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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 materials. For example, oxidizable from the electrode by anodic voltam-
to the determination of trace quanti- electrodes have been applied to the metry with linearly varying potential.
ties of silver ion has been investigated. determination of anions which form a One or more oxidation peaks were
The wax-impregnated graphite elec- deposit upon anodization of the obtained, and the amount of electricity
trode was applied in these studies electrode in solution (1, 17). Platinum involved in these peaks gave a measure
instead of the conventional hanging electrodes have been applied to the of the amount of silver deposited and of
mercury drop electrode, since, in determination of substances whose the bulk concentration. In this manner,
noncomplexing media, silver behaves electrodissolution potentials are more it was possible to analyze solutions of
more nobly than mercury. During the anodic than that of mercury, whether silver ion as dilute as 4 X 10~9Tf.
pre-electrolysis step o portion of the this be due to nobility (10) or to ir-
silver was electrodeposited on the reversibility (12). EXPERIMENTAL
electrode at constant potential. This Unfortunately, whenever solid elec-
step was followed by an anodic linear trodes are used for quantitative work, Apparatus. The instrument used in
potential sweep which resulted in the the usual problems of surface prepara- this work was the Sargent Model FS
quantitative stripping of the deposited tion, contamination, and reconditioning Polarograph (E. H. Sargent Co.,
silver from the electrode. The quan- become very prominent. It is often Chicago, 111.). This instrument pro-
tity of electricity involved in the anodic difficult to find a means of obtaining vides linear potential sweeps from
16.7 to 50.0 mv. per second in four
peaks is directly proportional to the reproducible surface conditions for the
product of the bulk concentration of equal steps. In addition, the initial
application of the electrode to a partic- potential can be set either by manual
silver ion and the pre-electrolysis time ular system. If a satisfactory elec-
adjustment of the slide-wrire for the
over a large range of concentrations. trode conditioning procedure is found, potential scan or by an auxiliary
The method was applied to solutions of it may be lengthy and inconvenient, continuously variable low-voltage po-
silver ion as dilute as 4.0 X 10-9M. and often must precede each run for tential source (+3.0- to 3.0-volt

In addition, the general characteristics best reproducibility. range) incorporated into the instru-
of graphite electrodes for further Because of these difficulties, the ap- ment.
The working electrode for all experi-
applications to stripping analysis were plication of graphite electrodes to ments was a 12-inch spectroscopic
evaluated. electroanalytical chemistry had been
graphite electrode (National Carbon
investigated previously. The general Co., N. Y., No. L4309) prepared for
electrochemical behavior of these use by immersion in melted paraffin
technique of stripping analysis electrodes compared favorably to that wax (Parowax, U. S. P.) for 60 minutes.
The
is a very sensitive electroanalytical of platinum and gold (11), and re- With about 4 inches of the electrode
technique. The method consists of two finements in their preparatione.g., left submerged in the liquid, the wax
steps. The first is the electrodeposition wrax impregnation (4, 6)and ap- was allowed to cool slowly, and the
of a small portion of the unknown plication (5, 7) were developed. The electrodes were removed when about a
electroactive material at a micro- 1- to 2-mm. coating had formed about
outstanding advantage of graphite
electrode under controlled conditions of the outside surface. This wax coating
electrodes, of course, is that a new sur- acted as an insulation in the voltam-
mass transfer. The second step face may be exposed for each run, and
involves the electrodissolution, or metric experiments. The tip was broken
reproducibility is greatly enhanced by off to expose the circular graphite
stripping, of the deposit. Analytical this feature. surface, and this was conditioned by
correlations are made between the This paper describes the application sanding, first with medium grade flint
Faradaic signal obtained in the stripping of wax-impregnated graphite electrodes sandpaper, and then with fine grade
step, the bulk concentration, and the to the determination of silver ion by flint sandpaper. The surface was then
plating time. stripping analysis. The method polished by rubbing on a piece of What-
The technique has been most useful involved the controlled-potential dep- man No. 1 filter paper on a flat surface
in the application to the determination osition of metallic silver on the graphite until no crevices were plainly visible
of trace quantities of metal ions in to the eye. The surface area was
surface from a solution of silver ion.
solution. In most of these applications The potential was selected cathodic approximately 0.32 sq. cm.
The reference electrode was a large
the mercury pool electrode (14) or enough to be in the limiting-current saturated calomel electrode connected
hanging drop mercury electrode (3, 8) region for the silver reduction, but not to the cell through two ultrafine-
has been used. These electrodes have so cathodic as to cause significant porosity sintered-glass junctions. Be-
been very satisfactory for applications reduction of the solvent. Stirring and tween these two junctions was placed
where amalgam formation is involved, other experimental variables were a 2M KN03 solution. This solution
provided the stripping step occurs at maintained as constant as possible acted as a bridge between the KC1 solu-
potentials where the electrode itself is tion of the saturated calomel electrode
during this pre-electrolysis step to en-
not oxidized. sure that a reproducible portion of the (S.C.E.) and the silver ion solution in
the cell. It was periodically replenished
However, the use of other types of silver was deposited during the timed to minimize the chances of cross-con-
electrodes for stripping analysis has been interval. tamination by silver and halide ions.
investigated recently to extend this After the pre-electrolysis step was The total cell resistance was 300 ohms.
sensitive method to other electroactive completed, the deposit was stripped The cell was a 125-ml. capacity poly-

VOL. 35, NO. 13, DECEMBER 1963 2091


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
Figure 1. Current-voltage curve for deposited during the pre-electrolysis
reduction of silver ion in stirred solution step, and that the deposit could be re-
2 X 10 ~4M Ag + n 0.2 KNO3 moved quantitatively by the subsequent
anodic electrolysis (stripping).
Pre-Electrolysis Step. Selection
styrene tumbler on which fit snugly a of Pre-Electrolysis Potential.
machined Teflon lid. The lid had To select an electrolysis potential
various sized holes for the working elec- which was sufficiently cathodic to be
trode, salt bridge, and nitrogen inlet in the limiting current region of the
(also for a Teflon scoop designed for silver reduction wave and yet not so
hanging drops on a hanging drop cathodic as to cause interference from
mercury electrode). In this work the reduction of solvent, current-voltage
Teflon scoop was used to scrape nitrogen Figure 2. Effect of pretreatment on
bubbles off the surface of the graphite curves were obtained at the graphite anodic stripping of silver deposits from
electrode. To eliminate the photo- electrode. The conditions were iden- graphite electrode
reduction of silver in these experiments, tical to those used later, in the pre- Silver ion concn. was 4.0 X 10*~8M. Pre
the cell was shielded from the light by electrolysis proceduree.g., stirring, electrolysis time was 15 minutes. Dashed lines
covering it with an opaque material, electrode, electrolyte, cell, etc. A are blanks.
with provision for periodic observation. typical curve is shown in Figure 1. A. Without pretreatment.
Reproducible stirring was furnished The effect of dilution on the half-wave B, With pretreatment.
by a Teflon-covered, Vi-inch magnetic potential also was considered in selecting
stirring bar and a Sargent synchronous the electrolysis potential. If reversible
rotator (E. H. Sargent Co., Chicago,
behavior is assumed for the reaction, to obtain reproducible stripping re-
111.) equipped with a magnet attach-
ment. No attempt was made to con- sults. Furthermore, if the electrodes
trol temperature in these experiments. Ag+ + le- Ag were not mistreated their characteristics
Materials. All chemicals were rea- did not deteriorate rapidly with time
and an activity of unity is assigned to
gent grade and were used without fur- and use. Numerous determinations
ther purification. The inert electro- the silver deposit, Nernst diffusion were made at the various concentration
lyte for all experiments was 0.2M theory (9) can be used to derive the levels over a period of several weeks
KNO3. All solutions were prepared expression: without the necessity of renewing the
in water purified by distillation and electrode surface. (See Table I.)
passing over a mixed cation-anion Em =
Const. + RT/nF In C*Ag+ (1)
Despite the stability of electrode
exchange resin bed. Silver nitrate
was used for stock solutions of silver where C*Ag+ is the bulk silver con- characteristics, the effect of freshly pre-
ion, and these were stored in the dark. centration; E1/2 is the half-wave paring the electrode surface (sanding,
Silver solutions as dilute as 10_6i potential, and R, T, n, and F have their polishing, etc.) before each run was
could be stored for at least 1 month usual significance. Thus, the half-wave investigated also (Table I). The re-
in preconditioned polyethylene con-
tainers without any noticeable changes.
potential is expected to shift approxi-
Stock solutions were not stored for any mately 60 mv. cathodic for each 10-fold
dilution of silver ion.
longer than 1 month, and solutions of
silver ion more dilute than 10~6 were At relatively high concentrations Table I. Reproducibility of Stripping
(>10-6M) the experimental behavior Data
prepared as needed. The preparation
and use of solutions more dilute than closely followed the above prediction. Rep- Average quantity of electricity,
10~6I required the equilibration of all However, for the more dilute solutions licate Q (/coulombs)
volumetric vessels and the cell assembly the half-wave potential apparently did no. ABC
with these solutions to minimize con- not shift cathodic with dilution as 1 2.66 2.56 286
centration changes due to adsorption rapidly as predicted, since considerably 2 2.72 2.57 254
or desorption at the surfaces. 3 2.65 2.63 255
more anodic electrolysis potentials could
High-purity nitrogen was bubbled 4 2.73 2.56 281
be used than expected. This behavior 5 3.01 2.59 259
through a gas-washing bottle containing
the inert electrolyte solution, and then is similar to that observed by Rogers 6 2.80 2.79 289
was dispersed through a coarse-porosity and coworkers (2, 15, 16) who at- Av. 2.71 2.62 271
sintered-glass disk in the cell to remove tributed it to activity effects when less Rel. std.
oxygen. 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
RESULTS AND DISCUSSION 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,
Extensive studies of electrodeposition was used throughout this study.
using same electrode, without resurfacing.
and stripping of silver deposits at a Electrode pretreatment. The The electrode was used many times in
platinum electrode had been carried out initial preparation of the graphite between for similar analyses. When not
by Rogers and coworkers (2, IS, 16), electrodes was described in the Experi- in use, it was stored in deionized water.
C. These data were obtained for a 2.0
and a coulometric method for the mental section. No further pretreat- X 10~6 Ag+ solution (1 minute pre-
determination of silver by electrolytic ment procedure was followed, except to electrolysis), resurfacing the electrode
stripping was developed (10). In hold the electrode at a potential of between each run.
addition, Lord and Rogers (11) have +0.90 volt vs. S.C.E. between runs

2092 ANALYTICAL CHEMISTRY


producibility was moderately good over the surface of the solution during
(6%) considering the extensive the rest of the experiment, and was
additional operations between runs and bubbled through the solution for 1
the probable variation of the electrode minute between replicate runs. The
surface with resurfacing. Thus, these graphite electrode was held at +0.90
experiments showed that the electrode volt vs. S.C.E. for a total of 2 minutes
could be useful even in cases where sur- between runs. Before the pre-electroly-
face deterioration occurred much more sis potential was applied the surface
rapidly than in this study. of the electrode was gently scraped
An alternate pretreatment was inves- with the Teflon scoop to remove the
tigated in an attempt to obtain better- adherent nitrogen bubbles. The elec-
shaped stripping curves at the lower trolysis potential of 0.39 volt vs.
concentrations. The multiple-peaked S.C.E. was then applied to the working
curves obtained at these concentrations electrode for an accurately measured
(Figure 2, curve A) are not unusual, period of time. The length of the pre-
since similar behavior had been ob- electrolysis step varied from 1 to 15
served by Nicholson {12, IS) in studies minutes, depending on the bulk con-
of the stripping of micro deposits of centration. Reproducible stirring ef-
nickel from platinum electrodes. In fects were obtained by maintaining the
addition, Rogers and coworkers {2, 15, cell arrangement and geometry as
16), while studying non-Nernstian be- constant as possible for a series of runs.
havior of submonolayer silver de- Figure 3. Anodic stripping of silver The pre-electrolysis step was ter-
from graphite electrode
posits on a platinum electrode, noticed minated by opening the cell circuit.
that a small portion of the silver deposit Dashed lines are blanks. Concentrations and Anodic Stripping Step. After com-
adhered so strongly to the electrode sur- pre-electrolysis times were: pleting the pre-electrolysis step, 30
A. 2.0 X 10~6M Ag4, minute
face that it could be removed only by 1

seconds were allowed to pass so that


B. 4.0 X 10"9M Ag+ 15 minutes
anodic electrolysis in cyanide solution. the solution came to rest. The un-
Both investigators concluded that the applied electrode potential was
activities of these deposits could vary changed to a value at the foot of the
with the extent of surface coverage, and of the various experimental parameters wave; the cell circuit was closed
this could cause the observed non- on the shape of the stripping curves again, and the deposit was removed
Nernstian behavior. Moreover, they were carried out. No consistent im- from the electrode by an anodic po-
concluded that bonding forces between provement could be obtained by chang- tential sweep. The height of the
the electrode and the deposit could be ing the pre-electrolysis time or potential. anodic peak(s) obtained is not linearly
stronger than those between the atoms Furthermore, the shapes of the curves dependent upon the size of the deposit
of the deposit, and that some portions might vary somewhat as a function of because of the variation of the activity
of the deposit might lie bonded quite the aging of the electrode (observed, during the stripping process {13).
firmly to the electrode surface. These primarily, as a variation in the relative Therefore, the relationship between the
phenomena could cause the multiple- sizes of the various peaks). This number of coulombs of electricity
peaked stripping curves observed in property of the system was not critical, involved in the stripping peak(s), the
Nicholsons work and also in this work. however, since the total stripping plating time, and the bulk concentration
On the assumption that problems coulombs always remained approxi- was investigated. This approach was
similar to those encountered by Rogers mately constant (within experimental used successfully for quantitative meas-
and coworkers were causing the error). Furthermore, the electrode urements in previous studies of electro-
anomalous stripping curves at low con- could always be returned to its original lytic stripping of deposits {10,12,13,17).
centrations in this study, the graphite state by resurfacing, although this was The area under the peak(s) can be
electrode was pretreated before each of rarely, if ever, necessary. determined with a planimeter and
a series of runs by anodic electrolysis in Pre-electrolysis Procedure. The readily converted to coulombs.
concentrated ammonium hydroxide cell and electrode assembly were equili- The selection of a rate of anodic
using 0.1 Af KNOs as the supporting brated with aliquots of the sample voltage scan was not critical. However,
electrolyte. The electrolysis was carried solution before a fresh portion of the better reproducibility was obtained and
out simply by imposing 0.6 volt between solution was added for analysis. Dis- no sacrifice of sensitivity resulted when
the working electrode and a graphite solved oxygen was removed by bubbling the slower rates of scan were used.
counter electrode for 1 minute. nitrogen through the solution for 10 Thus, a scan rate of 16.7 mv. per second
When electrodes pretreated in this to 15 minutes. Nitrogen was passed was used for all runs except at the most
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- Table II. Anodic Stripping Analysis of Silver Ion
ment was performed before each run.
Figure 2 compares these curves to those Pre- Average
obtained without the pretreatment. electrolyeis quantity of
Concn., C time, < electricity, Q Q/Ct X Rel. std.
The total quantity of stripping coulombs (moles/liter) (min.) (Mcoulombs) 10-= dev., %
is nearly identical in both cases, but
2.0 X 10"= 1.0 262 13.1 3.4
residual currents were slightly different. 2.0 10- 2.0 48.8 12.2 2.7
X
It was decided not to use this pre- 2.0 X "7 5.0 11.8 11.8 3.4
treatment in the analytical method, 4.0 X 10- 5.0 2.71 13.5 2.6
since the overall results were not 4.0 X 10~9 15.0 0.79 13.1 4.2
changed, and the omission of time- Data refer to

s x replicate determinations at each concentration.
consuming steps was highly desirable.
However, further studies of the effects

VOL. 35, NO. 13, DECEMBER 1963 2093


dilute concentrations. At 4 X 10_9Af approximately all of the deposited silver LITERATURE CITED
silver ion, the stripping scan rate was is removed by the subsequent stripping
(1) Ball, R. G., Manning, D. L., Menis,
increased to 33.3 mv. per second, and procedure. O., Anal. Chem. 32, 621 (1960).
sharper peaks were obtained. Thus, An entirely unexpected advantage of (2) Byrne, J. T., Rogers, L. B., Griess,
the graphite electrode found in this J. C., Jr., J. Electrochem. Soc. 98, 452
sensitivity was increased, and cor-
(1951)
respondingly shorter electrolysis times study is that the residual currents are
.

(3) De Mars, R. D., Shain, I., Anal.


could be used. not significantly greater than those Chem. 29, 1825 (1957).
Typical stripping current-voltage observed under similar conditions with (4) Elving, P. J., Krivia, A. F., Ibid., 30,
curves are shown in Figure 3. The the hanging drop mercury electrode (S). 1645 (1958).
residual current line was determined by This is despite the fact that the surface (5) Elving, P. J., Smith, D. L., Ibid., 32,
1849 (1960).
carrying out the pre-electrolysis and area (0.32 sq. cm.) of the graphite (6) Gaylor, V. F., Conrad, A. L., Landerl,
stripping procedure on blank solutions. electrode used in these studies is about J. H., Ibid., 29, 224 (1957).
The analytical results are summarized 6 times as large as that of a typical (7) Ibid., p. 228.
(8) Kemula, W., Kublik, Z., Anal. Chim.
in Table II. The dependence of the hanging drop electrode (ca. 0.05 sq. cm.). Acta. 18, 104 (1958).
stripping coulombs on the product of Thus, the ratio of the Faradaic signal (9) Kolthoff, I. M., Lingane, J. J.,
bulk concentration and electrolysis to the residual signal is greater, and Polarography, Vol. 2, p. 578, Inter-
sensitivity is increased by a factor of science, New York, 1952.
time is linear over a wide range. The (10) Lord, S. S., Jr., ONeill, R. C
relative error is not as small as would be about 6. This is obvious from the
Rogers, L. B., Anal. Chem. 24, 209
desired (4.7%), but this is due fact that only 15 minutes plating time (1952) .

was required to obtain the stripping (11) Lord, S. S., Jr., Rogers, L. B., Ibid.,
probably to the difficulty in preparing 26, 284 (1954).
and handling the very dilute solutions. data for 4 X 10-9Af silver ion. More-
(12) Nicholson, . M., Ibid., 32, 1058
The reproducibility, however, is much over, when the pre-electrolysis was (1960).
carried out for only 5 minutes, sen- (13) Nicholson, . M., J. Am. Chem.
better, as pointed out in Table II.
The correlation between the total sitivity was not found lacking, but the Soc. 79, 7 (1957).
results were less precise. (14) Nikelly, J. G., Cooke, W. D., Anal.
stripping coulombs and that predicted Thus, it is reasonable to speculate that
Chem. 29, 933 (1957).
from the convection-controlled cathodic (15) Rogers, L. B., Krause, D. P., Griess,
this method might be applicable to the J. C., Jr., Ehrlinger, D. B., J. Electro-
limiting currents is very good. For determination of silver ion somewhat chem. Soc. 95, 33 (1949).
example, in 2 X 10silver solution, more dilute than 4 X 10_9Af, perhaps (16) Rogers, L. B., Stehney, A. F., Ibid.,
the limiting cathodic current was as low as 10-10M. No attempts were p. 25.
4.2 /a. For a 60-second pre-electrolysis, (17) Shain, I., Perone, S. P., Anal. Chem.
made to study such dilute solutions in 33, 325 (1961).
then, a silver deposit corresponding to this work, since the preparation and
252 ^coulombs should be formed; the Received for review July 19, 1963.
handling of these solutions is con- Accepted September 9, 1963. Detroit
stripping results show 262 ^coulombs of siderably more difficult and time Anachem Conference, Wayne State Uni-
electricity. This is further evidence that consuming. versity, October 1963.

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 it forms the corresponding 4-nitro- graphic measurement are sufficiently
under mild conditions to produce 2,6-xylenol which is also polaro- different with respect to interferences,
the corresponding nitrosophenols. In graphically reducible. However, the simplicity of procedure, and the like
5:4:1 (volume ratio) sulfuric acid- appropriate potentials for diffusion that development of a complimentary
water-acetic acid, 2,6-xylenol reacts current measurement of the nitroso- polarographic procedure for nitrite
with nitrite to produce 4-nitroso-2,6- and nitroxylenols are sufficiently sepa- would be useful.
xylenol. The reaction is rapid, repro- rated that a 100-fold excess of
ducible, and nearly quantitative. The the latter can be tolerated without EXPERIMENTAL
product is polarographically reducible interference. The overall reproduci-
with a single diffusion-controlled wave bility of the method is less than 1% Apparatus and Reagents. Polaro-
which merges with the anodic dissolu- (expressed as relative standard devia- graphic apparatus and techniques
tion of mercury at 0.0 volt vs. the tion). were essentially those previously re-
ported by Hartley and Curran (8).
mercury-mercurous sulfate reference
electrode. The diffusion current at Reagents and solutions were prepared
react repro- according to the directions reported for

0.15 volt vs. the reference elec- and nitrite the spectrophotometric methods (7).
trode is linearly concentration depend- Nitrate
ducibly with 2,6-xylenol to produce The Hg/HgzSOj reference electrode
ent in the range 0 to 14 p.p.m. 4-nitro-2,6-xylenol and 4-nitroso-2,6- was prepared in the 5:4:1 (v./v.)
nitrite in the reaction mixture. De- xylenol, respectively (1). These re- H2SO4: H20 :HOAc solvent determined
terminations may be made directly on actions have been utilized in spectro- to be the optimum composition of re-
the sample within 10 minutes. Side photometric procedures for nitrate and/ action solvent. The dropping mercury
reactions, one of which produces or nitrite (7) and for polarographic electrode was of the common stand-tube
3,3 ',5,5 '-tetramethylindophenol limits determination of nitrate (8). The
the yield to approximately 92%. characteristics of spectrophotometric 1
Present address, California Research
Nitrate constitutes an interference since measurement compared with polaro- Corp., P.O. Box 1627, Richmond, Calif.

2094 ANALYTICAL CHEMISTRY