Designation: G 96 – 90 (Reapproved 2008)

Standard Guide for

Online Monitoring of Corrosion in Plant Equipment
(Electrical and Electrochemical Methods)1
This standard is issued under the fixed designation G 96; the number immediately following the designation indicates the year of original
adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript
epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope D 1125 Test Methods for Electrical Conductivity and Re-

1.1 This guide covers the procedure for conducting online sistivity of Water
corrosion monitoring of metals in plant equipment under G 1 Practice for Preparing, Cleaning, and Evaluating Cor-
operating conditions by the use of electrical or electrochemical rosion Test Specimens
methods. Within the limitations described, these test methods G 3 Practice for Conventions Applicable to Electrochemical
can be used to determine cumulative metal loss or instanta- Measurements in Corrosion Testing
neous corrosion rate, intermittently or on a continuous basis, G 4 Guide for Conducting Corrosion Tests in Field Appli-
without removal of the monitoring probes from the plant. cations
1.2 The following test methods are included: Test Method A G 15 Terminology Relating to Corrosion and Corrosion
for electrical resistance, and Test Method B for polarization Testing
resistance. G 59 Test Method for Conducting Potentiodynamic Polar-
1.2.1 Test Method A provides information on cumulative ization Resistance Measurements
metal loss, and corrosion rate is inferred. This test method G 102 Practice for Calculation of Corrosion Rates and
responds to the remaining metal thickness except as described Related Information from Electrochemical Measurements
in Section 5. 3. Terminology
1.2.2 Test Method B is based on electrochemical measure-
ments for determination of instantaneous corrosion rate but 3.1 Definitions—See Terminology G 15 for definitions of
may require calibration with other techniques to obtain true terms used in this guide.
corrosion rates. Its primary value is the rapid detection of 4. Summary of Guide
changes in the corrosion rate that may be indicative of
undesirable changes in the process environment. 4.1 Test Method A–Electrical Resistance—The electrical
1.3 The values stated in SI units are to be considered resistance test method operates on the principle that the
standard. The values in parentheses are for information only. electrical resistance of a measuring element (wire, strip, or tube
1.4 This standard does not purport to address all of the of metal) increases as its cross-sectional area decreases:
safety concerns, if any, associated with its use. It is the l
R5sA (1)
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
where:
bility of regulatory limitations prior to use. Specific precau-
R = resistance,
tionary statements are given in 5.6. s = resistivity of metal (temperature dependent),
l = length, and
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2. Referenced Documents
A = cross-section area.
2.1 ASTM Standards: 2 In practice, the resistance ratio between the measuring
element exposed to corrosion and the resistance of a similar
reference element protected from corrosion is measured, to
1
This guide is under the jurisdiction of ASTM Committee G01 on Corrosion of compensate for resistivity changes due to temperature. Based
Metals and is the direct responsibility of ASTM Subcommittee G01.11 on
Electrochemical Measurements in Corrosion Testing. on the initial cross-sectional area of the measurement element,
Current edition approved Aug. 15, 2008. Published September 2008. Originally the cumulative metal loss at the time of reading is determined.
approved in 1990. Last previous edition approved in 2001 as G 96–90(2001)´1. Metal loss measurements are taken periodically and manually
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
or automatically recorded against a time base. The slope of the
Standards volume information, refer to the standard’s Document Summary page on curve of metal loss against time at any point is the correction
the ASTM website. rate at that point. The more frequently measurements are taken,

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 G 96 – 90 (2008)
the better is the resolution of the curve from which the K 1 = a constant.
corrosion rate is derived. 4.2.4 Equivalent weight of an element is the molecular
4.1.1 The electrical resistance of the metal elements being weight divided by the valency of the reaction (that is, the
measured is very low (typically 2 to 10 mV). Consequently, number of electrons involved in the electrochemical reaction).
special measurement techniques and cables are required to 4.2.5 In order to obtain an alloy equivalent weight that is in
minimize the effect of cable resistance and electrical noise. proportion with the mass fraction of the elements present and
4.1.2 Various probe element cross-sectional areas are nec- their valence, it must be assumed that the oxidation process is
essary so that a wide range of corrosion rates can be monitored uniform and does not occur selectively; that is, each element of
with acceptable resolution. the alloy corrodes as it would if it were the only element
4.2 Test Method B–Polarization Resistance: present. In some situations these assumptions are not valid.
4.2.1 The polarization resistance test method involves inter-
4.2.6 Effective equivalent weight of an alloy is as follows:
action with the electrochemical corrosion mechanism of metals
in electrolytes in order to measure the instantaneous corrosion 1
m (5)
rate. Its particular advantage is its speed of response to nf
corrosion rate upsets. On a corroding electrode subject to
(l Wi ii
certain qualifications (see 12.1), it has been shown that the
where:
current density associated with a small polarization of the fi = mass fraction of ith element in the alloy,
electrode is directly proportional to the corrosion rate of the Wi = atomic weight of the ith element in the alloy,
electrode. ni = exhibited valence of the ith element under the condi-
4.2.2 The polarization resistance equation is derived in Test tions of the corrosion process, and
Method G 59. See Practice G 3 for applicable conventions. For m = number of component elements in the alloy (normally
small polarization of the electrode (typically DE up to 20 mV), only elements above 1 mass % in the alloy are
the corrosion current density is defined as: considered).
B Alloy equivalent weights have been calculated for many
icorr 5 R (2)
p engineering metals and alloys and are tabulated in Practice
G 102.
where:
B = a combination of the anodic and cathodic Tafel slopes 4.2.7 Fig. 1 represents an equivalent circuit of polarization
( ba, bc), and resistance probe electrodes in a corroding environment. The
Rp = the polarization resistance with dimensions ohm·cm2. value of the double layer capacitance, Cdl, determines the
charging time before the current density reaches a constant
value, i, when a small potential is applied between the test and
b a bc
B5 (3) auxiliary electrode. In practice, this can vary from a few
2.303 ~ba 1 bc!
seconds up to hours. When determining the polarization
4.2.3 The corrosion current density, icorr, can be converted resistance, Rp, correction or compensation for solution resis-
to corrosion rate of the electrode by Faraday’s law if the tance, Rs, is important when R sbecomes significant compared
equivalent weight (EW) and density, r, of the corroding metal to Rp. Test Methods D 1125 describes test methods for electri-
are known (see Practice G 102): cal conductivity and resistivity of water.
icorr 4.2.8 Two-electrode probes, and three-electrode probes with
corrosion rate 5 K 1 r EW (4)
the reference electrode equidistant from the test and auxiliary
electrode, do not correct for effects of solution resistance,
where:
without special electronic solution resistance compensation.

NOTE 1—Rs = Solution Resistance (ohm·cm−2) between test and auxiliary electrodes (increases with electrode spacing and solution resistivity).
Ru = Uncompensated component of solution resistance (between test and reference electrodes) (ohm·cm −2).
R p = Polarization Resistance Rp (ohm·cm2).
Cdl = Double layer capacitance of liquid/metal interface.
i = Corrosion current density.
FIG. 1 Equivalent Circuit of Polarization Resistance Probe
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 G 96 – 90 (2008)
With high to moderate conductivity environments, this effect of 4.2.11 Even with solution resistance compensation, there is
solution resistance is not normally significant (see Fig. 2). a practical limit to the correction (see Fig. 2). At higher
4.2.9 Three-electrode probes compensate for the solution solution resistivities the polarization resistance technique can-
resistance, Rs, by varying degrees depending on the position not be used, but the electrical resistance technique may be
and proximity of the reference electrode to the test electrode. used.
With a close-spaced reference electrode, the effects of Rs can be 4.2.12 Other methods of compensating for the effects of
reduced up to approximately ten fold. This extends the oper- solution resistance, such as current interruption, electrochemi-
ating range over which adequate determination of the polar- cal impedance and positive feedback have so far generally been
ization resistance can be made (see Fig. 2). confined to controlled laboratory tests.
4.2.10 A two-electrode probe with electrochemical imped-
ance measurement technique at high frequency short circuits 5. Significance and Use
the double layer capacitance, Cdl, so that a measurement of 5.1 General corrosion is characterized by areas of greater or
solution resistance, Rs, can be made for application as a lesser attack, throughout the plant, at a particular location, or
correction. This also extends the operating range over which even on a particular probe. Therefore, the estimation of
adequate determination of polarization resistance can be made corrosion rate as with mass loss coupons involves an averaging
(see Fig. 2). across the surface of the probe. Allowance must be made for

NOTE 1—See Appendix X1 for derivation of curves and Table X1.1 for description of points A, B, C and D.
NOTE 2—Operating limits are based on 20 % error in measurement of polarization resistance equivalent circuit (see Fig. 1).
NOTE 3—In the Stern-Geary equations, an empirical value of B = 27.5 mV has been used on the ordinate axis of the graph for “typical corrosion rate
of carbon steel”.
~µmhos! 1 000 000
NOTE 4—Conductivity cm 5 Resistivity ~ohm·cm!
NOTE 5—Effects of solution resistance are based on a probe geometry with cylindrical test and auxiliary electrodes of 4.75 mm (0.187 in.) diameter,
31.7 mm (1.25 ft) long with their axes spaced 9.53 mm (0.375 in.) apart. Empirical data shows that solution resistance (ohms·cm2) for this
geometry = 0.55 3 resistivity (ohms·cm2).
NOTE 6—A two-electrode probe, or three-electrode probe with the reference electrode equidistant from the test and auxiliary electrode, includes % of
solution resistance between working and auxiliary electrodes in its measurement of Rp.
NOTE 7—A close-space reference electrode on a three electrode probe is assumed to be one that measures 5 % of solution resistance.
NOTE 8—In the method for Curve 1, basic polarization resistance measurement determines 2Rp + Rs (see Fig. 1). High frequency measurement short
circuits Cdl to measure Rs. By subtraction polarization resistance, Rp is determined. The curve is based on high frequency measurement at 834 Hz with
Cdl of 40 µ F/cm2 on above electrodes and 6 1.5 % accuracy of each of the two measurements.
NOTE 9—Curve 1 is limited at high conductivity to approximately 700 mpy by error due to impedance of Cdl at frequency 834 Hz. At low conductivity
it is limited by the error in subtraction of two measurements where difference is small and the measurements large.
NOTE 10—Errors increase rapidly beyond the 20 % error line (see Appendix X1, Table X1.1).
FIG. 2 Guidelines on Operating Range for Polarization Resistance

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 G 96 – 90 (2008)
the fact that areas of greater or lesser penetration usually exist 6.2.2 If probe elements are flexed due to excessive flow
on the surface. Visual inspection of the probe element, coupon, conditions, a strain gage effect can be produced introducing
or electrode is required to determine the degree of interference stress noise onto the probe measurement. Suitable probe
in the measurement caused by such variability. This variability element shielding can remove such effects.
is less critical where relative changes in corrosion rate are to be 6.3 Process fluids, except liquid metals and certain molten
detected. salts, do not normally have sufficient electrical conductivity to
5.2 Both electrical test methods described in this guide produce a significant shorting effect on the electrical resistance
provide a technique for determining corrosion rates without the of the exposed probe element. Conductive deposits (such as
need to physically enter the system to withdraw coupons as iron sulfide) can cause some short–circuiting effect on the
required by the methods described in Guide G 4. element, reducing the measured metal loss, or showing some
5.3 Test Method B has the additional advantage of provid- apparent metal gain. Certain probe configurations are less
ing corrosion rate measurement within minutes. sensitive to this than others, depending on the path length
5.4 These techniques are useful in systems where process between one end of the exposed probe element and the other.
upsets or other problems can create corrosive conditions. An 6.4 When first introduced into a system, initial transient
early warning of corrosive attack can permit remedial action corrosion rates on a probe element may be different from the
before significant damage occurs to process equipment. longer term corrosion rates.
5.5 These techniques are also useful where inhibitor addi- 6.4.1 Establishment of a probe element surface typical of
tions are used to control the corrosion of equipment. The the plant by passivation, oxidation, deposits, or inhibitor film
indication of an increasing corrosion rate can be used to signal build up may vary from hours to several days.
the need for additional inhibitor. 6.5 Since the corrosion rate is usually temperature depen-
5.6 Control of corrosion in process equipment requires a dent, results will be comparable only for the alloy at the
knowledge of the rate of attack on an ongoing basis. These test process temperature to which the probes are exposed. In heat
methods can be used to provide such information in digital transfer environments actual plant metal temperatures may be
format easily transferred to computers for analysis. significantly different from that of the test probe.
6.6 Electrical resistance probe elements are by their nature
TEST METHOD A—ELECTRICAL RESISTANCE consumable. Hazardous situations may occur if probes are left
(1-6)3 in service for extended periods beyond their probe life. Crevice
corrosion can cause damage or leaks at the element in some
6. Limitations and Interferences specimen configurations, that can cause false readings and
6.1 Results are representative for average metal loss on the early failure of probe elements. Normally the probe life is
probe element. On wire-form measuring elements, pitting may limited to approximately 50 % of the probe element thickness
be indicated by rapid increases in metal loss reading after 50 % for safety reasons. Additionally, beyond this point measure-
of probe life is passed. The larger cylindrical measuring ments become increasingly erratic due to the irregular corroded
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elements are much less sensitive to the effect of pitting attack. surface of the probe element, and the particularly non-linear
Where pitting is the only form of attack, probes may yield characteristics of wire probe elements.
unreliable results. 6.6.1 Electrical resistance probes should be selected to
6.2 It should be recognized that the thermal noise and provide a suitable backup seal, that is compatible with the
stress-induced noise on probe elements, and electrical noise on process environment, in order to contain the process if the
these systems, occur in varying degrees due to the process and element seal fails.
local environment. Care should be exercised in the choice of
the system to minimize these effects. Electrical noise can be 7. Apparatus
minimized by use of correct cabling, and careful location of 7.1 Electrical Resistance Corrosion Probes:
equipment and cable runs (where applicable) to avoid electri- 7.1.1 A probe is composed of two elements of identical
cally noisy sources such as power cables, heavy duty motors, material. One is a measuring element and the other is a
switchgear, and radio transmitters. protected reference element. In addition, a further check
6.2.1 The electrical resistivity of metals increases with element is fully incorporated beyond the reference element to
increased temperature. Although basic temperature compensa- assist in monitoring of any process leakage into the probe.
tion is obtained by measuring the resistance ratio of an exposed 7.1.2 Process monitoring probes are available in both re-
test element and protected reference element, the exposed tractable and non-retractable configurations. The former en-
element will respond more rapidly to a change in temperature ables removal of the probe for inspection or probe replacement
than does the protected reference element. This is a form of under operating conditions, except where operational safety
thermal noise. Various probes have different sensitivities to precludes this.
such thermal noise. Where temperature fluctuations may be 7.1.3 There is a trade off between probe sensitivity and
significant, preference should be given to probes with the probe life. Care should be taken in selecting a probe suffi-
lowest thermal noise sensitivity. ciently sensitive for the corrosion conditions, particularly when
monitoring for process upsets.
7.1.4 Systems typically have a resolution of 0.1 % of probe
3
The boldface numbers in parentheses refer to a list of references at the end of life. However, for reasons of noise given in 6.2, it is generally
this standard. recommended that only changes of greater than 1 % of probe

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 G 96 – 90 (2008)
life are used for calculation of a corrosion rate or detection of 10.1.1 Check correct operation of the instrument with the
an upset. When monitoring steady metal loss rather than test probe provided according to the manufacturer’s instruc-
process upsets, probe life is generally more critical than tions.
response time. For example, a typical probe span suitable for a 10.1.2 Connect the instrument to the probe and log both the
six month probe life would have on average a 1 % change measure and check readings. Ensure that the check reading is
approximately every two days. within specified limits. Follow the manufacturer’s instructions
7.1.5 For process upset detection, response time to the upset to convert the measured reading to cumulative metal loss.
is much more critical than probe life. A probe sensitivity should Check that the readings are steady and record the midpoint and
be chosen such that 1 % of the probe life, at the upset corrosion extent of any variation of the reading.
rate, corresponds to the desired or maximum permissible 10.2 Automatic Continuous Monitoring Instruments:
response time to the upset condition. This generally will 10.2.1 These instruments are available in various single or
demand a more sensitive probe. However, since the upset multi-channel configurations. They may be standalone systems
condition will generally not exist for an extended period, the or interfaced with process computers, or both. These units
probe life will not be severely reduced. provide continuous information on metal loss or corrosion
7.1.6 Check compatibility of process fluid with probe ma- rates, or both.
terials and seals. 10.2.2 The system should be installed and tested according
7.2 Electrical Resistance Probe Monitoring Instruments: to the manufacturer’s instructions. Test probes are normally
7.2.1 Portable, intermittent instruments, and continuous provided to assist the set-up of all channels and cabling of the
single and multi-channel instruments are available. Since the system.
electrical resistance probe measures cumulative metal loss, the 10.2.3 Connect the operational probes into the system.
intermittent measurement permits the determination of the 10.2.4 Various output forms of information are available,
average corrosion rate only between the measurement points. together with alarms. Computerized systems will often allow
With continuous monitoring, corrosion in real time can be alarms to be set for excessive corrosion rates to draw attention
determined. to problem areas that may then be analyzed in detail from the
7.2.2 Automatic continuous monitoring systems may be metal loss versus time graph. Generally the most useful form of
standalone systems or interfaced to other process computers, or data is the graph of metal loss versus time for each monitored
both. point.
8. Probe Preparation 11. Interpretation of Results
8.1 Commercial probes are generally received in sealed 11.1 Plot the graph of metal loss versus time. Upsets and
plastic bags to protect prepared surfaces. Care should be taken changes in corrosion rate will be readily observable as changes
during installation to avoid handling the probe measurement in the slope of the curve. The average corrosion rate will be the
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element, that can cause additional corrosion. slope of the line connecting the two points on the curve over
8.2 Probe measurement element surfaces should be smooth the time period under consideration. The maximum corrosion
and free of indentations or signs of mechanical damage. rate will be the slope of the tangent to the curve at the steepest
Grit-blasting with 120 grit is suitable as a surface preparation point of the curve (see Fig. 3).
prior to degreasing. 11.2 Some systems automatically calculate corrosion rates
8.3 If probes are being moved from one system to another, over various periods.
they must be cleaned mechanically before reuse to ensure 11.3 Careful interpretation is necessary in correlating these
complete removal of oxide or inhibitor films. Degreasing is corrosion test results with actual metal corrosion in the plant.
necessary to complete the cleaning procedure. Practice G 1 Comparison with metal coupon results (see Guide G 4) or with
provides guidance on proper methods of cleaning various actual metal exposed in the plant is recommended.
materials. Some people do not recommend reusing the probes. 11.3.1 Actual mass loss incurred by the probe elements can
8.4 Mechanical or chemical cleaning will remove metal be used to establish correlations between the corrosion rate
from the probe measurement element, increasing its reading. estimated by the electrical resistance methods and actual
This new reading should be taken immediately after installa- corrosion losses. Practice G 1 provides guidance on methods of
tion in the new location. evaluating mass loss.
9. Probe Installation TEST METHOD B—POLARIZATION RESISTANCE
9.1 Install the probe in a position as representative of the (2, 3, 4, and 6-25)
corrosive environment as possible without causing deleterious
effects to the probe or the system. Do not mount probe 12. Limitations and Interferences
transversely in a high-flow pipeline without shielding (see 6.3). 12.1 In the case of polarization resistance measurements,
9.2 Do not install the probe in a dead-end section where interferences derive from both theoretical and practical as-
temperature or flow conditions, or both, are not representative sumptions and limitations.
of the system under examination. 12.1.1 The theoretical polarization resistance equations in
4.2.2 on which the measurement is based are derived on the
10. Procedure following assumptions: (2, 19)
10.1 Portable Intermittent Instrument: 12.1.1.1 The corrosion is uniform.

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FIG. 3 Typical Plot of Metal Loss Versus Time

12.1.1.2 The corrosion mechanism consists of only one 12.5.1.4 Current Interruption for Compensation of Solution
anodic and one cathodic reaction. The corrosion potential is not Resistance—Limited by noise on high impedance input at time
near the redox potential of either reaction. of current interruption measurement.
12.1.1.3 Other secondary reactions that are not directly 12.6 In actual plant measurements, fouling or bridging of
corrosion related but involve charge transfer are not significant. electrodes with conductive deposits may reduce the apparent
12.1.1.4 Metals or alloys should give Tafel kinetics for both value of polarization resistance thereby indicating a higher
anodic and cathodic reactions. corrosion rate. This will invalidate measurements until the
12.1.1.5 Measurements are made over a sufficiently small probe is cleaned.
polarization range that the potential-current plot is essentially 12.7 Probes of pitted metal or metal with sharp edges may
linear. yield unreliable results. General reuse of probe electrodes is
12.2 The polarization resistance technique is restricted to not recommended.
use in sufficiently conductive environments (refer to Fig. 2). 12.8 Since the corrosion rate is usually temperature depen-
12.3 Deposits on the electrodes may affect the results. dent, results will be comparable only for the alloy at the
12.4 When polarization of an electrode is made by the process temperature to which the probes are exposed. In heat
polarization resistance measurement, time is required to charge transfer environments actual plant metal temperatures may be
the double layer capacitance, Cdl, (see Fig. 1) before a significantly different from that of the test probe.
measurement can be taken. The assumption is that the corro- 12.9 The corrosion rates occurring on the probe electrodes
sion potential has remained constant through this measurement during the first few hours or days of exposure may not be
cycle. This assumption can be a limitation if long cycle times typical of corrosion occurring in the system. Establishment of
are used, particularly in a dynamic plant environment. a probe electrode surface typical of the plant by passivation,
12.5 The theoretical polarization resistance equation in oxidation, deposits, or inhibitor film build up may vary from
4.2.2 relates only to the corrosion interface. In practical hours to several days. Pre-conditioning of electrodes to corre-
measurements solution resistance becomes an increasing inter- spond to the chemical treatment of the plant may reduce this
ference in low conductivity environments. transient effect.
12.5.1 A general indication of limits of use are shown in 12.10 Corrosion rates may be affected by flow velocity.
Fig. 2. (For derivation of curves in Fig. 2 and examples of Consequently, probe electrodes should be used in a velocity
errors, see Appendix X1.) The main limitations of each typical of the plant conditions. Caution should be exercised in
technique in plant equipment are as follows: any laboratory tests to reproduce typical velocities and keep the
12.5.1.1 Two-Electrode Probes and Three Electrode Probes test fluid representative of plant conditions by preventing an
With Equidistant Reference Electrode—Limited as solution unrepresentative build up of corrosion product in solution, or
resistance becomes significant compared with polarization depletion of dissolved oxygen.
resistance. 12.11 Where flow dynamics or process fluid separation at a
12.5.1.2 Three-Electrode Probe With Close-Space Refer- pipe or vessel wall are particularly critical to the corrosion
ence Electrode—Compensation for solution resistance limited process, a flush-mounted probe may be more desirable than a
by physical proximity of reference electrode to test electrode probe with electrodes positioned near the center of the pipe or
and its position in the potential field between the test and vessel.
auxiliary electrode. 12.12 It should be recognized that polarization resistance
12.5.1.3 High Frequency Measurement for Compensation of measurement only determines metal lost by corrosion and not
Solution Resistance—Limited by error of small differences metal lost by mechanical removal (that is, erosion). In the case
between two large numbers at high solution resistance, and the of erosion corrosion, the corrosion component will be mea-
frequency of the resistance compensation measurement. sured.
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13. Apparatus 15.5 Probes should be removed at intervals to inspect for
13.1 Polarization Resistance Corrosion Probes: electrode deterioration, damage, or bridging of electrodes and
13.1.1 A probe is composed of two or three electrodes. With ensure continued quality of corrosion rate data.
a two-electrode probe, both electrodes are of the material under 16. Procedure
test. With a three-electrode probe, the test electrode is of the
alloy under test. The other electrodes may or may not be of the 16.1 Portable Intermittent Instrument:
same alloy. 16.1.1 Check correct operation of the instrument with the
13.1.2 Process monitoring probes are available in both test probe.
retractable and non-retractable configurations. The former 16.1.2 Connect the instrument to the probe and follow the
enables removal of the probe for inspection, cleaning, or manufacturer’s instructions. Some instruments have manual
electrode replacement under operating conditions except where zero adjustments, application, and reading of polarization
operational safety precludes this. current. Other instruments make these readings automatically.
13.2 Polarization Resistance Probe Monitoring Instru- Some instruments use probes with electrodes whose area is
ments: adjusted for the assumed equivalent weight of the alloy (see
13.2.1 Both portable intermittent and continuous single and 4.2.2) to give a direct readout of corrosion rate. Other instru-
multi-channel instruments are available. The polarization re- ments use probes with electrodes always of the same area.
sistance probe determines the corrosion rate only at the time of These latter instruments are normally calibrated for carbon
measurement. No cumulative metal loss or corrosion history is steel. Other alloys are determined from a theoretical or
stored by the probe as with the electrical resistance technique. empirical multiplier applied to the instrument reading. In
For this reason continuous monitoring is more critical for general, these instruments display a corrosion rate assuming a
polarization resistance measurement in order to detect system B value (see 4.2.2) that is generally typical for cooling water
or process upsets. environments.
13.2.2 Automatic continuous monitoring system may be 16.1.3 Manual or automatic instruments all require a minute
stand-alone systems or interfaced to other process computers, to several minutes to obtain a reading. During the measurement
or both. sufficient time must be allowed for the double layer capaci-
tance at the electrodes (see Fig. 1) to become charged before
14. Probe Preparation readings are determined.
14.1 Commercial probes are generally received in plastic 16.1.4 Since the polarization resistance technique records
bags for protection. Working electrodes of required alloys are only the corrosion rate at the time of the reading, measure-
generally supplied separately in sealed plastic bags to protect ments should be taken frequently and recorded or plotted on a
the prepared surfaces. Probe electrodes should be kept clean graph against time. For effective coverage, continuous moni-
during handling and installation by the use of clean gloves or toring is advisable.
clean paper to avoid causing additional corrosion. Where 16.1.5 To check for variations in the corrosion rate of the
electrodes are screwed onto connecting pins on the probe body, process, and for instrument repeatability, it is advisable to take
take care to ensure the insulating and sealing washers are in two or three readings for each measurement required, if
good condition and correctly installed to prevent any galvanic possible reversing the polarity of the applied potential on each
corrosion between electrodes and connecting pins. measurement.
14.2 When moving probes from one system to another, it is 16.2 Automatic Continuous Monitoring Instruments:
recommended that new electrodes are installed. If electrodes 16.2.1 These instruments are available in various single or
are reused, they should be cleaned mechanically to remove multi-channel configurations that may be stand-alone systems
oxide or inhibitor films. Degreasing is necessary to complete or interfaced with process computers, or both. These units
the cleaning procedure. Practice G 1 provides guidance on provide continuous information on instantaneous corrosion
proper methods of cleaning various materials. rates.
16.2.2 These systems should be installed and tested accord-
15. Probe Installation ing to the manufacturer’s instructions. Test probes are normally
15.1 Preferably install the probe directly into the plant in a provided to assist the set-up of all channels of the system.
position as representative of the corrosive environment as 16.2.3 Connect the operational probes onto the system.
possible without causing deleterious effects to the plant, such 16.2.4 Instrument outputs are in the form of various stan-
as a major flow restriction. Do not mount probe where damage dard process signals, meter or digital indication, or recorder
may occur from high velocities or debris. traces of the measured corrosion rate, or all of the above.
15.2 Install the probe so that the electrodes face the flow in
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Generally the most useful form of data is the graph of corrosion

a similar manner. Do not position them so that one electrode rate versus time for each monitored point.
shields the other electrodes from the flow.
15.3 Do not install the probe in a dead end section where 17. Interpretation of Results
temperature or flow conditions, or both, are not representative 17.1 Based on theoretical considerations of various corro-
of the system under examination. sion mechanisms of metals, it can be shown that the value of B
15.4 If a bypass loop is being used for containing the probe, can vary by a factor of 8 (2). In the broad range of practical
ensure that conditions in the loop are representative of those in applications, the variation is generally limited to factors of 2 or
the actual system. 3. If representative Tafel slopes are determined or a multiplier

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 G 96 – 90 (2008)
based on mass loss of electrodes is used, the factor is generally 17.4 Careful interpretation is necessary in correlating these
reduced to around 1.25. Variation in the B value and the corrosion test results with actual metal corrosion in the plant.
limitations of assumptions in 12.1.1 makes the technique less Comparison with metal coupon results (See Guide G 4), mass
suitable for determination of absolute corrosion rate, but useful loss on the probe electrode, or actual metal exposed in the plant
in determining the relative change in corrosion rates. is suggested to establish reliability as to estimation of service
17.2 For manual instruments, corrosion rates are calculated life. For comparative inhibitor tests or process upset detection
based on the relationships in 4.2.2. Most instruments have a the absolute value of the corrosion rate is often less critical than
nominal B value for carbon steel built into the instrument for the relative magnitude of the change.
ease of use. Other alloys are accommodated by different
electrode sizes or by an alloy multiplier. 18. Keywords
17.3 For automatic instruments, the output will usually be 18.1 corrosion monitoring in plant equipment; electrical
directly in corrosion rate unit of mils per year (mil = 0.001 in.) resistance method of corrosion measurement; online corrosion
or mm per year based on a nominal B value. Some instruments monitoring; polarization resistance method of corrosion
have provision for modifying the nominal B value. measurement

APPENDIX

(Nonmandatory Information)

X1. DERIVATIONS AND EXAMPLES OF OPERATING LIMITS GIVEN ON Fig. 2

X1.1 Corrosion Rate and Solution Resistance Calculation X1.2.1

X1.1.1 From Eq 2 and Eq 4: Rs
Measured polarization resistance 5 Rpm 5 R p 1 2 . (X1.4)
k1 3 B 3 E.W.
corrosion rate 5 r 3 Rp (X1.1) measured corrosion rate
3
X1.2.2 When actual corrosion rate 5 0.8 (that is,
X1.1.2 Assuming density of carbon steel at 7.86 g/cm , a B
value of 27.5 mV, and an equivalent weight of 27.92: 20 % error as Note 2 on Fig. 2):
Rp 2Rp
0.1288 3 106 3 0.0275 3 27.92 Rpm 5 2Rp 1 Rs 5 0.8 Rp 5 2Rs (X1.5)
corrosion rate 5 7.86 3 Rp
X1.2.3 By substitution of Eq X1.2 and Eq X1.3 in X1.1,
12.58 3 103 Curve 3 in Fig. 2 is generated. Conductivity (µmhos/
5 Rp mpy (X1.2) cm) = 87.44 3 corrosion rate (mpy).
X1.1.3 From Note 4 and Note 5 on Fig. 2:
X1.3 Derivation of Curve 2 on Fig. 2 (see 12.5.1.2)
0.55 3 10.6
solution resistance 5 Rs 5 conductivity ~µmhos/cm! (X1.3) X1.3.1 Based on X1.2.3 of Fig. 2:
Rs
X1.2 Derivation of Curve 3 on Fig. 2 (see 12.5.1.1) measured Rp 5 R p 1 20 (X1.6)

TABLE X1.1 Examples of Errors in Polarization Resistance Techniques, (Reference 2)

Conductivity Measured Rp True Value Rp Error inA Corrosion
Probe Configuration Text Section Location on 2
(µmhos/cm) ohms·cm2 ohms·cm2 Rate, %
2 electrode 11.5.1.1 A 2000 1395.5 1258 − 9.9
3 electrode (triangular configura- 11.5.1.1 A 2000 1395.5 1258 − 9.9
tion)
2 electrode 11.5.1.1 B 500 1808 1258 − 30.4
3 electrode (triangular configura- 11.5.1.1 B 500 1808 1258 − 30.4
tion)
3 electrode close-space refer- 11.5.1.2 C 100 1533 1258 − 17.9
ence
2 electrode 11.5.1.3 C 100 1156.6 1258 + 8.77
+ high frequency compensation 1359.3 −7.46
2 electrode + high frequency 11.5.1.3 D 20 826.6 1258 + 52.2
compensation 1689.4 − 25.5
A
C.Rm 2 C.R 1/Rpm 2 1/Rp R p 2 Rpm / RpRpm R p 2 Rpm Rp R pm Rp
Error in corrosion rate = 5 5 5 5 2 5 2 1.
C.R 1/Rp 1/Rp Rpm Rpm Rpm Rpm

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 G 96 – 90 (2008)
measured corrosion rate X1.4.4 By algebraic subtraction of the two measurements to
X1.3.2 When actual corrosion rate 5 0.8 (that is, 20 %
give the measured polarization resistance:
error as Note 2 on Fig. 2).
Rp measured 5 R1 2 R 2 (X1.11)
Rp 20Rp
Rpm 5 20Rp 1 Rs 5 0.8 Rp 5 0.2Rs (X1.7) measured corrosion rate
X1.4.5 When actual corrosion rate 5 0.8 (for ex-
X1.3.3 By substitution of Eq X1.2 and Eq X1.3 in X1.1,
ample, 20 % error as in Note 2 on Fig. 2):
Curve 2 in Fig. 2 is generated. Conductivity (µmhos/
cm) = 8.744 3 corrosion rate (mpy). Rp Rp
Rpm 5 R1 2 R2 5 0.8 (X1.12)
X1.4 Derivation of Curve 1 on Fig. 2 (see 12.5.1.3)
By reiterative substitution of values based on X1.3 of Fig. 2,
X1.4.1 From Fig. 1 the electrochemical impedance between
Curve 1 in Fig. 2 is generated.4
the two electrodes, namely the test and auxiliary electrode is as
follows: X1.4.6 Calculation Example:
Conductivity µmhos/cm 100 100
2Rp 2vRp 2Cdl Corrosion rate mpy 24 23
Z 5 Rs 1 2 2 2 2j (X1.8) Actual polarization resistance Rp (ohm·cm2)
1 1 v R p Cdl 1 1 v 2Rp 2Cdl 2 524.17 546.96
Polarization resistance measurement (R1) 3274.17 3296.96
with + 1.5 % error (R3) 3323.28 3346.40
where: with − 1.5 % error (R4) 3225.06 3247.50
v = frequency of applied signal. High frequency measurement (R2) 2750.05 2750.05
X1.4.2 When a high frequency measurement is made be- with + 1.5 % error (R5) 2791.30 2791.30
with − 1.5 % error (R6) 2708.80 2708.80
tween the two electrodes to provide correction for solution Measured polarization resistance range
resistance to the initial normal polarization resistance measure- (R3 − R6) 614.49 637.62
ment, the first measurement from normal polarization resis- (R4 − R5) 433.76 456.21
Error range in corrosion rate + 20.8 % + 19.9 %
tance is as follows: measurement5 −14.7 % − 14.2 %
Rs
R1 5 R p 1 2 (X1.9)

X1.4.3 The second measurement at high frequency is as

follows:

R2 5 ŒS Rs Rp
2 1 1 1 v 2Rp 2C dl 2 D S 2
1
vRp2C dl
1 1 v 2Rp 2Cdl 2 D 2
4
Error in corrosion rate =
R p 2 Rpm / RpRpm R p 2 Rpm Rp
C.Rm 2 C.R
C.R
R pm
5
Rp
1/Rpm 2 1/Rp
1/Rp
5

(X1.10) 1/Rp
5
Rpm
5
Rpm
2
Rpm
5
R pm
2 1.

REFERENCES

(1) Freedman, A. J. and Canapary, R. C., “Corrosion Monitoring by the Second International Congress of the Metallic Corrosion, New York
Electrical Resistance Method,” Oil in Canada, August 24, 1959. City, March 10, 1963.
(2) NACE Publication 3D170, “Electrical and Electrochemical Methods (12) Annand, R. R., “An Investigation of the Utility of Instantaneous
for Determining Corrosion Rates,” (1984 revision). Corrosion Rate Measurement for Inhibitor Studies,” Corrosion, Vol
(3) Dean, S. W., “Overview of Corrosion Monitoring in Modern Industrial 22, 1966, p. 215.
Plants,” ASTM STP 908, ASTM International, pp. 197–218. (13) Feitler, H., “Instantaneous Corrosion Measurement,” Materials Pro-
(4) Cooper, G., “Sensing Probes and Instruments for Electrochemical and tection and Performance, Vol 9, October 1970, p. 37.
Electrical Resistance Corrosion Monitoring,” ASTM STP 908, ASTM (14) Townsend, C. R., “Comparison of Two and Three Electrode Polar-
International, pp. 237–250. ization Resistance Methods of Corrosion Measurements,” Paper No.
64, Corrosion/74, March 1974.
(5) Cameron, G. R. and Coker, L. G., “Oil Production Corrosion Inhibitor
Optimization by Laboratory and Field Application of Electrochemical (15) Callow, L. M., Richardson, J. A., and Dawson, J. L., “Corrosion
Techniques,” ASTM STP 908, ASTM International, pp. 251–265. Monitoring Using Polarization Resistance Measurements, II. Sources
of Error,” British Corrosion Journal, Vol 11, No. 3, March 1976, p.
(6) Crowe, D. C., and Yeske, R. D.,“Corrosion Rate Monitoring in Kraft
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Pulping Process Liquids,” Paper No. 272, Corrosion/86, March 1986.
(16) Heitz, E., and Schwenk, W., “Theoretical Basis for the Determination
(7) Stern, M., “A Method for Determining Corrosion Rates from Linear of Corrosion Rates for Polarization Resistance,” British Corrosion
Polarization Data,” Corrosion, Vol 14, 1958, p. 440t. Journal, Vol 11, No. 2, February 1976, p. 74.
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(11) March, G. A., “The Measurement of Instantaneous Corrosion Rates,” 167–186.
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 G 96 – 90 (2008)
(21) Mansfeld, F., “Evaluation of Electrochemical Techniques for Moni- International, pp. 289–304.
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