The Application of Stripping Analysis to the
Determination of Silver(l) Using Graphite Electrodes
S. P. PERONE
Department of Chemistry, Purdue University, Lafayette, Ind.
The extension of stripping analysis
to the determination of trace quanti-
ties of silver ion has been investigated.
The wax-impregnated graphite elec-
trode was applied in these studies
instead of the conventional hanging
mercury drop electrode, since, in
noncomplexing media, silver behaves
more nobly than mercury. During the
pre-electrolysis step o portion of the
silver was electrodeposited on the
electrode at constant potential. This
step was followed by an anodic linear
potential sweep which resulted in the
quantitative stripping of the deposited
silver from the electrode. The quan-
tity of electricity involved in the anodic
peaks is directly proportional to the
product of the bulk concentration of
silver ion and the pre-electrolysis time
over a large range of concentrations.
The method was applied to solutions of
silver ion as dilute as 4.0 X 10-9M.
In addition, the general characteristics
of graphite electrodes for further
applications to stripping analysis were
evaluated.
technique of stripping analysis
The
is a very sensitive electroanalytical
technique. The method consists of two
steps. The first is the electrodeposition
of a small portion of the unknown
electroactive material at a micro-
electrode under controlled conditions of
mass transfer. The second step
involves the electrodissolution, or
stripping, of the deposit. Analytical
correlations are made between the
Faradaic signal obtained in the stripping
step, the bulk concentration, and the
plating time.
The technique has been most useful
in the application to the determination
of trace quantities of metal ions in
solution. In most of these applications
the mercury pool electrode (14) or
hanging drop mercury electrode (3, 8)
has been used. These electrodes have
been very satisfactory for applications
where amalgam formation is involved,
provided the stripping step occurs at
potentials where the electrode itself is
not oxidized.
However, the use of other types of
electrodes for stripping analysis has been
investigated recently to extend this
sensitive method to other electroactive
materials. For example, oxidizable
electrodes have been applied to the
determination of anions which form a
deposit upon anodization of the
electrode in solution (1, 17). Platinum
electrodes have been applied to the
determination of substances whose
electrodissolution potentials are more
anodic than that of mercury, whether
this be due to nobility (10) or to ir-
reversibility (12).
Unfortunately, whenever solid elec-
trodes are used for quantitative work,
the usual problems of surface prepara-
tion, contamination, and reconditioning
become very prominent. It is often
difficult to find a means of obtaining
reproducible surface conditions for the
application of the electrode to a partic-
ular system. If a satisfactory elec-
trode conditioning procedure is found,
it may be lengthy and inconvenient,
and often must precede each run for
best reproducibility.
Because of these difficulties, the ap-
plication of graphite electrodes to
electroanalytical chemistry had been
investigated previously. The general
electrochemical behavior of these
electrodes compared favorably to that
of platinum and gold (11), and re-
finements in their preparatione.g.,
wrax impregnation (4, 6)and ap-
plication (5, 7) were developed. The
outstanding advantage of graphite
electrodes, of course, is that a new sur-
face may be exposed for each run, and
reproducibility is greatly enhanced by
this feature.
This paper describes the application
of wax-impregnated graphite electrodes
to the determination of silver ion by
stripping analysis. The method
involved the controlled-potential dep-
osition of metallic silver on the graphite
surface from a solution of silver ion.
The potential was selected cathodic
enough to be in the limiting-current
region for the silver reduction, but not
so cathodic as to cause significant
reduction of the solvent. Stirring and
other experimental variables were
maintained as constant as possible
during this pre-electrolysis step to en-
sure that a reproducible portion of the
silver was deposited during the timed
interval.
After the pre-electrolysis step was
completed, the deposit was stripped
VOL. 35, NO. 13, DECEMBER 1963
from the electrode by anodic voltam-
metry with linearly varying potential.
One or more oxidation peaks were
obtained, and the amount of electricity
involved in these peaks gave a measure
of the amount of silver deposited and of
the bulk concentration. In this manner,
it was possible to analyze solutions of
silver ion as dilute as 4 X 10~9Tf.
EXPERIMENTAL
Apparatus. The instrument used in
this work was the Sargent Model FS
Polarograph (E. H. Sargent Co.,
Chicago, 111.). This instrument pro-
vides linear potential sweeps from
16.7 to 50.0 mv. per second in four
equal steps. In addition, the initial
potential can be set either by manual
adjustment of the slide-wrire for the
potential scan or by an auxiliary
continuously variable low-voltage po-
tential source (+3.0- to 3.0-volt
range) incorporated into the instru-
ment.
The working electrode for all experi-
ments was a 12-inch spectroscopic
graphite electrode (National Carbon
Co., N. Y., No. L4309) prepared for
use by immersion in melted paraffin
wax (Parowax, U. S. P.) for 60 minutes.
With about 4 inches of the electrode
left submerged in the liquid, the wax
was allowed to cool slowly, and the
electrodes were removed when about a
1- to 2-mm. coating had formed about
the outside surface. This wax coating
acted as an insulation in the voltam-
metric experiments. The tip was broken
off to expose the circular graphite
surface, and this was conditioned by
sanding, first with medium grade flint
sandpaper, and then with fine grade
flint sandpaper. The surface was then
polished by rubbing on a piece of What-
man No. 1 filter paper on a flat surface
until no crevices were plainly visible
to the eye. The surface area was
approximately 0.32 sq. cm.
The reference electrode was a large
saturated calomel electrode connected
to the cell through two ultrafine-
porosity sintered-glass junctions. Be-
tween these two junctions was placed
a 2M KN03 solution. This solution
acted as a bridge between the KC1 solu-
tion of the saturated calomel electrode
(S.C.E.) and the silver ion solution in
the cell. It was periodically replenished
to minimize the chances of cross-con-
tamination by silver and halide ions.
The total cell resistance was 300 ohms.
The cell was a 125-ml. capacity poly-
2091

Figure 1. Current-voltage curve for
reduction of silver ion in stirred solution
2 X 10 ~4M Ag + n 0.2 KNO3
styrene tumbler on which fit snugly a
machined Teflon lid. The lid had
various sized holes for the working elec-
trode, salt bridge, and nitrogen inlet
(also for a Teflon scoop designed for
hanging drops on a hanging drop
mercury electrode). In this work the
Teflon scoop was used to scrape nitrogen
bubbles off the surface of the graphite
electrode. To eliminate the photo-
reduction of silver in these experiments,
the cell was shielded from the light by
covering it with an opaque material,
with provision for periodic observation.
Reproducible stirring was furnished
by a Teflon-covered, Vi-inch magnetic
stirring bar and a Sargent synchronous
rotator (E. H. Sargent Co., Chicago,
111.) equipped with a magnet attach-
ment. No attempt was made to con-
trol temperature in these experiments.
Materials. All chemicals were rea-
gent grade and were used without fur-
ther purification. The inert electro-
lyte for all experiments was 0.2M
KNO3. All solutions were prepared
in water purified by distillation and
passing over a mixed cation-anion
exchange resin bed. Silver nitrate
was used for stock solutions of silver
ion, and these were stored in the dark.
Silver solutions as dilute as 10_6i
could be stored for at least 1 month
in preconditioned polyethylene con-
tainers without any noticeable changes.
Stock solutions were not stored for any
longer than 1 month, and solutions of
silver ion more dilute than 10~6 were
prepared as needed. The preparation
and use of solutions more dilute than
10~6I required the equilibration of all
volumetric vessels and the cell assembly
with these solutions to minimize con-
centration changes due to adsorption
or desorption at the surfaces.
High-purity nitrogen was bubbled
through a gas-washing bottle containing
the inert electrolyte solution, and then
was dispersed through a coarse-porosity
sintered-glass disk in the cell to remove
oxygen.
RESULTS AND DISCUSSION
Extensive studies of electrodeposition
and stripping of silver deposits at a
platinum electrode had been carried out
by Rogers and coworkers (2, IS, 16),
and a coulometric method for the
determination of silver by electrolytic
stripping was developed (10). In
addition, Lord and Rogers (11) have
2092 ANALYTICAL CHEMISTRY
applied the graphite electrode to the
voltammetric study of silver reduction.
Thus, the objectives of this study were
to investigate the electrochemical be-
havior of micro deposits of silver at a
graphite electrode and to determine
whether this electrode could be used for
stripping analysis. This involved
experiments designed to show that re-
producible quantities of silver could be
deposited during the pre-electrolysis
step, and that the deposit could be re-
moved quantitatively by the subsequent
anodic electrolysis (stripping).
Pre-Electrolysis Step. Selection
of Pre-Electrolysis Potential.
To select an electrolysis potential
which was sufficiently cathodic to be
in the limiting current region of the
silver reduction wave and yet not so
cathodic as to cause interference from
reduction of solvent, current-voltage
Figure 2. Effect of pretreatment on
curves were obtained at the graphite anodic stripping of silver deposits from
electrode. The conditions were iden- graphite electrode
tical to those used later, in the pre- Silver ion concn. was 4.0 X 10*~8M. Pre
electrolysis proceduree.g., stirring, electrolysis time was 15 minutes. Dashed lines
electrode, electrolyte, cell, etc. A are blanks.
typical curve is shown in Figure 1. A. Without pretreatment.
The effect of dilution on the half-wave B, With pretreatment.
potential also was considered in selecting
the electrolysis potential. If reversible
behavior is assumed for the reaction, to obtain reproducible stripping re-
sults. Furthermore, if the electrodes
Ag+ + le- Ag were not mistreated their characteristics
did not deteriorate rapidly with time
and an activity of unity is assigned to
and use. Numerous determinations
the silver deposit, Nernst diffusion were made at the various concentration
theory (9) can be used to derive the levels over a period of several weeks
expression: without the necessity of renewing the
electrode surface. (See Table I.)
Em =
Const. + RT/nF In C*Ag+ (1)
Despite the stability of electrode
where C*Ag+ is the bulk silver con- characteristics, the effect of freshly pre-
centration; E1/2 is the half-wave paring the electrode surface (sanding,
potential, and R, T, n, and F have their polishing, etc.) before each run was
usual significance. Thus, the half-wave investigated also (Table I). The re-
potential is expected to shift approxi-
mately 60 mv. cathodic for each 10-fold
dilution of silver ion.
At relatively high concentrations Table I. Reproducibility of Stripping
(>10-6M) the experimental behavior Data
closely followed the above prediction. Rep- Average quantity of electricity,
However, for the more dilute solutions licate Q (/coulombs)
the half-wave potential apparently did no. ABC
not shift cathodic with dilution as 1 2.66 2.56 286
rapidly as predicted, since considerably 2 2.72 2.57 254
3 2.65 2.63 255
more anodic electrolysis potentials could
4 2.73 2.56 281
be used than expected. This behavior 5 3.01 2.59 259
is similar to that observed by Rogers 6 2.80 2.79 289
and coworkers (2, 15, 16) who at- Av. 2.71 2.62 271
tributed it to activity effects when less Rel. std.
than a monolayer was present on the dev., %2.6 3.4 6.1
surface. Thus, by trial and error a pre- A, B. Stripping analysis results for
electrolysis potential of 0.39 volt vs. 4.0 X 10~%M Ag+ (5-minute pre-electroly-
S.C.E. was found to be satisfactory and sis time). Data in column B were ob-
tained 2 months after those in column A,
was used throughout this study.
using same electrode, without resurfacing.
Electrode pretreatment. The The electrode was used many times in
initial preparation of the graphite between for similar analyses. When not
electrodes was described in the Experi- in use, it was stored in deionized water.
C. These data were obtained for a 2.0
mental section. No further pretreat- X 10~6 Ag+ solution (1 minute pre-
ment procedure was followed, except to electrolysis), resurfacing the electrode
hold the electrode at a potential of between each run.
+0.90 volt vs. S.C.E. between runs
producibility was moderately good
(6%) considering the extensive
additional operations between runs and
the probable variation of the electrode
surface with resurfacing. Thus, these
experiments showed that the electrode
could be useful even in cases where sur-
face deterioration occurred much more
rapidly than in this study.
An alternate pretreatment was inves-
tigated in an attempt to obtain better-
shaped stripping curves at the lower
concentrations. The multiple-peaked
curves obtained at these concentrations
(Figure 2, curve A) are not unusual,
since similar behavior had been ob-
served by Nicholson {12, IS) in studies
of the stripping of micro deposits of
nickel from platinum electrodes. In
addition, Rogers and coworkers {2, 15,
16), while studying non-Nernstian be-
havior of submonolayer silver de-
posits on a platinum electrode, noticed
that a small portion of the silver deposit
adhered so strongly to the electrode sur-
face that it could be removed only by
anodic electrolysis in cyanide solution.
Both investigators concluded that the
activities of these deposits could vary
with the extent of surface coverage, and
this could cause the observed non-
Nernstian behavior. Moreover, they
concluded that bonding forces between
the electrode and the deposit could be
stronger than those between the atoms
of the deposit, and that some portions
of the deposit might lie bonded quite
firmly to the electrode surface. These
phenomena could cause the multiple-
peaked stripping curves observed in
Nicholsons work and also in this work.
On the assumption that problems
similar to those encountered by Rogers
and coworkers were causing the
anomalous stripping curves at low con-
centrations in this study, the graphite
electrode was pretreated before each of
a series of runs by anodic electrolysis in
concentrated ammonium hydroxide
using 0.1 Af KNOs as the supporting
electrolyte. The electrolysis was carried
out simply by imposing 0.6 volt between
the working electrode and a graphite
counter electrode for 1 minute.
When electrodes pretreated in this
fashion were applied to 4 X 10-8M
silver solutions, well defined double-
peaked stripping curves were obtained.
The shapes and sizes of these curves
were reproducible when the pretreat-
ment was performed before each run.
Figure 2 compares these curves to those
obtained without the pretreatment.
The total quantity of stripping coulombs
is nearly identical in both cases, but
residual currents were slightly different.
It was decided not to use this pre-
treatment in the analytical method,
since the overall results were not
changed, and the omission of time-
consuming steps was highly desirable.
However, further studies of the effects
over the surface of the solution during
the rest of the experiment, and was
bubbled through the solution for 1
minute between replicate runs. The
graphite electrode was held at +0.90
volt vs. S.C.E. for a total of 2 minutes
between runs. Before the pre-electroly-
sis potential was applied the surface
of the electrode was gently scraped
with the Teflon scoop to remove the
adherent nitrogen bubbles. The elec-
trolysis potential of 0.39 volt vs.
S.C.E. was then applied to the working
electrode for an accurately measured
period of time. The length of the pre-
electrolysis step varied from 1 to 15
minutes, depending on the bulk con-
centration. Reproducible stirring ef-
fects were obtained by maintaining the
cell arrangement and geometry as
constant as possible for a series of runs.
Figure 3. Anodic stripping of silver The pre-electrolysis step was ter-
from graphite electrode
minated by opening the cell circuit.
Dashed lines are blanks. Concentrations and Anodic Stripping Step. After com-
pre-electrolysis times were: pleting the pre-electrolysis step, 30
A. 2.0 X 10~6M Ag4, minute
1
seconds were allowed to pass so that
B. 4.0 X 10"9M Ag+ 15 minutes
the solution came to rest. The un-
applied electrode potential was
changed to a value at the foot of the
of the various experimental parameters wave; the cell circuit was closed
on the shape of the stripping curves again, and the deposit was removed
were carried out. No consistent im- from the electrode by an anodic po-
provement could be obtained by chang- tential sweep. The height of the
ing the pre-electrolysis time or potential. anodic peak(s) obtained is not linearly
Furthermore, the shapes of the curves dependent upon the size of the deposit
might vary somewhat as a function of because of the variation of the activity
the aging of the electrode (observed, during the stripping process {13).
primarily, as a variation in the relative Therefore, the relationship between the
sizes of the various peaks). This number of coulombs of electricity
property of the system was not critical, involved in the stripping peak(s), the
however, since the total stripping plating time, and the bulk concentration
coulombs always remained approxi- was investigated. This approach was
mately constant (within experimental used successfully for quantitative meas-
error). Furthermore, the electrode urements in previous studies of electro-
could always be returned to its original lytic stripping of deposits {10,12,13,17).
state by resurfacing, although this was The area under the peak(s) can be
rarely, if ever, necessary. determined with a planimeter and
Pre-electrolysis Procedure. The readily converted to coulombs.
cell and electrode assembly were equili- The selection of a rate of anodic
brated with aliquots of the sample voltage scan was not critical. However,
solution before a fresh portion of the better reproducibility was obtained and
solution was added for analysis. Dis- no sacrifice of sensitivity resulted when
solved oxygen was removed by bubbling the slower rates of scan were used.
nitrogen through the solution for 10 Thus, a scan rate of 16.7 mv. per second
to 15 minutes. Nitrogen was passed was used for all runs except at the most
Table II. Anodic Stripping Analysis of Silver Ion
Pre- Average
electrolyeis quantity of
Concn., C time, < electricity, Q Q/Ct X Rel. std.
(moles/liter) (min.) (Mcoulombs) 10-= dev., %
2.0 X 10"= 1.0 262 13.1 3.4
2.0 10- 2.0 48.8 12.2 2.7
X
2.0 X "7 5.0 11.8 11.8 3.4
4.0 X 10- 5.0 2.71 13.5 2.6
4.0 X 10~9 15.0 0.79 13.1 4.2
Data refer to
s x replicate determinations at each concentration.
VOL. 35, NO. 13, DECEMBER 1963 2093
dilute concentrations. At 4 X 10_9Af
silver ion, the stripping scan rate was
increased to 33.3 mv. per second, and
sharper peaks were obtained. Thus,
sensitivity was increased, and cor-
respondingly shorter electrolysis times
could be used.
Typical stripping current-voltage
curves are shown in Figure 3. The
residual current line was determined by
carrying out the pre-electrolysis and
stripping procedure on blank solutions.
The analytical results are summarized
in Table II. The dependence of the
stripping coulombs on the product of
bulk concentration and electrolysis
time is linear over a wide range. The
relative error is not as small as would be
desired (4.7%), but this is due
probably to the difficulty in preparing
and handling the very dilute solutions.
The reproducibility, however, is much
better, as pointed out in Table II.
The correlation between the total
stripping coulombs and that predicted
from the convection-controlled cathodic
limiting currents is very good. For
example, in 2 X 10silver solution,
the limiting cathodic current was
4.2 /a. For a 60-second pre-electrolysis,
then, a silver deposit corresponding to
252 ^coulombs should be formed; the
stripping results show 262 ^coulombs of
electricity. This is further evidence that
Polarographic Determination of Nitrite
as 4-Nitroso-2,6-xylenol
A. M. HARTLEY and R. M. BLY1
Department of Chemistry and Chemical Engineering, University of Illinois, Urbana, III.
Phenols react with nitrosonium ion
under mild conditions to produce
the corresponding nitrosophenols. In
5:4:1 (volume ratio) sulfuric acid-
water-acetic acid, 2,6-xylenol reacts
with nitrite to produce 4-nitroso-2,6-
xylenol. The reaction is rapid, repro-
ducible, and nearly quantitative. The
product is polarographically reducible
with a single diffusion-controlled wave
which merges with the anodic dissolu-
tion of mercury at 0.0 volt vs. the
mercury-mercurous sulfate reference
electrode. The diffusion current at
0.15 volt vs. the reference elec-
trode is linearly concentration depend-
ent in the range 0 to 14 p.p.m.
nitrite in the reaction mixture. De-
terminations may be made directly on
the sample within 10 minutes. Side
reactions, one of which produces
3,3 ',5,5 '-tetramethylindophenol limits
the yield to approximately 92%.
Nitrate constitutes an interference since
2094 ANALYTICAL CHEMISTRY
approximately all of the deposited silver
is removed by the subsequent stripping
procedure.
An entirely unexpected advantage of
the graphite electrode found in this
study is that the residual currents are
not significantly greater than those
observed under similar conditions with
the hanging drop mercury electrode (S).
This is despite the fact that the surface
area (0.32 sq. cm.) of the graphite
electrode used in these studies is about
6 times as large as that of a typical
hanging drop electrode (ca. 0.05 sq. cm.).
Thus, the ratio of the Faradaic signal
to the residual signal is greater, and
sensitivity is increased by a factor of
about 6. This is obvious from the
fact that only 15 minutes plating time
was required to obtain the stripping
data for 4 X 10-9Af silver ion. More-
over, when the pre-electrolysis was
carried out for only 5 minutes, sen-
sitivity was not found lacking, but the
results were less precise.
Thus, it is reasonable to speculate that
this method might be applicable to the
determination of silver ion somewhat
more dilute than 4 X 10_9Af, perhaps
as low as 10-10M. No attempts were
(17) Shain, I., Perone,
made to study such dilute solutions in
this work, since the preparation and
handling of these solutions is con-
siderably more difficult and time
consuming.
it forms the corresponding 4-nitro-
2,6-xylenol which is also polaro-
graphically reducible. However, the
appropriate potentials for diffusion
current measurement of the nitroso-
and nitroxylenols are sufficiently sepa-
rated that a 100-fold excess of
the latter can be tolerated without
interference. The overall reproduci-
bility of the method is less than 1%
(expressed as relative standard devia-
tion).
react repro-
and nitrite
Nitrate
ducibly with 2,6-xylenol to produce
4-nitro-2,6-xylenol and 4-nitroso-2,6-
xylenol, respectively (1). These re-
actions have been utilized in spectro-
photometric procedures for nitrate and/
or nitrite (7) and for polarographic
determination of nitrate (8). The
characteristics of spectrophotometric
measurement compared with polaro-
LITERATURE CITED
(1) Ball, R. G., Manning, D. L., Menis,
O., Anal. Chem. 32, 621 (1960).
(2) Byrne, J. T., Rogers, L. B., Griess,
J. C., Jr., J. Electrochem. Soc. 98, 452
(1951)
.
(3) De Mars, R. D., Shain, I., Anal.
Chem. 29, 1825 (1957).
(4) Elving, P. J., Krivia, A. F., Ibid., 30,
1645 (1958).
(5) Elving, P. J., Smith, D. L., Ibid., 32,
1849 (1960).
(6) Gaylor, V. F., Conrad, A. L., Landerl,
J. H., Ibid., 29, 224 (1957).
(7) Ibid., p. 228.
(8) Kemula, W., Kublik, Z., Anal. Chim.
Acta. 18, 104 (1958).
(9) Kolthoff, I. M., Lingane, J. J.,
Polarography, Vol. 2, p. 578, Inter-
science, New York, 1952.
(10) Lord, S. S., Jr., ONeill, R. C
Rogers, L. B., Anal. Chem. 24, 209
(1952) .
(11) Lord, S. S., Jr., Rogers, L. B., Ibid.,
26, 284 (1954).
(12) Nicholson, . M., Ibid., 32, 1058
(1960).
(13) Nicholson, . M., J. Am. Chem.
Soc. 79, 7 (1957).
(14) Nikelly, J. G., Cooke, W. D., Anal.
Chem. 29, 933 (1957).
(15) Rogers, L. B., Krause, D. P., Griess,
J. C., Jr., Ehrlinger, D. B., J. Electro-
chem. Soc. 95, 33 (1949).
(16) Rogers, L. B., Stehney, A. F., Ibid.,
p. 25.
S. P., Anal. Chem.
33, 325 (1961).
Received for review July 19, 1963.
Accepted September 9, 1963. Detroit
Anachem Conference, Wayne State Uni-
versity, October 1963.
graphic measurement are sufficiently
different with respect to interferences,
simplicity of procedure, and the like
that development of a complimentary
polarographic procedure for nitrite
would be useful.
EXPERIMENTAL
Apparatus and Reagents. Polaro-
graphic apparatus and techniques
were essentially those previously re-
ported by Hartley and Curran (8).
Reagents and solutions were prepared
according to the directions reported for
the spectrophotometric methods (7).
The Hg/HgzSOj reference electrode
was prepared in the 5:4:1 (v./v.)
H2SO4: H20 :HOAc solvent determined
to be the optimum composition of re-
action solvent. The dropping mercury
electrode was of the common stand-tube
1
Present address, California Research
Corp., P.O. Box 1627, Richmond, Calif.