A Guide to A

s indicated in a number of NACE

International standards, includ-
ing SP0169-2007,1 the critical
decision as to whether or not a

Understanding
buried or submerged metallic structure is
cathodically protected (polarized) to a
sufficient degree is based on a measure-
ment of the metals polarized potential,
in its environment (soil, seawater, etc.),

Reference
relative to the potential of a reference
electrode. Consequently, no equipment
item is of more fundamental importance
to the cathodic protection (CP) industry

Electrode
than the reference electrode.
There are a number of different refer-
ence electrode types available, including
those that are identified in SP0169-2007,
that are acceptable alternatives to the

Readings
copper/copper sulfate (Cu/CuSO4) ref-
erence electrode (CSE). It is important
for the corrosion engineer to appreciate
the characteristics of the various electrode
types and, in particular, how readings
Robert M. Park, M.C. Miller Co., Inc., Sebastian, Florida taken with different reference electrodes
can be adjusted to the CSE potential.
The purpose of this article is not to
discuss the relative merits of the various
Reference electrodes are essential to evaluate reference electrode types, but to provide
a guide to the corrosion engineer regard-
ing their application. A universal formula
corrosion and cathodic protection on buried and is provided that allows readings taken
with alternative reference electrode types
submerged structures. This article discusses the to be adjusted to the CSE potential.

nature of structure-to-electrolyte readings employing Electrode Potentials

The starting point to understanding
copper/copper sulfate (Cu/CuSO4) electrodes (CSEs) how different reference electrodes pro-
vide for different metallic structure-to-
electrolyte readings is to examine elec-
and various other acceptable reference electrode trode potential values. Just as different
metals have different electrode potentials,
types. A universal formula is presented that allows also known as corrosion potentials or
open-circuit potentials, different refer-
readings taken with non-CSE reference electrodes to ence electrode types have different elec-
trode potential values. And, even within
be adjusted to the CSE potential. a particular reference electrode family,
the electrode potentials can have a sig-
nificant range of values. Figure 1 presents

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 C AT H O D I C P R O T E C T I O N

FIGURE 1

electrode potential values (in mV at

25 C), relative to the standard hydrogen
electrode (SHE) potential, for pure Fe,2
pure Zn,3 and CSE.4 Also shown are the
electrode potential values for the refer-
ence electrode types identified in SP0169-
2007 as alternative reference electrode
types to CSE, namely, the silver/silver
chloride (Ag/AgCl [saturated KCl]) and
calomel (saturated KCl) electrode types.5
The Zn electrode potential is indicated in
Figure 1, since a Zn (metal) electrode is
also used in the corrosion industry as a
Electrode potential values (in mV at 25 C), relative to the SHE potential, for the
quasi-reference electrode. Finally, the Fe metal example under test (Fe), the CSE, two other reference electrode types, and a
electrode potential is indicated in Figure quasi-reference electrode (Zn). See Table 1 for the various expected voltmeter
1 as an example of a metallic component readings.
that may be buried or submerged.
Low-carbon steel (CS), for example,
having a clean and shiny surface, should potential (corrosion potential) to a more tral soils, a small current flows between
have a similar electrode potential (corro- negative value (such as 540 mV vs. SHE, the electrodes, causing the potential dif-
sion potential) value (440 mV relative to for the Fe example) would be the goal of ference to translate to a voltage reading.
the SHE potential). As the surface of a a CP system. Table 1 shows expected native Fe
metal, such as pure Fe or low-CS, begins potentials in neutral soils as measured by
to corrode freely, its electrode potential Electrode Potential the various reference electrodes illus-
(corrosion potential) decreases (becomes Difference Readings trated in Figure 1. As indicated in the
less negative) relative to the SHE poten- When a high input impedance volt table, once the two electrode potentials
tial. Of course, the goal of CP is to mini- meter is connected between two elec- involved in the measurement are known
mize corrosion, so moving the electrode trodes having different potentials in neu- (the potential of the metal under test and

table 1
Expected native Fe potential in neutral soil as measured by a variety of reference
electrodes(A)
Voltmeter Potentials of Electrodes
Configuration Involved in Voltage P (Expected Expected Readings Adjusted
(Figure 1) Reading (at 25 C) Voltage Reading) to the CSE Potential
1 Fe [P = 440 mV] 440 mV 316 mV = 756 mV N/A
CSE [P = 316 mV]
2 Fe [P = 440 mV] 440 mV 199 mV = 639 V 199 mV 316 mV + reading =
Ag/AgCl (sat. KCl) [P = 199 mV] [199 316 + (639)] mV =
756 mV
3 Fe [P = 440 mV] 440 mV 244 mV = 684 mV 244 mV 316 mV + reading =
Calomel (sat. KCl) [P = 244 mV] [244 316 + (684)] mV =
756 mV
4 Fe [P = 440 mV] 440 mV (762 mV) = 322 mV 762 mV 316 mV + reading =
Zn [P = 762 mV] [762 316 + 322] mV =
756 mV
Measurements are based on the voltmeter configurations indicated in Figure 1. Also shown are the expected readings adjusted to the CSE
(A)

potential.

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 C AT H O D I C P R O T E C T I O N A Guide to Understanding Reference Electrode Readings

table 2
Expected native Fe potential in neutral soil as measured by a number of Ag/AgCl reference
electrodes having various molarities of KCl filling solution(A)
Voltmeter Potentials of Electrodes
Configuration Involved in Voltage P (Expected Expected Readings Adjusted
(Figure 2) Reading (at 25 C) Voltage Reading) to the CSE Potential
1 Fe [P = 440 mV] 440 mV 316 mV = 756 mV N/A
CSE [P = 316 mV]
2 Fe [P = 440 mV] 440 mV 199 mV = 639 V 199 mV 316 mV + reading =
Ag/AgCl (sat. KCl) [P = 199 mV] [199 316 + (639)] mV =
756 mV
3 Fe [P = 440 mV] 440 mV 205 mV = 645 mV 205 mV 316 mV + reading =
Ag/AgCl (3.5 M KCl) [P = 205 mV] [205 316 + (645)] mV =
756 mV
4 Fe [P = 440 mV] 440 mV 222 mV) = 662 mV 222 mV 316 mV + reading =
Ag/AgCl (1.0 M KCl) [P = 222 mV] [222 316 + (662)] mV =
756 mV
5 Fe [P = 440 mV] 440 mV 250 mV = 690 mV 250 mV 316 mV + reading =
Ag/AgCl (0.5 M KCl) [P = 250 mV] [250 316 + (690)] mV =
756 mV
Measurements are based on the voltmeter configurations indicated in Figure 2. Also shown are the expected readings adjusted to the CSE
(A)

potential.

table 3
Expected native Fe potential as measured by Ag/AgCl elements directly exposed to
seawater and diluted-seawater electrolytes(A)
Voltmeter Potentials of Electrodes
Configuration Involved in Voltage P (Expected Expected Readings Adjusted
(Figure 3) Reading (at 25 C) Voltage Reading) to the CSE Potential
1 Fe [P = 440 mV] 440 mV 316 mV = 756 mV N/A
CSE [P = 316 mV]
2 Fe [P = 440 mV] 440 mV 250 mV = 690 V 250 mV 316 mV + reading =
Ag/AgCl (seawater) [P = 250 mV] [250 316 + (690)] mV =
756 mV
3 Fe [P = 440 mV] 440 mV 370 mV = 810 mV 370 mV 316 mV + reading =
Ag/AgCl (<1% seawater) [370 316 + (810)] mV =
[P = 370 mV] 756 mV
Measurements are based on the voltmeter configurations indicated in Figure 3. Also shown are the expected readings adjusted to the CSE
(A)

potential.

the potential of the reference electrode in of the voltmeter connects to the metal by a CP system to, say, 100 mV above
use), expected readings can be deter- under test, which is Fe in the example the native potential, the effective Fe po-
mined. As the table illustrates, since the shown, and the negative side of the volt- tential will be 540 mV vs. SHE and the
potentials of the various reference elec- meter connects to the reference electrode. instant-off voltage reading will be 856
trodes are different from each other, For a given reference electrode in use, for mV vs. CSE (540 mV minus 316 mV).
different Fe potentials are expected vs. example a CSE, the potential value of the
the different reference electrodes. metal under test will determine the volt- Universal Adjustment
All of the voltage reading values shown age reading. As indicated in Table 1, a Formula
in Table 1 (and also in Tables 2 and 3) native Fe potential of 440 mV vs. SHE As the tables indicate, voltage readings
correspond to a particular voltmeter will yield a voltage reading of 756 mV taken vs. a non-CSE reference electrode
configurationnamely, the positive side vs. CSE. If, however, the Fe is polarized can be adjusted to the CSE potential.
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 C AT H O D I C P R O T E C T I O N

FIGURE 2

Equation (1) is a universal adjustment

formula for the voltmeter configuration
shown in Figure 1.
Reading adjusted to CSE potential =
P(RE) P(CSE) + (reading vs. RE) (1)

where P(RE) is the electrode potential of

the electrode in use (vs. SHE), P(CSE) is
the electrode potential of a CSE (vs.
SHE), and reading vs. RE is the volt-
age reading taken by the electrode in use.
For example, if an instant-off voltage
reading of 222 mV is recorded from a
polarized Fe pipe using a Zn quasi-refer-
ence electrode, the voltage reading ad-
justed to the CSE potential is 762 mV
316 mV + 222 mV = 856 mV, since
P(Zn) = 762 mV and P(CSE) = 316 mV
(Figure 1).
Electrode potential values (in mV at 25 C), relative to the SHE potential, for the
metal example under test (Fe), the CSE, and a number of Ag/AgCl electrodes
Ag/AgCl Land-based having various molarities of KCl filling solution. See Table 2 for the various
Reference Electrodes expected voltmeter readings.
Ag/AgCl reference electrodes that are
typically used in land-based applications FIGURE 3
(i.e., non-submersion applications) have
a KCl filling solution to which the Ag/
AgCl element makes intimate contact
(Figure 2). The KCl solution can have a
variety of molarities (concentrations) and
the molarity of the KCl filling solution
determines the electrode potential for a
given KCl solution temperature. The
maximum KCl concentration is 4.6 M at
25 C, which represents the solubility
limit of KCl in water (at 25 C). This
would be the saturated KCl concentra-
tion (at 25 C).
As indicated in Figure 2, the Ag/AgCl
electrode potential vs. SHE varies sig-
nificantly with KCl filling solution molar-
ity in the range of 4.6 M (saturated) to 0.5
M. Consequently, as indicated in Table
2, expected native Fe potentials in
neutral soils measured vs. Ag/AgCl (KCl
filling solution) reference electrodes are
significantly dependent on the specified Electrode potential values (in mV at 25 C), relative to the SHE potential, for the
metal example under test (Fe), the CSE and Ag/AgCl elements directly exposed to
KCl molarity. As above, readings can be seawater, and diluted-seawater electrolytes. See Table 3 for the various expected
adjusted to the CSE potential. For ex- voltmeter readings.

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 C AT H O D I C P R O T E C T I O N A Guide to Understanding Reference Electrode Readings

ample, if an instant-off voltage reading given electrolyte temperature.6 As shown Conclusions

of 745 mV is recorded from a polarized in Figure 3, a significant range of electrode As illustrated in this article, for a given
Fe pipe using an Ag/AgCl (3.5 M KCl) potentials vs. SHE is indicated for electro- structure material, a structure-to-electro-
reference electrode, the voltage reading lytes ranging from natural seawater to lyte reading is significantly dependent on
adjusted to the CSE potential is 205 mV highly diluted seawater. In turn, as indi- the nature of the reference electrode used
316 mV + (745 mV) = 856 mV, since cated in Table 3, expected native Fe in the measurement, and, of primary
P(Ag/AgCl [3.5 M KCl]) = 205 mV, and potential readings recorded using Ag/ significance is the electrode potential of
P(CSE) = 316 mV (Figure 2). AgCl (seawater) reference electrodes ex- the reference electrode in use. Should a
hibit a range of values. As above, readings reading require adjustment to the CSE
Ag/AgCl Seawater can be adjusted to the CSE potential. For potential, the universal adjustment for-
Reference Electrodes example, if an instant-off voltage read- mula presented in this article can be
Ag/AgCl reference electrodes that are ing of 790 mV is recorded from a polar- employed, assuming that an appropriate
typically used in submersion applications ized (submerged in natural seawater) Fe electrode potential can be identified, vs.
do not have a KCl filling solution, but pipe using an Ag/AgCl element (seawater) the SHE potential, for the reference elec-
rather, the Ag/AgCl element makes direct reference electrode, the voltage reading trode in use.
contact to the electrolyte itself, which is adjusted to the CSE potential is 250 mV
typically seawater (Figure 3). In this sce- 316 mV + (790 mV) = 856 mV, since References
nario, the electrodes potential is a func- P(Ag/AgCl [seawater]) = 250 mV, and 1 NACE Standard SP0169-2007, Con-
tion of the salinity of the electrolyte at a P(CSE) = 316 mV (Figure 3). trol of External Corrosion on Under-
ground or Submerged Metallic Piping
Systems (Houston, TX: NACE
International, 2007).
2 P. Atkins, Physical Chemistry, 6th ed. (New
York, NY: W.H. Freeman and Co.,
1997).
3 P. Vanysek, Electrochemical Series,
Handbook of Chemistry and Physics, 88th ed.
(Boca Raton, FL: Chemical Rubber Co.,
2007).
4 J. Lichtenstein, Reference Electrodes
(Half-Cells), MP 40, 10 (2001).
5 D.T. Sawyer, A. Sobkowiak, J.L.
Roberts, Jr., Electrochemistry for Chemists,
2nd ed. (New York, NY: John Wiley &
Sons, 1995).
6 M.H. Peterson, R.E. Groover, Tests
Indicate the Ag/AgCl Electrode is Ideal
Reference Cell in Seawater, MP 11, 5
(1972): pp. 19-22.

ROBERT M. PARK is currently director of research at

the M. C. Miller Co., 11640 U.S. Highway 1,
Sebastian, FL 32958. Previously, he spent six years
as a research scientist with the 3M Co. and 10
years as a professor of materials science and
engineering at the University of Florida. He holds
B.Sc. and Ph.D. degrees in electronics and electrical
engineering from the University of Glasgow,
Scotland. He has published more than 70 papers in
referenced scientific journals and holds two U.S.
patents. He is a six-year member of NACE
International.

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