Metrohm White Paper

Fundamentals of Electrochemical Corrosion Research

 r Page 1
Metrohm White Paper
mical Corrosion
Title / Cover Page 1
Title / Cover Page
Page 11
and analysis
Electrochemical Corrosion
Corrosion
Electrochemical
Electrochemical Corrosion
Measurement and analysis
Measurement analysis
Measurement and
and analysis

2 Introduction
Corrosion
Page 2 refers to a process that involves deterioration
Pitting Corrosion
Pitting corrosion is a localized form of corrosion by which
Page 2
or degradation of metal. The most common example of pits or pin holes are produced in the material. Pitting is
corrosion is the degradation of metals or alloys. Most considered to be more dangerous than uniform corrosion
Introduction
Introduction
corrosion phenomena are electrochemical
s to a process that involves deterioration or degradation of metal.damage in nature and The most common
because it is more difficult to predict and design
Corrosion
consist
Corrosion of refers
at
refers to two
least
to a process
a process that on
reactions
that involves
the
involves deterioration
surface of
deterioration the or degradation
or degradation
against.of metal.
of metal.
CorrosionThe most
The most common
products often cover the pits making
osion is the formation of rust on steel. Most corrosion phenomena are of electrochemical
Corrosion refers to a process that involves deterioration or degradation of metal. The mostcommon
common
example
corroding
example of
of corrosion
metal.
corrosion One is
is the
of
the formation
the reactions
formation of
of rust
is
rust on
the
on steel. Most
oxidation
steel. Most corrosion
corrosion phenomena
the detection
phenomena are
are of
often
of electrochemical
very difficult.
electrochemical A small, narrow pit with
example
sist of at least two of corrosion on is the formation ofofrust on steel. Mostmetal.corrosion phenomena are of electrochemical
nature
(e.g., andreactions
consist of
dissolution of at
of at
iron),
the
least surface
two
also reactions
referred
the
toonascorroding
the surface
the anodic of the One
the corroding
corrodingof metal.
minimal
the reactions
Onemetal
overall of theisreactions is
the loss can lead
nature
e.g., dissolution
and
and consist
of consist
iron)
least
of at referred
also
two reactions
least two reactions
to asalso
on
the
the
on anodicsurface
the surface of
of thereaction. metal.
corroding metal. One of
One ofisthe reactions
a reactions is to the failure of an entire
is
the oxidation
the oxidation
partial reaction. (e.g.,
The
(e.g., dissolution
other
dissolution is aofreduction
of iron)
iron) also reaction
referred topartial
referred (e.g.,
to as the
as the anodic
anodic Thereaction.
partial
engineering
partial
other
system.
reaction. The
The other is
other is aa
the oxidation (e.g., dissolution of iron) also referred to as the anodic partial reaction. The other is a
ion (e.g., reduction
reductionreaction
reduction
reduction ofofoxygen),
oxygen),
(e.g.,and and
reductionis referred
is referred to asto
of oxygen),
oxygen), ascathodic
and
the the cathodic
is referred
referred aspartial
to as reaction.
the cathodic
cathodic partialThereaction. The
The
reduction reaction
reaction (e.g.,
(e.g., reduction
reduction of
of oxygen), and
and is
is referred to to as the
the cathodicpartial
partialreaction.
reaction. The
products
electrochemical of the
reactions electrochemical
Thecan react withreactions
theeach can react
other with each other non-electrochemically to form the
partial
products
products reaction.
of
of the products
the electrochemical
electrochemical of
reactions
reactions can reactnon-electrochemically
electrochemical
can react with
witheach eachother to form thetotoform
non-electrochemically
otherCrevice Corrosion
non-electrochemically formthethe
final product
reactions can (e.g., rust).
react For
chemicallyexample, the corrosion of iron to form rust proceeds according to the overall
.g., rust). For
finalexample,
final product
product the
(e.g.,
(e.g., corrosion
rust).
rust). For ofwith
For example,
example, each
ironthe
the formother
tocorrosion
corrosion to
rust
of form
ofproceeds
iron
ironto tothe
form
formaccording
rust
rust to the
proceeds
proceeds
Crevice overall
according
is atoto
according
corrosion the
theoverall
localizedoverall
form of corrosion that occurs
reaction:
final product (e.g., rust). For example, the corrosion of iron
reaction:
reaction: in the presence of stagnant solution in a small (micro) crevice.
to form rust proceeds according to the overall reaction: Local chemistry changes in crevices (shielded areas) such as
2 𝐹𝐹𝐹𝐹 + 2 𝐻𝐻' 𝑂𝑂 + 𝑂𝑂' → 2 𝐹𝐹𝐹𝐹(𝑂𝑂𝑂𝑂)'
those formed under gaskets, washers, insulation material,
2 𝐹𝐹𝐹𝐹
2 𝐹𝐹𝐹𝐹++2 𝐻𝐻
2 𝐻𝐻''𝑂𝑂𝑂𝑂++𝑂𝑂𝑂𝑂'' →
→2 𝐹𝐹𝐹𝐹(𝑂𝑂𝑂𝑂)
2 𝐹𝐹𝐹𝐹(𝑂𝑂𝑂𝑂)'' fastener heads, surface deposits, disbonded coatings,
2 𝐹𝐹𝐹𝐹 + 2 𝐻𝐻' 𝑂𝑂 + 𝑂𝑂' → 2 𝐹𝐹𝐹𝐹(𝑂𝑂𝑂𝑂)'
threads, lap joints and clamps, can result in crevice corrosion.
This reaction
This
This includes
reactionincludes thethe
includes dissolution of iron,
dissolution iron, the reduction
of iron, reduction of oxygen
oxygen and formation
the reduction formation of rust:
This reaction
reaction includes the
the dissolution
dissolution of
of iron, the
the reduction of
of oxygenand
and formationofofrust:
rust:
cludes theof oxygen and
dissolution offormation of rust:
iron, the reduction of oxygen and formationGalvanic
of rust: Corrosion
Galvanic corrosion refers to corrosion damage induced when
',
𝐹𝐹𝐹𝐹 → 𝐹𝐹𝐹𝐹
𝐹𝐹𝐹𝐹', 2 𝑒𝑒-- (Anodic)
+ 2 𝑒𝑒 (Anodic)
𝐹𝐹𝐹𝐹
𝐹𝐹𝐹𝐹 → + 2 𝑒𝑒 - (Anodic)
→ 𝐹𝐹𝐹𝐹 ', + (Anodic) two dissimilar materials are coupled in a corrosive electrolyte.
2 𝐻𝐻' 𝑂𝑂 ++ 𝑂𝑂' + + 4 𝑒𝑒--- →→ 4 𝑂𝑂𝑂𝑂--- (Cathodic)
(Cathodic) For example, it occurs when two (or more) dissimilar metals
2 𝑒𝑒 - (Anodic)
2 𝐻𝐻
2 𝐻𝐻''𝑂𝑂𝑂𝑂 + 𝑂𝑂
𝑂𝑂'' + 4 𝑒𝑒
4 𝑒𝑒 → 4 𝑂𝑂𝑂𝑂4 𝑂𝑂𝑂𝑂 (Cathodic)
(Cathodic) are brought into electrical contact under water. When a
', -
𝐹𝐹𝐹𝐹', + 2 𝑂𝑂𝑂𝑂- → 𝐹𝐹𝐹𝐹 (𝑂𝑂𝑂𝑂 ) (Electrochemical) galvanic couple forms, one of the metals in the couple
𝐹𝐹𝐹𝐹 -+ 2 𝑂𝑂𝑂𝑂
2 𝑂𝑂𝑂𝑂- →→ 𝐹𝐹𝐹𝐹 𝑂𝑂𝑂𝑂))'' (Electrochemical)
𝐹𝐹𝐹𝐹((𝑂𝑂𝑂𝑂
'
𝐹𝐹𝐹𝐹 ',
4 𝑒𝑒 - → 4 𝑂𝑂𝑂𝑂 +(Cathodic) (Electrochemical)
(Chemical)
becomes the anode and corrodes faster than it would all by
→ 𝐹𝐹𝐹𝐹(𝑂𝑂𝑂𝑂)' (Electrochemical) itself, while the other becomes the cathode and corrodes
Types of Corrosion
Corrosion slower than it would alone. Either metal in the couple may
Types
Types of
of Corrosion corrode when in seawater.
Types of Corrosion
rosion Uniform Corrosion
Uniform
Uniform Corrosion Microbiologically Induced Corrosion (MIC)
Uniform Corrosion
Corrosion
Uniform corrosion
Uniform corrosion
corrosion is is characterized
is characterized
characterized by by
by corrosive corrosive
corrosive attack attack
attack proceeding Microbiologically
proceeding evenly
evenly over the
the entire Inducedarea,
entire surface
surface Corrosion
or or MIC refers to
Uniform
Uniform
proceeding corrosion
evenly is characterized
over the by corrosive
entire surface attackorproceeding
area, evenly
a largecorrosion over
over the entire surfacearea,
area,oror
a large fraction of the area of the metal under attack. Uniform corrosion caused
results in lossby
of biological
material organisms
until or microbes. These
afraction
large
large fraction
afailure. fraction of the
the area
ofarea area of
of the
the metal
metal under
under attack. Uniform
attack.that
Uniform corrosion
corrosionresults
resultsin loss
lossofofmaterial until
of isthe
This the most of the
widespreadmetal
formunder
of attack.
corrosion Uniform
is microbes
observed. arein categorized
material
by until
common characteristics such
ion failure.
failure. This
corrosion is
is the
the most
Thisresults most
in thewidespread
widespread form
formof
loss of material ofcorrosion
corrosion
until that isisobserved.
thatThis
failure. observed.
is as their by-products (i.e., sludge producing) or compounds
the most widespread form of corrosion that is observed. they effect (i.e., sulfur
on is characterized by corrosive attack proceeding evenly over the entire surface area, oroxidizing). They all fall into one of two
groups based upon their oxygen requirements; one being
of the area of the metal under attack. Uniform corrosion results in loss of material until
aerobic (requires oxygen) such as sulfur oxidizing bacteria,
he most widespread form of corrosion that is observed. and the other being anaerobic (requires little or no oxygen)
Page 1 of 10
such as sulfate reducing bacteria.
Page 1 of 10
Page 1 of 10

1 2 3

Page 1 of 10

4 5 6

Figure 1. Different types of corrosion:

1. Uniform corrosion 2. and 3. Pitting corrosion 4. Galvanic corrosion
5. Crevice corrosion 6. Microbiologically induced corrosion

2
 Metrohm White Paper

Electrochemical Measurement of 3
Characterization Methods for Corrosion Rates
Corrosion The simplest way of measuring the corrosion rate of a
Linear sweep voltammetry (LSV) metal is to expose the sample to the test medium (e.g., sea
Linear sweep voltammetry or LSV is one of the most water) and measure the loss of weight of the material as
commonly used methods for characterizing corrosion a function of time. Although these tests are simple, there
investigation. Moreover, some corrosion processes occur with no
phenomenon. It involves sweeping the potential of the is no easy way to extrapolate the results to predict the
investigation. Moreover, some corrosion
working electrode and measuring the current response. corrosion)
processes
lifetime ofmakingoccur
themwith
the system no
difficult
under significant mass change
to detect Moreover,
investigation. by some(e.g.
gravimetric pittin
methods.
corrosion) making them difficult to detect by
corrosiongravimetric
processes methods.
occur with no significant mass
With LSV valuable information can be discovered about the investigation. Moreover, some corrosion processes occur with no change
Electrochemical methods provide an alternative to traditional me
corrosion mechanisms, corrosion rate and susceptibility of (e.g., pitting corrosion) making them difficult to detect by
corrosion)
Electrochemical methods provide ancorrosion.
alternative making them difficult
to traditional
gravimetricDirect and
methods. methods
quantitative to determination
detect
used tobydetermine
gravimetric methods
the raterao
of corrosion
specific materials to corrosion in various environments.
corrosion. Direct and quantitative determination electrochemicalofmeasurement corrosion rates like can a linear be determined
sweep voltammetry from simpl (LSV
investigation. Moreover,
Electrochemical some methodscorrosion provide processes an occur
alternative withto no significant
traditional m
electrochemical measurement like a linear sweep voltammetry
Electrochemical methods provide (LSV).an alternative to traditional
investigation.
Electrochemical Moreover,
impedance some corrosion
spectroscopy (EIS) processes
corrosion) making occur
corrosion.
methods them withDirect
used no
to significant
difficult and toquantitative
determinedetectthe mass
byrate change
gravimetric
determination
of corrosion.(e.g. pitting
methods. of corrosion r
Direct
In recentcorrosion) making them
years, Electrochemical difficult to
Impedance Spectroscopy orinvestigation.
detect by gravimetric methods.
electrochemical Moreover,
and quantitative measurement
some
determination like
corrosion processes
a linear sweep
of corrosion rates can
occur
voltammetry
be
with no(LS s
Electrochemical
corrosion) methods
Electrochemical making provide
tests
them
EIS has been successfully applied to the study of corrosion determined from simple electrochemical measurement like an
difficult alternative
to detect to by traditional
gravimetric methods
methods. used
systems.Electrochemical methods
One of the Electrochemical
advantages of provide
over an
EIStests alternative
corrosion.
direct current Direct to traditional methods used to determine the rate of
LSV. and quantitative determination of corrosion rates can be
corrosion. Direct and quantitative determination
(DC) techniques is the possibility of using very smallelectrochemical
amplitude Most
Electrochemical
of corrosion
corrosion
measurement phenomena
methods
rateslike beare
canaprovide
linear of
anelectrochemical
determined
sweep alternative fromtosimple
voltammetry nature
(LSV). andmeth
traditional cons
electrochemical
signals without Most corrosion
measurement
significantly disturbing thephenomena
like are of
a linear being
properties Electrochemical
electrochemical
corroding
corrosion.
sweep voltammetry metal.
Direct and
(LSV).tests
nature and
Therefore
quantitativeconsist of
electrochemical reactions
determination on
tests the
of surface
methods
corrosion of the
can
rate
Most corrosion phenomena are electrochemical in nature
measured. corroding metal. Therefore electrochemical
mechanisms
electrochemical
and consist testsand methods
predict corrosion
ofmeasurement
reactions can
on likethe be used
rates. sweep
asurface
linear to characterize
of the voltammetry
corroding corrosion
(LSV).
Most corrosion phenomena are of electrochemical nature and con
mechanisms and predict corrosion rates. metal. Therefore electrochemical tests methods can be used
Electrochemical corroding
Calculationtests of metal.
corrosion Therefore electrochemical tests methods can
to characterize corrosionrates mechanisms and predict corrosion
Electrochemical
Electrochemical Noise tests
Calculation of corrosion rates
(ECN) mechanisms and predict corrosion rates.
rates.
During localized corrosion, electrochemical noise isMost corrosion
generated phenomena
Electrochemical
The corrosion tests
rate are of electrochemical
depends on the kinetics nature
of both andanodic
consist of reac
(oxidatio
Most corrosion
by a combination ofThe phenomena
corrosion
stochastic aredepends
rate
(random) ofprocesses,
electrochemical
corroding
on the
suchkinetics nature
Calculation
metal.
According of and
Therefore
both ofconsist
corrosion
anodic
to Faraday's of reactions
rates
electrochemical
(oxidation)
law,rates and on the
tests
cathodic surface
methods
there is a linear relationship between of
(reduction)the
can be usedth
reactions
Most Calculation
corrosion of corrosion are
phenomena of electrochemical nature and consis
corroding of
as the breakdown metal. Therefore
According
passive andelectrochemical
to Faraday's
films mechanisms
law,
repassivation.thereECN istests
arate,and
linearmethods
predict
relationship cancorrosion
corrosion be used
between rates. to
thethecharacterize
metal 𝑖𝑖2344dissolution corrosionrate or corrosion
The
The 0 , and the
𝑅𝑅corrosion
corrosion rate
rate depends
depends
current
on
on the kinetics
kinetics
: of both
of both anodic
anodic (oxidatio
involves mechanisms
the measurement and predict
rate, andcorrosion
𝑅𝑅of0 ,the current and/or
the corrosion currentcorroding
rates.potential 𝑖𝑖2344 :
(oxidation)
metal. Therefore electrochemical tests methods can b
noise and analysis of the data using Fast Fourier Calculation Transformmechanismsof corrosion
According toand
and rates cathodiclaw,
Faraday's
predict
(reduction)
corrosion there rates.is areactions.
linear relationship According between
to Faraday’s law, there is a linear relationship between
(FFT). Calculation of corrosion rates rate, 𝑅𝑅0 , and the corrosion current 𝑖𝑖2344 : 𝑀𝑀
The corrosion the
Calculationratemetal depends 𝑀𝑀 on therates
ofdissolution
corrosion kinetics
rate of both anodic
or corrosion rate, 𝑅𝑅0(oxidation)
,=and𝑛𝑛𝑛𝑛𝑛𝑛 2344 and cath
the
𝑖𝑖
The corrosion rate depends on the kinetics of both corrosion
anodic
According to Faraday's law, 𝑅𝑅 current
(oxidation)
= 𝑖𝑖 and: cathodic (reduction) reactions.
0
𝑛𝑛𝑛𝑛𝑛𝑛there is a linear relationship between the metal di
2344

According to Faraday's law, there is a linear ,The

rate, 𝑅𝑅relationship
and corrosion
the between
corrosion rate depends
the
current metal on the
: kinetics
dissolution
𝑖𝑖2344 rate of or both anodic
corrosion 𝑀𝑀 (oxidation)
0 " 𝑅𝑅0 = 𝑖𝑖2344
rate, 𝑅𝑅0 , and the corrosion current 𝑖𝑖2344 : According
where 𝑀𝑀tois Faraday's the atomic1. 𝑅𝑅 law,
" =there
weight of is𝑖𝑖the
a linear
)*++ metal, relationship
𝜌𝜌 is the between
density,
𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛 isthe
th
$%&'
where 𝑀𝑀 is the atomic weight of the rate,metal,
number 𝑅𝑅0 , and 𝜌𝜌 is the corrosion
the
of electrons density, is theincharge
𝑛𝑛current
exchanged 𝑖𝑖the : number which
2344dissolution reaction indicates
and 𝐹𝐹 th is t
𝑀𝑀
number of electrons exchanged in theThe dissolution
ratio M/n is also reaction and 𝐹𝐹 is the Faraday constant, (96.485 C/mol)
2. sometime referred 𝑅𝑅0 = to as equivalent weight.
4
where
where
𝑀𝑀 𝑀𝑀 isis the
theatomic
atomic 𝜂𝜂 weight
=weight
𝑏𝑏 ∙ of 𝑙𝑙𝑙𝑙𝑙𝑙
ofthe 3the 8𝑛𝑛𝑛𝑛𝑛𝑛 𝑖𝑖is2344
metal,
metal, the the
𝜌𝜌 is density, density, 𝑛𝑛 is t
The ratio M/n is also sometime referred 𝑅𝑅0 = to𝑖𝑖2344 as equivalent weight.. 45677
number of electrons exchanged in the dissolution
is
𝑛𝑛𝑛𝑛𝑛𝑛 the charge number which indicates the
𝑅𝑅0 = reaction
number 𝑀𝑀of
𝑖𝑖 and 𝐹𝐹 is
electrons
The ratio M/n exchanged
is 3.also𝜂𝜂insometime
the dissolution referred reaction
4 to asand 𝑛𝑛𝑛𝑛𝑛𝑛is 2344 weight.
equivalent
where 𝑀𝑀 isCalculation
the
the atomic
Faradayof weight
corrosion
constant, =currents
of (96.485
the −𝑏𝑏
metal, ∙ 𝑙𝑙𝑙𝑙𝑙𝑙
) C/mol), 𝜌𝜌 is:4 Athe is:the density,
area of is the charge n
𝑛𝑛 the
5677
where 𝑀𝑀 is the atomic weight
Calculation of the metal,
of corrosion number
currents ofthe
𝜌𝜌 is density,
electrons
sample. is the
𝑛𝑛ratio
exchanged
The M/n charge
inisthe number
alsodissolution
sometimes which reaction
referredindicates and
to as𝐹𝐹the is the Faraday
number of electrons exchanged in the dissolution Calculation
wherereaction 𝑀𝑀
equivalent is the
and of
weight.
𝐹𝐹 corrosion
atomic
is the weight
Faraday
The ratio M/n is also sometime referred to as equivalent weight. rates
of the requires
constant, metal, (96.485 the
𝜌𝜌 is thedetermination
density,
C/mol). of
𝑛𝑛 is the
Calculation of corrosion rates requires
The ratio M/n is also sometime referred to as equivalent weight. numberCalculation
mechanisms the
of of
electrons corrosion
determination
for the corrosion
exchanged currents
of incorrosion
reaction
the are
dissolution currents.
known, reactionWhen
the reaction
corrosion
and 𝐹𝐹 is thc
mechanisms for the corrosion reaction The Slope are known,
ratioAnalysis. the corrosion currents
M/n is also sometime referred to as equivalent weight. can be calculated using Tafe
Calculation of corrosion rates requires the determination of
Slope Analysis.
CalculationThe of corrosion
mechanisms
relationship currents
forbetween
the corrosion current reaction
densityare andknown, potential theofcorrosion
anodic an
Calculation of corrosion
The relationshipcurrents
between current density charge transfer control is given by the Butler-Volmer equation:unde
Slope and potential
Analysis. of anodic and cathodic electrode reactions
Calculation of corrosion
Calculation of corrosionrates currentsrequires the determination of corrosion
charge transfer control is given by the Butler-Volmer equation:
Calculation of corrosion rates requires the determination
mechanisms Theforrelationship
the corrosion of between
corrosion
reaction currents.
are
current known,
density When the reaction currents
andcorrosion
potential of anodic can
a
mechanisms for the corrosion reactionSlope are known, Calculation
Analysis. the of
corrosion corrosion
currents rates
can berequires
charge transfer control is given by the Butler-Volmer=equation: calculated the determination
using Tafel of co
=
Slope Analysis. mechanisms for the corrosion reaction are 𝑖𝑖 =known,
𝑖𝑖2344 9𝑒𝑒 the>?corrosion
'.;<;
− 𝑒𝑒
'.;<;
>A Bcur
= =
The relationship =between
Slope𝑖𝑖 Analysis.𝑖𝑖2344 9𝑒𝑒 current
'.;<;
>? − 𝑒𝑒 density
'.;<;
>A B and potential of anodic and cathodic
The relationship between current density and potential of anodic and cathodic electrode reactions 𝜂𝜂 =under
𝐸𝐸 − 𝐸𝐸2344
charge transfer control is given by the Butler-Volmer equation:
3 charge transfer control is given by the Butler-Volmer The relationship 𝜂𝜂 = 𝐸𝐸 − 𝐸𝐸
equation: between current density and
2344 𝑖𝑖 = potential
𝑖𝑖2344 9𝑒𝑒
'.;<;
=
of
>? anodic
− 𝑒𝑒
'.;<;
=
>and
AB

charge transfer control is given by the Butler-Volmer equation:

In the above equation 𝐸𝐸 is the applied potential𝜂𝜂 and = 𝐸𝐸 − 𝐸𝐸2344measure
𝑖𝑖 the
 atomic weight of the metal, thecorrosion
density, 𝑛𝑛current is the charge 𝑛𝑛𝑛𝑛𝑛𝑛 𝑅𝑅0 = 𝑖𝑖2344
rate, 𝜌𝜌 isthe
𝑅𝑅0 , and 𝑖𝑖2344 : number which 𝑛𝑛𝑛𝑛𝑛𝑛 indicates the
he
in the
rons dissolution
dissolution
exchanged in the reactionreaction
dissolution and
0 = and
reaction
𝑀𝑀
is𝐹𝐹
𝐹𝐹𝑛𝑛𝑖𝑖2344
and the
isischarge
thethe
Faraday
FaradayFaraday constant,
constant, constant,
indicates(96.485
(96.485
the (96.485
C/mol). C/mol). C/mol).
Metrohm White Paper
𝑅𝑅 𝐹𝐹
omic weight of the metal, 𝜌𝜌 is the density, 𝑛𝑛𝑛𝑛𝑛𝑛 is the number which
also sometime referred to as equivalent weight.
erred
referred to as
where
ns exchanged to
𝑀𝑀 equivalent
as
inisthe equivalent
thedissolution
atomic𝑀𝑀weight
where weight.
isreaction
the ofweight.
the
andmetal,
atomic 𝐹𝐹 is the
weight 𝜌𝜌 is the metal,
Faraday
of the density,
constant,𝑛𝑛 is𝑀𝑀
𝜌𝜌 is thedensity,
(96.485
the charge number
C/mol).
𝑛𝑛 which indicates
is the charge the indicates the
number which
numberreferred
so sometime of electrons to asexchanged
number equivalent
of electrons inweight.
the dissolution
exchanged in reaction and
𝑅𝑅0
the dissolution
= is
𝐹𝐹𝑛𝑛𝑛𝑛𝑛𝑛 the
𝑖𝑖2344Faraday constant, (96.485 C/mol).
reaction and 𝐹𝐹 is the Faraday constant, (96.485 C/mol).
s the atomic weight
The ratio M/n of isThethe metal,
also sometime the density,
𝜌𝜌 isreferred to as is the charge
𝑛𝑛equivalent number which indicates the
weight.
electronscurrents
exchanged in the ratio M/n is also
dissolution sometime
reaction and 𝐹𝐹referred to as equivalent
is the Faraday constant, weight. (96.485 C/mol).
orrosion
M/n is alsoCalculation
sometime wherereferred
of corrosion to asatomic
𝑀𝑀 is the equivalent
currents weight weight.
of the metal, 𝜌𝜌 is the Thedensity, 𝑛𝑛 is thepredict
Tafel equations chargeanumber which
straight line for indicates theof
the variation
osion currents
corrosion rates requires the determination requires of corrosion currents. When reaction
sthe corrosion
Calculation
Calculation
of corrosion
number
of corrosion
reaction
of electrons
are known,
ratesexchanged
currents the corrosion
the
in determination
the dissolution
currents for canthe
the logarithm
reaction
be calculated
and 𝐹𝐹
using
ofis current
the
oftenTafel
density
Faraday with potential.
constant, (96.485 Therefore,
C/mol).
rrosion ratesof corrosion
TheCalculation
requires currents.
theM/n
ratio isofalso
When corrosion
determination reaction
sometime currents
ofmechanisms
corrosion
referred to currents. currents
as equivalent When are
reaction
weight. shown in semilogarithmic plots known as
corrosion
Calculation reaction
of Calculation
corrosionare known, the corrosion currents can be Tafel plots. This type of analysis is referred to as Tafel Slope
he
n ofcorrosion
corrosion reaction
currents are known,rates the requires currents
corrosion
of Analysis.
corrosion the determination
rates can be the
requires calculated of corrosion
using Tafel
determination currents. When
of corrosion reaction
currents. When reaction
equires
requires the
calculated
mechanisms the determination
using
for thedetermination
Tafel Slope
corrosion reaction of are of
corrosion
known, corrosion
the currents.
corrosion currents.
Analysis.
currents When
can When
be reaction
calculated reaction
using Tafel
4
between The
n of corrosion
current density
relationship
rates requires
and
mechanisms potential
between for the
the current
of corrosion
anodic
determinationdensity andreaction
cathodic
and electrode
are
potential
of corrosion
known, reactionsthe corrosion
currents. When reaction
under currents can be calculated using Tafel
eaction
tion
control
etween
ms
are
Slope are
current
for the
known,
of Analysis.
is given
anodic
corrosion
known,
byCalculation
the
density Slope
and the
Butler-Volmerthe
of
andAnalysis.
reaction
cathodic corrosion
corrosion
corrosion
potential
are known,
equation:
electrode
of anodic
currentscurrents
reactions currents
under
and cathodic
the corrosion
can
charge
currents
can
electrode
be
can bereactions
calculated
be
calculated
calculated
under
using
using Tafel
using Tafel Tafel
transfer control is given by the Butler-Volmer equation:
ysis. isThe
ntrol given relationship
by the between
Butler-Volmer
Calculation
The ofcurrent
relationship equation:
corrosion density
between rates andrequires
current potential
density ofand
the anodic and0,0000
determination
potential cathodic
of anodic of electrode
corrosion
and cathodic reactions
currents. under
electrode When reaction
reactions under
charge transfer control
mechanisms
charge is given
for thecontrol
transfer by the
= corrosion
Butler-Volmer
isof=givenreaction
byandtheare equation:
known, the corrosion
Butler-Volmer equation: currents can be calculated using Tafel

Current (A)
nship between current density
𝑖𝑖 = 𝑖𝑖2344and9𝑒𝑒 potential
'.;<; '.;<;
>Aanodic cathodic electrode reactions under
nt
ensity
density and and
potentialpotential of anodic
=of anodic = andand cathodic cathodic electrode electrode reactions
reactions under under
>? − 𝑒𝑒 B
Slope Analysis.
nsfer control is given by the Butler-Volmer
'.;<;
equation:
'.;<;
𝑖𝑖 = 𝑖𝑖2344 9𝑒𝑒𝜂𝜂 = 𝐸𝐸>?−−𝐸𝐸𝑒𝑒2344 >A B
by
hethe Butler-Volmer
Butler-Volmer The relationship equation:equation:
between current density
𝑖𝑖 = 𝑖𝑖2344 9𝑒𝑒
'.;<; and potential
=
>? − 𝑒𝑒
'.;<;
= of
>A B '.;<; =
anodic and
-0,0005
'.;<;
=
cathodic electrode reactions under
In the above charge transfer
equation 𝜂𝜂 = 𝐸𝐸 − control
is 𝐸𝐸the 2344 is
applied given by
potential the Butler-Volmer
and 𝑖𝑖 =
the 𝑖𝑖2344 9𝑒𝑒 equation:
>? − 𝑒𝑒 >A B

uation 𝐸𝐸 ismeasured current density.and The𝑖𝑖 '.;<;overpotential = is= defined as

'.;<; 𝜂𝜂 current𝐸𝐸 − 𝐸𝐸2344
=
the applied potential 𝑖𝑖 = 𝑖𝑖2344 9𝑒𝑒 the measured
>? − 𝑒𝑒 >A B density. 𝜂𝜂 =The𝐸𝐸 −overpotential,
𝐸𝐸2344
the difference between applied potential and the corrosion
he difference between applied potential and the corrosion potential 𝐸𝐸2344 . The corrosion
tion 𝐸𝐸 is the appliedThe
potential. potential
corrosion andpotential,
𝑖𝑖𝜂𝜂the= 𝐸𝐸measured
− 𝐸𝐸2344 is the current
opendensity.circuit The =overpotential, =
-0,6

is theInopenthe circuit
above of potential
equation =𝐸𝐸
of a
is = corroding
the applied metal.
potential The andcorrosionthe current,
𝑖𝑖2344measured
𝑖𝑖 potential
'.;<; 𝑖𝑖 '.;<;, and the
− 𝑒𝑒current
2344
Potential (V)
B density. The overpotential,
difference between
potential applied
Ina corroding
the'.;<;
'.;<;
potential
above metal.
equation
'.;<;
and The=the
'.;<; 𝐸𝐸 corrosion
corrosion
= the applied
is potential
current,𝑖𝑖 = ,9𝑒𝑒
𝐸𝐸2344and . The
>?
corrosion
𝑖𝑖 the
> A
measured current density. The overpotential,
𝑏𝑏F , and 𝑏𝑏 can
𝑖𝑖 =circuit be
𝑖𝑖2344 measured
= potential
𝑖𝑖2344 from
9𝑒𝑒𝜂𝜂, is9𝑒𝑒defined the experimental data.
𝜂𝜂,
the open is
2 defined
and the as the
Tafel of a−
>
difference
constants ? > 𝑒𝑒as−
,
corroding
? between
and 𝑒𝑒 > B
metal.
A >
applied
can A B
beThe potential
measured
the difference between applied Figure corrosion and
from current,
𝜂𝜂 = the corrosion
𝑖𝑖
potential
𝐸𝐸 − 𝐸𝐸 , and potential
the
2344 and the corrosion
2344
𝐸𝐸2344 .potential
The corrosion
2344 . The
𝐸𝐸screw corrosion
ve equation the 𝐸𝐸 is the
experimentalapplied data.potential and 𝑖𝑖 the measured current density. 2 The
- overpotential,
Current potential plot for, iron the 𝑖𝑖immersed in
, and 𝑏𝑏potential,
2 can be measured
is the
𝐸𝐸2344potential, fromopen the
𝐸𝐸 circuit
experimental
is thepotential
open of a corroding
data.
circuit potential metal.
of a The corrosion
corroding Pagecurrent,
metal. The
4 of 10 𝑖𝑖2344
corrosion and
current, , and the
d as the difference
large 𝜂𝜂 between applied 2344 potential
(𝜂𝜂/𝑏𝑏F and the corrosion potential seawater. 𝐸𝐸2344 . The corrosion 2344
For
Tafel constants =
anodic 𝜂𝜂
𝑏𝑏 𝐸𝐸
Tafel , =−
and𝐸𝐸𝐸𝐸𝑏𝑏−
overpotentials
2344 𝐸𝐸
can 2344
constants 𝑏𝑏F(𝜂𝜂/𝑏𝑏 be measured
,( andF 𝑏𝑏>>
>> 1) fromthe theButler-Volmer
experimental equation
data. simplifies to the Tafel equation
2 can be
themeasured from equation
the experimental data.
F 2
𝐸𝐸2344 isFor the
for
Forlarge
the
large
open anodic
In
anodic
anodic
circuit
the overpotentials
overpotentials
potential
above
reaction: equationof"a corroding 𝐸𝐸 is the 1)
1) the
metal.
applied Butler-Volmer
Butler-
The corrosion
potential and 𝑖𝑖current,
the measured 𝑖𝑖simplifies
Page, 4
2344 and to
thethedensity.
current
of 10 Tafel equation
The overpotential,
1. 𝑅𝑅 = 𝑖𝑖
ants 𝑏𝑏Ffor the𝑏𝑏anodic reaction:
Volmer equation simplifies
" to the Tafel
)*++ equation for the To perform Tafel analysis it is necessary to
Pagehave4 ofinformation
10
, and 2 can 𝜂𝜂, be
is measured
defined as from
the $%&' the experimental
difference between data.
applied potential and the corrosion potential 𝐸𝐸 2344 . The corrosionPage 4 of 10
anodic reaction: on the electrode surface area, equivalent weight and the
potential, 𝐸𝐸2344 is"the open 4 circuit potential of a corroding density of metal. the material.The corrosion
The current, 𝑖𝑖2344 , and the
1.
2. 𝑅𝑅𝜂𝜂"==𝑏𝑏𝑏𝑏.$%&' 𝑖𝑖)*++ 8 𝜂𝜂𝜂𝜂be= 𝑙𝑙𝑙𝑙𝑙𝑙(𝑖𝑖2344 ) + 𝑏𝑏F ∙ 𝑙𝑙𝑙𝑙𝑙𝑙(𝑖𝑖) Page 4 ofTafel
10 slope analysis provides
applied
lied potential potential Tafelandand 𝑖𝑖 the
constants 𝑖𝑖 Fthe measured
∙, 𝑙𝑙𝑙𝑙𝑙𝑙
and measured
3𝑏𝑏 can
45677
2 = current
measured
𝑙𝑙𝑙𝑙𝑙𝑙(𝑖𝑖 current
2344 ) + F density.
from
𝑏𝑏 ∙ the density.
𝑙𝑙𝑙𝑙𝑙𝑙(𝑖𝑖)
the experimental
corrosion Therate The
overpotential,
andoverpotential,
data. polarization resistance. However a
correct estimate of the Tafel slopes is possible if the linear
etween
een applied
applied
Analogously,
Analogously, potential
Analogously,
forpotential
for
forlarge
2.large
large
3. and
cathodic
cathodic
𝜂𝜂𝜂𝜂cathodic
=
= 𝑏𝑏−𝑏𝑏 andthe
. ∙ 𝑙𝑙𝑙𝑙𝑙𝑙
) ∙ 3 : the
corrosion
: corrosion
overpotentials
4
overpotentials
48
overpotentials
𝑙𝑙𝑙𝑙𝑙𝑙
4
potential
((𝜂𝜂/𝑏𝑏2 <<
(𝜂𝜂/𝑏𝑏2 by:
<< -1)potential
Tafel
the Tafel 2344
region . The
-1) the Tafel𝐸𝐸equation
<< -1) 𝐸𝐸2344
covers
equation
for.the
The
at the
for corrosion
least corrosion
cathodic
1 decade
cathodic
reaction is
in current.
reaction is
Page 4 of 10
given by: equation for the cathodic reaction
the Tafel 4 is given 5677

uit
potential
potential of aofcorroding
a corroding metal. metal. TheThe corrosion
corrosion current,
current, , and, and
thethe
5677
given by:
4
𝑖𝑖2344 𝑖𝑖2344
3. 𝜂𝜂 = −𝑏𝑏) ∙ 𝑙𝑙𝑙𝑙𝑙𝑙 :4 :
measured
e measured from from
thethe experimental
experimental data. data. 5677

𝜂𝜂 = 𝑙𝑙𝑙𝑙𝑙𝑙(𝑖𝑖2344 ) − 𝑏𝑏2 ∙ 𝑙𝑙𝑙𝑙𝑙𝑙|𝑖𝑖|

𝜂𝜂 = 𝑙𝑙𝑙𝑙𝑙𝑙(𝑖𝑖2344 ) − 𝑏𝑏2 ∙ 𝑙𝑙𝑙𝑙𝑙𝑙|𝑖𝑖|
PagePage
4 of 4
10of 10
The Tafel equations predict a straight line for the variation of the logarithm of current density with
The Tafel equations predict a straight line for the variation of the logarithm of current density with
potential. Therefore, currents are often shown in semilogarithmic plots known as Tafel plots. This type of
potential. Therefore, currents are often shown in semilogarithmic plots known as Tafel plots. This type of
analysis is referred to as Tafel Slope Analysis.
analysis is referred to as Tafel Slope Analysis.

Polarization Resistance, Rp
Polarization Resistance, Rp
WE(1).Current (A)

An electrode is polarized when its potential is forced away from its value at open circuit or corrosion
An electrode is polarized when its potential is forced away from its value at open circuit or corrosion
potential. Polarization of an electrode causes current to flow due to electrochemical reactions it induces
potential. Polarization of an electrode causes current to flow due to electrochemical reactions it induces
at the electrode surface. The polarization resistance or 𝑅𝑅M is defined by the following equation:
at the electrode surface. The polarization resistance or 𝑅𝑅M is defined by the following equation:

∆𝐸𝐸
𝑅𝑅M = 9∆𝐸𝐸 B
𝑅𝑅M = 9 ∆𝑖𝑖B ∆O→<
∆𝑖𝑖 ∆O→<

Where, ∆𝐸𝐸 variation of the applied potential around the corrosion potential and ∆𝑖𝑖 is the resulting
Where, ∆𝐸𝐸 variation of the applied potential around the corrosion potential and ∆𝑖𝑖 is the resulting
polarization current. Potential applied (V)
polarization current.
Polarization resistance, 𝑅𝑅 M , behaves like a resistor and can be calculated by taking the inverse of the slope
Figure 3 - Tafel plot for iron screw immersed in seawater. The linear parts of the Tafel plot are identified.
Polarization resistance, 𝑅𝑅M , behaves like a resistor and can be calculated by taking the inverse of the slope
of the current potential curve at open circuit or corrosion potential.
of the current potential curve at open circuit or corrosion potential.
During the polarization of an electrode, the magnitude of the current is controlled by reaction kinetics
4 During the polarization of an electrode, the magnitude of the current is controlled by reaction kinetics
and diffusion of reactants both towards and away from the electrode. In the previous application note,
and diffusion of reactants both towards and away from the electrode. In the previous application note,
the Butler-Volmer equation was introduced as:
 2344 2
1 𝑏𝑏F 𝑏𝑏2 1
2344 ) − 𝑏𝑏2 ∙ 𝑙𝑙𝑙𝑙𝑙𝑙|𝑖𝑖| S T 𝑖𝑖2344 =

Metrohm White Paper

𝜂𝜂 = 𝑙𝑙𝑙𝑙𝑙𝑙(𝑖𝑖2344 ) − 𝑏𝑏2 ∙ 𝑙𝑙𝑙𝑙𝑙𝑙|𝑖𝑖| 2.303 𝑏𝑏F + 𝑏𝑏2 𝑅𝑅M
The Tafel equations predict a straight line for the variation of the logarithm of current density 1 with
𝑏𝑏F 𝑏𝑏2 1
The Tafel equations
Polarization predict
Resistance,
potential. Rp a straight
Therefore, currentsline for the
are often variation
shown of the logarithm
in semilogarithmic plotsofknown
current
as density
Tafel plots.with
𝑖𝑖2344 =This type of S T
1 𝑏𝑏F𝑏𝑏+
2.303 F 𝑏𝑏𝑏𝑏22 𝑅𝑅1M
he variation of theTherefore,
potential. logarithm
analysis of current
currents
is referred to density
areasoften
Tafelof shownwithAnalysis.
Slope in semilogarithmic plots known as Tafel plots. This type
𝑖𝑖2344 of
= S T
ations predict a straight
An electrode line for the variation
is polarized when the logarithm of current density with
Or, when the expression is rearranged:
itsThispotential
2.303 𝑏𝑏 + 𝑏𝑏 𝑅𝑅
type ofis forced away from its value at open circuit or corrosion
F 2 M
semilogarithmic
analysis plots
is referredknown toas
asinTafel
Tafel plots.
Slope Analysis.
efore, currents
potential.are often shown
Polarization ofsemilogarithmic
an electrode causes plotscurrent known to as flow
Tafeldue plots. to This type of
electrochemical reactions it induces
red to as Tafel Slope Analysis. Or, when the expression is rearranged:
at the electrode
Polarization surface. The polarization
Resistance, Rp resistance or 𝑅𝑅Or, M is defined theby the arefollowing equation:
Measurement of
Polarization Resistance, Rp
Ifwhen
the Tafel expression
slopes
mechanism is not known), the 𝑅𝑅M can
notisknown
rearranged: (e.g. when corrosion
1 𝑏𝑏F 𝑏𝑏2
= still be used9as a B
1

esistance,An
Polarization Resistance
An electrode is polarized when its thepotential
open circuit is forced
Rpelectrode is polarized when its potential is forced away from its value at open circuit or corrosion 1 𝑏𝑏F 𝑏𝑏2 2344
potential awayofparameter
quantitative from its value
a corroding at open
metal.
to compare
2.303
the circuit
The
𝑏𝑏
corrosion
corrosion
+ 𝑏𝑏 𝑖𝑖
F or2 corrosion
current,
2344
resistance 𝑖𝑖
1
, and
potential. Polarization of an electrode and 𝑏𝑏causes can
2 ∆𝐸𝐸
current
be measured
of to
metals flow
from
under due theto
various electrochemical
experimental
conditions. data.
Highreactions
𝑅𝑅 M of
= a it
metal induces 9 B
orced away from its value at open circuit orThe corrosion 2.3031 𝑏𝑏F𝑏𝑏+ 𝑏𝑏𝑏𝑏 𝑖𝑖 1
s polarized potential.
Polarization
when its Polarization
atpotential
the
Resistance, isofforced
electrode an electrode
Rsurface. away causes
from itscurrent
polarization value attoBopen
𝑅𝑅M = 9resistance
∆𝑖𝑖 flowimplies
due or
circuit toMhigh
𝑅𝑅 electrochemical
is
or defined
corrosionbyresistance
corrosion the reactions
following
and low itequation:
induces
𝑅𝑅M implies
= lowF 22 9 2344 B
Ifsmall 𝜂𝜂,
the Tafel slopes are known, one can calculate the corrosion 2.303 𝑏𝑏F currents
+ 𝑏𝑏2 𝑖𝑖2344from
5
p ∆O→<
rent to flow
atAnthedue to electrochemical
electrode surface. Thereactions
polarization it induces Foraway
resistance or 𝑅𝑅i.e.
M isfor definedpotentialsby close to corrosion potential, the above equation can
itthe following equation:
electrode is polarized when its potential is forced from corrosion resistance.
rization of an electrode causes current to flow due to electrochemical
using the above reactions
equations. induces
If the Tafel slopes are not known (e.g. when co
nce or 𝑅𝑅M is defined by the following equation:
its value at open circuit or corrosion potential. Polarization of
e surface. an Theelectrode
polarization resistance or 𝑅𝑅 is defined
M due to electrochemical by the following If the Tafel
equation:
Measurement slopes are
of R known,
using
known), the 𝑅𝑅M can still be used pas a quantitative parameter to compare the LSVone can calculate the corrosion curre
cor
Where, ∆𝐸𝐸 variation causes current of the to flowapplied potential around using the
If Incorrosion
the ∆𝐸𝐸Tafel
the
Figure 4slopes
above the potential
are
equations.
results of and
known, a If
LSV ∆𝑖𝑖
one
the is the
can
Tafel
experiment resulting
calculate
slopes
performed arethe corrosion
not
on known
an curre
(e.g.
reactions it induces
polarization current. at the electrode surface. The polarization under various
𝑅𝑅M = 9 conditions.
B High 𝑅𝑅M of a metal 1implies 𝑏𝑏slopes high1 corrosion resistan
∆𝐸𝐸 using ∆𝑖𝑖the above F 𝑏𝑏2 The
resistance is defined by the following equation: 𝑅𝑅Mcorrosion = 9 B known), iron screw
the
∆O→< canequations.
𝑅𝑅Mimmersed still be in used 𝑖𝑖 If the
seawater as=a areTafel shown.
quantitative are not of
Tslope
S parameter known
to compa (e.g
∆𝐸𝐸 ∆𝑖𝑖 ∆O→< resistance.
the curve at corrosion potential
2344
(- 2.303 𝑏𝑏V)
0.319 F+ can𝑏𝑏2 be 𝑅𝑅Mcalculated
=9 B ∆𝐸𝐸 known),
under the 𝑅𝑅
various Mconditions.can still be used
High as a
𝑅𝑅M ofof quantitative
a the
metal parameter
implies high corrosion to compa
∆𝑖𝑖 ∆O→<Polarization resistance, 𝑅𝑅 𝑅𝑅M =M9, behaves B like a resistor and can be
bycalculated
performingby takingregression
a linear the inverse on data fromslope - 0.329 V to
of the current potential ∆𝑖𝑖 ∆O→<
curve atofopen under
corrosion various
resistance.conditions. High 𝑅𝑅 of a metal implies high corrosio
Where, ∆𝐸𝐸 variation the circuit
applied or potential
corrosion potential.
around
- 0.309the corrosion
V (i.e. 10 mV cathodic potential and M
and
10 mV ∆𝑖𝑖 is anodicthe resulting
relative to
Where, isvariation of theof applied potential around
Or, Measurement
when thethe corrosion
corrosion
expression resistance.
potential and ∆𝑖𝑖 is the methods resulting
Where ∆𝐸𝐸polarization
During the
the variation
polarization
current.
of an
the applied
electrode,
potential
the magnitude
around
of
the
the 𝐑𝐑 𝐩𝐩isusing
corrosion
ofcurrent
rearranged:
potential).
electro-chemical
is controlled by reaction kineticsLinear Sweep Volta
round the corrosion
polarization
the corrosion potential
potential and
current. and ∆𝑖𝑖 isis the theresulting
resultingpolarization
riation of and
potential thea diffusion
of applied
corroding potential
ofmetal. around
The corrosion the corrosion
current, potential and ∆𝑖𝑖 isconstants
the resulting
current. Polarization
The reactants
polarization both
resistance, 𝑅𝑅
resistance, towards
M ,behaves
behaves andlike 𝑖𝑖like
away a, resistor
Ina Figure
2344 and the
from
resistor the Tafel
and
1Measurement
the electrode.
can be
results InLSV
ofcalculated
aof the𝑏𝑏F ,previousby taking application
the inverse note,
onofmethods
anthe slope
rrent.
easured Polarization
from thebe experimental
resistance, 𝑅𝑅 data., behaves like
The a resistor
results of and
the can be
regression calculated
are shownby
𝐑𝐑
taking𝐩𝐩experiment
in
using
the
Figure inverse
2.
performed
electro-chemical
The of the slope
polarization
iron screw
resistance
Linear immersSwe
𝑅𝑅M is c
the
and Butler-Volmer
can calculated equation
by taking
M was
the
of the current potential curve at openThe introduced
inverse of the as:
slope of
circuit the or The
corrosion
Measurement
results of
potential. the
of
regression
𝐑𝐑 using
are shown
electro-chemical
in Figure 5.
slope of the curve at corrosion 𝐩𝐩 potential (- 0.319
1 𝑏𝑏F V)
𝑏𝑏2 can be calculated by Sw
1methods Linear per
and canof be calculated
the
current current
potential by takingatthe
potential
curve curve
open inverse
at open
circuit of
orthecircuit
inverse slope
corrosion of or
the corrosion
potential.
slope (1/slope)
In The polarization
potential.
Figure and
1 is
the found
results resistance
to ofbea 𝑅𝑅M is
9.442
LSV = calculated
kΩ.
experiment from 9 inverse
performed B of
sistance, 𝑅𝑅
or potentialsM , behaves
close to like a resistor
corrosion and canthe
potential, be above
calculated on
equation by data
taking
can fromthethe
be inverse
- 0.329
reduced ofV
to: the
to -slope
0.309 V (i.e. 2.303
10 mV𝑏𝑏F + 𝑏𝑏2 𝑖𝑖2344 andon
cathodic 10 anmV iron scre
anodi
orrosion During
potentialpotential.
of theDuring
a corroding polarization the polarization
metal. of an
The of an
electrode,
corrosion electrode,
the
current, 𝑖𝑖2344 ,the
magnitude and ofmagnitude
the Tafel slope ofthethe current
(1/slope) 𝑏𝑏and isisfound
controlled by reaction
to be 9.442 kΩ. kineticsan iron scre
potentialDuring
curve at open circuit or by corrosion potential. potential). The slopeconstants
In Figure 1of theresults
curve Fat,ofcorrosion
a LSV experiment
potentialperformed (- 0.319 V) on can be calcula
the currentthe polarization
is controlled
and diffusiondata. of an
reaction electrode,
kinetics
of reactants both towards '.;<; theand magnitude
diffusion of
and=away of the fromcurrent the is controlled
electrode. by reaction
In the previous kinetics
application note,
easured from the experimental The
on𝑒𝑒 data slope
'.;<;
=
of the curve at corrosion
>A Bfrom - 0.329 V to - 0.309 V (i.e. 10 mV cathodic potential (- 0.319 V) can be andcalcula
10 m
nitude of reactants
thediffusion
current isButler-Volmer
controlled byequation
reaction kinetics
arization and theof reactants and both towards and Ifaway
both towards away from the 𝑖𝑖 = 𝑖𝑖2344
electrode. 9𝑒𝑒 from >? −
the electrode. Inkinetics
the previous application note, currents from the
of an electrode, the magnitude of thewas current introduced
the is Tafel as:
controlled slopes by are known,
reaction one can calculate
on data from - 0.329 V to - 0.309 V (i.e. 10 mV cathodic and 10
potential). the corrosion
y from
or the
potentials
the electrode.
close to the
Butler-Volmer
Considering In the
corrosion previous
potential,
equation 1 was application
the1above
F 𝑏𝑏2introduced
𝑏𝑏equation note,equation
as: can be reduced to: If the Tafel slopes are not known (e.g. when corro
f reactants both towards𝑖𝑖Butler-Volmer
and
2344 =away from the Tfor small
S electrode. using ,=the
𝜂𝜂In i.e.
𝐸𝐸 −
the for
𝐸𝐸2344
above
previous equations.
potential). application note,
2.303
potentials close to corrosion F potential, 𝑏𝑏 + 𝑏𝑏 2 𝑅𝑅M the Butler-Volmer
mer equation was introduced as: known), the 𝑅𝑅M can still be used as a quantitative parameter to compare the corros
equation can be reduced to: = =
𝐸𝐸 is the applied potential and 𝑖𝑖 the measured undercurrent 𝑖𝑖various conditions.
'.;<;
= =𝑖𝑖2344 density.
9𝑒𝑒 =
>? − 𝑒𝑒 High
The
'.;<;
>A B 𝑅𝑅M of a metal implies high corrosion resistance a
overpotential, 𝜂𝜂, is defined as the
1 𝑏𝑏F 𝑏𝑏2 1 '.;<; '.;<;
pression
= is rearranged:
difference
= 𝑖𝑖2344 = S T
between applied potential and the corrosion𝜂𝜂potential 𝑖𝑖 = 𝑖𝑖 corrosion
2344 9𝑒𝑒 >?resistance.
− 𝑒𝑒 >A B
= 𝐸𝐸 − 𝐸𝐸 𝐸𝐸 . The corrosion potential, 𝐸𝐸 is
'.;<; '.;<; 2.303 𝑏𝑏F =+ 𝑏𝑏2 𝑅𝑅M = 23442344 2344
𝑒𝑒 >? − 𝑒𝑒 >A B
'.;<; '.;<;
𝑖𝑖 = 𝑖𝑖2344 9𝑒𝑒 >? − 𝑒𝑒 >A B Figure
𝜂𝜂 = 𝐸𝐸3−
– 𝐸𝐸
The
2344calculated
Figure 5regression line equation
– The calculated for theline
regression corrosion of anfor
equation iron
thescrew in sea
= 𝐸𝐸 − 𝐸𝐸2344
Or, when the expression is rearranged: Page 5 of 10
𝜂𝜂 = 𝐸𝐸 − 𝐸𝐸2344 corrosion of an iron screw in seawater
𝐸𝐸 is the applied
pression is rearranged: 1 potential
𝑏𝑏F 𝑏𝑏2 1 and 𝑖𝑖 the measured current
Measurement density.
of 𝐑𝐑 𝐩𝐩 using The overpotential,
electro-chemical 𝜂𝜂, is defined
methods Linear as the Voltamm
Sweep
𝑅𝑅M = 9 B
𝐸𝐸 is the applied potential
difference between
2.303 𝑏𝑏and 𝑏𝑏𝑖𝑖2 the
F + applied 𝑖𝑖2344measured
potential current
and the density.
corrosionThe overpotential,
potential 𝐸𝐸2344 . The is definedpotential,
𝜂𝜂, corrosion as the 𝐸𝐸2344 is
urrent density. Thebetween
overpotential, Measurement
is defined of 𝐑𝐑 𝐩𝐩 using Electrochemical Impedance Spectroscopy (EIS)
d potentialdifference
andTafel
If the 𝑖𝑖 the areapplied
measured
slopes
𝜂𝜂,potential
current
known, andas
density.
one can The
calculate
the
theIn Figure 1 the
corrosion
overpotential,
the results
𝜂𝜂, is 𝐸𝐸of
potential a LSV
defined
2344 . Theexperiment
ascorrosion
the performed
potential, 𝐸𝐸on anisiron screw immersed
2344
rosion potential 𝐸𝐸2344 . Thefrom
corrosion 𝑏𝑏Fpotential, 𝐸𝐸2344Theis resistance Page 5 of 10
ween
es areapplied
corrosion
known,
currents
potential
one can and
𝑅𝑅M the
1the polarization
= corrosion
calculate the
Polarization
resistance
𝑏𝑏2 potential
1
corrosion
9 Bcurrents .slope
𝐸𝐸2344using
from
of the
The the
corrosion
the
curve
can also atbecorrosion
potential,
polarization 𝐸𝐸2344potential
measured
resistance
(- 0.319 V) can be
is with electrochemical calculated
impedance
Page 5 of 10
by perfor
spectrosco
above equations. systemsPage
2.303 𝑏𝑏F + 𝑏𝑏2 𝑖𝑖2344 on datathe
where from - 0.329
Nyquist plotVshows
to - 0.309 V (i.e. 10 amV
one semicircle, cathodic
Randles and 10 circuit
equivalent mV anodic
shownre
equations. If the Tafel slopes are not known (e.g. 5 of 10
when corrosion mechanism is 2Page
Figure not
– LSV
potential). 5 ofdata
10 for the corrosion of an iron screw in sea w
be used to estimate 𝑅𝑅M . In Figure 5 Nyquist plot of experimental data for the corrosion of
can still be used as a quantitative parameter to compare the corrosion resistance of metals
solution is shown. The solid line represents the regression of the Randles circuit to
es are known,
onditions. Highone𝑅𝑅M can
of acalculate the corrosion
metal implies currents
high corrosion from theand
resistance polarization resistance
low 𝑅𝑅M implies lowFigure 2 – LSV data for the corrosion of an iron scre
polarization resistance 𝑅𝑅M . Figure 2 – LSV data for the corrosion of an iron scr
equations. If the Tafel slopes are not known (e.g. when corrosion mechanism is not
ance.
an still be used as a quantitative parameter to compare
For the corrosion
more complex systems resistance
please referof metals
to application note TBD.
onditions. High 𝑅𝑅M of a metal implies high corrosion resistance and low 𝑅𝑅M implies low
nce.
of 𝐑𝐑 𝐩𝐩 using electro-chemical methods Linear Sweep Voltammetry (LSV)
esults of a LSV experiment performed on an iron screw immersed in seawater are shown.
WE(1).Current (A)

curve
of 𝐑𝐑 𝐩𝐩 at corrosion
using potential (- 0.319
electro-chemical V) canLinear
methods be calculated
Sweep by performing a(LSV)
Voltammetry linear regression
0.329 V to - 0.309 V (i.e. 10 mV cathodic and 10 mV anodic relative to the corrosion
esults of a LSV experiment performed on an iron screw immersed in seawater are shown.
curve at corrosion potential (- 0.319 V) can be calculated by performing a linear regression
0.329 V to - 0.309 V (i.e. 10 mV cathodic and 10 mV anodic relative to the corrosion
Figure 2 – LSV data for the corrosion of an iron screw in sea wate

Figure 4 – The Randles equivalent circuit

Potential applied (V)

Figure 4 – LSV data for the corrosion of an iron screw in seawater

5
he experimental data.

lose
en circuit
Metrohm White Paper
to corrosion potential,
potential the above
of a corroding equation
metal. can be reduced
The corrosion
can be measured from the experimental data.
current,to:
𝑖𝑖2344 , and the Tafel constants 𝑏𝑏F ,

all 𝜂𝜂, i.e. for potentials

1
close to1 corrosion potential, the above equation can be reduced to:
𝑏𝑏 𝑏𝑏
F 2
𝑖𝑖2344 = S T
2.303 𝑏𝑏F + 𝑏𝑏2 𝑅𝑅M
Measurement of Rp using Electrochemical Impedance
Spectroscopy (EIS) 1 𝑏𝑏F 𝑏𝑏2 1
𝑖𝑖2344 = S T
ranged: Polarization resistance can also
2.303 be
𝑏𝑏F + 𝑏𝑏measured
2 𝑅𝑅M with
electrochemical impedance spectroscopy. For simple systems
where the Nyquist plot shows one semicircle, a Randles
6
en the expression
equivalentis circuit
1 rearranged:
𝑏𝑏F 𝑏𝑏2
shown in Figure 6 can be used to estimate
1
𝑅𝑅M .=In Figure 7, the9 NyquistB plot of experimental data for the
2.303 𝑏𝑏F + 𝑏𝑏2 𝑖𝑖2344
corrosion of iron in sulfate solution is shown. The solid line
represents the regression of the Randles circuit to calculate
1 𝑏𝑏F 𝑏𝑏2 1
the polarization resistance 𝑅𝑅M .= 9 B
one can calculate the corrosion currents from
2.303 the
𝑏𝑏F + 𝑏𝑏2 polarization
𝑖𝑖2344 resistance
the Tafel slopes are not known (e.g. when corrosion mechanism is not
as a quantitative parameter to compare the corrosion resistance of metals
Tafel slopes are known, one can calculate the corrosion currents from the polarization resistance
𝑅𝑅M of a metal implies high corrosion resistance and low 𝑅𝑅M implies low
he above equations. If the Tafel slopes are not known (e.g. when corrosion mechanism is not
), the 𝑅𝑅M can still be used as a quantitative parameter to compare the corrosion resistance of metals
various conditions. High 𝑅𝑅M of a metal implies high corrosion resistance and low 𝑅𝑅M implies low
on resistance.
ectro-chemical methods Linear Sweep Voltammetry (LSV)

experiment performed on an iron screw immersed in seawater are shown.

urement of 𝐑𝐑(-𝐩𝐩0.319
ion potential usingV)electro-chemical
can be calculated methods Linear
by performing Sweep
a linear Voltammetry (LSV)
regression
Figure 6 – The Randles equivalent circuit
.309 V (i.e. 10 mV cathodic and 10 mV anodic relative to the corrosion
re 1 the results of a LSV experiment performed on an iron screw immersed in seawater are shown.
pe of the curve at corrosion potential (- 0.319 V) can be calculated by performing a linear regression
a from - 0.329 V to - 0.309 V (i.e. 10 mV cathodic and 10 mV anodic relative to the corrosion
ial).
-Z" (Ω )

– LSV data for the corrosion of an iron screw in sea water

Figure 2 – LSV data for the corrosion of an iron screw in sea water

Z' (Ω )
Page 6 of 10

Figure 7 – Nyquist Plot for Estimation of Rp for corrosion of iron in seawater using EIS

Page 6 of 10

6
 Metrohm White Paper
Corrosion Inhibitors
Volatile Corrosion Inhibitors
A corrosion inhibitor is a substance that when added
Volatile Corrosion Inhibitors (VCI), also called Vapor Phase
in a small concentration to an environment reduces the
Inhibitors (VPI), are compounds transported in a closed
corrosion rate of a metal exposed to that environment.
Inhibitors often play an important role in the oil extraction
environment to the site of corrosion by volatilization from 7
a source. In boilers, volatile basic compounds, such as
and processing industries where they have always been
morpholine or hydrazine, are transported with steam to
considered to be the first line of defense against corrosion.
prevent corrosion in the condenser tubes by neutralizing
Anodic inhibitors acidic carbon dioxide or by shifting surface pH towards less
Anodic inhibitors usually act by forming a protective oxide acidic and corrosive values. In closed vapor spaces, such as
film on the surface of the metal causing a large anodic shift shipping containers, volatile solids such as salts of dicyclo-
of the corrosion potential. This shift forces the metallic hexylamine, cyclohexylamine and hexamethylene-amine are
surface into the passivation region. They are also sometimes used.
referred to as passivators. Chromates, nitrates, tungstate, When these inhibitors come in contact with the metal
molybdates are some examples of anodic inhibitors. surface, the vapor of these salts condenses and is hydrolyzed
by any moisture to liberate protective ions. It is desirable, for
Cathodic inhibitors
an efficient VCI, to provide inhibition rapidly while lasting
Cathodic inhibitors act by either slowing the cathodic
for long periods. Both qualities depend on the volatility of
reaction itself or selectively precipitating on cathodic areas
these compounds; fast action wanting high volatility while
to limit the diffusion of reducing species to the surface.
enduring protection requires low volatility.
The rates of the cathodic reactions can be reduced by the
use of cathodic poisons. However, cathodic poisons can also
increase the susceptibility of a metal to hydrogen induced
cracking since hydrogen can also be absorbed by the metal
during aqueous corrosion or cathodic charging.
The corrosion rates can also be reduced by the use of
oxygen scavengers that react with dissolved oxygen. Sulfite
and bisulfite ions are examples of oxygen scavengers that
can combine with oxygen to form sulfate.

Mixed Inhibitors
Mixed inhibitors work by reducing both the cathodic and
anodic reactions. They are typically film forming compounds
that cause the formation of precipitates on the surface
blocking both anodic and cathodic sites indirectly.
Hard water that is high in calcium and magnesium is less
corrosive than soft water because of the tendency of the
salts in the hard water to precipitate on the surface of the
metal forming a protective film.
The most common inhibitors of this category are the silicates
and the phosphates. Sodium silicate, for example, is used in
many domestic water softeners to prevent the occurrence
of rust water. In aerated hot water systems, sodium silicate
protects steel, copper and brass. However, protection is
not always reliable and depends heavily on pH. Phosphates
also require oxygen for effective inhibition. Silicates and
phosphates do not afford the degree of protection provided
by chromates and nitrites, however, they are very useful in
situations where non-toxic additives are required.

7
 Metrohm White Paper
Evaluation of Corrosion
Inhibitors
Electrochemical methods are used routinely for the evaluation
8 of the efficiency of corrosion inhibitors. The advantages of
electrochemical methods are short measurement time and
mechanistic information that they provide which help not
only in the design of corrosion protection strategies but also
in the design of new inhibitors.
The LSV experiments can evaluate the performance of the
corrosion inhibitor. Beginning the experiments at cathodic
potentials ensured that any oxide layer present prior to the
start of the experiments was reduced.
Figure 8 shows the polarization curves for solutions with
and without inhibitor, in red and in blue, respectively. The
anodic part of the polarization curve without inhibitor is
typical for active metal dissolution.
Current (A)

Potential (V)

Figure 8 – Linear polarization measurement in the absence (blue) and presence (red) of a corrosion inhibitor

The data suggests that when an anodic inhibitor is added

to the solution there is a shift of the corrosion potential in
the anodic direction and a reduction in the anodic current.
The corrosion inhibitor also results in the formation of the
passive film evidenced by the appearance of the passivation
plateau.

8

Resources
Now that you have been introduced to the fundamental
corrosion concepts you may like to explore the topic
more thoroughly. We offer this list of resources to help
you deepen your knowledge of the topic.
9
Application Notes
We created a number of application notes that can help you
explore corrosion electrochemically in your laboratory:

• Critical Pitting Temperature (CPT) as per ASTM G150

ASTM International – Standards Worldwide
www.astm.org/Standard/standards-and-publications.html
NACE International Standards
nace.org/resources
• Electrochemical impedance spectroscopy (EIS) of three
coated aluminum samples
• Equivalent circuit models
• Hydrogen permeation experiments

Introduction to Corrosion Science • Stepwise dissolution measurement

Author: E. McCafferty
Springer 2010
Log on to www.metrohm.com/applications to find these
The Fundamentals of Corrosion notes. The list above is subject to change and you can use a
Author: JC Scully Full Text Search AN-COR to discover additional corrosion
Pergamon 3e 1990 applications as they become available.

Principles and Prevention of Corrosion

Author: Denny A Jones
Pearson 2e 2013
WP-044EN, published March, 2019

Dedicated to research www.metrohm.com/electrochemistry