REFERENCE ELECTRODES FOR MONITORING

CATHODIC PROTECTION ON BURIED PIPELINES

PRE-STANDARD: CEOCOR WORKING GROUP

PUBLICATION

CEOCOR Commission 2
External Corrosion and Cathodic Protection

Working Group E
Chaired by Brian S Wyatt: Corrosion Control, UK
Rev11: Approved by WG E and CEOCOR Board Brussels
November 2018

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TABLE OF CONTENTS

Page
Table of
Contents.......................................................................................................... 2

1.0 Scope.................................................................................................... 3

2.0 Normative references and terms………............................................. 3

3.0 Definition and Types of Reference Electrodes................................. 5

4.0 Permanent Reference Electrodes………………………………………17

5.0 Portable Reference Electrodes ……………………………………...... 20

6. 0 Reference Electrode Parameters: Permanently Installed................21

7.0 Reference Electrode Parameters: Portable...................................... 23

8.0 Installation Procedures for Permanent Reference Electrodes....... 24

9.0 Pre-Commissioning and Commissioning Procedures.................... 26

Appendix A 26

Possible Scheme for Control/Calibration of Reference Electrodes

Appendix B 30

Target values for Maximum Agreed Errors (MAEs) and Parameters as Basis
of Purchase Specification

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1.0 Scope

This technical recommendation has been prepared by CEOCOR Working Group

members and defines minimum requirements for both fixed (permanently installed)
and portable reference electrodes used for cathodic protection (CP) monitoring
purposes for buried onshore pipelines. It defines accuracy requirements,
calibration, testing and installation of reference electrodes for this application.

Reference electrodes are essential for monitoring the cathodic protection

effectiveness as defined in EN ISO 15589-1, EN ISO 12696, EN 12954, EN 13509,
EN 13636, EN ISO 15257, EN 15280, EN 50162, EN 50443, EN 14505, EN ISO
18086.

There is a range of reference electrodes with different electrode potentials; it is

essential that when pipe/soil potentials are measured and reported that which
reference electrode and which voltmeter are used are recorded. Without such a
record the value recorded has no meaning.

2.0 Normative references

EN ISO 15589-1: Petroleum and natural gas industries – Cathodic protection of

pipeline transportation systems – Part 1: Onshore pipelines
EN ISO 12696: Cathodic protection of steel in concrete
EN 12954: Cathodic protection of buried or immersed metallic structures –
General principles and application for pipelines (in process of being replaced with a
revision of ISO 15589-1)
EN 13509: Cathodic protection measurement techniques
EN 13636: Cathodic protection of buried metallic tanks and related piping
EN ISO 15257: Cathodic Protection – Competence levels of cathodic protection
persons – Basis for certification scheme
EN 15280: Evaluation of a.c. corrosion likelihood of buried pipelines applicable to
cathodically protected pipelines
EN 50162: Protection against corrosion by stray current from direct current systems
EN 50443: Effects of electromagnetic interference on pipelines caused by high
voltage a.c. electric traction systems and/or high voltage a.c. power supply systems
EN 14505: Cathodic Protection of Complex Structures
EN ISO 18086 Corrosion of metals and alloys – Determination of AC corrosion –
Protection criteria
ISO EN 10012: Measurement management systems — Requirements for
measurement processes and measuring equipment

Although not a Normative reference, there is a CEOCOR recommendation for

Coupons: ‘Application of Coupons and Probes for Cathodic Protection Monitoring
Purposes’ which was completed in CEOCOR Commission 2 WG B in April 2013.

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This is available from the CEOCOR web site1.

The terms and symbols used in this Document correspond to those used in EN
12954 and EN 13509, with the exception that the ENs refer to copper/saturated
copper sulphate and this document (to be consistent with terminology for other
reference electrodes) uses the term copper/copper sulphate (saturated).

1
CEOCOR document ‘Remote Monitoring and Control of cathodic Protection’ 2104 http://ceocor.lu
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3.0 Definition and Types of Reference Electrodes

EN ISO 15589-1 defines a reference electrode as “an electrode whose open circuit
potential is constant under similar conditions of measurement, used to measure the
structure to electrolyte potential”.

In the application of cathodic protection to pipelines a specific potential is applied to

the pipeline/electrolyte interface in order to achieve specific equilibrium of reactions
such that the rate of corrosion becomes insignificant. The significance of this
demands it is accurately measured and that a stable and accurate reference
electrode is required.

A reference electrode must have specific electrical, physical and chemical

properties. It must facilitate the measurement of accurate pipe/soil/reference
electrode potentials on pipelines2. It must ideally have a stability that is sustainable
for years. For this to occur it should not be polarised by the very low electrical
current that will flow in a measurement circuit. The potential should be measured
with a high impedance multi-meter or voltmeter (typically of 10MΩ or higher).

Dedicated CP voltmeters are available with switchable impedance between 100MΩ

and 1000MΩ; if measurements at both impedance values are equal this confirms
there is no measurable error due to electrode to soil resistance. The use of higher
impedance instruments is specified and used for CP potential measurements in
very high resistivity soils where the electrode to soil resistance can reduce the
current flow and cause a false reduction in the displayed voltage3. Only in this way
can measurements from what are considered to be competent reference electrodes
be considered to be reliable.

Reference electrodes must operate without excessive electrode potential change in

varying conditions and must be resistant to specific reactions within electrolytes in
which they are installed. An example that causes changes in the electrode potential
is chloride containing environments causing contamination and hydrated cupric
chloride formation in copper/copper sulphate reference electrodes. All reference
electrode potentials are affected by temperature.

Portable or temporary reference electrodes, if properly maintained, generally

perform very well as they do not suffer from degradation in the same way as more
permanent electrodes. Permanent or semi-permanent reference electrodes may be
incorrectly specified for their function and may become inaccurate. This
performance prevents their long-term ability to be competent for validation of
Cathodic Protection system performance. Portable electrodes may be more
vulnerable to mechanical damage due to their handling and storage and will also
exhibit greater variability due to changes in air temperature affecting the electrode

2
It is acknowledged that such measurements are liable to errors due to field gradients and unstable
pipe/soil potentials due to fluctuating stray current. The key issue is that the reference electrode’s own
electrode potential should not add unknown or significant additional errors or uncertainties to the measured
values by virtue of its own instability.
3
For example, AS 2832.1: 2015 Cathodic protection of metals. Part 1: Pipes and cables paragraph 3.2
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temperature.

Permanently buried reference electrodes are typically used to facilitate the

measurement of pipe/soil potential where it is not practical to access with standard
portable electrodes, in key locations critical to the pipeline integrity and where
remotely telemetered monitoring is employed (See CEOCOR Remote Monitoring
Document4). When Cathodic Protection current is flowing, the high and sometimes
varying, resistances of soils introduce IR errors (See CEOCOR Coupon
Document5) to potential measurements which are often significant. These errors
can be minimised by the measurement of Instant OFF potentials using portable,
calibrated electrodes but permanent electrodes buried in the soils very close to a
pipeline will also minimise IR errors.

The electrode itself should have a low internal impedance in terms of its
construction and its installation in the ground. Of particular importance is the
interface of the porous plug of the electrode which must be in intimate contact with
the ground and not affected by damage, impaction, contamination, or by poor soil
contact.

True reference electrodes follow reversible (redox) chemical reactions. Provided

there is no contamination, over time there is no loss of mass due to the process.
They are readily polarisable and small currents passing through the electrode will
cause the potential to drift. However, they do typically return to the equilibrium
potential after a ‘rest’ period without current passing through them.

Other materials sometimes used as ‘reference electrodes’ (e.g. zinc used in sea
water) follow reactions which are not actually reversible. These are more accurately
known as pseudo-reference electrodes; they do not have a thermodynamic
equilibrium as there is no common component in the two adjacent phases. The
pseudo-electrode is simply a single body component that is placed in the same
electrolyte as the pipeline. There are advantages and disadvantages in using
pseudo-electrodes in soils. They are simple and rarely can be contaminated. They
can, when suitably selected, provide relatively stable electrode potential, although
they are affected by polarisation and are often only stable in limited ranges of soil
chemistry. Although they are generally not as initially accurate as reference
electrodes; they may be more stable over long periods (within a wider range) than
reference electrodes. This document addresses reference electrodes and not
pseudo-reference electrodes.

Reference electrodes are used in two discrete ways in buried pipeline applications.

They can be used in permanent applications, possibly buried. In this case a

reference electrode is usually installed close to the pipeline (different arrangements
are summarised below). The electrode is intended to be used for many years for
measurement of pipe/soil potential. These buried or permanent reference

4
CEOCOR document ‘Remote Monitoring and Control of Cathodic Protection’ 2104
5
CEOCOR document ‘Application of Coupons and Probes for Cathodic Protection Monitoring Purposes’ 2013.

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electrodes may also be used to deliver a pipe/soil potential for remote potential
monitoring or for automatic potential control of d.c. power supplies. In some
applications the reference electrode can be installed for permanent use within or
below an underground box to facilitate access to it; this permanent reference
electrode can then be relatively easily removed or calibrated when necessary.

Alternatively, calibrated portable reference electrodes are placed temporarily in

contact with the soil relatively close to the pipeline (different arrangements are
detailed below). In this case, they are intended to be used for relatively short
periods (minutes through to weeks, subject to the testing being undertaken).

3.1 Cu/CuSO4 (sat) Reference Electrodes

The reference electrodes most widely used in buried pipeline CP applications are
copper/copper sulphate (saturated); Cu/CuSO4 (sat). These are available in a
variety of constructions for both permanent and portable applications.

This electrode comprises a pure copper electrode immersed in a super-saturated

solution of copper sulphate. The electrolyte is contained within a container which is
either fitted with a porous plug (this may be hardwood, porous sintered glass,
porous ceramic or porous plastic) or is itself a porous container. This enables ionic
contact between the electrode and the buried pipeline via the soil, sufficient to allow
measurement of the voltage or potential between them. The electrode, maintained
in the saturated copper sulphate electrolyte, is in a near equilibrium reversible
redox reaction:

𝐶𝑢2+ + 2𝑒 − ⇌ 𝐶𝑢(𝑚𝑒𝑡𝑎𝑙𝑙𝑖𝑐)

The Nernst equation defines the dependence of the electrode potential on

concentration (or activity) of the copper ions and temperature:

0 𝑅𝑇
𝐸 = 𝐸𝐶𝑢/𝐶𝑢 2+ + ln 𝑎𝐶𝑢2+
2𝐹

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Where:
E0Cu/Cu2+ is the standard electrode potential of the copper / copper sulphate
electrode, 0.337V at 25°C
R is the Universal Gas Constant = 8.315 JK-1mol-1
T is absolute temperature (K)
a is the activity of copper ions (Activity is dimensionless. The activity of a solute is
the actual concentration / 1M x the activity coefficient. The activity coefficient is
typically considered to be 1 for simplicity but is often not. For example, the activity
coefficient in 0.1M H2SO4 is 0.265. 10M HCl it is 10.44 and 1M NaCl is 0.657)
F is the Faraday Constant = 9.649x 104 C mol-1.

At 25°C the copper/copper sulphate electrode has a potential of approximately

+0.316V with respect to the Standard Hydrogen Electrode (SHE). In practice,
Shreir 2nd edition 19796 quotes this as approximately +0.30V. The temperature
variation is approximately +0.9mV/°C thus a pipe/soil potential measured with a
reference electrode at 25°C as ‘protected’ to -0.850V will display -0.832V if the
electrode temperature is 5°C.

It is reported7 that portable Cu/CuSO4 (sat) electrodes are sensitive to sunlight.

Errors of ca. -50mV are reported in extreme sunlight with respect to an electrode in
total darkness; thus -0.850V could be measured as -0.800V to an affected
electrode but the same source reports that these effects appear to decrease with
exposure and may limit at ca. -10mV. Portable electrodes should, preferably, be
enclosed in UV filtered, non-transparent or taped enclosures. However, doing this
prevents the important easy visual inspection of the copper electrode and the
copper sulphate electrolyte which is necessary to detect contamination and is an
essential routine maintenance activity. Some manufacturers provide a non-
transparent enclosure with a narrow viewing window to overcome this.

In environments where chloride ions can migrate into the copper sulphate solution,
the redox reaction is impaired, and the potential varies. This is evidenced by the
clear blue copper sulphate electrolyte becoming opaque and green/white in colour
and the copper rod turning dark green/black in colour. With 5000ppm chloride
contamination of the electrolyte the same source5 indicates that the error is ca. -
20mV (-0.850V measured as -0.830V) and with 12000ppm the error is ca. -120mV
(-0.850V measured as -0.730V).

Some recent proprietary Cu/CuSO4 electrodes include selective, or ion exchange,

semi permeable membranes which claim to prevent chloride ion contamination.
Their types and performance are proprietary and do not appear to be published.

Copper contamination raises environmental concerns. Although the quantities are

minimal, there should be a moral responsibility that influences the choice and
application of copper / copper sulphate reference electrodes. When copper is

6
Shreir’s Corrosion, 2010 Elsevier ISBN 978 0 444 52787 5
7
Ansuini FJ, Dimond JR, Factors affecting the Accuracy of Reference Electrodes, MATERIALS PERFORMANCE, Vol. 33,
No. 11, pp 14-17 (1994) November
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released into soil it can become attached to organic material and clay, sand, etc. in
the top layers of soil and may not move very far. When copper and copper
compounds are released into water, the copper that dissolves can be carried in
surface waters either in the form of copper compounds or as free copper or, more
likely, copper bound to particles suspended in the water. Even though copper binds
strongly to suspended particles and sediments, there is evidence to suggest that
some water-soluble copper compounds do enter groundwater. Copper that enters
water eventually collects in the sediments of rivers, lakes, and estuaries.8

3.2 Ag/AgCl/XXX Reference Electrodes

Silver/Silver Chloride electrodes have not been used until relatively recently (mid
2000’s) as permanent reference electrodes for buried pipelines; however, they can
be usefully applied in high salinity soils where Cu/CuSO4 electrodes would
become contaminated and in brackish water crossings or estuarine crossings.
Their use has been reported in preference to Cu/CuSO4 electrodes for permanent
electrodes for buried pipelines following long term stability testing.9

Silver/Silver Chloride electrodes utilise the reversible relationship shown below:

𝐴𝑔𝐶𝑙 + 𝑒 − ⇌ 𝐴𝑔 + 𝐶𝑙 −

The Nernst equation for the above reaction is

0 𝑅𝑇
𝐸 = 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + ln 𝑎𝐶𝑙−
𝐹

Silver/Silver Chloride/Potassium Chloride electrodes, with a range of potassium

chloride electrolytes (e.g. Ag/AgCl/0.5M KCl), are used for permanent buried
electrode applications, they are commonly used in CP applications for steel in
concrete and used in estuarine waters. These are electrodes comprising a pure
silver wire or mesh, onto which pure potassium chloride has been fused or
deposited from a concentrated solution.

The commonly (inadequately) called Ag/AgCl reference electrode used in sea

water (more correctly termed Ag/AgCl/sea water electrode, Ag/AgCl/sw) relies
upon the chloride concentration of the sea water to determine electrode potential.
This electrode (in pure sea water with a chloride content of 35000ppm {19400mg/l})
has an electrode potential of approximately +0.250V with respect to the Standard
Hydrogen Electrode. This electrode is of no practical use in buried (or concrete)
applications and if used it will either be open circuit or grossly erroneous if ground
water of low chloride content does manage to wet the chloridised silver electrode.

8
US Environment Protection Agency, Office of Solid Waste and Emergency Response. OSWER Directive 9285.7-68. Rev
February 2007
9
Wyatt B S, Permanent Buried Reference Electrodes: Technical Note on Significant Inaccuracies and Medium Term Trials,
CEOCOR Florence 2013

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Silver/Silver Chloride/Potassium Chloride electrodes are available with a range of
concentrations of potassium chloride electrolyte; they have different electrode
potentials dependent on the activity (concentration) of chloride ions used.

In the UK, a favoured concentration is 0.5M KCl and this electrode has an
electrode potential of approximately +0.240V with respect to the Standard
Hydrogen Electrode; this is within 5mV of the potential of the previously commonly
used Saturated Calomel Electrode (Hg/HgCl2/KCl(sat)), now in reduced use in
laboratories due to the health/environment threat from mercury and banned in
Europe for these reasons. It is similarly close in electrode potential to the
Ag/AgCl/sea water electrode when used in pure sea water as above.

Commonly used reference electrodes include 0.1M KCl (potential of approximately

+0.290V with respect to the Standard Hydrogen Electrode), 3M KCl (potential of
approximately +0.210V with respect to the Standard Hydrogen Electrode), 4M KCl
(potential of approximately +0.200V with respect to the Standard Hydrogen
Electrode) and saturated KCl (Sat) (potential of approximately +0.200V with respect
to the Standard Hydrogen Electrode). In the table below, there is ca. 6mV between
3.5M KCl and saturated KCL electrolyte in the Ag/AgCl/X M KCl system. Saturated
potassium chloride is approximately 4.6M at 20° C.

Silver chloride-based electrodes are interfered with by reactions with other ions of
lower solubilities than silver chloride. The most likely ions to be encountered are
bromide, which is present in the sea at concentrations of 65mg/l. The effect of the
presence of bromide has been reported as increasing the potential of the electrode
by approximately 10mV in concentrations similar to those found in seawater,
although the effect varied from electrode to electrode. It is possible to make
silver/silver bromide electrodes or silver / silver iodide electrodes both of which
would not be affected by the presence of bromide.10

Electrodes made with silver salts are photoelectric. The silver salt decomposes to
silver and chlorine as electrons are emitted from the surface in response to incident
light. To avoid this, silver/silver chloride electrodes are packaged such that light
cannot penetrate them.

The temperature coefficient for Ag/AgCl/0.5M KCl is reported11 as - 0.65mV/°C.

Thus, a pipe/soil potential measured with a reference electrode at 25°C as
‘protected’ to -0.850V will display -0.863V if the electrode temperature is 5°C.

The temperature coefficient for Ag/AgCl/Sat KCl is reported5 as -0.13mV/°C. In this

case a pipe/soil potential measured with a reference electrode at 25°C as
‘protected’ to -0.850V will display -0.853V if the electrode temperature is 5°C.

Of course, there is literature on the variation of pipe/soil protection criteria with

temperature.
10
D. G. Ives & G. J, Janz, Reference Electrodes, Theory and Practice, (New York, NY: Academic
Press, 1961).
11
Silvion, Old Somerby, Grantham, Lincs NG33 4 AB, UK, technical literature
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3.3 Other Electrodes

There are other electrodes offered in the market including Zn, Zn/ZnSO4, metallic
antimony electrodes which can be used in conjunction with an Ag/AgCl/0.5M KCl
reference electrode to measure pH, Redox electrodes (or reduction - oxidation
electrodes) for indication of microbial activity, etc. There are many other electrodes
used in the laboratory which are not commonly used by CP practitioners in the
field. These electrodes are not in extensive use for CP and are not intended to be
the subject of this document. This document does not address the particular
application of reference electrodes built within coupons; these are partially
addressed in the CEOCOR document on coupons.3

There are no known uses of MnO2/0.5M NaOH electrodes in buried pipeline

applications. They are widely used embedded in concrete for the monitoring of CP
systems for steel in concrete12. Theoretically this electrode could be used in buried
applications if first embedded in a concrete block.

3.4 Electrode Potentials

From EN ISO 12696: 2016 (CP of steel in concrete), the following equivalents are
established; CEOCOR have ‘rounded’ the numbers to maintain a ‘standard’ 0.240V
difference between vs NHE and vs SCE values; the quoted NHE values have been
assumed to be correct. Ag/AgCl/0.5M KCl and Cu/CuSO4 (sat) are added by
CEOCOR into the Table 1 below:

12
Force Technology, Park Allé 345, DK-2605 Brøndby, Denmark, ERE 20 electrode
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Table 1: Reference Electrode Potentials

Electrode Potential at 25°C Volts Literature Source

vs NHE vs SCE
Ag/AgCl/0.1M KCl 0.288 0.048 Ref 1013
Ag/AgCl/0.5M KCl 0.250 0.010 Ref 8 8 Revised as
Silvion
Ag/AgCl/3M KCl 0.210 -0.030 Ref 1114
Ag/AgCl/3.5M KCl 0.205 -0.035 Ref 1215
Ag/AgCl/KCl (sat) 0.197 -0.043 Ref 1316
0.199 -0.041 Ref 1212
0.1988 -0.041 Ref 1212
Ag/AgCl/3M NaCl 0.209 -0.036 Ref 1417
Ag/AgCl/NaCl (sat) 0.197 -0.043 Ref 1014
Ag/AgCl/sea water 0.250 0.010 Ref 1518
MnO2/0.5M NaOH 0.434 0.186 Ref 1019
0.445 but 0.170 to Force data sheets
variable 0.220 stable after
+20/-30mV manufacture 9
Cu/CuSO4 (sat) 0.320 0.080 Ref 1120
0.316 0.074 Ref1821

NHE: Normal Hydrogen Electrode

SCE: Saturated Calomel Electrode

13
Handbook of Analytical Chemistry. L. Meites, ed. McGraw Hill, NY, 1963
14
Friis E P, Anderson JET, Madsen LL, Bonander N, Moller P, Ulstrop J. Electrochim. Acta 43 1998 pp 1114 - 1122
15
Electrochemistry for Chemists 2nd Ed. Sawyer DT, Sobkowiak AJ, Roberts J Jnr. Wiley, NY, 1995
16
Electrochemical Methods: Fundamentals & Applications. Baird AJ, Faulkner LR, Wiley, NY, 2000
17
Application of Physical Methods to Inorganic and Bioinorganic Chemistry. Scott RA ed. Section Table 3. Wiley, NY, 2007
18
http://www.corrosion-doctors.org/References/Potential.html
19
Paper 243, NACE Corrosion 97, Arup H, Klinghoffer O, Mietz J
20
Handbook of Reference Electrodes, Inzelt G, Lewenstam A, Scholtz F, Springer Heidelberg, NY 2013 ISBN 978-3-642-
36187-6
21
Reference Electrodes (Half-Cells)", J Lichtenstein, Materials Performance, Oct., 2001
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Table 2: Temperature Variations of Reference Electrode Potentials

Potential -850 mV wrt -950 mV wrt -1200 mV wrt

wrt Cu/CuSO4 (sat) Cu/CuSO4 (sat) Cu/CuSO4 (sat) Cu/CuSO4 (sat) at
at 25°C mV at 250C mV at 250C mV 250C mV

Cu/CuSO4 (sat)

50C -868 -968 -1218

100C -863.5 -963.5 -1213.5
150C -859 -959 -1209
200C -854.5 -954.5 -1204.5
250C -850 -950 -1200
300C -845.5 -945.5 -1195.5
350C -841 -941 -1191

Ag/AgCl/0.5M KCl -850 mV wrt -950 mV wrt -1200 mV wrt

Cu/CuSO4 (sat) at Cu/CuSO4 (sat) Cu/CuSO4 (sat) at
250C mV at 250C mV 250C mV

50C -793 -893 -1143

100C -790 -890 -1140
150C -787 -887 -1137
200C -783 -883 -1133
250C -780 -880 -1130
300C -777 -877 -1127
350C -774 -874 -1124

Ag/AgCl/KCl(sat) -850 mV wrt -950 mV wrt -1200 mV wrt

Cu/CuSO4 (sat) at Cu/CuSO4 (sat) Cu/CuSO4 (sat) at
250C mV at 250C mV 250C mV

50C -733 -833 -1083

100C -732 -832 -1082
0
15 C -731.5 -831.5 -1081.5
0
20 C -731 -831 -1081
250C -730 -830 -1080
0
30 C -729 -829 -1079
350C -728.5 -828.5 -1078.5
Note: Values rounded to nearest 0.5mV

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3.5 Electrode Construction issues

The porosity of the ‘porous plug’ will significantly affect the life and accuracy of both
permanent and portable reference electrodes but the effect is much more
significant for permanent electrodes which, when buried, cannot be easily
inspected, tested, cleaned and refilled with uncontaminated electrolytes. Not only
can contaminants such as chlorides (and other halides and sulphides) enter the
electrode and contaminate it but, for example for Cu/CuSO4 (sat), the copper ions
will also diffuse through the porous plug until the solution is no longer saturated and
the potential changes in accordance with the Nernst equation above.

The porous plug pore size and path length will determine the diffusion rates of
species through the plug. The concentration gradient across the porous plug will
also influence the rate of diffusion. As such the diffusion rate (loss) of chlorides
from a 0.5M KCl electrolyte in a Ag/AgCl/KCl electrode (see below) will be less
than from a 4M KCl electrode, if all other factors are identical. However, the
logarithmic relationship between potential and electrolyte concentration offsets the
potential change arising from diffusion.

Junction potentials also form across the porous plug due to differing diffusion rates
between cations and anions.

Most permanent electrodes and some of those portable electrodes which include
fixed concentration electrolytes utilise gelling agents to limit the diffusion of
electrolyte through the porous lug. Historically permanent Cu/CuSO4 (sat)
reference electrodes have used ‘gelling agents’ of wood dust (saw dust) and
‘plaster of Paris’ (gypsum plaster, or calcined gypsum, CaSO4.0.5 H2O, which re-
hydrates to CaSO4.2H20 when mixed with water) have been used. The latter has
also been used in a variety of Ag/AgCl/ KCl portable and permanent electrodes.

There are commercially available gelling agents such as carbopol polyacrylic acid
gelling agents neutralised with NaOH, acrylic acid, carboxy polymethylene,
carboxymethyl cellulose, methyl cellulose, algin, agar, polyethylene oxide, polyvinyl
alcohol, and mixtures thereof, as suitable gelling agents. Of these, agar and
agarose have been widely used for laboratory electrodes but suffer from drying and
microbial activity.20 Hydroxyethyl cellulose and methyl cellulose are both reported
to have been used commercially.20

3.6 Diffusion and Streaming Potentials: Errors

In order to measure the electrochemical potential of a pipeline steel/electrolyte

interface, a reference electrode has to be positioned22 somewhere in the soil
electrolyte that is in contact with the pipeline and the potential measured with a
voltmeter. Other examples are the measurement of the potential of reinforcement

22
In the case of measurements of coupon or probe potentials, the reference electrode is placed near the
coupon or the probe or may be integrated into the probe or coupon.
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steel in concrete, where the reference electrode is placed on the concrete surface, or
the measurement of the potential of an offshore structure, where the reference
electrode is positioned in the seawater.

The reference electrode should, preferably, be as close to the working electrode (the
steel), as possible. However, for practical reasons, this is often not the case. Thus, in
many situations, the reference electrode is some distance from the steel/electrolyte
interface. Consider, for example, the reference electrode inserted in the upper 10
centimeters of soil, used to measure the pipe/soil potential buried tens of meters
away.

There are two effects that arise under such conditions and that may markedly impair
the accuracy of the potential measurement. The first effects are “diffusion potentials”,
and the second “streaming potentials”.

Diffusion potentials arise whenever there are differences in chemical composition

between the electrolyte directly in contact with the working electrode (steel) and the
electrolyte directly in contact with the reference electrode. In other words, in cases
where the soil liquid has a different chemistry at the location of the pipeline than within
the uppermost soil layer (where the reference electrode is located), a diffusion
potential will arise and arithmetically add to the electrochemical potential of the
pipeline. The measured potential at the voltmeter is thus the sum of the “true pipeline
potential” and the diffusion potential. Thus, diffusion potentials are a source of error
for potential measurements.

In soil, the chemistry of the pore liquid will certainly differ from one location to another,
e.g. in terms of pH or concentrations of sulfate, chloride, etc. Particularly, a pH
gradient will give rise to pronounced diffusion potentials. In any case, this source of
error can easily exceed 10 mV or even 100 mV (strongly depending on the actual
conditions) and thus contribute a significant error in the pipe/soil potential
measurement.

In the case of movement of a liquid through a porous system, interaction between the
dissolved ionic species and the pore walls is likely to occur. This means that some
species are “held back” by this electrical interaction, while other species less strongly
affected. For instance, positively charged particles are decelerated, while negatively
charged particles are not (or less) affected. This gives again rise to a potential
difference that affects the measurement. These potential differences are usually
termed “streaming potentials”. Porous materials (soil, concrete, etc.) seldom exhibit
homogenous moisture distributions, and thus, streaming potentials arise. For the case
of concrete, these streaming potentials may easily exceed 100 mV.

As a conclusion, diffusion and streaming potentials are serious error sources for
potential measurements whenever the reference electrode cannot be placed in direct
vicinity of the working electrode. Their magnitude depends strongly on the actual

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conditions, but they can establish errors of several tens of mV or even exceed 100
mV.23

Particularly significant errors are likely when attempting to measure pipe/soil potential
values under concrete hard-standings or road crossings with portable reference
electrodes placed on the concrete surface.

3.7 Nomenclature

In all of the above, the strictly correct designation of, for example, the commonly
referred to Cu/CuSO4 (sat) reference electrode is actually Cu│CuSO4 (sat)
reference electrode. The Ag/AgCl/0.5M KCl reference electrode is more correctly
Ag│AgCl│0.5M KCl. The latter (using │) format is found in some scientific texts and
very occasionally in cathodic protection engineering texts by those trying to
impress. The former (using /) is in ubiquitous technical and engineering use and is
used in this document.

23
Angst U, Vennesland, Ø, Myrdal, R. Diffusion potentials as source of error in electrochemical measurements
in concrete, Materials and Structures 42 (2009) 365-375.

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4.0 Permanent Reference Electrodes

Reference electrodes are regularly buried for permanent monitoring close to buried
pipelines. The installation can be either by direct burial of the reference electrode
close to the pipe or, in some applications, the reference electrode can be installed
within or directly below a chamber or box with access at ground level, typically
above the pipeline. This is to facilitate calibration and replacement of the reference
electrode with the avoidance of excavation, resulting in reduced costs.

These permanent reference electrodes may be included with or integrated into

coupons which facilitate measurement of IR error free pipe/soil potentials.

Permanent reference electrodes are frequently used in conjunction with permanent

monitoring systems which enable pipe/soil potential data to be recorded and
transmitted to the pipeline operator or specialist surveillance contractors. In areas
of dc fluctuating stray current, such as rail or tram traction currents they may be
used in conjunction with automatic potentiostatic (potential controlled) transformer
rectifiers (dc power supplies) to maintain relatively stable pipe/soil potentials under
fluctuating stray current conditions.

In these applications reference electrodes can be subjected to different operating

parameters. They may be:

a. Normally open circuit; only used for intermittent measurement when

personnel visit the installation with portable instrumentation to measure
pipe/soil potentials. These measurements may be of ON potentials
(including unquantified IR errors) or may be Instant OFF measurements with
reduced or no IR errors (either by switching OFF all the CP and interaction
current related to the pipeline or using coupons).
b. Regularly interrogated by a monitoring system that measures
pipe/soil/reference electrode potential perhaps daily or many times per day
(often to immediately or later transmit the data) but open circuit between
these measurements.
c. Regularly interrogated by a monitoring system that measures
pipe/soil/reference electrode potential perhaps daily or many times per day
(often to immediately or later transmit the data) but remaining closed circuit,
and effectively measuring, between these measurements.
d. Permanently connected into a closed loop potential control circuit which
results in a constant function of the reference electrode and determines the
operating parameters of a dc power source or transformer rectifier. In this
application there is a continuous current drain through the reference
electrode, the magnitude is determined by the input impedance of the DC
power source measurement circuit. High input impedance is necessary to
mitigate polarisation of the electrode.

These four options result in different operational characteristics for the reference
electrode and may be important in determining the appropriate input impedance of
the measurement device and its influence on both the accuracy and life of the
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reference electrode.

Permanently buried electrodes generally cannot be cleaned, recharged with

electrolyte or otherwise maintained, unless installed within or immediately below a
chamber or box with access at ground level. If they are very inaccurate, or
damaged, they should be replaced; methods for assessing their accuracy are
necessary.

4.1 Accuracy and Environmental Issues

The electrode potential of reference electrodes is dependent on the concentration

of and species within the electrolyte. Changes in concentration of copper sulphate
with permanent Cu/CuSO4 (sat) reference electrodes or contamination by chlorides
(or other halides or sulphides) will affect accuracy. Similarly changes in chloride
concentration or contamination for Ag/AgCl/0.5M KCl or other molarity reference
electrodes will seriously affect accuracy.

The accuracy of reference electrodes for permanent applications is dependent

upon maintaining the fixed concentration of electrolyte (CuSO4 saturated in
Cu/CuSO4 (sat) reference electrodes and various concentrations of KCl in
Silver/Silver Chloride/Potassium Chloride electrodes). Accuracy is also dependent
on these electrolytes not being contaminated with species that would change the
electrode potential (e.g. halides affecting Cu/CuSO4 (sat) reference electrodes). It
is obvious that the longevity and accuracy of permanently installed reference
electrodes is strongly dependent on the diffusion characteristics of the porous pots
or porous plugs of the electrode housing and on any influence on mobility of the
dissolved salts in the electrolyte of any gelling agents.

These factors are seldom disclosed by manufacturers and there is little published
data on commercially available reference electrodes. These factors are likely to be
of particular importance in environments with freely draining soils such as sands
and gravels where the water table is above the electrode burial depth; if the
diffusion rate of the electrolyte from within the electrode body is too high, and the
volume within the body too low, significant errors will be established quickly.

It is normally required that the current drain though reference electrodes is

minimised by the use of high impedance measurement circuits, either in the
portable digital voltmeters or in the fixed monitoring and/or control applications
within either fixed/remote monitoring applications or in the use of potentiostatically
controlled transformer rectifiers/power supplies.

A field study presented in CEOCOR 20137 presented field data for a range of
proprietary ‘high quality’ reference electrodes from reputable manufactures in
Europe and North America; many were significantly inaccurate after only a few
months of burial subjected to operating parameter a. above. One electrode type
exhibited errors of over 300mV, others had errors of around 200mV. ‘Old style’
large porous pot electrodes performed relatively well in the test period; only 3 of 11
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Cu/CuSO4 (sat) reference electrodes tested were stable to within 20mV during the
test period of 32 weeks. One type of Ag/AgCl/0.5M KCl reference electrode was
one of the most stable electrodes tested and was selected for permanent
installation.

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5.0 Portable Reference Electrodes

Portable reference electrodes are used by personnel for intermittent measurements

at test facilities and also in close interval potential surveys (CIPS) and DC voltage
gradient surveys (DCVG). They are generally utilised in conjunction with high input
impedance digital voltmeters (although some DCVG survey equipment utilises
relatively low input impedance analogue instruments).

Generally, the accuracy and life of portable reference electrodes is not adversely
affected by characteristics of the measurement devices (unless inappropriately low
in quality and price plus low input impedance digital or analogue voltmeters are
used). The life of portable reference electrodes is generally determined by
mechanical damage, wear and tear and maintenance. Some electrodes (notably
the copper/copper sulphate (saturated) reference electrode) can be regularly
cleaned and recharged with electrolyte.

All portable reference electrodes can be and should be regularly check calibrated
according to their use.

All test leads shall be clean, fully insulated, fitted with appropriate plugs and
connection clips for the measurement device and test facility and should be
undamaged. Significant errors can be introduced if corrosion products, moisture
and ‘dirt’ are in place at the various connections.

The same issues are applicable, at least in part to permanently installed electrodes.
It is essential that all cable connections to electrode elements are
insulated/encapsulated in a suitable manner for long term burial/immersion and that
all connections and terminations are protected from contamination and moisture.

The use of multiple input impedance voltmeters (100MΩ and 1000MΩ units are
manufactured specifically for CP, historically some general-purpose digital
voltmeters have been switchable between 10MΩ and 1000MΩ) can be useful in
detecting if electrode to soil resistance is introducing errors into the potential
measurements. Historically Wheatstone Bridge based instruments with low
impedance moving coil meters were used which allowed the measurement current
to be zeroed and there to be no significant error due to electrode/soil contact.

The Australian Standard for CP of Pipes and Cables 3 includes specific

requirements with respect to circuit resistance and the impact of high soil resistivity
on electrode to soil resistance.

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6.0 Reference Electrode Parameters: Permanently Installed Electrodes

As detailed above, the selection of reliable and accurate permanent reference

electrodes is not well documented. The following recommendations are proposed
in order to enhance and define the quality of reference electrodes and to optimise
their use in the field.

I. Permanently buried reference electrodes are subject to errors and shall not
be used as the sole source of data for cathodic protection performance
evaluation without routine checking and evaluation of measurement
accuracy.

II. Permanent reference electrodes may be used as sensing electrodes for

permanent remote monitoring of buried pipeline cathodic protection or for
the control of potential controlled DC power supplies, but the
pipeline/structure operator and CP assessment specialists shall take into
account that reference electrode errors may be significant and vary in
magnitude with time.

III. Permanent reference electrode accuracy should be assessed using

calibrated portable reference electrodes taking into account the purpose of
the data. As a minimum, this should be conducted during every detailed and
comprehensive assessment of Cathodic Protection performance. This is
particularly important where the pipeline potential levels are maintained by
values recorded against reference electrodes i.e. in potentiostatic (also
known as auto-potential) mode because the control potentials can fluctuate
significantly due to erroneous and changing reference electrode potential
values. The practice of operating potential-controlled systems on the basis
that the reference electrode typically has errors of +/-200mV from a
calibrated electrode should be discouraged.

Testing facilities and intervals between testing shall be sufficient to ensure

that any reliance on the accuracy of permanent reference electrodes is
supported by adequate measurements with calibrated portable reference
electrodes at time intervals based upon known performance of the
permanent reference electrodes used.

It is recommended that all permanent reference electrodes used for assessment of

Cathodic Protection performance shall have provision for the proximate (close)
location of calibrated portable reference electrodes so that the electrode potential
of the permanent unit can be checked with respect to the calibrated portable unit at
time intervals determined as necessary to ensure adequate performance of the CP
system. Such a provision may be the installation of the reference electrode within,
or immediately below, an easily accessible chamber or box, the installation of a
plastic pipe that can be filled with water or the installation of a plastic tube that
allows for lowering a mobile reference electrode to the level of the permanent one.

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This is particularly important, but difficult to install after construction, at locations
where the pipeline is covered by concrete or tarmac. Even in green field locations,
if the electrode is buried at pipe level, such provisions are valuable.

The following are optimum target performance parameters for permanent reference
electrodes; it is recommended that these are used in purchase specifications for
the reference electrodes. It is noted that most reference electrode producers do not
disclose the full details of their products or warrant accuracy or life.

This may be addressed by undertaking the following:

a. Undertake medium term trials (minimum 6 months) in the intended

environment
b. Analysing build quality and check components with respect to composition
and purity
c. Publishing the collecting the results and build a database within CEOCOR

This would allow for a mutual increase in understanding of the very basic
performance aspects of reference electrodes.

Target Parameters and Basis of Proposed Purchase Specification are given in

Annex B.

Other methods of approximately check calibrating permanently buried reference

electrodes without access tubes or Luggin probes have been proposed and trialled,
notably by Spanish experts from Gas Natural Fenosa and Guldager Electrólisis.

These techniques have been presented within the CEOCOR Work Groups but not
yet formally published. They show promise and involve the recording of field
gradients in fluctuating interaction conditions and the concurrent measurement of
permanent electrode to a portable electrode placed above it. If the field gradient is,
at times, zero then the voltage gradient between the permanent and portable
electrodes should also be zero. Thus, the measured potential difference at
effectively zero voltage gradient can be used as a check calibration value. 24

24
Verification of Permanent Reference Electrodes. Orta A, Gomila A. CEOCOR Work Group presentation
Weimar 2014. Accessible from Lluis Gomila <[email protected]>
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7.0 Reference Electrode Parameters: Portable Electrodes

Portable reference electrodes used for buried pipeline applications are almost
exclusively examples of the Cu/CuSO4 (sat) reference electrode.

Even in high chloride environments such as pipeline landfalls, crossings of

estuaries, saline swamps etc. where contamination of the electrode electrolyte with
chlorides is a real threat to accuracy, with appropriate frequent visual inspection of
the electrolyte and copper electrode, regularly calibration checks, cleaning the
porous plug and, as necessary changing the electrolyte and cleaning, this
reference electrode can maintain accuracy. For such locations portable
Ag/AgCl/0.5M KCl reference electrodes are also available.9. They are widely used
for surveying steel/concrete potentials in reinforced concrete highway structures,
marine civil structures and similar and can be used on and in soils. It should be
obvious that Ag/AgCl/sea water portable electrodes which rely on the sea water as
the electrolyte cannot be used in soil applications.

Portable reference electrodes are generally purchased as proprietary items and not
against performance specifications or with extensive data sheets. The optimum
target performance parameters for portable reference electrodes that should be
used in purchase specifications for these units are given in Annex B.

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8.0 Installation Procedures for Permanent Reference Electrodes

The ideal position for installing the permanent reference electrode depends on a
number of factors:

The measurement value of interest influences the correct position of the reference
electrode. The parameter to be assessed e.g. on-potential, the local field gradients,
an approach to an IR-free potential, impact on the optimum reference electrode
location. Correspondingly the optimum position of the reference electrode may be
at remote earth, or at some "relevant position" or within 100-500 mm from the
pipeline at invert level.

The presence, location and magnitude of field gradients generated by the pipeline,
the anode bed or third-party infrastructure may influence the selected reference
electrode location. The field gradients may have a time dependence and no single
location may be optimum for all conditions.

The environment may change; both ground water and sea water level change with
time and it may be necessary to measure pipe/soil potentials at different elevations
around the pipeline.

When permanent Cu/CuSO4 (sat) reference electrodes are buried at pipeline depth,
in soil, the distance to the pipeline must be sufficient to prevent electro-deposition
of copper onto the pipeline. Similarly, if permanent reference electrodes are used
with coupons they should, if Cu/CuSO4 (sat), be spaced to prevent this effect, or
alternative reference electrodes should be used.

For installation post construction, ‘no dig’ or ‘minimum dig’ techniques can be used
for installation including hand and machine screw auger, water jetting auger and
vacuum auger techniques, to prepare a hole, sometimes lined, to electrode depth.
These techniques may dictate the use of reference electrodes of limited diameter.
Care should be taken when positioning electrodes so that they are not ‘choked’
inside tubes by debris or animals. If geotextiles are used to prevent sand of similar
ingress into tubes it shall be selected and tested to not be hydrophobic or to form
an electrolytically resistive barrier between the electrode and the soil.

Alternatively, the installation of reference electrodes within, or immediately below,

surface chambers or boxes can be used in order to allow for easy check calibration
and replacement. When doing so, the above requirements must also be
considered.

It is recommended that all permanent reference electrodes should be provided with

methods of field function check and re-calibration when installed. One method is to
provide a plastic tube from ground level to immediately adjacent to the electrode
allowing the introduction of a portable calibrated reference electrode close to the
permanent reference electrode for calibration when the site is visited by CP
personnel. It is theoretically possible to introduce a form of Luggin capillary probe
between the above ground test facility and the reference electrode; this may be
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more satisfactory in some applications to the provision of a plastic tube between
the ground level and the electrode. This is particularly important, but difficult to
install after construction, at locations where the pipeline is covered by concrete or
tarmac. Even in green field locations, if the electrode is buried at pipe level, such
provisions are valuable. These provisions for checking depend primarily on the
presence of IR-errors and are especially important in the case of field gradients
generated by third parties.

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9.0 Pre-Commissioning and Commissioning Procedures

All permanent reference electrodes should be subject to the calibration and

validation stages detailed in Annex B.

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 ANNEX A

Possible Scheme for Control/Calibration of Reference

Electrodes

A-1 Suggested Glossary

i.Primary Standard Reference Electrode (PSRE): standard reference electrode,

used only in the laboratory. This may be a standard hydrogen electrode.

ii.Secondary Standard Reference Electrode (SSRE): reference electrode used in

laboratory. This electrode is used on the arrangement detailed in A-2 below for the
measurement (or ‘control’) of the electrode potentials of other reference electrodes,
in particular the ‘Master Working Reference Electrode’ below. This electrode is
itself periodically calibrated against a PSRE by an external accredited laboratory.

iii.Master Working Reference Electrode (MWRE): reference electrode used on site,

for site calibration of reference electrodes. The MWRE is calibrated against the
SSRE.

iv.Measurement Reference Electrode (MRE): Reference electrode which is used on

site or in laboratory in order to carry out potential measurements. The MRE is
controlled against the MWRE. During field surveys it is common practice to check
different MREs against each other.

v.Maximum Agreed Error (MAE): corresponds to the maximum accepted deviation

between the potential of the electrode to be calibrated and the SSRE. The MAE
can be determined by the maximum achievable precision of the reference electrode
but it can also be much less restrictive than the theoretical minimum value and be
determined pragmatically depending on the accuracy/precision of the measurement
requirements.

The above scheme is one developed and reportedly in use by a large operating
pipeline company with many field CP operatives using many reference electrodes.
For those companies with fewer reference electrodes deployed it would be possible
to delete one layer of complexity as is detailed below in A-2

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A-2 Scheme for laboratory calibration/control of Reference Electrodes

Key:
1 : ‘Secondary Standard Reference Electrode (SSRE)’ (saturated calomel electrode
or Ag/AgCl/0.5M KCl electrode), 1. This electrode is only used in the laboratory and
is itself traceable back to a Primary Standard Reference Electrode

2 : ‘Master Working Reference Electrode (MWRE)’ which is being

calibrated/subject to control, in this test in the laboratory. This electrode is then
used on site to calibrate/control ‘Measurement Reference Electrodes’ which are
used for site potential measurements

3 : Voltmeter (DC. mV scale), high impedance (≥ 10 MΩ), sensitivity ≥ 0.01mV,

accuracy of, or better than, +/- 0.1%. This voltmeter should be calibrated in a
traceable manner back to a National Standard and should be check calibrated at
the start of this process to a portable or laboratory calibrator, itself calibrated in a
traceable manner back to a National Standard. The calibrator should have an
accuracy of, or better than, +/- 0.05% +/- 2 counts

4 : Saturated Potassium Chloride (KCl) solution if saturated calomel electrode is

being used as the ‘Secondary Standard Electrode’. IF using Ag/AgCl/0.5M KCl as
the ‘Secondary Standard Electrode’, this should be 0.5M KCL

5 : Solution; KCl (saturated for calomel, 0.5MKCl for Ag/AgCl/0.5M KCl) or

saturated CuSO4 if Cu/CuSO4 (sat) electrode)

6 : Sponge

7 : Cap/stopper

8 : Electrolytical bridge (porous material)

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 A-3 Calibration/Control Procedure

The difference of potential which should be read on the voltmeter is given by the
following formula:
E = E2 – E1,

With:
• E1 : potential of the Secondary Standard Electrode’
• E2 : potential of the ‘Reference or Master Site Reference Electrode’ which is
subject to this laboratory Calibration/Control

E Theoretical is deduced from the Theoretical Electrode Potentials in the Table

below.
Thus Cu/CuSO4 (sat) should be +74 mV to calomel; +66 mV to Ag/AgCl/0.5M KCl.

Ag/AgCl/0.5M KCl should be +8mV to calomel.

It is suggested that the ‘Reference or Master Site Reference Electrode’ should be

within +/- 5mV of the E Theoretical at the laboratory control/calibration stage.

The potential of the ‘Secondary Standard Electrode’ calomel or Ag/AgCl/0.5M KCl

electrode (E1) is indicated on a standard certificate issued from an external
accredited laboratory which completed its calibration/control; this should be
traceable to a National Standard if one exists in the country of operations.

Theoretical Electrode Potentials of reference electrodes are the following:

Type of Cu/CuSO4 Ag/AgCl/KCl Ag/AgCl/0.5M Ag/AgCl /sea Saturated

Reference saturated saturated KCl water calomel
Electrode (laboratory) (laboratory or electrode
field)
Potential + 316 mV (b) + 197 mV (b) +250 mV (b) + 250 mV (b) + 242 mV (b)
(a) (25°C)

(a) With respect to the standard hydrogen electrode

(b) See Table 1 in Section 3

A-4 Maximum Agreed Error (MAE)

The MAE should be determined by the user, according to their technical

requirements and experience. Proposals for MAE values are given in Annex B.
The assessment of the MAE should be based on EN ISO 10012.

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ANNEX B

Target values for Maximum Agreed Errors (MAEs) and

Parameters as Basis of Purchase Specification
Introduction

Annex B provides target values for Maximum Agreed Errors (MAE). This
terminology is based on the one used in Annex A.

B-1 Permanent (Measurement) reference electrodes

i. The permanent measurement reference electrode (MRE) shall be

calibrated with respect to a Secondary Standard Reference Electrode
(SSRE) according to Annex A by the manufacturer before despatch. The
reference electrodes shall be within a Maximum Agreed Error of their
advertised potential, as defined by the purchaser according to the needs and
practices of the intended user. Typical values are +/- 5 to +/-10mV of their
advertised potential. Each electrode shall have a unique serial number. The
calibration record shall be made available to the purchaser.

It is noted that some types of Cu/CuSO4 (sat) reference electrodes are

shipped by the manufacturer ‘dry’ and these need to be soaked before their
electrode potential can be measured. It is suggested that item (i),. above is
replaced in such cases with typical data for electrodes of identical design,
materials and assembly testing intermittently by the manufacturer.

ii. Reference electrodes may be validated with respect to a Master Working

Reference Electrode (MWRE) by the purchaser or installer immediately
before installation and typically are within a corresponding 10 to 20mV range
of their advertised potential or some larger Maximum Agreed Error defined
by the user according to its needs and practices. These pre-installation
validations shall either be at 20°C (to avoid temperature variations between
different types of electrode) or shall utilise electrodes of an identical type,
and thus the same temperature coefficient. The calibration record,
identifying the unique serial number shall be maintained as a record related
to the installation. Details of the intended installation and conditions shall
also be recorded.

iii. Reference electrodes shall be validated (or controlled) with respect to a

Master Working Reference Electrode (MWRE) by the purchaser or
installer immediately after installation (including cable termination) and
should be within the appropriate range 0 to 10/20mV (depending on above)
of their advertised potential, or some larger Maximum Agreed Error defined
by the user according to its needs and practices. The validation record,

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 identifying the unique serial number shall be maintained as a record related
to the installation.

iv. The reference electrode design and quality should be such that during the
service life of the reference electrode its potential should be expected to
remain within +/- 30mV of their declared electrode potential, or some larger
Maximum Agreed Error defined by the user according to its needs and
practices. This shall be measured with respect to Master Working
Reference Electrode (MWRE) temporarily placed close to the permanent
electrodes, at intervals determined by the pipeline/structure operator and CP
assessment specialists advising them, as appropriate to demonstrate
adequate functionality and accuracy for the purpose for which the
permanent reference electrode is utilised in accordance with EN ISO 15589-
1. It is noted that many reference electrodes fail to meet this +/-30mV
requirement during service.

v. The minimum design service life of permanent reference electrodes should

be 10 years. The optimum service life of permanent reference electrodes
shall be 25 years. These requirements are proposed to be used in purchase
specifications, but it should be acknowledged within the pipeline/structure
operator team and by CP assessment specialists that this service life and
the target accuracy may not be met. Further, claims by manufacturers of
accuracy or extended service lives may not be demonstrated or delivered in
practice. Appropriate measures shall be in place to determine failure or loss
of required accuracy of reference electrodes and to ensure that these likely
occurrences do not adversely affect pipeline cathodic protection levels or
their assessment.

B-2 Portable (Measurement) reference electrodes

i. If the portable MRE is supplied complete i.e. ‘wet’ and filled with the
electrolyte, they shall be calibrated with respect to a Secondary Standard
Reference Electrode (SSRE) according to Annex A by the manufacturer
before despatch. The reference electrodes shall be within a Maximum
Agreed Error of their advertised potential, as defined by the purchaser
according to the needs and practices of the intended user. Typical values
are +/- 5mV of their advertised potential. Each electrode shall have a unique
serial number. The calibration record shall be made available to the
purchaser.

ii. Some portable copper/copper sulphate electrodes are supplied dry,

sometimes with a small deposit of Cu/CuSO4 crystals dispensed in the tube,
and it may not be possible for the manufacturer to calibrate every cell. In
such cases, the manufacture shall establish a formal Quality Management
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 programme and inspection and testing regime to prove that the electrodes
have this accuracy.

iii. Portable measurement reference electrodes shall be calibrated with respect

to a Secondary Standard Reference Electrode (SSRE), according to
Annex A, by the user immediately before first use and shall be within ±
10mV of their advertised potential or some larger Maximum Agreed Error
defined by the user according to its needs and practices. The calibration
record, identifying the unique serial number, shall be maintained as a record
related to the electrode.

iv. Portable MREs shall be maintained clean externally, with their cables and
any terminals/leads in good condition. Cu/CuSO4 (sat) reference electrodes
shall be regularly visually inspected for their electrolyte level, colour (clear
bright blue), the presence of excess suspension of hydrous CuSO 4.5H2O in
de-ionised water, and the electrode condition which should be clean, bright
copper surface with no black or green deposits).

v. Portable measurement reference electrodes shall be inspected and

controlled / calibrated in the field with respect to a Master Working
Reference Electrode (MWRE) based on a regular schedule. This schedule
shall take into account the significance and relevance of the measurements
in which the portable measurement reference electrodes are used. It may be
appropriate to control / calibrate the portable measurement reference
electrodes on a daily basis, or weekly, or at the start and end of each critical
campaign of data collection in order to ensure that the Maximum Agreed
Error is not exceeded.

vi. Depending on the type of measurements for which the measurement

reference electrodes are deployed, additional checks among different
measurement reference electrodes may be required during the daily
measurement routine. This may be especially relevant in case of
measurement techniques that intend to measure small and absolute voltage
gradients, such as the intensive measurement technique.25

vii. The life of the portable reference electrode will likely be determined by
mechanical damage; wear to the porous plug or failure of seals especially
rubber seals. Some manufacturers offer replaceable porous plugs and seals.
A reasonable life expectancy is 5 years. In reality, most portable electrodes
are lost, and so having at least two spares is essential.

viii. Some manufacturers offer refurbishment of sealed portable reference

electrodes such as Ag/AgCl/0.5M KCl reference electrodes.

25
EN ISO 15589-1 Cathodic Protection of Pipeline Systems – Part 1: On Land Pipelines Annex D.3.2
Page 32 of 32

CEOCOR Commission 2
Reference Electrodes
BSW SF MB DC FB Rev 11 221118 Final Approved
© CEOCOR