 0.35 V; (C) between 0.35
and 0.5 V.
When E
d
is chosen in the range A, a single
stripping des-red peak at about 0.65 V is ob-
served. The height of this peak varies with poten-
tial E
d
between +0.05 and 0.15 V. The plot of
i
p
as a function of E
d
is a bell-shaped curve with
a maximum at about 0.05 V [95,96]. The de-
pendence of i
p
on [Se(IV)] is non-linear with two
linear segments, one up to 210
7
M Se and the
other above 310
7
MSe [63].
The adsorbate formed under these conditions
adheres so strongly to the electrode surface, that
the drop with the adsorbate can be transferred
into another solution and the stripping can be
carried out in a blank supporting electrolyte [94].
As an electrolyte either 0.1 M HClO
4
([63]) or
preferably 0.1 M HCl [94,95] are used. The peak
potential of the stripping peak is shifted with
increasing concentration of HCl or HBr to more
negative potentials [94]. The peak height decreases
with increasing temperature [94]. The interfer-
ences differ from those observed at E
d
=0.35 V
(see below). The stripping des-red peak is unaf-
fected by large excess of Pb(II), Cd(II), As(III),
Te(IV), Mn(II), Tl(I) and Zn(II). Only Sb(III) and
Bi(III) interfere when present in 10-fold, Cu(II)
and Fe(III) in twofold excess [94].
When the deposition potential (E
d
) is chosen in
the range B, ill-dened, multiple stripping peaks
are observed, unsuitable for analysis. Poor shape
of i E curves is observed particularly at higher
concentration of Se(IV) and longer accumulation
times [63].
In the C range, starting at 0.3 V the stripping
peak of Se(IV) increases with increasingly nega-
tive potential [95] until it reaches a limiting value
between about 0.45 and 0.6 V [96]. A differ-
ent dependence of the height of the stripping peak
on E
d
, a bell-shaped one with a maximum at
0.3 V has been reported for studies in sea water
[98] (no information on E
p
of the stripping peak),
in 0.24 M HClO
4
and 0.12 M HCl [99] and when
the stripping peak at about 0.0 V was followed
[100] using a mercury coated graphite wax
electrode.
The stripping current at about 0.6 V depends
on duration of the pre-electrolysis and this de-
pends naturally on concentration of Se(IV) [95].
The dependence of the peak current on concentra-
tion of Se(IV) consists again of two linear seg-
ments, one up to 710
7
M Se and the other
above 210
7
M Se [101], but the shape of the
plot i =f {[Se(IV)]} is different from that ob-
served for E
d
=0.05 V [63]. At E
d
=0.4 V
Fe(III), Cu(II), Pb(II), Cd(II), As(III), and Tl(I)
interfere already at concentrations comparable
with that of Se(IV) [94]. By addition of EDTA, at
[EDTA] B10
6
M, interferences of these ions
were suppressed. The shape of the i
p
=f [Se(IV)] is
affected by the presence of EDTA, so for a given
calibration curve concentration of EDTA must be
kept constant.
When E
d
=0.45 V is applied, one or two
stripping peaks were obtained with square wave
cathodic stripping voltammetry [91]. At 10
5
M
Se(IV) a single peak was observed, when the
squarewave amplitude was 40 mV, but that split
into two peaks, when the amplitude was 100 mV.
At 10
4
M Se(IV) two peaks are observed [91], a
sharp one at about 0.55 V and a round one at
0.7 V. First peak, at 0.55 V, corresponds to
a reversible electrode process and its height in-
creases rapidly after E
d
=0.45 V has been ap-
plied. It reaches within 2 s a maximum value after
E
d
=0.45 has been applied and decreases only
very slightly over next 200 s. On the other hand,
the height of the peak at 0.7 V increases slowly
over a period of hundreds of seconds. For both
peaks, at 0.55 and 0.7 V, the peak current is
not a linear function of concentration of Se(IV).
The curves obtained with the stripping peak at
about 0.6 V obtained with SWV is by a factor
of 23 larger than the peak, obtained with the
same solution, using DPV.
3.1.3.2. Role of the metal ion. As mentioned in
Sections 3.1.1.1 and 3.1.3.1, the determination of
Se(IV) is affected by the presence of heavy metal
ions [94]. Such interferences may be due to an
overlap of a signal due to metal ion with the
signal of Se(IV) which is measured. Alternatively
in the presence of a metal ion the signal due to
Se(IV) is changed, or the change in the signal of
Se(IV) is accompanied by an increase of a new
signal. Only some of these interferences can be
eliminated by addition of a strong complexing
agent like EDTA.
Even when the role of numerous metal ions on
stripping peaks of Se(IV) was observed (e.g. [94])
greatest attention has been paid to the role of
Cu(II) ions, as their effect is most pronounced
and as they are often present in various samples
at concentrations higher than that of Se(IV). The
situation is somewhat confusing, as with increas-
ing concentration of Cu
2+
ions the height of the
stripping peak of Se(IV) was reported either de-
creasing [96,102] remaining unchanged (with a
shift of the peak potential) [103] or increasing
[97,98,100,104,105]. Alternatively a replacement
of one peak by another was reported [105]. This
discrepancy is due to the fact that the electro-
chemical behavior of Se(IV) in the presence of
Cu
2+
depends on initial concentration of Se(IV),
on the ratio [Se(IV)]:[Cu(II)], on composition of
the supporting electrolyte, on the deposition po-
tential used, on the duration of accumulation and
on the stripping peak observed.
The increase of the height of the Se(IV) strip-
ping peak reaches with increasing concentration
of Cu(II) a limiting value, above which the peak-
height is independent of concentration of Cu(II).
In the presence of 310
5
M Cu
2+
and 8
10
3
M EDTA the height of the Se(IV) stripping
peak is independent of E
d
from 0.0 V to 0.4 V
[105].
The independence of the peak of Se(IV) of a
sufciently high concentration of Cu
2
is the basis
of numerous recent analytical applications of the
Se(IV) stripping peak. At sufcient excess of
Cu(II) the height of the Se(IV) stripping peak is a
strictly linear function of [Se(IV)] and indepen-
dent of smaller variations in [Cu
2+
]. To samples,
which do not contain a sufciently high concen-
tration of Cu
2+
, excess of a Cu(II) compound is
added.
Using square wave cathodic stripping voltam-
metry the inuence of Cu
2+
on stripping peaks of
Cu
2+
has been studied in some detail [91]. Addi-
tion of Cu(II) ions to a solution of 310
8
M
Se(IV) results at low concentrations of Cu
2+
in a
stripping peak at about 0.5 V to be at concen-
tration larger than about 110
6
M gradually
replaced by a sharp peak at 0.6 V. This latter
peak is at concentrations larger than 710
5
M
Cu
2+
the predominant one and is about four-
times higher than the peak at concentration of
Cu
2+
smaller than 110
6
M. The potential of
the peak at 0.5 V is independent of concentra-
tion of Cu
2+
, that of the peak at 0.6 V is
shifted to more negative potentials with increasing
concentration of Cu
2+
. The peak current at 0.6
V is a linear function of the logarithm of the
frequency. The peak current at 0.6 V also
increases with scan increment and depends on the
amplitude of the square wave in a bell-shaped
curve [91].
At higher concentrations of Se(IV), such as
110
5
M, and at shorter deposition times,
different results are obtained. The peak height
does not increase with scan increment and no split
of the peak is observed at high amplitude. At
110
5
M Se(IV) and deposition time of 2 s the
electrode reaction at 0.6 V is reversible both in
the absence and presence of Cu
2+
: product and
reactant are adsorbed in the absence, but only the
reactant in the presence of Cu
2+
. On the other
hand at 110
7
M Se(IV) and much longer
deposition time (60 s) the electrode process is
reversible in the absence, but irreversible in the
presence of Cu
2+
. Under these conditions the
product and reactant are both adsorbed in the
absence, whereas only the reactant in the presence
of Cu
2+
.
Stripping peaks of Se(IV) and As(III) are non-
additive. Peak of As(III) in 0.18 M H
2
SO
4
at
0.72 V increases with increasing concentration
of Se(IV), even if Se(IV) yields in this medium
using a linear voltage sweep a peak at 0.58 V
[106]. In 1 M HCl containing 210
3
M Cu
2+
and 310
8
M As(II) addition of Se(IV) re-
sulted in an increase of the Se(IV) peak at 0.6
V and a decrease of the As(III) peak at 0.75 V
[107].
In 0.1 M H
2
SO
4
containing 110
7
Rh(III) a
large, sharp stripping peak at about 1.0 V is
observed in the presence of 310
9
M Se(IV)
after accumulation at 0.20 V for 60 s. This
peak, attributed to desorption-reduction of
Rh
2
Se
3
, is a nonlinear function of the scan rate.
Its peak current varies with E
d
in a bell-shaped
curve with a maximum at 0.2 V and increases
by about 50% when the concentration of sulfuric
acid is increased from 0.01 to 0.2 M.
Analytical method based on this peak is much
more (at least 10 times) more sensitive than the
determination of Se(IV) in the presence of Cu
2+
and enables 10
10
to 10
11
M Se(IV) solutions to
be analyzed. No interference is observed for 100
fold excess of Cu(II), Zn(II), Pb(II), Cd(II),
Co(II), Ni(II), Bi(III), Mn(II), Fe(III), Tl(I),
As(III), Mo(VI), Ti(IV), V(V), Cr(VI), In(III),
Pd(II), U(VI), Pt(II), Zr(IV), Ge(IV), Nb(V) and
La(III). Only Te(IV) is limited to a vefold excess
[108].
3.1.3.3. Applications of stripping analyses. In prac-
tical applications, the sensitivity of the determina-
tion of Se(IV), which is often present in ultralow
levels, is essential. This can be achieved by reduc-
ing Se(IV) and accumulating mercury selenide in
one of the potential ranges mentioned in Section
3.1.3.1 and measuring the desorptionreduction
current (des-red) usually at about 0.6 V. This
accumulation, together with a stripping procedure
using pulse and square-wave techniques and the
effect of some metal ions, allows to reach suf-
cient sensitivity, in some cases up to 10
11
M.
The reliability of such determinations is neverthe-
less limited by changes in the measured signal
(peak current) in the presence of some metal ions,
as well as As(III) and Te(IV), in the sample. To
minimize these interferences several physical,
chemical, and electrochemical approaches have
been proposed.
In some instances it was possible to carry out
the stripping analysis directly in the analyzed
sample, probably because the samples contain a
sufcient excess of Cu
2+
. The stripping can be
carried out in HCl using a linear potential sweep
[99,109112] as well as in 1 M (NH
4
)
2
SO
4
con-
taining 0.4 M EDTA [113]. In the presence of an
excess of thioglycolic acid the observed des-red
peak of the reaction product was 23 times higher
than the peak of free Se(IV). Moreover, the peak
of the product is unaffected by a 100-fold excess
of Cd(II), Pb(II), Ni(II), Cr(III) and Sb(III) and
its height decreases only in the presence of Cu(II)
[35]. When a graphite wax electrode coated with
mercury [114] was used for the stripping at E
D
=
0.6 V, following the peak at 0.1 V enabled
determination of Se(IV) without interference from
Fe(III), Cu(II), and Pb(II) [115]. Differential pulse
stripping voltammetry has also been successfully
used for such direct analyses [116118].
In the presence of excess of Cu
2+
ions, the
stripping can be followed using a linear voltage
ramp [98,100,109], possibly in the presence of
citrate as complexing agent [120]. Alternatively,
differential pulse [103,107] or square wave voltam-
metry [91] can be used. Stripping was also carried
out in the presence both of Cu
2+
and EDTA,
using linear voltage ramp [97,121], differential
pulse [97] or ac voltammetry [121]. Differential
pulse voltammetry was also used for stripping in
the extremely sensitive procedure in the presence
of Rh(III) [108].
Anion-exchange resins were used to separate
Se(IV) from the sample [95] and cation-exchange
resins for removal of interfering cations [102].
Another example of pre-separation based on
physicochemical principles is the application of
extraction using pentanol [122,123] and accumula-
tion on a mercury plated graphite wax electrode
[114]. Esterication of selenious acid by the alco-
hol is assumed. When oxygen ask combustion
was used for sample decomposition, volatile Se
was absorbed in a persulfatesulfuric acid mix-
ture. Treatment with HCl enabled cleavage of the
excess of persulfate and conversion of Se(VI) into
Se(IV), which was determined by stripping analy-
sis [102]. Alternatively, after wet ashing selenium
was converted into 3%, 4%-diaminophenylpiazse-
lenol and extracted into benzene. Back extraction
into dilute acid enabled selective stripping analysis
[124,125].
In a unique approach, Se(IV) was reduced with
borohydride to Se
2
, converted into volatile H
2
Se
which was separated by a stream of a gas from
the sample, trapped in an alkaline solution and
analyzed by differential pulse cathodic stripping
voltammetry [126].
Stripping peaks were also used in detectors for
HPLC [127] and ow injection analysis [128130].
Because of its physiological importance, numer-
ous stripping determinations of Se(IV) were used
for analyses of biological material. Thus analyses
were carried out of blood and serum
[99,109,115,123], urine and liver [110,118], and
food, in particular of milk [95,130], bovine liver
[95,110112,118], animal muscle [95,110,118],
sausage and pig kidney [130], seafood and sh
[110112], rapeseed oil [124] and brewers yeast
[103]. It had also been used for analyses of plants
[120], seed [124] and orchard leaves [110,118] as
well as of soils [102].
Another area of frequent applications are deter-
mination of Se(IV) in waters, such as rain and
snow [91,117,118], ground, well and river water
[108,128], tap water [119,128] and seawater
[98,125].
Cathodic stripping can be used for analyses of
samples containing both Se and Te [97,121] and
was used for analyses of minerals, such as basalt
[107] and also of semiconductor alloys [113].
3.1.3.4. Adsorpti6e stripping. The adsorptive strip-
ping is based either on adsorption of a compound
(usually organic) at the surface of an electrode or
on conversion of an ion into a bulky, usually
uncharged, hydrophobic species which is ad-
sorbed at an electrode. Such adsorption results in
an accumulation of the species at the electrode
surface. Potential sweep is then applied and the
peak current at the potential where the desorption
occurs is used for analysis.
For the determination of Se(IV) the adsorbed
species was in most instances a piazselenol,
formed in a reaction of an aromatic diamine with
Se(IV). As the reagent, 3, 3%-diaminobenzidine
[101], o-phenylenediamine [131], or 2, 3-diaminon-
aphthalene [132] were used for this purpose. For
o-phenylenediamine in BrittonRobinson buffer
pH 2.0 the peak stripping current at 0.62 V
changes with E
d
in the bell-shaped curve with a
maximum at 0.45 V [131]. At 610
6
M
Se(IV) a smaller peak at 0.13 V was observed,
controlled by adsorption. For 310
7
M Se(IV)
in the presence of 2, 3-diaminonaphthalene the
peak at 0.06 V was predominant and its peak
current in 0.1 M HClO
4
or HNO
3
and in acetate
buffer pH 4.5 was independent of E
d
between
+0.2 and 0.0 V. In 0.1 M HCl the dependence of
i
p
on E
d
had a maximum at +0.05 V [132].
Neither the mechanism of the process involved in
the desorption-reduction peak at 0.62 V nor
that at 0.06 V is understood, as the electro-
chemical reduction of piazselenol also is not un-
derstood in sufcient detail, but it seems that in
the electroreduction of piazselenol HgSe is formed
which is adsorbed at more positive potentials, but
desorbed and reduced at 0.6 V. Similarly, HgSe
can be formed and stripped at about 0.65 V,
when Se(IV) is reacted with 2, 5-dimercapto-
1, 3, 4-thiadiazole [133].
3.2. Electroanalytical beha6iors of Se(IV) on
other metals and their applications
Most attention has been paid to reduction of
Se(IV) and properties of its reduction products on
gold and carbon electrodes, but some reports deal
with electrochemistry of Se(IV) on other metals
and metal oxide electrodes.
3.2.1. Beha6ior on gold and sil6er electrodes
Contrary to an earlier report [134], the reduc-
tion of Se(IV) on gold (and similarly on carbon
and platinum, see below) electrodes is a six-elec-
tron process yielding Se
2
[135]. Any formation
of Se(0) which can be observed, is due to a
chemical reaction between Se
2
formed at the
electrode and Se(IV) transported to the electrode
by diffusion from the bulk of the solution [135],
following Eq. (25). The reaction takes place in
acidic solutions and Se(IV) acts as oxidant proba-
bly in the form of H
3
SeO
3
+
.
Under comparable conditions, namely, similar
surface area, central rotation speed and scan rate
of 33 mV s
1
[134] or 10 mV s
1
[135] peak-
shaped current voltage curves were recorded in
0.1 M HClO
4
containing 510
5
M Se(IV)
[134], whereas in 510
3
M solutions of Se(IV)
in 1 M H
2
SO
4
limiting currents were observed
[135]. In the latter case, a single wave with E
1/2
about 0.4 V was observed, which appeared in a
similar potential range as corresponding waves
obtained with platinum or carbon electrodes. The
process at 0.4 V was earlier [134] erroneously
attributed to H
2
-evolution. In the 510
5
M
solution a cathodic adsorptiondesorption peak
at +0.25 V and a wave at about 0.0 V were
observed [134]. On the reverse sweep appeared
three anodic peaks at +0.63, +0.8 and +1.15
V. Their attribution to oxidation of Se(0) in view
of the above observation is doubtful. On gold
plated glassy carbon electrode only an indistinct
cathodic wave at 0.0 V occurred together with
anodic peaks at +0.67, +0.8 and +1.0 V on the
reverse sweep.
No interference was observed for Pb(II), Cd(II)
and even Cu(II) which was anodically stripped at
+0.1 V. No evidence for multiple peaks for Cu or
Se was reported. Determination of Se(IV) based
on anodic stripping using the peak at 0.8 V was
used for analysis of bovine liver and gave excel-
lent agreement with certicate value [134].
In a solution of 510
4
M Se(IV) in 1 M
H
2
SO
4
in the presence of 0.1 M CdSO
4
, the
six-electron reduction of Se(IV) occurs at 0.5
V, followed by an increase in current at 0.7 V
due to the reduction of Cd
2+
. Reversal of the
scan-direction at 0.7 V yields a sharp anodic
peak, which corresponds to a re-oxidation of Cd
superimposed on the Se(IV) reduction wave. The
potential of the Se(IV) reduction wave is shifted
to 0.4 V. This shift is caused by the reduction
of Se(IV) not on the gold surface, but on a
deposited layer of CdSe. The shift is attributed to
a high nucleation over-potential caused by the
layer of CdSe on the gold surface. Similar effect
was observed also on a carbon electrode [135].
At low concentrations of Se(IV) the CdSe lm
formed contains only a small excess of Se(0). On
the other hand at concentrations of Se(IV) be-
tween 1 and 310
3
M (in the same supporting
electrolyte as above), it is possible to deposit CdSe
lms on both gold and carbon surfaces. Such
lms contain usually larger amount of Se(0). This
is supported by a p-type behavior after illumina-
tion with white light.
When Se(IV) was deposited at 0.4 V on a
glassy carbon electrode plated with gold, a single
anodic stripping peak was observed at about +
1.0 V, if the concentration of Se(IV) was lower
than about 510
6
M. At higher concentrations
of Se(IV) another anodic peak increased at poten-
tials by about 0.2 V more negative. Using the
peak at 1.0 V it was possible to carry out determi-
nation of Se(IV) in the range from 210
9
M to
210
6
M. This procedure too showed an excel-
lent agreement with certicate value for determi-
nation of Se(IV) [136].
To determine selenium and tellurium in elec-
trolytic copper, the sample is dissolved in nitric
acid. To eliminate interferences due to nitrite (lib-
erated during dissolution of the metal sample in
nitric acid), antimony and arsenic, hydrogen per-
oxide is added. After addition of ammonia, the
solution is passed through a Chelex-100 resin
column. From the eluate, Se and Te are deposited
on a gold lm electrode at 0.1 V. On linear
sweep voltammogram on the anodic branch, the
oxidation stripping peak of Te is at +0.65 V that
of Se at +0.95 V. Analysis of certied samples of
electrolytic copper shows a very good agreement
both for the Se and Te content [137].
Investigations of the reduction of Se(IV) using
CV and electrochemical quartz crystal micro-
gravimetry were marred by using an unbuffered
solution of 0.5 M Na
2
SO
4
as supporting elec-
trolyte [138]. Due to variations of pH during the
voltage scan the obtained results have no simple
meaning.
Anodic stripping voltammetry with a gold disk
electrode was used for determination of traces of
Se(IV) in bodily uids [139]. Gold electrode
modied by poly(3, 3%-diaminobenzidine) interacts
with Se(IV) to form piazselenol at the electrode
surface. Such electrode was used for selective ac-
cumulation and stripping analysis of Se(IV) [140].
Anodic stripping from a tubular gold electrode
[141] or an ultramicroelectrode [142] was used to
determine Se(IV) in a chromatographic efuent
[141] or in ow injection analysis [142].
The reduction of Se(IV) on a silver electrode
involves also a six-electron reduction, but Se
2
ions formed interact with Ag
+
ions and form
several types of adsorbates, similarly as on Hg
and Cu electrodes [135]. Accumulation of about
+0.35 V in the presence of potassium acetate at
pH 910 (where the buffer capacity is very small)
and stripping at about +0.1 V is claimed to be
suitable for determination of Se(IV) [143].
3.2.2. Reduction on Carbon electrodes
An investigation of the reduction of Se(IV)
using a rotating disk carbon electrode indicated
that the reduction occurs in a six-electron transfer
[135]. On carbon electrodes no interaction of
Se
2
with the material of the electrode material
takes place, similarly as for gold and platinum
electrodes. Any Se(0) observed results from a
reaction of Se
2
with Se(IV) following Eq. (25)
[135].
The reduction of Se(IV) on stationary carbon
rod electrodes yielded well developed CV and
stripping voltammetry curves, when a soft
graphite electrode was used [144]. When a glassy
carbon electrode was used, only poorly dened
i-E curves were obtained. Authors concluded, that
red form of Se(0) is formed by a chemical reaction
(25) at some distance from the electrode and only
a small part of it is further reduced to Se
2
.
Electrochemically generated grey form of Se(0) on
the other hand is assumed to be further reduced
to Se
2
. This form of Se(0) is assumed to be
generated only by reduction of the conjugate acid
form of Se(IV) (actually H
3
SeO
3
+
) as its produc-
tion decreases with increasing pH. At pH\4 where
the reduction of H
2
SeO
3
predominates, Se
2
is the
major product. But all these conclusions are based
on visual observations of some Se(0) formed, on
total charges that may be affected by adsorption
and on attribution of CV-peaks to consecutive
electron transfers rather than formation of different
adsorbates. Whereas these authors [144] claim that
neither cathodic nor anodic stripping using carbon
electrodes can be recommended [144], others [145]
used deposition at 0.6 V on such electrodes and
a stripping peak at +0.22 V for determination of
selenium in highly pure copper [145].
When solid Na
2
SeO
3
was dispersed in a carbon
paste electrode, a well developed, probably adsorp-
tive cathodic peak was observed at 0.02 V,
followed by an ill developed one at 0.45 V. On
the reverse sweep anodic peaks at 0.11 V (the
shape of which indicates a role of adsorption
phenomena) were followed by peaks at +0.98 and
+1.07 V. The authors [146] did not consider
adsorption and attributed individual peaks to con-
secutive electron transfers, involving formation of
Se(0) as an intermediate. When a 0.02 M solution
of selenite was dispersed into carbon paste, a
similar CV was obtained as with the solid selenite
[146].
Avery similar pattern of CVcurves was observed
when a potential scan 0 V+1.2 V0.8 V0.0
V was applied to a carbon paste electrode, in which
CuSe was dispersed [147]. In 2 M H
2
SO
4
anodic
peaks were observed at +0.92 and +1.05 V and
cathodic peaks at +0.05 and 0.35 V, so that
only the anodic peak at 0.11 V was missing,
when compared with the carbon electrode with
dispersed solid selenite [146]. As in the previous
case, attempts were made to attribute individual
peaks to consecutive electron transfers and the
possible role of adsorption was neglected. Authors
used total charges in their interpretation, but due
to the lack of consideration of the nonfaradaic
component of the current the conclusions are
doubtful. When the ratio Cu: Se was varied from
2.0 to 3.55, several additional anodic peaks ap-
peared between 0.0 and +0.4 V [147]. A dispersion
of elemental Se(0) into graphite paste electrode
[148,149] was electroinactive and showed no oxida-
tion or reduction signals.
Adsorptiondesorption phenomena play evi-
dently an important role in processes leading to a
formation of copper selenide, which were followed
using cyclic voltammetry on a vitreous carbon
rotating disk electrode [150]. The deposition of
copper selenide occurs at potentials which are more
positive than required both for deposition of cop-
per and formation of selenide. The primary product
formed is Cu
2
Se, which is rst oxidized to CuSe,
then to Cu
2+
and Se.
3.2.3. Reduction on Platinum electrodes
At high concentration of Se(IV) (5 mM) the
reduction on a rotating platinum disk occurs in a
single six-electron step to Se
2
. Similarly as on gold
or carbon electrodes, selenide ions formed on
platinum electrodes do not undergo consecutive
reaction involving the metal of the electrode [135].
No experimental evidence is offered to support
assumption [150] that electroreduction of Se(IV) on
platinum electrodes yields in an electrochemical
processes Se(0). When the reduction of Se(IV) at
constant current on a rotating wire platinum elec-
trode in 1 M H
2
SO
4
was carried out in the presence
of a threefold excess of Cu(II), the stripping re-
sulted in a peak at +1.2 V which is proportional
to concentration of Se(IV) [151].
3.2.4. Reduction on other metals and metal oxides
Considerable attention has been paid [152159]
to the effect of Se(IV) on the reduction of Cu
2+
ions on a copper electrode. On such electrode in 0.1
M H
2
SO
4
the reduction of Se(IV) occurs in two
steps [135,160,161]. In the rst step, Se
2
ions
formed in a six-electron reduction of Se(IV) react
with Cu ions to yield CuSe(or Cu
2
Se). This reduc-
tion current at potentials more positive than about
0.65 V is superimposed on current of the
anodic dissolution of copper following Cu
Cu
2+
+2e. Due to additivity of these two cur-
rents, the limiting current at potentials between
0.1 and 0.65 V corresponds to a four-elec-
tron process. At potentials more negative than
0.65 V such interaction between Cu
2+
and
Se
2
cannot take place, as the concentration of
Cu
2+
ions is too low. Consequently, a six-elec-
tron limiting current is observed at potentials
more negative than 0.65 V. When a copper
amalgam electrode is used, the current voltage
curve is complicated by adsorption peaks, corre-
sponding to a formation of mercury or mixed
selenides. Reductions of Se(IV) on nickel and tin
electrodes were unfortunately studied only in un-
buffered solutions of 0.1 M LiClO
4
in water [160]
and mixed solvents [162] and due to changes in
acidity at the electrode surface cannot be simply
interpreted [160,162].
Using a copper microelectrode with 5 mm di-
ameter and accumulation of Se at +0.1 V, ca-
thodic stripping yielded a sharp peak at 0.05 V,
which is a linear function of concentration of
Se(IV) [163].
This determination is unaffected by the pres-
ence of Cu
2+
ions and enables determination of
Se(IV) between 510
6
and 310
5
M Se(IV).
A titanium electrode was used [42] to study the
electroreduction of Se(IV) in the presence of me-
thinonine. The reduction is manifested by two
pH-dependent peaks in acidic media, one between
0.3 and 0.4 V, the other between 0.5 and
0.6 V.
In a solution containing 0.01 M H
2
SO
4
, 0.1 M
K
2
SO
4
and 110
3
M Se(IV) the reduction of
Se(IV) at a rotating tin oxide electrode occurs in a
single peak at about 0.5 V (SCE), superim-
posed on a limiting current. The limiting current
is about ten times smaller than the sixelectron
diffusion controlled current observed under the
same conditions for reduction of Se(IV) on a
rotating copper electrode. On the tin oxide elec-
trode Cu(II) is reduced in a wave at about 0.15
V. Addition of Se(IV) does not practically affect
the limiting current of the Cu(II) wave, but results
in a wave at about 0.3 V. The height of this
wave increases with increasing concentration of
Se(IV) and reaches a maximum height at [Cu
2+
]:[Se(IV)] :1:0.9. Further increase in concentra-
tion of Se(IV) results in an increase in peak
current at about 0.5 V. This peak, on an elec-
trode covered with copper selenide is about ten
times higher than the peak of Se(IV) on a clean
SnO
2
electrode. A reverse scan results in a forma-
tion of a single anodic peak at about 0.15 V
corresponding to a stripping of Cu
2+
ions. Ex-
trapolation of currents to equilibrium conditions
results in a current-voltage curve showing a two-
electron reduction of Cu(II) with E
1/2
about 0.1
V and a six-electron reduction of Se(IV) at about
0.2 V [164].
The product of electroreduction at 0.3 V was
identied as Cu
3
Se
2
by X-ray diffractometry. At
more negative potentials only Cu
2
Se is formed. In
the presence of excess Se(IV), it reacts with copper
selenide and forms a red suspension of Se(0) at
the surface.
On a stationary tin oxide electrode in 0.4 M
citric acid containing 110
3
M Cu
2+
the depo-
sition of Cu is observed at about 0.3 V (SCE)
with a sharp anodic peak at about 0.0 V after
reversal of the voltage scan [165]. An addition of
Se(IV) results in a small shift of the cathodic peak
of Cu(II) to about 0.25 V with peak current
remaining constant. With increasing [Se(IV)] is
formed another increasing cathodic peak at about
0.35 V. On the reverse scan the anodic peak,
corresponding to the oxidation of Cu to Cu
2+
,
decreases in the presence of Se(IV) and its peak
potential is shifted by about 0.05 V to more
negative potentials. A new anodic peak is formed
at about +0.15 V (SCE) the height of which
increases slightly with increasing concentration of
Se(IV). An indistinct peak, probably correspond-
ing to an anodic stripping of a selenide, is ob-
served at +1.0 V. With varying the ratio
[Cu(II)]:[Se(IV)] and applied potential, formal
numbers of transferred electrons varied for Cu
from 2.0 to 0.95 and for Se from 4 to 5.3. Films
formed at various potentials and at varying the
ratio [Cu(II)]: [Se(IV)] were analyzed using polar-
ography and X-ray uorescence. With increasing
concentration of Cu(II) in the solution, the com-
position of the solid phase varied. The ratio
w
Cu
:w
Se
in the solid phase was found at about 0.0
V (SCE) varying from 0.14 to 1.87 and at 0.4 V
from 0.16 to 2.76. The composition of the solid
phase depends on initial concentrations of Cu(II)
and Se(IV) in the solution. For ratio [Cu(II)]:
[Se(IV)] between 0.0 and 1.5, CuSe and Se are at
a predominating species, for the ratio between 1.5
and 2.2 a mixture of CuSe and Cu
3
Se
2
was found,
for the ratio from 2.2 to 2.9 the solid phase at
electrode surface contained Cu
3
Se
2
and Cu
2
Se and
at a larger excess of Cu(II) and ratio from 2.9 to
4.0, the composition of the surface layer was
Cu
2
Se and Se.
Films prepared at 0.2 V and transferred to a
solution containing only 0.4 M citric acid yield
three anodic peaks-sharp peaks at about 0.0 and
+0.1 V. The shape of these peaks indicates role of
adsorption-desorption phenomena. The third peak
at +0.3 V is diffusion controlled. The peak at 0.0
V is attributed to an oxidation of Cu in the lm
consisting of Cu
2
Se following (28) and peak at
+0.3 V to oxidation of Cu
3
Se (29) and of CuSe
(30):
Cu
2
SeCu
3
Se
2
+Cu(II) +2e (28)
Cu
3
Se
2
2CuSe+Cu(II) +2e (29)
CuSeSe+Cu(II) +2e (30)
The composition of the deposit is controlled
between 0.2 and 0.4 V by diffusion, but at
potential more positive than 0.2 V also by the
kinetics of the charge transfer. At potentials more
negative than 0.4 V Cu
2
Se is the predominant
product in the solid phase, as CuSe and Cu
x
Se
(where XB2) are not stable and are reduced to
Cu
2
Se [165].
Investigations of the reduction of Se(IV) Bi, Pb,
Cd, Zn and Nu amalgams [166168] did not offer
additional information.
4. Conclusions
Se(IV) is reduced in aqueous solutions in forms
H
3
SeO
3
+
, H
2
SeO
3
and HSeO
3
. All these three

forms are reduced in a six-electron process to Se
2
.
The dianion SeO
3
2
is not reducible. Reductions of
H
2
SeO
3
and HSeO
3
, observed at pH\5, occur at

such negative potentials that electrogenerated Se
2
ions do not react with material of any studied
electrode. At pHB4, where H
3
SeO
3
+
is the pre-
dominating reducible form, the reduction of Se(IV)
on Au, Pt, and carbon electrodes forms Se
2
which
on these electrodes does not react with the material
of the electrode. Electrogenerated Se
2
can react
in solution in a homogeneous reaction with
H
3
SeO
3
+
and yield Se(0) which forms colloidal
species in the solution in the vicinity of the elec-
trode.
On Hg, Ag and Cu electrodes at pHB4 at
potentials more positive than about 0.6 V (SCE),
the generated selenide ions can interact with elec-
trochemically dissolved metal ions and form
slightly soluble selenides. This composition can
vary with the metal ion-Se(IV) ratio and with
potential of generation of Se
2
. These selenides are
adsorbed at the electrode surface. Depending on
the potential applied and on concentration of
Se(IV) one, two or more types of adsorbates can
be formed. These adsorbates may differ in chemical
composition and/or physical properties. On the
surface of these adsorbates elemental Se(0) can be
formed. H
3
SeO
3+
is a strong oxidizing agent and
can dissolve in a chemical reaction the material of
the electrode. Thus Se(IV) in acidic solutions reacts
with metallic Hg and resulting mercury ions are
reduced at positive potentials. In solutions contain-
ing in addition to Se(IV) also Cu
2+
, Cd
2+
, or Pb
2+
ions underdeposition is observed. Mechanism of
the involved process is not yet fully understood.
Electrochemical properties of Se(IV) enable use
of electroanalytical techniques for determination of
Se(IV) in various materials.
The choice of the technique depends on sample
composition and concentration levels. For ultra-
trace determination cathodic stripping methods
offer sensitivity enabling analyses of solutions con-
taining up to 10
11
M Se(IV).
5. Note
After this paper was accepted, the authors were
sent a manuscript by B. Lange and MG. van den
Berg submitted to Analytica Chimica Acta, de-
scribing determination of Se(IV) by cathodic strip-
ping voltammetry. The method is based on
measurement of a catalytic hydrogen wave at 1.5
V in the presence of 0.3 M HCl and 75 ppb Rh(III),
which enables to reach a detection limit of 2.4
10
12
M Se(IV), when deposition at 0.2 V was
used. As organic substances can be surface and
catalytically active, they were eliminated by UV-di-
gestion, which also reduced Se(VI) to Se(IV).
Cu(II), Pt(II), and Fe(III) increased the peak at
concentrations higher than 510
9
M, As(III)
decreased it when present in concentration higher
than 310
9
M. Method was used for determina-
tion of selenium in sea and lake waters.
Acknowledgements
This publication was made possible by award-
ing the Senior Fulbright Fellowship to one of us
(P.Z.).
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Polarographic and voltammetric behavior of selenious acid

to be quantitative, pH should be smaller

). At higher pH-values the selenopentathion-

ions other reactions men-

. All these three

, observed at pH\5, occur at

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