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Talanta 50 (1999) 247 252

A flow system with an electrochemical reduction cell for

spectrophotometric determinations of major constituents in
Fe/V alloys
Antonio O. Jacintho a, Luiz F.R. Machado b, Amauri A. Menegario a,
Iolanda A. Rufini a, Maria Fernanda Gine a,*

Centro de Energia Nuclear na Agricultura, Uni6ersidade de Sao Paulo, A6. Centenario 303, C. Postal 96,
13400 -970 Piracicaba, Brazil
Instituto de Qumica de Sao Carlos, Uni6ersidade de Sao Paulo, Sao Paulo, Brazil
Received 22 July 1998; received in revised form 29 September 1998; accepted 2 October 1998

Insertion of an electrochemical cell in a flow injection system to evaluate the on-line reduction of ionic species is
presented. The cell comprised Pt electrodes installed in two sections separated by a Nafion membrane. The sample
was injected into an acidic carrier stream and passed through the cathode compartment of the electrolytic chamber
where the species were reduced as consequence of an applied DC voltage. The sample solution leaving the cell
received a confluent reagent stream (1,10-phenanthroline buffered at pH 4.7) and the reacted products were dropped
off in an open tube for gas/liquid separation. Efficiency of the Fe3 + to Fe2 + reduction in acidic medium was
evaluated in the presence of strongly reducing species of V and Mo by monitoring the Fe(II) colored complex.
Interferences from Pb2 + , Co2 + , Ni2 + , Zn2 + , Cu2 + , V5 + and Mo6 + were evaluated. Production of strongly
reducing species of V at the electrolytic cell presented higher efficiency for Fe reduction than the electrolytic chamber
itself. Total reduction of Fe3 + in solutions containing up to 10 mg l 1 Fe plus 100 mg l 1 V or 100 mg l 1 of Mo
was achieved by the electrolytic process at 2 A. The quantitative determination of Fe and V in low silicon Fe/V alloys
was achieved. Accuracy was assessed with the certified Euro-standard 577-1 ferrovanadium alloy produced by the
Bureau of Analysed Samples Limited and no difference at the 95% confident level was found. 1999 Elsevier Science
B.V. All rights reserved.
Keywords: Electrochemical cell; Iron reduction; Flow analysis; Iron alloys

1. Introduction
* Corresponding author. Tel.: +55-194-292-4636; fax: +
E-mail address: mfgine@cena.usp.br (M.F. Gine)

In flow injection analysis reducing columns

have been used for different applications. A
column with copperized cadmium filings was em-

0039-9140/99/$ - see front matter 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 9 1 4 0 ( 9 9 ) 0 0 0 2 3 - 5


A.O. Jacintho et al. / Talanta 50 (1999) 247252

ployed for reduction of nitrate to nitrite [1]. Several applications used the Jones reductor of amalgamated Zn packed in an on-line column to
reduce Cr3 + to Cr2 + [2,3], V4 + and V5 + to V2 +
[2] and U6 + to U3 + [4]. In these papers, the
generation of strongly reducing agents in flow
systems which are unstable under atmospheric
conditions was demonstrated. The determination
of total Fe and Fe2 + was also attained after
reduction in a column with the Jones reductor in
a flow system [5].
Electrochemical reduction of ionic species was
reported for the hydride forming elements [6]. The
approach was accomplished by using a flowthrough electrolytic cell [7,8]. Papers published on
the last years described the electrochemical hydride generation (EcHG) of selenides, arsines,
stibines and others coupled to different spectrometers, atomic absorption with a T-tube atomizers
(ETAAS) [7,8] or with graphite furnaces
(GFAAS) [9] or atomic emission microwave induced plasmas (MIP-AES) [10]. Electrodes of different materials: vitreous carbon [7], platinum
[7,8,10], lead and pyrolytic graphite [9] were
In the present work the electrochemical approach using a flow-through cell is proposed to
reduce Fe3 + to Fe2 + . The spectrophotometric
detection of the ferroine complex was used to
estimate the reduction process. The on line production of reduced species of V and Mo and the
effect on reducing Fe3 + was evaluated. The determination of Fe in ferrovanadium alloys and the
possibility of the indirect determination of V is

2. Experimental

2.1. Apparatus
The flow system comprised a peristaltic pump
(mp-13R Ismatec, Zurich, Switzerland) provided
with Tygon pumping tubing, an automatic injector (Model 352, Micronal, Sao Paulo, Brazil) a
flow-through electrolytic cell described below, a
spectrophotometer (Model 432, Femto, Sao
Paulo, Brazil) furnished with a flow cell (10 mm

optical path, 80 ml inner volume) and a strip-chart

recorder (REC 61, Radiometer, Copenhagen,
Denmark). Accessories such as Y-shaped connectors, and mixing coils of polyethylene tubing (0.8
mm i.d.) were used.
The electrochemical cell was constructed by
assembling layers of Perspex of different thickness, with two compartments, (anode 1.6 cm3 and
cathode 0.4 cm3) separated by a Nafion membrane and electrodes of platinum sheets (3.2 cm2)
connected to a home made electrical source,
which could be varied from 0.2 to 3.0 A. The
Nafion membrane was conditioned by immersing
it in hot water 20 min before installing at the cell
protected between two rubber layers.
The gas phase separator (PS) was constructed
from a 10 cm 5 mm i.d. glass tube, with two
lateral exits at opposite sides as described earlier

2.2. Reagents and solutions

All reagents were of analytical grade and distilled, de-ionized water was always used. The electrolyte solution was 2.0 M H2SO4. The
1,10-phenanthroline solution (0.25% w/v) was
prepared weekly by dissolving 0.6250 g of 1,10phenanthroline hydrochloride in 250 ml of 0.1 M
HCl. Acetate buffer solution (pH 4.7) was prepared with 1.0 M ammonium acetate plus 1.0 M
acetic acid.
Stock solution containing 1000 mg l 1 Fe3 +
was prepared from Fe(NO)3 9H2O (Merck,
Darmstadt, Germany). Solutions of the individual
concomitants containing 1000 mg l 1 Zn2 + ,
Co2 + and Cr3 + from the metals and Ni2 + from
NiSO4 6H2O (Johnson and Matthey Chemicals
JMC), Pb2 + from Pb(NO3)2, V5 + from NH4VO3
and Mo6 + from (NH4)6MO7O24 4H2O (Merck,
Darmstadt, Germany) were prepared. Solutions
used to test interference containing 10.0 mg l 1
Fe3 + plus 10.0 and 100 mg l 1 of each element
were used. A freshly prepared solution containing
10.0 mg l 1 Fe2 + was employed to estimate the
reduction efficiency.
Working standard solutions, 0.00, 2.50, 5.00
and 10.0 mg l 1 Fe3 + plus 100 mg l 1 of V5 + ,
were used to determine Fe in the diluted sample.

A.O. Jacintho et al. / Talanta 50 (1999) 247252

Standard solutions, 0.00, 2.00, 5.00 and 10.0 mg

l 1 V or Mo plus 10.0, 20.0 and 30.0 mg l 1 of
Fe were prepared. Three synthetic solutions containing Fe and V concentrations in different proportions (50/50; 60/40 and 40/60 w/w) in 0.25 M
HCl, simulating alloy samples with low silicon
contents were analyzed together with the standard
reference material Euro-standard 577-1 produced
by the Bureau of Analysed Samples Limited
(Middlesborough, UK). About 100 mg of the
reference alloy were accurately weighted, received
10 ml of acqua-regia and were heated in a hot
plate until complete dissolution. After cooling to
room temperature 5 ml of perchloric acid (70%
v/v) were added and heated until evolution of
white fumes. The residual solution was diluted to
100 ml [12]. Aliquots of 5.0 ml of this solution
received 50 ml of 2.5 M HCl and 50 ml of 1000
mg l 1 of V before diluting to 500 ml.

2.3. The flow system

The electrochemical reduction of Fe3 + was performed by using the flow set up depicted in Fig. 1.
The electrolyte solution was continuously recycled


through the anode compartment of the electrolytic cell (EC). In the situation specified in Fig.
1, the sample solution at loop L was carried by C
through the EC cathode compartment and the
mixing coil B1. At the confluent point X, the
sample solution received a buffered reagent
stream (B+ R). After passing reaction coil B2 the
solutions was dropped off in an open tube PS to
separate gaseous components. Part of this solution was aspirated from the bottom of the tube
towards the detector D with wavelength adjusted
to 512 nm. Moving down the central part of the
injector, L was filled with another sample solution
while part of solution at the PS was drained.
After 30 s, the injector returned to the position
shown in Fig. 1 and simultaneously the electrical
power at the EC was switched on during 30 s. The
injector rested in this position during 60 s and the
spectrophotometric detection occurred.
Speciation of Fe2 + and Fe + 3 in acidified water
samples (0.25 M HCl) could be accomplished with
the flow system in Fig. 1. The injection of the
sample allowed the direct Fe + 2 determination and
in a second injected sample volume simultaneously the EC is switched on and the reduction

Fig. 1. A. Flow diagram for electrochemical reduction of Fe3 + to Fe2 + . The three rectangles at the left represent the injector in
the injection position with sample in loop L. The arrow below represent the displacement of the central part to the alternative
position. Lines indicate the tubing used for flowing solutions of electrolyte E, carrier C, sample S, reagent R, buffer B, and the
residual W. Numbers in brackets indicate the flow rates in ml min 1, and arrows indicate the pumping direction. The
electrochemical cell (EC) is schematized with the Nafion membrane N and the electrodes connections. Other devices are the mixing
and reaction coils B1 and B2 of 25 cm tubing each, the connector X, the phase separator (PS) and the detector D. Dashed line after
the EC, indicates the optional inlet to introduce the Fe3 + solutions.

A.O. Jacintho et al. / Talanta 50 (1999) 247252


Table 1
Regression data obtained with solutions from 0.00 to 10.0 mg
l1 Fe3+ at electrolytic currents of 1.0, 2.0 and 3.0 A
Current (A)

y= ax+b







Relative standard deviations (R.S.D.) for the 10 mg l1 Fe

standard based on three replications.

of Fe + 3 occurred permitting the determination of

total iron.
The flow system in Fig. 1 presents an alternative configuration to introduce the Fe3 + solutions
(dashed line after the cell), to study the effect of
the reduced species of V and Mo produced at EC.

3. Results and discussion

The efficiency of the proposed electrolytic reduction of Fe3 + to Fe2 + is dependent on several
parameters such as flow-rates, cell compartment
dimensions, type and electrode surface, sample
acidity and electrolytic voltage. One liter of the
electrolyte solution (2 M H2SO4) was continuously pumped at 2.5 ml min 1, through the anode compartment. This solution was replaced
periodically to maintain its characteristics. Under
DC current the electrolyte solution yielded H3O +
which crossed the Nafion membrane towards the
cathode compartment. The temperature at the EC
increased when the current was raised just to 3 A,
sample flow rate was lower than 1.0 ml min 1
and the sample acidity was B 0.05 M HCl. Under
these conditions a damage of the Nafion membrane was observed. On the other hand, after
increasing the sample acidity beyond 0.25 M HCl
the large quantity of gases evolved impaired the
Fe3 + reduction. Therefore, sample solutions at
0.25 M HCl flowing at 2.5 ml min 1 were employed throughout.
Effect of raising the electrolytic current at the
EC to reduce solutions of Fe3 + produced data in
Table 1. Despite higher absorbances being attained with 3 A data presented poor precision
probably due to higher gas evolution at the cham-

ber. Thus, further experiments were carried out at

2 A yielding results characterized by good linearity and precision.
Solutions containing 10.0 mg l 1 of Fe3 + plus
10.0 and 100 mg l 1 of Pb2 + , Co2 + , Ni2 + ,
Zn2 + , Cu2 + , V5 + and Mo6 + were injected using
the electrolytic current switched on and off to
verify the possibility of being interfering either on
reduction or on the complexation reaction. The
effects of concomitant additions are presented in
Table 2. Cobalt solutions were colored and raised
the background at 512 nm. Using a EC with clean
Pt electrodes a signal increase of 10% due to Pb
addition was observed. After passing repeatedly
the Pb solution (total mass of 0.1 mg Pb) the
signal stabilized. When the EC was opened, Pb
deposition on the Pt cathode could be observed
by naked eyes.
Addition of V5 + and Mo6 + increased the signal proportionally to the applied current emphasizing the formation of strongly reducing species
The efficiency of reduction was evaluated at
different electrolytic currents by comparing absorbances of a 10 mg l 1 Fe3 + after reduction
with that corresponding to a 10 mg l 1 Fe2 +
Table 2
Results after addition of different ionic species to 10 mg l1

Added amount (mg l1)




0.188 90.003
0.199 9 0.010
0.189 90.001
0.191 90.001
0.189 90.003
0.183 90.003
0.177 90.001
0.179 9 0.001
0.320 90.003
0.407 90.008
0.189 9 0.006
0.196 9 0.009
0.315 9 0.005
0.472 9 0.004
0.353 9 0.005
0.471 9 0.009


The analytical signal related to 10 mg l1 Fe2+ was
0.180 9 0.004 A (n = 3).

A.O. Jacintho et al. / Talanta 50 (1999) 247252

Fig. 2. Effect of the electrolytic current and the presence of

V5 + on Fe3 + reduction (a) 10 mg l 1 Fe3 + ; (b) 10 mg l 1
Fe3 + +10 mg l 1 V5 + ; and (c) 10 mg l 1 Fe3 + +100 mg
l 1 V5 + . A is absorbance. Dashed line indicates the signal
obtained by injecting a solution of 10 mg l 1 of Fe2 + .

solution injected in the same way. Results are

presented in Fig. 2. No signal was observed for
Fe3 + without current at the EC. Increasing the
current up to 3 A the reduction of Fe3 + alone
increased linearly (r=0.9968) attaining 55% of
reduction. The effect of reducing 10 mg l 1 Fe3 +
alone or together with 0.00, 10.0 or 100 mg l 1 of
V5 + could be appreciated by comparing curves at
Fig. 2. The addition of 100 mg l 1 V5 + to Fe3 +
provided the best reduction efficiency, attaining
total reduction after a current of 2 A (curve c,
Fig. 2).
To elucidate the influence of V and Mo reduced
species on the reduction of iron, an experiment
involving addition of a Fe3 + solution after the
EC was performed. Solutions of V5 + and Mo6 +
were injected instead of the sample and while
flowing through the EC (2 A) produced reduced
species which merged with the Fe3 + solution. The
reduction of 10 mg l 1 Fe3 + occurred in an
extent of 80% with 100 mg l 1 V5 + and 45% with
100 mg l 1 Mo6 + . Therefore, the reduced V
species which formed from 100 mg l 1 V5 + at the
EC cell at 2 A allowed the attainment of 80%
efficiency on Fe3 + reduction, while the efficiency
of the EC alone was 38% (curve a, Fig. 2). No
signal corresponding to the reduced species of V
and Mo was observed probably due to their oxidation until reaching the detector unity.


The expected probable competition of Fe2 +

and V2 + for 1,10-phenanthroline [5] was not observed even though a diluted solution of the
reagent (0.1% w/v) and a concentrated solution of
V5 + (100 mg l 1) reduced at 2 A was used.
The quantification of iron in dissolved ferrovanadium alloys (dilution factor of 105) was
achieved by adding 100 mg l 1 V to the samples
and standards, assuming complete reduction of
Fe3 + (Fig. 2).
The analytical curves in Fig. 3 were used for V
quantification. The effect of increasing the V concentrations up to 10 mg l 1 in solutions with 10,
20 and 30 mg l 1 of Fe was characterized by
linear coefficients and slopes depending on the
Fe3 + concentrations following the relationship
A= 0.018 CFe + 0.0008 CFeCV. For the dissolved
samples, the Fe concentration previously determined was used to calculate the V concentration,
but this is only valid for V concentrations lower
than 10 mg l 1. When CV = 10CFe maximum
absorbance was attained (Fig. 2). Thus, the proposal is to add Fe to the diluted samples to ensure
the determination of V in the linear analytical
range (Fig. 3) for samples with a CFe B CV. The
effect of adding up to 10 mg l 1 Mo to solutions
in three different iron concentrations presented
good correlation (Fig. 3 dashed lines). In this
situation, the slope of the curves were not depen-

Fig. 3. Effect of adding different V (solid lines) and Mo

(dashed lines) concentrations to solutions containing 10.0, 20.0
and 30.0 mg l 1 Fe3 + . A is absorbance and C is the concentration of V or Mo added. Regression curves in bold correspond to V and those in italic to Mo.

A.O. Jacintho et al. / Talanta 50 (1999) 247252


Table 3
Results of a reference standard ferrovanadium alloy and V
results in three synthetic FeV solutions containing 50, 40 and
60% w/w V

Fe (% w/w) V (% w/w)
Certified value 47.21
Found valuea 47.29 0.5

50.16 9 0.13
50.1 91.8
52.1 91.7
38.9 90.9
60.59 0.8

ing both elements, once these elements are determined indirectly by its effect on iron reduction.

Financial support from FAPESP (Fundacao de
Amparo a` Pesquisa do Estado de Sao Paulo) and
CNPq (Conselho Nacional de Desenvolvimento
Cientfico e Tecnologico) was greatly appreciated.

Mean 9S.D., n= 3.

dent on the Fe concentration as found for V.

Results for three ferrovanadium synthetic solutions and one certified reference material Eurostandard 577-1 are shown in Table 3. The certified
and found results were not statistically different
from each other at the 95% confidence level.

4. Conclusions
The proposed electrochemical reduction approach is efficient for on-line reduction of Fe3 +
to Fe2 + in acid solutions. Addition of V and Mo
increased significantly the Fe3 + reduction to
Fe2 + .
The proposal suits well for the quantitative
determination of Fe2 + and total Fe, the determination of Fe and V or Fe and Mo in the respective solubilized iron alloys by using the
electrolytic chamber reduction and 1,10-phenanthroline. Application of this approach could not
be used to determine V or Mo in samples contain-

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