Fresenius' Journal of

Fresenius J Anal Chem (1993) 346: 952- 956

© Springer-Verlag1993

Nickel and cobalt determination by constant current potentiometry

I. Method development
Eduardo Pinilla Gil2 and Peter Ostapczuk 1
1 Institute of Applied Physical Chemistry, Research Center Jfilich, P.O. Box 1913, D-52425 Jtilich, Germany
2 One leave from Departamento de Quimica Analitica y Electroquimica, Universidad de Extremadura, E-06071 Badajoz, Spain

Received July 8, 1992; revised October 1, 1992

Summary. Constant current potentiometry was used for
nickel and cobalt determination in water. All parameters like
deposition potential and time, buffer and D M G concen-
tration, and current density which have an influence on the
determination sensitivity were optimized (deposition poten-
tial: - 0 . 5 V vs. Ag/AgC1 (sat KC1); buffer concentration
0.01 mol/1, pH 9.3; D M G concentration 0.05 mmol/1 and
deposition time 10 s, current: - 1 5 gA). No significant dif-
ferences of the determination sensitivity between cathodic
stripping voltammetry and constant current potentiometry
were found. The latter method is advantageous for auto-
matization.
Introduction
The biological and toxicological relevance of nickel and
cobalt is well known. Cobalt is an essential element for
humans and other living organisms, due to its occurrence in
cyanocobalamine (Vitamin B12), excess or default can yield
serious health diseases [1]. Nickel has been found to be
essential for some metabolic processes [2, 3], but is also an
allergenic and in some of its compounds even a carcinogenic
element [4]. These facts, and the widespread distribution
of these metals (specially of nickel) in the industrialized
environment, have prompted the developments of many ana-
lytical methods. Among these, th e investigation of stripping
voltammetric methods based on the adsorption of Ni and
Co complexes with a variety of organic chelates onto mer-
cury static surfaces has been a very active field of research
during the past decade. Since the pioneer work of Pihlar et
al. [5], using dimethylglyoxime (DMG) as the organic ligand,
many other methods have been developed, also using D M G
[6-18], and a variety of other organic ligands [19-26].
Less attention has been devoted, however, to the stripping
chronopotentiometric technique, mainly since reliable
equipment for high real time sampling rate, which is essential
for analysis at low analyte concentration, has not been
widely available until very recently. The first reported
method for potentiometric stripping determination of
Correspondence to: P. Ostapczuk
nickel(II) and cobalt(II), developed by Eskilsson et al. [27]
was based on the adsorption of their D M G complexes onto
a mercury film electrode in a flow system, followed by re-
duction of the complexed ions by means of a constant cur-
rent. The method included a medium exchange procedure to
avoid sample deoxygenation. The method was improved
by Huiliang et al. [28], by using carbon fiber flow-through
electrodes as the base for the mercury film, at which the
constant current reduction step can be performed without
sample deoxygenation. Although these methods are sensitive
and reliable, and easily automatizable, a batch configuration
may be preferable in some instances, since instrumentation
is less complex and hence easier to handle, and a higher
reliability can often be achieved. Moreover, automatic
sample changers allow batch procedures to be readily auto-
mated. The only approach to the determination of Ni and
Co by such a method has been reported very recently by
Jagner et al. [29], in a paper devoted to a new electrode design
for stripping measurements on a single drop of sample, with
unreported detection limits and no application to real
samples.
The aim of the present work is the development of a
simple and sensitive novel batch procedure for the simul-
taneous potentiometric determination of Ni and Co as their
D M G complexes adsorbed on a mercury film previously
plated onto a glassy carbon surface. Ni and Co concen-
trations are related to their respective reduction time when
a constant current is applied through the working electrode.
The chemical composition of the samples and experimental
parameters of the technique are discussed.
Experimental
Equipment
A TraeeLab system (Radiometer, Copenhagen), consisting
of a SAM20 sample station and a PSU potentiometric strip-
ping unit was used to perform all the measurements. The
SAM20 sample station consists of a 3 electrode configur-
ation with a glassy carbon working electrode (surface area
7.068 mm2), an Ag/AgC1 (KClsa0 reference electrode and
a platinum wire auxiliary electrode. A purging-blanketing
device and a mechanical propeller stirrer are also mounted.

Ni
I 0.7 s/V
Co
_ j ._.A.___
v prising 10 s at a stirring speed of STIR 3 (approximately
-1000 -1200 -1400
E (mV)
Fig. 1. Stripping signals obtained in form of a sample containing
2.0 ng/ml of Ni z + and 0.2 ng/ml of Co 2+. Buffer concentration,
0.0t tool/l; DMG concentration, 10 .4 mol/1; adsorption poten-
tial, -0.5 V; adsorption time, 60 s; constant current, - 1 5 gA. (A)
Ni signal; (B) Co signal
The TraceLab system is operated by a connected PC
equipped with the TAP2 TraceTalk Method Builder and
Commander program (Radiometer), which enables the de-
velopment of complete analytical procedures including con-
trol of electrolysis potentials and applied currents, regis-
tration of stripping potentials at a real time rate of 30 KHz,
manipulation of registered curves and statistical treatment
of data.
Reagents and glassware
All reagents used were of Suprapur (when available) or
analytical reagent grade (Merck). Deionized water was
obtained from a Milli-Q system (Millipore, Germany) and
used to prepare all the solutions. HNO3 was subboiled prior
to use. 1 tool/1 NH3/NH4C1 stock buffer solutions were pre-
pared by mixing the appropriate amounts of HC1 and NH3.
0.1 tool/1 dimethylglyoxime solution was prepared by dis-
solving an appropriate amount of D M G (p.a., Merck) in
ethanol. 8 g/1 Hg 2 + plating solution was prepaed by dissolv-
ing the necessary amount of HgCI2 (Suprapur, Merck) in
1.3 mol/1 HC1. Stock standard solutions (1 g/l) of Ni 2 + and
Co 2+ were prepared from Titrisol solutions (Merck) and
acidified to pH 2 with HC1. Dilute standards were prepared
daily by dilution with deionized water (pH 2).
All glassware and polypropylene measurement cells, were
soaked at 60°C in a 2 mol/1 HNO3 bath for at least 3 days,
rinsed with deionized water and kept at 60°C in a 1 mol/1
HNOa bath until needed.
Samples
For the developement of the method pure water and stock
solutions were used.
Procedures
Mercury film plating: To a sample beaker, 20 ml ofdeionized
water and i ml of plating solution were added, and the stirrer
speed was set to STIR 4 (approximately 1200 rpm). The
working electrode potential was then scanned from - 0 . 3
953
to - 0 . 8 V in 1 min steps, so that an homogeneous mercury
film is deposited onto the glassy carbon surface.
Potentiometric determination: 10 ml of water, 5 lal of
0.1 tool/1 D M G solution and 75 gl of Hg z+ plating solution
were pipetted into a measurement cell. Deoxygenation with
argon was then carried out for 5 rain. 100 lal of ammonia
buffer (pH 9.2) and 10 ~1 of sample (unless otherwise indi-
cated) were then added. Further deoxygenation was
performed for 1 min and the determination was carried out
under the following conditions: adsorption potential:
- 0 . 5 V; adsorption time: a certain number of cycles com-
900 rpm) and 15 s of rest time; constant reductive current: -
15 gA; stripping limits: - 0 . 4 and - 1 . 5 V. The equipment
performs a dt/dE mathematical conversion of the stripping
curve and signals are given as peak areas. The reduction
peak potentials for Ni 2+ and Co 2+ were - 1 . 0 5 and -
1.17 V, respectively. The concentration of cobalt and nickel
in the samples was quantified by the standard addition
method.
Results and discussion
Optimum chemical conditionsfor the determination
The simultaneous determination of nickel(II) and cobalt(II)
by adsorptive stripping analysis of their D M G complexes is
threatened by interferences unless the solution pH is properly
adjusted. A pH 9.2 ammonia-ammonium chloride medium
has been shown to be the best choice [5, 13, 27, 28], so it was
also chosen for the present work. A typical constant current
dt/dE vs. potential curve, obtained after collection of Ni 2 +
and Co 2+ D M G complexes on the mercury film in this
medium is shown in Fig. 1. The stability of the mercury film
after several measurement cycles was f r s t inspected. A main
disadvantage of the flow system models previously reported
[27, 28] is that the mercury film has to be completely de-
stroyed and regenerated after each measurement cycle,
which is a time consuming and waste producing step. In
potentiometric stripping batch configurations it is possible,
however, to use the same film for many determinations if a
certain amount of mercury(II) is added to the sample for "in
situ" regeneration of the film during measurement. In the
present method is not possible to add mercury(II) to the
solution, due to its unstability in the alkaline medium essen-
tial for Ni 2+ and Co 2 + determinations. Nevertheless, the
film can be reused without lack of performance if the work-
ing electrode is kept immersed in the plating solution be-
tween the determinations with an applied potential of -
0.8 V. Operation without this caution may be however possi-
ble for sex~eral determinations. This was inspected by running
fifteen sequential replicates of a sample containing 2.0 ng/
ml of nickel(II) and 0.2 ng/ml of cobalt(II), the results of
which are shown in Fig. 2. A slow decay was observed for
Ni and Co signals, the slopes being - 1.24 and - 1.42% per
replicate, respectively. In the present work not more than
three determinations were performed without placing the
film in the plating solution for at least 1 rain.
The influence of changing the D M G concentration was
checked in the range from 2.5 × 10 -5 to 10 -3 mol/1 on 10
replicates of samples containing 2.0ng/ml of N i 2+
(3.4 × 10 -8 tool/l) and 0.2 ng/ml of Co 2+ (3.4 × 10 -9 tool/l).
As shown in Table 1, the peak area of the Co signal increases
with increasing of D M G concentration, the Ni signal has a
954

P e a k a r e a (s/V) Table 1. Influence of the DMG concentration on peak areas and

60 peak potentials of nickel and cobalt"
Nickel DMG concen- Peak area s/V Peak potential mV
50
tration
tool/1 x 10'~ Ni Co Ni Co
40
0.25 57.737 4.127 -1076 - 1224
30 0.50 61.606 5.760 -1074 - 1222
1.00 69.423 6.087 - 1072 - 1215
2.50 76.773 9.499 - 1070 - 1208
20 5.00 76.796 7.530 - 1070 -1208
10.0 60.399 10.007 - 1074 - 1210
Cobalt
10
a Assay conditions as in Fig. 1
0 I J ] I I I

2 4 6 8 10 12 14 16
Replicate number Table 2. Influence of buffer concentration on peak areas and peak
potentials of nickel and cobalt"
Fig. 2. Reproducibility of Ni and Co signals without interassay
mercury film regeneration. (A) Ni signals; (B) Co signals. Assay Buffer Peak area s/V Peak potential mV
conditions as in Fig. 1 concentration
mol/1 Ni Co Ni Co

0.005 61.417 7.220 -1072 - 1204

maximum at a D M G concentration between 0.1 - 0 . 5 mmol/1,
and the p e a k resolution is slightly better at lower D M G
levels, the reproducibility o f the results being also improved.
The results found for cobalt are in g o o d agreement with the
results o f A d e l o j u et al. [10] on a mercury d r o p electrode
with voltammetry. In contrast to Adeloju et al., the N i p e a k
area at the mercury film electrode demonstrates a m a x i m u m
with an increase o f the D M G concentration in constant
current potentiometry. A D M G concentration o f
5.0 x / 0 . 5 mol/1 was used for further work.
The a p p r o p r i a t e choice of the a m m o n i a buffer concen-
tration is a critical p o i n t in the simultaneous determination
o f Ni 2+ and Co 2÷ by adsorptive stripping, since it affects
p e a k resolution, and moreover its c o n t a m i n a t i o n by nickel
is in most cases the m a j o r source o f a N i b l a n k signal. This
last fact makes it desirable to operate with a m i n i m u m buffer
concentration, but it cannot be decreased to a point where
the p H control o f the solution gets impossible during the
assay. This m i n i m u m concentration was estimated by means
o f p H measurements in 0.005 mol/1 of buffer. The effect o f
changing the buffer concentration from 0.005 to 0.04 mol/1
on 10 replicates o f samples containing 2.0 ng/ml o f Ni 2÷
and 0.2 ng/ml o f Co 2 +, was investigated. The' results, given
in Table 2, show a better resolution, but also a decreasing
of the Co peak area that is achieved for increasing buffer
concentration. This results are also in accordance with those
o f A d e l o j u et al. reported on a mercury d r o p electrode. A
0.01 tool/1 buffer concentration was chosen for the present
method.
Experimental parameters of the technique
The value o f the constant current applied for the reduction
o f a d s o r b e d nickel(H) and cobalt(II) complexes is a decisive
factor for the signal size. A c c o r d i n g to the theory o f po-
tentiometric stripping analysis [30], a linear relationship
should be expected between the inverse o f current ( i - 1) and
the peak area. This correlation was investigated by running
a sample containing 2.0 ng/ml o f Ni 2 + and > 0.2 ng/ml o f
Co 2+ with different current values ranging from - 5 to
- 5 0 gA. The results for nickel are given in Fig. 3. The
0.010 61.506 5.760 - 1074 - 1222
0.020 72.264 3.829 - 1070 -1224
0.040 67.777 1.023 - 1062 -1228
" Assay conditions: [DMG] = 5 x 10 .5 mol/1 and as in Fig. 1
expected linear relationship is accomplished in the current
range from - 15 to - 50 gA. F o r smaller values, a significant
deviation and also a high b a c k g r o u n d were observed. A
similar behaviour was found for the cobalt signal. The in-
crease o f the absolute value of the current caused negative
shifting o f the peak potentials for the reduction processes,
with slopes of 1.20 m V / g A for Ni and 1.52 m V / g A for Co.
Thus, the peaks were better resolved when high currents were
applied. As a c o m p r o m i s e between sensitivity, b a c k g r o u n d
noise and peak resolution, a constant current of - 1 5 ~tA
was chosen for Ni and Co determination.
The a d s o r p t i o n potential has been shown to be another
significant factor for the sensitivity and selectivity o f the
method. In the voltammetric m e t h o d with hanging mercury
d r o p electrodes, some authors [5, 13] have found an almost
negligible influence o f the a d s o r p t i o n potential on the Ni
signal in the range from - 0 . 1 to - 0 . 8 V (vs. Ag/AgC1 sat
KC1), whereas others have found a decrease [10] or a slight
increase [18]. F o r Co, o p t i m u m potentials o f - 0 . 7 [18]
and - 0 . 8 [10] have been reported. In potentiometric strip-
ping flow methods [27, 28], a d s o r p t i o n potentials o f - 0 . 5 V
for Ni and - 0 . 7 5 V for Co have been used. In the present
configuration, the influence o f the a d s o r p t i o n potential was
investigated in the range from - 0 . 1 to - 0 . 9 V, and the
results are presented in Fig. 4. A n o p t i m u m potential o f
- 0 . 5 V was found for Co, whereas for Ni a peak area
decrease was found when decreasing the a d s o r p t i o n poten-
tial. In consequence, a potential of - 0 . 5 V was selected as
most suitable for the simultaneous determination of Ni and
Co. Finally, the influence o f the a d s o r p t i o n time was investi-
gated. In Fig. 5, the advantage o f using multiple integrated
scans instead o f the continuous adsorption time o f the Ni
signal is demonstrated in a sample containing 2.0 ng/ml o f
Ni 2+ and 0.2 ng/ml of Co 2+. Line "A" shows the trend
 955

Peak area (s/V) Peak area (s/V)

700 1000

A
600 800

500 600

400 400

300 200

200 0 I I I
0 50 100 150 200
Ads time (s)
100
Fig. 5. Relationship between adsorption time and peak area in a 2.0
mg/ml Ni 2+ sample with (A) sum of stripping measurements each
0 after 10 s of adsorption and (B) stripping measurement after con-
50 100 150 200 250 tinuous adsorption. Assay conditions as in Fig. 4
(-1/i)x 10E3 (I/pA)

Fig. 3. Relationship between inverse of current and peak area in a At this concentration level the reproducibility is very good.
sample containing 2.0ng/ml of Ni 2+. DMG concentration, Signals were obtained summing 3 scans each after 10 s ac-
5 x 10 -s mol/1. Other conditions as in Fig. 1 cumulation time.
The detection limit was estimated according to the
IUPAC definition [31], by determining the nickel and cobalt
Peak area (s/V) concentration in 14 blank solutions by the standard addition
70 method. For Ni, an average value of 62 ng/1 was found, with
a standard deviation of 16 ng/1. This yield a detection limit
60 (35) of 110 ng/1. For Co, an average value of 8 ng/1 was
Nickel
found, with a standard deviation of 4 ng/1. The detection
limit for Co is estimated to be 20 ng/1.
4O

30
Cobalt
2010 ~ =i'-'~'~'4''~'~'~'b'-'-~+
0 ~ I I
0 200 400 600 800
-Eads (mV)
Fig. 4. Influence of the adsorption potential on the peak area of
nickel and cobalt. DMG concentration, 5 x 10 5 mol/1; adsorption
time, 10 s. Other conditions as in Fig. 1
obtained for an increasing number of integrated scans each
one obtained after ] 0 s of adsorptive accumulation, and line
"B" was obtained after continuous accumulation time. A
similar trend was found for the Co signal. The number of
accumulation + scan cycles can be adjusted as function of
the sample concentration.
Reproducibility and detection limit
The relative standard deviation of the results obtained in the
determinations of 12 standard samples containing 1.000 ng/
ml of Ni 2+ and 0.100 ng/ml of Co 2÷ were 3.63% for Ni
(mean: 1.043 ng/ml) and 7.46% for Co (mean: 0.097 ng/ml).
Conclusions
Constant current potentiometry (CCP) can be used for nickel
and cobalt determinations in the ng/1 range. The detection
limit is defined by nickel and cobalt blanks for chemicals
and accumulation time used. There are no big differences
between the detection limits of voltammetry and CCP. Due
1000 to the constant surface area fo the mercury film electrode
the reproducibility of individual determinations obtained
in routine work by CCP is better than those obtained by
voltammetry. Comparison between TraceLab and EG&G
Polarographic Analyzer 384B with 303A SDME electrode
demonstrates that the reproducibility of individual analyti-
cal signals obtained by the voltammetric system depend very
strongly on the age of the electrode. The reproducibility
of the mercury drop changes rapidly with the age of all
mechanical parts of the electrode. This system is not suitable
for automation.
The second system tested was the 646 VA-Processor with
a 675 VA-Sample Changer and a 665 Dosimat (all from
Metrohm). The reproducibility of this system is better than
that of the EG&G equipment. It is not possible to determine
cobalt with the Metrohm equipment at concentrations lower
than 40 ng/1. Using the sample changer it is possible to
analyze only 10 samples. By means of TraeeLab with sample
changer it is possible to determine 20 samples and only small
mercury waste (only mercury film) is produced. The plating
solution for the film preparation can be used many times.
956
The appropriate test in water samples demonstrates that
CCP can be used for routine determination of Ni and Co.
Presently this m e t h o d is being tested with S R M s and samples
from the G e r m a n Environmental Specimen Bank.
Acknowledgement. E. P. G. gratefully acknowledges support re-
ceived from the Deutscher Akademischer Austauschdienst (DAAD)
during his stay in Germany.
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