DOI: 10.

1595/147106708X297855

Platinum as a Reference Electrode in

Electrochemical Measurements
By Kasem K. Kasem* and Stephanie Jones
Department of Natural, Information, and Mathematical Science, Indiana University Kokomo, Kokomo, IN, 46904-9003, U.S.A.;
*E-mail: [email protected]

The usefulness of platinum as an electrochemical reference electrode was investigated. Well

known redox systems with one-electron single or multiple redox waves, and two-electron
multiple redox waves were used as test regimes. The effects on electrode performance of
variables such as the solvent, the physical state of the electrolyte and its temperature were
investigated. Cyclic voltammetry (CV) was used to derive kinetic parameters for comparison
with corresponding measurements on traditional reference electrodes. The results indicate
that Pt can be used as a reference electrode under specific conditions in which traditional
reference electrodes cannot be used.

Traditional reference electrodes used for electrochemical measurements, such as the calomel
and silver/silver chloride electrodes, have a limited
range of applicability. The liquid junction is problematic with these electrodes, and they cannot be
used either with wholly solid-state electrochemical
cells or for very high-temperature reactions such as
those in molten electrolytes. The use of solid platinum electrodes in molten salts has been reported
(114), but there are problems associated with the
use in molten media of Pt electrodes. Under
strongly alkaline conditions, they actually function
as oxidation electrodes (2). It has been demonstrated that Pt foil cannot act as a reference electrode in
molten electrolytes, since it is neither stable nor
depolarised (4). On the other hand, Pt wire
immersed in molten NaCl/KCl can maintain a
steady electrode potential for more than 12 hours,
and shows electrochemical irreversibility. It can
therefore can be used as a pseudo-reference electrode for the study of electrode reaction kinetics,
with the advantages of simplicity, convenience and
ease of operation (7). The Pt reference electrode
performs well in geothermal brine solutions at high
pressure and temperature (~ 250C). Unlike conventional reference electrodes (even when
modified for high temperature), the Pt reference
electrode is applicable to measurements in complex polluted brines (8).

Platinum Metals Rev., 2008, 52, (2), 100106

In certain electrolytes, modification of the Pt

surface is important for its stability. Anodised, nonporous Pt has demonstrated its usefulness as a
solid-state reference electrode by virtue of its nearNernstian behaviour, low hysteresis and rapid
response (15). Modifications to Pt wire may extend
its usefulness to more electrochemical systems. The
use of polypyrrole (16), poly-1,3-phenylendiamine
(15) or polyvinyl ferrocene (17) as a surface modifier can successfully suppress significant interference
by any coupled redox systems or contaminants.
The fact that a Pt electrode can be modified with
nitrogen-based polymers or be incorporated as part
of a biosensor assembly (18) indicates its resistance
to interference from these compounds.
Some of the problems associated with the reference electrode can be solved outside the
electrochemical cell. A reference electrode is
defined as an ideal non-polarisable electrode; thus
its potential does not vary with the current passing.
In practice, no electrode follows this ideal behaviour; consequently, the interfacial potential of the
counterelectrode in the two-electrode system
varies with the flow of current passed through the
cell. In order to overcome this problem, a threeelectrode cell can be used. The functions of the
counterelectrode (in a three-electrode cell) are
divided between the reference and auxiliary electrodes. The passage of current between the

100

working and auxiliary electrodes ensures that less

current passes through the reference electrode.
Furthermore, the three-electrode cell allows the
potential between the working and reference electrodes to be controlled. Most electrochemical
devices include an operational amplifier of high
input impedance for the reference electrode input,
to eliminate the possibility of any current passing
through the reference electrode. Since no Faradaic
process takes place at the reference electrode, its
area relative to that of working electrode has no
effect on the electrochemical results.
The physical form of the Pt reference electrode
may contribute to its performance. Studies (19)
indicate that the Pt mesh electrode yields very
reproducible results, and that it can be used as a
convenient reference electrode. On the other
hand, Pt sheet or wire has been used in all-solidstate electrochemical cells at room temperature
(2022), and in reactions in frozen agar or frozen
aqueous electrolytes (23, 24). Most of these studies involved only one-electron redox systems.
In this study, the usefulness of Pt as a reference
electrode in electrochemical systems was investigated using CV techniques. Single or
multi-electron redox systems involving one- or
two-electron redox waves were used in this study.
To verify the suitability of Pt as a reference electrode, kinetic parameters were determined for
comparison with corresponding measurements on
traditional reference electrodes.

cyanoferrate (III)) electrolyte. The two electrodes

were connected briefly to the inputs of a Fluke 27
multimeter that has input impedance 200 M.
The voltage reading was used to assess the quality
and suitability of the Pt reference electrode.
Electrochemical experiments were carried out
using a 10 cm3 cylindrical cell (Figure 1). The reference electrode, unless otherwise stated, was Pt.
CV was performed first using Pt as a reference
electrode and then using Ag/AgCl/Cl as a reference electrode. The counter (auxiliary) electrode
was a Pt wire, and the working electrodes were
glassy carbon (0.07 cm2) or Pt (0.02 cm2) in disc or
microelectrode (10 m diameter or 7.85 107
cm2) configuration. Electrodes were positioned in
the cell in a similar way. The Pt wire reference
electrode was coiled around the Teflon jacket of
the working electrode; the counter electrode was
placed at a distance from both the reference and
working electrodes. The working electrodes were
cleaned by polishing with 1 m -alumina paste or
diamond paste, and rinsed with water and acetone
prior to use. A BAS 100B Electrochemical
Analyzer (Bioanalytical System, Inc.) was used to
Working electrode
Reference electrode

Counter electrode

Experimental Details
The reagents FeCl3, KCl, K3[Fe(CN)6] and
K4[Fe(CN)6] were of analytical grade. A purified
agar powder was obtained from Sigma Chemical
Co. All other reagents were of at least reagent
grade and were used without further purification.
Analytical grade nitrogen gas was used to purge
oxygen from the electrolyte. Unless otherwise stated, experiments were performed at 25C and 1 atm
pressure.
To test the suitability of Pt as a reference electrode, a Pt wire reference electrode was coupled
with a standard Ag/AgCl/Cl reference electrode
in a beaker containing 0.5 M KCl with or without
the addition of 2 mM K3Fe(CN)6 (potassium hexa-

Platinum Metals Rev., 2008, 52, (2)

Electrode
cross-section
Fig. 1 Schematic drawing for the electrochemical cell
used in this study

101

perform the electrochemical studies. For frozen

electrolyte experiments, the electrolyte was first
frozen at 20C and measurements were performed at 5C.

Suitability Tests on Platinum Wire

Reference Electrodes
Prior to use as a reference electrode, Pt wire
was mechanically polished using 600 grade sandpapers, followed by 2 m diamond paste, and rinsed
with deionised water. In an alternative method, the
mechanically cleaned Pt wire was heated to 1000C
for 10 minutes. The Pt wires with the different
treatments were each coupled with a reference
electrode of known potential as described in the
Experimental Details section. The voltammetric
reading was less than 0.2 mV in each case. This
value is much lower than the standard maximum
allowed for this test, which is 3 mV. These results
indicate that Pt wire is an adequate reference electrode for routine laboratory use.
The suitability test showed that stirring or agitation has no effect on the performance of the Pt
wire reference electrode. Several Pt wires of different lengths were subjected to the reference
electrode suitability test. The results indicate that
the surface area of the Pt wire has no effect on performance.
One of the most undesirable effects which a
reference electrode can cause is a change in potential during the course of an experiment. In CV
studies, the quantity Ep (the difference between
the reduction peak potential Epc and the oxidation
peak potential Epa) is very important in the calculation of the charge transfer rate constant kCT
when diffusion is the dominant process. The calculation is made using Equation (i) (25):

(DO/DR) kCT

(i)

(NF DO/RT)

1/2

where: is a dimensionless rate parameter, the

value of which decreases from 20 to 0.1 as Ep
increases from 0.061 V to 0.212 V (25); DO = diffusion coefficient of oxidation; DR = diffusion
coefficient of reduction; N = number of electrons;
= scan rate (V s1); F = Faraday constant;
T = temperature; R = gas constant; = transfer

Platinum Metals Rev., 2008, 52, (2)

coefficient. The validity of Pt as a reference electrode has been tested in each of the three systems
described below.

One-Electron Redox System

Liquid aqueous, agar gel and frozen systems
containing 5 mM of K3Fe(CN)6 and 100 mM KCl
as supporting electrolytes were chosen as model
systems for one-electron redox reactions. Figure
2(a) indicates that the use of Pt as a reference electrode shows a clear potential window in a
redox-free electrolyte, whereas Figure 2(b) shows
only a parallel shift in both Epc and Epa without
affecting the value of Ep, even in agar medium.
Typical characteristics of diffusional redox waves
are reported and displayed in Figures 2(c)2(e).
The use of Pt as a reference electrode in a
frozen electrolyte shows CV outcomes similar to
those generated when Ag/AgCl/frozen Agar (KCl
saturated) was used as a reference electrode. The
results are displayed in Figure 3. These results were
interpreted using a high pressure effect model (24).

Multi One-Electron System

1 mM of TCQN (7,7,8,8-tetracyanoquinodimethane) in acetonitrile containing 0.2 M LiClO4
(lithium perchlorate) was used as a medium to
investigate a multi-one electron redox system.
Figure 4 displays the CV of this system using a Pt
disc working electrode with a Pt wire electrode
(solid trace), and Ag/AgCl/KCl (dashed trace) as
reference electrodes. Two one-electron redox
waves can be identified. It can be observed that
increasing the scan rate from 5 mV s1 (Figure 4(a))
to 50 mV s1 (Figure 4(b)) generated well defined
redox waves. Measured Ep for redox waves after
IR compensation (for the ohmic potential drop)
indicates a typical one-electron wave character
(amplitude 61 mV) which is very close to the theoretical amplitude of 59 mV. The fact that the
TCQN CV shows a consistent behaviour regardless of the reference electrode used indicates that
the results are attributable to the redox system and
not to the type of reference electrode. This conclusion demonstrates the usefulness of Pt as reference
electrode in non-aqueous media for multi oneelectron redox systems.

102

(b)

(a)

20 A

+1.0

1.0

2.0
E, V

+1.0

+0.5

0.4
E, V

(c)
20 A
+0.4

(d)

(e)

50

50

40

40

30

30

ip, A

ip, A

0.4
E, V

20
= ipc
= ipa

10
0

0.1 0.2 0.3 0.4 0.5

V

20
= Epc
= Epa

10
0

0.1
V s1

0.2

Fig. 2 (a) CV at 0.20 V s1 of: GCE; - - - Pt reference electrode, in agar gel containing KCl; (b) CV at 100 V s1 of
Pt electrode in agar gel containing 5 mM K3[Fe(CN)6]/KCl: vs. Ag/AgCl (agar saturated KCl) as reference
electrode; - - - vs. Pt electrode; (c) CV of Pt electrode (0.02 cm2) in agar gel containing 5 mM K4[Fe(CN)6]/KCl at:
0.020, 0.050, 0.10 and 0.150 V s1 (inner to outer CV traces, respectively); (d) Plot of ip vs. V ( = ipc, = ipa);
(e) Plot of ip vs. V sec1 ( = Epc, = Epa)

Multi Two-Electron Redox System

Conclusions

5 mM H3PMo12O40 (a Keggin heteropolyacid)

immobilised in agar gel containing H2SO4/KCl
was used as a model for a multi two-electron redox
system. Either a glassy carbon microelectrode (10
m diameter) or a disc electrode (0.07 cm2) was
used as a working electrode. The results are displayed in Figure 5(a) (microelectrode) and Figure
5(b) (disc electrode). Figure 5 clearly illustrates the
multi two-electron redox waves typical of phosphomolybdic acid. The measured Ep for each of
the first two redox waves was less than 28 mV.
The position of the formal potential of each of
these waves was negatively shifted by approximately 600 mV from that observed when a
Ag/AgCl/KCl reference electrode was used.

Under certain conditions, such as high temperature or in molten electrolytes, where the usual
reference electrodes such as calomel or
Ag/AgCl/KCl electrodes cannot be used in electrochemical measurements, this study has
demonstrated that Pt is the reference electrode of
choice. Our study also shows that, under conditions where traditional reference electrodes are
viable, Pt can replace them. Furthermore, in highpressure electrochemical systems the change in the
formal potential of the redox system follows
Equation (ii):

Platinum Metals Rev., 2008, 52, (2)

V = (E)TNF/P

(ii)

where P is the partial derivative of the pressure.

103

(a)

(b)

6 A

+0.6

+0.6

0.6
E, V

0.6
E, V

10 A

(c)

500 pA

+0.6

+0.3

0.3
E, V

Fig. 3 CV at 100 mV s1 for 5 mM [Fe(CN)6]3/4: (a) Pt disc in aqueous KCl; (b) Pt disc in frozen KCl electrolyte;
(c) Pt microelectrode in frozen KCl electrolyte

In liquid electrolytes the change of the volume

(V) originates in the outer sphere molecules in
the solvation layer. Traditional reference electrode
components contribute to this volume change. The
capability of a Pt wire to act alone as a reference
electrode without any associated solvated ions,
eliminates the error in calculation of V.
Consequently, the measured E relates more
specifically to the particular redox system. Our
studies show a 3.5 mV change in the formal potential (E) of [Fe(CN)6]3/4 when the aqueous liquid
electrolyte is frozen. E was 98 mV when aqueous
gel electrolyte is frozen. It has been reported (26)
that a change in the formal potential of the
[Fe(CN)6]3/4 system in a liquid electrolyte of 3.93
105 V atm1 took place when the system was subject to pressure. This change in the formal potential
is equivalent to applying 89 atm and 2500 atm to
frozen aqueous and gel electrolytes of [Fe(CN)6]3/4

Platinum Metals Rev., 2008, 52, (2)

respectively. The volumes of both the reference and

counter electrode components will remain constant,
because Pt wires were used as reference and counter
electrodes; the change in the formal potential is due
to the change in the volume of the redox ion. This
is an additional advantage of using Pt as a reference
electrode over the use of a traditional reference
electrode under these conditions.
In conclusion, we have shown that where conventional reference electrodes are not suitable for
some electrochemical measurements, Pt wire is a
satisfactory reference electrode in various electrochemical systems such as aqueous, non-aqueous,
gel or frozen electrolytes, and for measurements
under high pressure. Single or multi one- or twoelectron redox systems were studied, with peak
separation (Ep) indicating that Pt can be used
reliably as a reference electrode under a variety of
conditions.

104

(a)

(a)
4.0 A

1 nA
+0.2

0.2

0.4

0.6
E, V

(b)

+0.2

0.5

1.1
E, V

3.0 A

0.2

0.4

(b)

0.6
E, V

Fig. 4 CV of GCE (0.07 cm2) in agar gel containing 1

mM TCQN (7,7,8,8-tetracyanoquinodimethane) in 0.2 M
LiClO4 in acetonitrile: Pt reference electrode, - - Ag/AgCl/Cl reference electrode: (a) at 0.005 V s1; (b) at
0.50 V s1

+1.0

1.0
E, V

10 A

Fig. 5 CV at 0.5 V s1 in 5 mM H3PMoO40 in agar gel

containing H2SO4/KCl for: (a) carbon microelectrode;
(b) GCE (0.07 cm2)

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The Authors
Dr Kasem K. Kasem is a Professor of Chemistry at Indiana
University Kokomo, U.S.A. He is interested in
developments in the field of applied electrochemistry,
especially in physical and analytical applications of
chemically-modified electrodes. He also has interests in
semiconductor photoelectrochemistry, the electrochemical
behaviour of polymeric thin films, activation and
metallisation of polymers, and the electrodeposition of
metals and alloys.

Platinum Metals Rev., 2008, 52, (2)

Stephanie Jones participated in this work during her senior

year at Indiana University Kokomo, of which she is now an
alumna, having graduated with a bachelors degree in
chemistry. She works with a chemical company in
Bloomington, Indiana, U.S.A.

106