MICROCHEMICAL JOURNAL 29, 361-367 (1984)

An Inexpensive Potentiostat for Controlled

Cathode-Potential Electrolyses

JOHN T. STOCK

Department of Chemistry, University of Connecticut. Stows. Connecticut 06268

Received December 10, 1982

INTRODUCTION
Quantitative electrolyses based on Faraday’s laws are usually operated
under conditions of constant current or of constant working electrode
potential. Basically, the constant current technique requires only simple
instrumentation and, analytically, is usually encountered in the form of
coulometric titration. Controlled potential coulometry is valuable for mi-
crodeterminations that are not amenable to titrimetry or are subject to
interferences such as may occur in the analysis of mixtures. Controlled
potential techniques are also valuable in the study of electrode reactions
(I) and for carrying out certain preparations (2).
The principles, apparatus, and applications of controlled potential cou-
lometry are well documented (4, 7, 11, 14). Instrumentally, the key re-
quirements are a coulometer and a potentiostat. The present account
describes a simple and inexpensive potentiostat for electrolyses in which
the cathode potential is controlled.

EXPERIMENTAL
Electrolysis cells. Preliminary experiments were made with a double-
frit cell similar to that described by Meites (8). Most of the actual test
runs were made with a small version of this cell in which lo-ml portions
of solution could be conveniently electrolyzed. A small single-f& cell
similar to that of Booman (3) was used for electrolyses in nonaqueous
media.
All cathode potentials were measured with respect to the saturated
calomel electrode. This had a 6-mm-o.d. salt bridge with a thread-type
tip (16). Constant-speed stirring at 600 rpm was used. When at rest, the
stirrer blade just touched the surface of the mercury pool cathode.
Reagents. m-Dinitrobenzene (DNB) was recrystallized from methanol.
2,2-Dinitropropane (DNP) was a commercial sample that assayed at
96.5% (1.5). All other reagents were of analytical grade. Stock aqueous

361
0026-265X/84 $1.50
Copyright 0 1984 by Academx Press, Inc.
All rights of reproduction in any form reserved.
362 JOHN T. STOCK

FIG. 1. Circuit details. (a) Pin arrangement of LM324 quad operational amplifier. Capac-
itor, C, 0.002 pF. Resistors (except where specified all are l/4 W, 5% tolerance), RI, 22OfI,
2 W; R2 (see text); R3, 5 kR variable (SET POTENTIAL); R4, 470 kfl; R5, 5 k0 variable
(BIAS); R6, RlO, 10 k0; R7, 1 MfJ; R8, R9, 150 kO; RI 1, approximately 9 0 (10 M shunted
by 68 fJ). Switch, S, SPDT. Transistors, Ql, Q3, 2N2222A or equivalent; Q2, TIP 29 or
equivalent, mounted on small heat sink.

solutions of CuSO, and of CoCl, were standardized by EDTA titrimetry

(6). Standard methanolic solutions of DNB and of DNP were prepared
by direct weighing of the solids. The standard solutions were measured
into the electrolysis cells by Gilmont microburetts.
Construction and operating principles of the potentiostat. Figure 1
shows the circuit arrangement of the potentiostat. The components
shown retail for a total of slightly less than $10. All components except
switch S, SET POTENTIAL control R3 and the three binding posts are
mounted on a 3 x 2-in. perforated circuit board. A 25-V single-power
supply based on a type LM 317T adjustable regulator was used (12). This
permits electrolyses to be run with systems of only mediocre conduc-
tance. Unless a cell of unusually high internal resistance is in use, most
electrolyses in aqueous media can be run with a power supply of lower
voltage. In fact, most of the preliminary experiments with the present
device were made with a 12-V supply based on a type 7812 fixed regulator
(Z.?), the values of R2 and R4 in the potentiostat being appropriately
decreased.
Operational amplifiers 1, 2, and 3 within the LM 324 integrated circuit
package are connected as voltage followers and thus draw negligible cur-
rents from the respective sources of potential. The potential of the ref-
erence electrode (REF) with respect to the grounded working electrode
 CONTROLLED CATHODE-POTENTIAL ELECTROLYSES 363

(WKG) is handled by OA 1 and passed by resistor R6 to the inverting

input (pin 13) of OA 4, which acts as a comparator with gain. The desired
potential is set by means of R3 and is passed by R8 to the noninverting
input (pin 12) of OA 4. Darlington-connected transistors Ql and Q2,
driven by the output (pin 14) of OA 4, control the voltage applied to the
auxiliary electrode (AUX) and hence the magnitude of the electrolysis
current. This current flows through low-value resistor Rll, so that cur-
rent-limiting action can be provided. As the current through Rll rises,
so does the base-to-emitter potential of cut-off transistor Q3. Eventually,
this transistor begins to conduct, so that drive from the output of OA 4
is given a path alternative to that leading to the Ql-Q2 combination.
Negative feedback from the emitter of Q2 through resistor R7 to the
inverting input of OA 4 controls the actual operation of the potentiostat.
Bias control RS allows a small additional signal to be applied to pin 12
of OA 4. This is useful when finally adjusting the controlled potential to
match that indicated by the scale associated with the SET POTENTIAL
control R3. When switch S is in the STANDBY position, the potentiostat
current merely flows through resistor Rl. Electrolysis cannot proceed
until S is moved to RUN. A hand-drawn 0- to 2-V scale and a pointer-
type knob on R3 enable the controlled potential to be set reproducibly.
Alternatively, a commercial 50-division potentiometer dial plate may be
used, so that each division represents 40 mV.
Preliminary adjustment is made by use of a “dummy cell,” which is
merely a milliammeter with a 100-n 10-W resistor inserted in one of the
input leads. This combination is connected between the WKG post and
the AUX post. A voltage reference source (VRS), such as the Heath
model EU-80A, with the output set at 1.00 V, is connected so that the
positive goes to the REF post and the negative to the WKG post. With
RS in approximately midposition, R2 is then selected to produce a mil-
liammeter reading that is a little above zero when the SET POTENTIAL
control is also at 1.00 V. It should then be possible to bring the current
to zero by adjustment of R5. In the prototype, the value of R2 was ap-
proximately 60 kfI, obtained by trial shunting of a lOO-kR resistor with
others of higher value until the desired result was obtained. Alternatively,
R2 may be a multiturn lOO-kR variable resistor. Final match of the SET
POTENTIAL indication to the actual controlled potential is made by
adjustment of R5 during a trial electrolysis. A digital voltmeter reading
to the nearest millivolt, connected between the REF and WKG posts, is
used in this operation.
General procedure. Electrolyses were performed according to the rec-
ommendations of Meites (8-10) and of Ehlers and Sease (5). A coulo-
meter reading directly in microequivalents was used (17). Nitrogen for
removal of dissolved oxygen was presaturated by passage through a bub-
364 JOHN T. STOCK

TABLE 1
SIMULATIONOFEFFECTOFCATHODE-POTENTIALERRORON CELLCURRENT
Error, mV 0 10 15 20 30 40 50
Current, mA 0 0.1 5.0 9.8 18.9 28.1 31.2

bler that contained the same supporting solution as that in the electrolysis
cell.

RESULTS
Electrical checkout. Using the dummy cell and VRS arrangement, the
SET POTENTIAL control was adjusted to give a current of 10.0 mA.
Observed at intervals during a period of 2 hr, the current remained within
kO.3 mA of the preset value.
With a VRS output of 60 mV, the SET POTENTIAL control was used
to bring the current just to zero. The VRS output was then reduced in
steps, to simulate a succession of increasing errors (cathode insufficiently
negative) in the potential being controlled. The results, summarized in
Table 1, indicate that the current change is approximately 0.9 mA per 1
mV error when this error is larger than about 15 mV.
The 100-R resistor in the dummy-cell arrangement was replaced by a
500-O variable resistor, which was set at maximum value. SET POTEN-
TIAL and VRS output were both initially at 1.00 V, so that the current
was zero. The VRS output was then decreased until the current rose to
a constant value. Similar observations, summarized in Table 2, were made
with the variable resistor set at lower values. With a resistance of 500 R,
the potentiostat is developing its maximum output drive, approximately
22.5 V. This indicates that, in an actual electrolysis, the effective cell
resistance must not exceed 2200 fl is a maximum current of approxi-
mately 10 mA is required.
As the resistance is decreased, the maximum current rises to approx-
imately 120 mA and does not increase further even when the resistance
has become very small. This demonstrates the current-limiting action that
protects transistor Q2 if a fault such as a cell short circuit occurs.
Passage of nitrogen through 30 ml of 0.1 M NaOH in the large elec-
trolysis cell was stopped while a little dissolved oxygen still remained. A
current of approximately 2 mA was obtained when the solution was elec-
trolyzed with the SET POTENTIAL at -0.70 V. Measured by digital
voltmeter, the actual potential of the mercury pool cathode was -0.689
TABLE 2
SIMULATION OF EFFECT OF CELL RESISTANCE ON MAXIMUM CELL CURRENT
Resistance, 0 500 400 300 200 150 80 40 20 10 3
Current, mA 45 55 11 101 121 121 119 120 120 120
 CONTROLLED CATHODE-POTENTIAL ELECTROLYSES 365

OCO TIME, MIN.

FIG. 2. Decay of current in successive electrolyses of 50-p.eq/V amounts of cobalt(H) in
10 ml of 1 M NH,-NH&l. Cathode potential, - 1.45 V. 0, first run: 0, second run.

V. During a 60-min period, observed random fluctuations of potential did

not exceed +- 2 mV.
Controlled potential electrolyses. Figure 2, plotted from data obtained
during preliminary experiments, illustrates the exponential decay of cur-
rent during two successive electrolyses of identical amounts of cobalt
(II). Although a single response line has been drawn, the slopes associ-
ated with the individual runs are not quite identical. This is not surprising,
because the rate of electrolysis is quite sensitive to the position of the
stirrer blade with respect to the surface of the mercury pool cathode.
Table 3 summarizes the results of typical controlled potential electro-
lyses. The main aim of this portion of the investigation and its associated
preliminary runs was to observe the behavior of the potentiostat under
various conditions for a total operating period of approximately 100 hr.
No attempt was made to reach the maximum precision and accuracy
obtainable in such electrolyses (5, 8-10). Generally, a given set involved
only 3 runs, so that the results are given as ranges of values.
Conclusions. Requiring only a single-power supply, the simple and in-
expensive potentiostat performs satisfactorily in the controlled cathode-
potential electrolysis of various substances.

SUMMARY

The construction of a simple potentiostat from inexpensive components is described.

Satisfactory results were obtained in the controlled cathode-potential coulometry of sub-
millimolar amounts of copper( cobalt(H), 2,2-dinitropropane, and m-dinitrobenzene.
366 JOHN T. STOCK

TABLE 3
CONTROLLEDPOTENTIALELECTROLYSES
Sample weight, mg
Supporting Volume Potential
Sample solution (ml) 07 Taken Found

Copper(H) 1 MHCI 100 -0.50 6.67 6.60-6.73

10 - 0.50 1.33 1.30-1.37
1 M NH,-1 M NH&l 100 - 0.75 6.67 6.59-6.66
10 -0.75 1.33 1.28-1.32
Cobalt(H) 1 M NH,- 1M NH&l 100 - 1.45 6.03 5.91-6.02
10 - 1.45 1.33 1.25-1.35
10 - 1.45 0.67 0.58-0.66
DNP 0.1 M NaOH 50 -0.70 13.41 13.30-13.39
10 -0.70 1.34 1.28-1.32
15 -0.70 0.84 0.76-0.82
DNB 0.1 M LiCl-0.1 M 10 -1.15 3.36 3.26-3.35
H,BO, in MeOH”
phthalate buffer, 50 -0.60 1.68 1.64-1.70
pH 4.1b 15 -0.60 0.84 0.76-0.82
10 - 0.60 0.42 0.35-0.40

a Double-junction salt bridge used, with methanolic supporting solution in the lowerjunc-
tion tube.
b Potassium hydrogen phthalate (450 ml of 0.100 M) + 11.7 ml of 0.100 M NaOH.

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 CONTROLLED CATHODE-POTENTIAL ELECTROLYSES 367

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