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1 - INTRODUCTION TO CORROSION
Definition

Corrosion may be defined as the deterioration of materials due to their interaction with the
environment. This phenomenon is experienced in our day to day life. The most common
examples of corrosion include the rusting of iron or tarnishing of copper and silver articles.

Why do metals corrode?

A significant amount of energy is put into a metal when it is extracted from its ores, placing
it in a high-energy state. These ores are typically oxides of the metal such as hematite
(Fe2O3) for steel or bauxite (Al2O3.H2O) for aluminum. According to the principle of
thermodynamics a material always seeks the lowest energy state. In other words, most
metals are thermodynamically unstable and will tend to seek a lower energy state, which is
an oxide or some other compound. The process by which metals convert to the lower-
energy oxides is called corrosion.

Free energy

Metals corrode due to their thermodynamic instability. Most of the metals are stable in the
oxidized form. There is a decrease in free energy (G) during the corrosion process of
metals. For example.

Mg + H2O (l) + O2 Mg (OH)2 G = -142,600 Cal.


This type of decrease in free energy occurs for all meals except gold

Au + 3/2 H2O (l) + 3/4 O2 (g) Au (OH)3 (S) G = + 15,700 Cal.

Since the change in free energy is positive, gold is free from corrosion reaction

Importance of corrosion education

The importance of corrosion engineering education assumes significance from the point of
view of economics (cost of corrosion), depletion of resources, health and safety aspects.

Cost of corrosion

The cost of corrosion is estimated to be 4% GNP (GNP for the year 2014 : Rs. 56738.60
billion) which works out to be nearly Rs.2,00,000 crores. The losses due to corrosion may
be divided into direct losses and indirect losses.

Direct losses

Direct losses include the cost for the replacement of corroded materials, use of more
corrosion-resistant materials, use of protective coatings and inhibitors for the application of
corrosion control measures.
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Indirect losses

In most of the cases, indirect losses form a substantial part of the corrosion cost.
Sometimes corrosion of critical parts may result in the loss of human life, which is very
serious.

Indirect losses of corrosion are due to the following:


Plant shutdowns: Shutdown of nuclear plants, process plants, power plants and
refineries may cause severe problems to industry and consumers
Loss of products: Leaking storage tanks, petroleum product transportation lines
and fuel tanks cause significant loss of product and may generate severe accidents
and hazards.
Loss of efficiency: Insulation of heat exchanger tubings due to scale formation
reduces heat transfer.
Contamination of product: Corrosion products may contaminate chemicals,
pharmaceuticals, dyes, packaged goods, etc. with dire consequences to the
consumers.

Depletion of resources:

Corrosion puts a heavy constraint on natural resources of a country because of their


wastage by corrosion. The process of depletion outweighs the discovery of new resources
which may lead to a future metal crisis. To preserve these valuable resources, we need to
understand how these resources are destroyed by corrosion and how they must be
preserved by applying corrosion control methods.

Health and Safety:

Sudden failure can cause explosions and fire, release of toxic products and collapse of
structures. Several incidents of fire have been reported due to corrosion causing leakage
of gas and oil pipelines

CORROSION SCIENCE AND CORROSION ENGINEERING

The term science covers theories, laws and explanation of phenomena confirmed by
observation or experiments. For instance, the explanation of different forms of corrosion,
rates of corrosion and mechanism of corrosion is provided by corrosion science.

Corrosion engineering is the application of the principles evolved from corrosion science to
minimize corrosion. Corrosion engineering covers designing of corrosion control schemes
such as cathodic protection, designing to prevent corrosion and coating of structures etc.
However, corrosion science and engineering go hand-in-hand and they cannot be
separated: it is a permanent marriage to produce new and better methods of protection
from time to time.

INTER-DISCIPLINARY NATURE OF CORROSION

The subject of corrosion is inter-disciplinary and it involves all basic sciences, such as
physics, chemistry, biology and all disciplines of engineering, such as chemical, civil,
mechanical, electrical and metallurgical engineering.
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2 - CORROSION BASICS

Classification of corrosion

Generally, the corrosion process can be classified into dry corrosion and wet corrosion.

Dry Corrosion

These are generally metal/gas or metal vapour reaction involving oxygen or halogen etc.

Wet Corrosion

These are reactions of metals with aqueous environment, which is known as immersion
corrosion. Besides the corrosion of metals in atmosphere, underground corrosion is also
classified as wet corrosion.

Electrochemical Reactions

All wet type of corrosion reactions are electrochemical in nature. An electrochemical


reaction is defined as a chemical reaction involving the transfer of electrons. It is also a
chemical reaction which involves oxidation and reduction.

Oxidation

Oxidation is the term applied to loss of one or more electrons from an atom or a molecule
which forms a positively charged ion.

For example, when iron atom oxidizes it may lose two or three electrons producing
positively charged iron ions (Fe2+, Fe3+)

Reduction

Reduction is the term applied to the gain of one or more electrons to an atom or a
molecule which then forms a negatively charged ion or neutral element.

For example, when hydrogen ion (H +) is reduced, it gains one electron producing neutral
hydrogen atom (H).

Corrosion Cell

Corrosion is an electrochemical process involving the flow of electrons and ions. Corrosion
(metal loss) occurs at the anode. No metal loss occurs at the cathode (the cathode is
protected).

There are certain basic requirements for a corrosion cell to operate.

There must be an Anode


There must be a Cathode
There must be a conducting Electrolyte - Electrolytic conductance
There must be an electronic conductance - Metallic Path
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When all these conditions are met current will flow and corrosion occurs at the anodic
area.

Anode: The electrode of an electrochemical cell at which oxidation occurs. Anode is a less
noble metal. Electrons flow away from the anode to the cathode. Corrosion usually occurs
and metal ions enter solution at the anode.

Cathode: The electrode of an electrochemical cell at which reduction is the principal


reaction. Electrons flow towards the cathode in the external circuit. The cathode is a more
noble metal. The electrochemical reaction continues at the cathode. The reaction generally
ionises the electrolyte to form species such as H 2 and hydroxyl ion. Thereafter combining
with metal ion to form Fe(OH)2. The electrons generated at the anode are consumed at the
cathode

Electronic conductance (Metallic pathway):

The metallic pathway allows the electron generated at the anode to move to the cathode.

Electrolyte:

The electrolytes conduct ionic rather than electric current. Electrolyte acts as a pathway to
transport the ions between the anode and cathode. The electrolyte completes the circuit in
the corrosion cell.

Fig. 2.1 Corrosion cell

Anodic Reactions
The anodic reaction is an oxidation reaction that occurs at the anode.
Oxidation is the loss of electrons as shown in the following reaction:

Mo Mn+ + ne- where n is the number of electrons involved

The anodic reaction for iron is

Feo Fe++ + 2e
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Cathodic Reactions
Cathodic reaction, is a reduction reaction that occurs at the cathode. Reduction is the gain
of electrons. The actual cathodic reaction that occurs will depend on the electrolyte. The
following reactions are the two most common reduction reactions that occur at the surface
of the cathode.

Oxygen Reduction - Neutral environments.


2H2O + O2 + 4e- 4OH
Hydrogen evolution - Acidic environments
2H+ + 2e- H2
Corrosion never occurs at the cathode of a corrosion cell.
For corrosion to occur there must be formation of ions and release of electrons at the
anodic surface, where oxidation or deterioration of metal occurs. There must be a
simultaneous reaction at the cathode surface to consume the electrons generated at the
anode. These electrons can serve to neutralise positive ions such as, the hydrogen ion (H +
in the acid medium). The anodic and cathodic reaction must go on at the same time and at
an equivalent rate. However, corrosion process occurs only at the areas that serve as
anodes.
Dry cell An example of corrosion cell
The graphite-zinc dry cell, as shown in Figure 2.2, often is used to illustrate the corrosion
cell. As illustrated, zinc (anode) is electrically connected through an external load to carbon
(cathode) in the presence of a corrosive electrolyte (NH 4Cl). When they are electrically
connected, the corrosion cell is completed with the anodic reaction at the zinc and the
cathodic reaction at the carbon electrode. Zinc anode (Negative terminal) releases two
electrons and these two electrons move from zinc electrode to the graphite rod cathode
(positive terminal) through the electronic conductor. Conventional current will flow from the
anode to the electrolyte and reaches the cathode and hence due to the flow of current the
bulb glows. The battery is depleted as the zinc is consumed.

Figure 2.2 Graphite - Zinc (Dry cell)

Local corrosion cell:

The anode and the cathode can be on different metals or on the same metal as shown in
Figure 2.3.
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Fig. 2.3 : Enlarged view of metal surface showing schematic


arrangement of local corrosion cells.

Referring to Figure 2.3, let us examine the process of corrosion for a local corrosion cell
consisting of a local anode and a local cathode existing on the same metallic surface
exposed to electrolyte. The metal provides the anode, cathode, and electronic path of the
corrosion cell. The electrolyte provides the electrolytic conductance to complete the
corrosion cell. The electrolyte has ionized so that hydrogen (H +) and hydroxyl (OH) ions
are present in small amounts (10 -7). Metal ions leave the local anodic surface going into
the electrolyte, leaving behind electrons, which flow in the metallic path to the cathodic
surface. At the cathodic surface, the electrons from the anode meet hydrogen ions from
the solution. One hydrogen ion accepts one electron and is converted into a hydrogen
atom. The hydrogen atom may combine with another hydrogen atom to form a molecule of
hydrogen gas, which may either cling to the cathodic surface or be released as a bubble.

The formation of cathodic and anodic areas during corrosion may be due to heterogeneity
of metal or environment. Foreign metal inclusions, grain boundaries, oxides, carbides etc
act as cathodes during corrosion. Differential salt concentration and oxygen concentration
create the conditions for corrosion. When a metal is in contact with low and high metaI ion
concentration, then the portion in contact with low concentration will act as anode, while
the portion in contact with high concentration will act as cathode.

CORROSION RATE EXPRESSIONS

Mostly the rates of corrosion of metals are expressed as mpy or mmpy. The relative scale
for corrosion of metal is given as

Safe Less than 5 mpy or 0.125 mmpy

Moderate 5 mpy to 50 mpy or 0.125 mmpy to 1.25 mmpy

Severe Greater than 50 mpy or 1.25 mmpy

The rate of corrosion of metal is usually measured either by gravimetric method or


electrochemical methods.
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Gravimetric method
Weighed specimens are exposed to the environment for a specified period and the loss of
metal is measured. From the weight loss, corrosion rate is determined by the relationship.

87.6 x weightloss (mg)


Corrosion rate (mmpy) =
Area (cm2) x time (hrs) x Density (g/cc)
The coupons can be in the form of discs, rods, plates or any convenient shape, but the
edges should be machined and polished to avoid preferential attack due to residual from
the cropping operation. Comprehensive guidance for preparation of specimens is given in
ASTM-G4-68. The specimens are mounted on the racks and exposed. After exposure, the
coupons are cleaned either mechanically or pickled in inhibited acids in order to remove
the corrosion products.
This techniques is still widely used since many different materials can be exposed at one
site and unambiguous data on the form of corrosion on the specimen can be obtained.
This method yields average corrosion rate and is inherently inaccurate when it involves
measuring small differences in weight. Besides continuous monitoring of corrosion rate is
not possible.
Faradays laws of electrolysis and its application in determining corrosion rate of
metals

Refer the hand written material already provided

Determination of corrosion current density i corr

Electrochemical method (Tafel polarisation method)

The electrochemical cell with three electrodes is connected to potentiostat/galvanostat.


After attaining stable open circuit potential (OCP), the potential was shifted in small steps
in both anodic and cathodic directions and the corresponding current response was noted.
This is continued upto a potential of 200 or 300 mV on either side of OCP. The potential is
plotted against logarithmic current. After few mV from the OCP, say 30-50mV on either
side of OCP, there exists a liner relationship between potential and log current (Figure
2.4). This linear region is called Tafel region. Extrapolation of these anodic and cathodic
tafel regions to Ecorr will yield the corrosion current density I corr. The slopes of anodic tafel
and cathodic tafel lines are respectively called anodic tafel slope b a and cathodic tafel
slope bc
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Fig. 2.4 : A hypothetical Tafel plot

Factors influencing corrosion

The various factors influencing the atmospheric, immersion and underground corrosion are
given below:

Atmospheric corrosion

The atmosphere consists of air which is a gas mixture of uniform composition (21% O 2 and
79% N2 ) but with varying amounts of minor constituents like SO 2, H2S chlorine, carbon
particles etc. These minor constituents of the atmosphere are the source of differences in
the observed corrosion behaviour of a given metal in different locations. Atmospheres are
accordingly classified as rural, marine, urban and industrial. The most important factors
that influence the corrosivity of atmosphere are (i) atmospheric moisture, (ii) atmospheric
dust and (iii) atmospheric gaseous pollutants.

Atmospheric Moisture

It is found that the corrosion of metals is more in tropics due to high humidities. In normal
atmospheres, there is a critical relative humidity above which corrosion takes place. This
value depends upon the nature of the pollutants. For example, in the case of steel,
presence of S02 is 65-75% and in the presence of chloride is as low as 40%.

Atmospheric dust

Dust particles on settlement on metal surface absorb moisture and initiate corrosion.
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Atmospheric gaseous pollutants

Atmospheric carbon dioxide has no deleterious corrosive effects and in fact might actually
beneficial. Traces of hydrogen sulphide results in tarnishing of silver (Ag 2S) and copper
(Cu2S). In industrial atmosphere oxides of sulfur (S0 2 S03) are the most important corrosive
constituents. Due to the formation of H 2SO4 severe corrosion of metals takes place. In the
case of marine atmosphere, the influence of salt content is very marked. The rate of
corrosion of steel is dependent on the distance from the sea, the height above the ground
and the wind direction. The results given in ASTM Special Technical Publication 435
(1968) are given below

Distance 1/2 mile from ocean = 0.18 mmpy


60 yards from ocean = 0.90 mmpy
Height 30 ft from ground sea level = 0.33 mmpy
60 ft from ground sea level = 0.28 mmpy

Immersion Corrosion

The factors influencing the immersion corrosion of metals are: pH, dissolved gases,
dissolved salts, presence of bacteria, temperature, velocity and the depth of immersion (in
the case of seawater) and surface film.

pH

Metals such as iron dissolve rapidly in acidic solution. In the middle pH range (4 to
10), the conc of H+ ions is low. Hence, the corrosion rate is controlled by the rate of
transport of oxygen.

Certain amphoteric metals dissolve rapidly in either acidic or basic solution. E.g. Al
and Zn.

Noble metals are not affected by pH. E.g. gold and platinum.

H + ions capture electrons and promote anodic corrosion.

Dissolved Gases

Gases such as CO2, H2S, NH3, Cl2 and O2 affect the corrosion rate markedly. CO2 acts by
promoting acid-type corrosion. H2S attacks the metals by forming loose sulfide, which is
non-protective. Ammonia corrodes copper and copper base alloys, forming soluble
complexes. Chlorine forms HCI or HClO, which accelerate corrosion.
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Because oxygen plays a predominant role in cathodic reactions in neutral media, increase
in oxygen concentration accelerates corrosion of iron (Fig. 2.6). However, at very high
oxygen concentrations, the rate drops due to passivity. In seawater, the oxygen
concentration decreases with depth. This is due to the photosynthesis of marine plants at
the surface. Due to this the corrosion rate of steel decreases with the depth (Fig.2.6 ). But
for aluminium and stainless steels at higher depths, pitting corrosion takes place due to
lower oxygen availability, which evidently reduces the protective effect of oxide films.
Effect ofFig.
Fig. 2.5 Dissolved 2.6 Corrosion
oxygen
Salts
of carbon steel at
concentration
different distances from the surface
On corrosion of mild steel in slowly moving
Distilled water
The presence of calcium and magnesium in the water decreases the corrosion due to
formation of protective scales. But alkaline metal salts such as NaCl, Na 2S04, KCI
accelerate corrosion. Similarly, the presence of oxidizing salts, complexing salts accelerate
corrosion. Besides the above salts, H+ ion concentration in the water influences the
corrosion of metals markedly.
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Bacteria

The presence of sulphate-reducing bacteria, slime forming bacteria and iron oxidizing
bacteria accelerates the corrosion of metals.

Temperature

The rate of corrosion usually increases with temperature. In general, there is a linear
variation with doubling of corrosion rate for rise of 10C in the water temperature in
seawater.

Velocity

In neutral solution, the rate of corrosion depends on the rate of motion of the corrosive
solutions since the motion of electrolyte increases the supply of oxygen to the metal
surface. Generally, carbon steel and zinc corrode at greater rates with increased velocity.

Depth

Oxygen varies with increasing depth, tending to drop at 1000-2000 m and then rise again.
Besides, temperature falls with increasing depth. Generally, the corrosion rate decreases
with the depth, although there appear to be exceptions.

Surface film

Insoluble slats such as carbonates and sulphates may be precipitated from hot
solution on the metal surfaces. These protects the metal surfaces.

If the film is porous (e.g. ZnO) corrosion continues. Nonporous films (Cr 2O3 on iron)
prevents further corrosion.

Oil and grease films may occur on the surface either intentionally or naturally. These
films protect surface from direct contact with corrosive substance. E.g. metals
submerged in sewage .

Underground corrosion

The major importance of corrosion of underground derives from the fact that there are
million miles of buried crude, petroleum product and gas pipelines. The major factors that
influence underground corrosion are porosity, electrical resistivity, dissolved substances,
moisture, stray current and bacteria present in the soil. Less porous, less moisture and
high resistive soils (10000 ohm.cm) are mildly corrosive. Dissolved compounds present in
the soil influence the corrosion in the same way as that under immersed conditions.
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REFERENCE ELECTRODES

Reference electrode is a reversible electrode used for measuring the potentials of other
electrodes. A reversible electrode must be at equilibrium, which means that there is no net
change in the electrode over time. Desirable properties of a good reference electrode
include the following:

Easy to use and maintain Stable potential over time

Potential varies little with current flow (does not polarize readily) Not easily contaminated
Does not contaminate what is being measured.

The hydrogen electrode can be used as a reference electrode but it is cumber-some, even
in the laboratory. Other common reference electrodes include silver-silver chloride,
calomel, and copper-copper sulfate

Table - Potentials of Common Reference Electrodes

Potential (V)
Electrode @ 25C
Cu/CuSO4 (Saturated) [CSE] 0.300
Calomel (Saturated KCl) [SCE] 0.241
Ag/AgCl (Saturated KCl) 0.196
Ag/AgCl (0.6 M Cl) [seawater] 0.250

HYDROGEN ELECTRODE

The hydrogen electrode is used as a reference electrode for potential measurements.


Theoretically, it is the most important electrode for use in aqueous solutions. The
reversible hydrogen electrode in a solution of hydrogen ions at unit activity exhibits a
potential, which is assumed to be zero at all temperatures. The electrode consists of a
platinum wire immersed in a solution containing hydrogen ions and saturated with
hydrogen gas. Platinum is immersed completely in aqueousarsenic free hydrochloric acid,
and hydrogen gas free from oxygen and carbon monoxide is bubbled to the platinum
surface.

Salt

bridge

platinum coated
with Pt black

+
[H ] = 1 M
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SILVER-SILVER CHLORIDE ELECTRODE

This electrode is composed of a silver wire coated with silver chloride and immersed in a
solution of chloride ions.

The following are the values of Ag/AgCl electrode potential for different HCl
concentrations:
Concentration (M) Electrode potential (volts)
0.1 0.28
0.01 0.34
0.001 0.40

CALOMEL ELECTRODE

It is the most commonly used reference electrode. It has a constant and reproducible
potential. The electrode basically consists of a platinum wire dipped into pure mercury
which rests in a paste of mercurous chloride and mercury. The paste is in contact with a
solution of potassium chloride which acts as a salt bridge to the other half of the cell. The
most commonly used concentrations of KCl are 0.1 N, 1.0 N and 3.5 N and saturated KCl.
The potential of electrode at 25C is 0.241 V in saturated KCl solution.
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Figure Saturated calomel reference electrode

The electrode potential of calomel electrode in different KCl solution are given in the
following table

Electrode Volt vs SHE


Hg/Hg2Cl2/KCl (Sat.) 0.241
Hg/Hg2Cl2/KCl (1.0 N) 0.289
Hg/Hg2Cl2/KCl (0.1 N) / Salt bridge 0.3356

COPPER - COPPER SULFATE ELECTRODE

This reference electrode is mainly used in cathodic protection measurements, such as the
measurement of pipe-to-soil potential. It has a lower accuracy than other electrodes used
for laboratory work. It consists of copper metal placed in a solution containing copper
sulfate and copper sulphate crystals placed in a non-conducting holder with a porous
plug. The copper sulphate crystals maintain the solution at a fixed ion concentration.
Necessary contact with the earth is made through the porous plug. It is easily recharged
when it becomes contaminated. The potential of Copper / copper sulphate reference
electrode is 0.30 Volts vs SHE.

Figure Copper-copper sulfate reference electrode


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EMF AND GALVANIC SERIES

EMF series is an orderly listing of standard half-cell electrode potentials of pure metals.
The standard potential (Eo) of various pure metals are measured at a temperature of 25 oC,
in a solution of 1 molar concentration of the metal ions. Table gives the standard electrode
potential of metals with reference to hydrogen electrode, which is arbitrary defined as zero

Table Standard Electrochemical Series for Some Common Metals

CHARACTERISTICS OF EMF SERIES

(1) Metals with large positive potentials are called 'noble' metals because they do not
dissolve easily. Examples are copper, silver, gold, etc. The potential of a noble
metal is preceded by a positive (+) sign.
(2) The electrode potentials are thermodynamic quantities and have little relevance to
potential of metals in solution encountered in service.
(3) The emf series lists only the electrode potentials of metals and not alloys. Alloys are
not considered in the emf series.
(4) Na, Mg, Al, Zn are called 'active metals'
(5) From the standard emf series of metals, it is possible to predict whether a particular
metal will spontaneously dissolve.
(6) It gives an indication of how active the metal
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APPLICATION OF EMF SERIES

The applications of emf series are :

(1) A less electropositive metal would displace a more electropositive metal from one of its
salts in aqueous solution. For instance, if a rod of zinc is placed in a solution of copper
sulfate, zinc would dissolve in the solution and copper would be discharged:

Zn+CuSO4 > ZnSO4+Cu


Zn Zn +2e (oxidation)
++

Cu +2e Cu (reduction)
++

Consequently, copper will deposit on the zinc rod.

(2) Metal ions above hydrogen are more readily reduced than the hydrogen ions
(3) The metals in the series with high positive potentials are recognized as metals with
good corrosion resistance.
(4) The metal with a more negative potential is generally the anode, and the metal with a
less negative potential, the cathode. If zinc and aluminum are coupled, aluminium would
become the anode and zinc as the cathode

LIMITATIONS OF EMF SERIES

The limitations of the EMF series are:


(1) The emf series lists only pure metals which have only a limited use in engineering
applications. Alloys are of major interest to engineers rather than pure metals.
(2) The electrode potential has little relevance to potentials of metals in solutions, in
which the potential of interest is the corrosion potential and not the electrode
potential of the metal.
(3) The emf series predicts the tendency to corrode but it cannot predict whether
corrosion would actually take place. For instance, on the basis of some negative
potential, iron shows tendency to corrode, however, if it develops a passive film in
some environment it would not corrode.

Galvanic series

The electrochemical series is derived from thermodynamic data and represents equilibrium
conditions. One rarely encounters such conditions in the real world except for the case of
reference electrodes.

A galvanic series is a table of metals and alloys arranged according to their relative
corrosion potential in a given environment. The following table shows a galvanic series
produced on a number of metals in seawater. The series was generated by measuring the
stable potential between the metal and a saturated calomel electrode (SCE) in a seawater.
This potential is referred to as a corrosion potential or an open circuit potential. The
galvanic series provides an indication of the relative reactivity of the different metals.

Galvanic potential series for metals in seawater Volts vs. SCE


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More Active Magnesium -1.48


Zinc - 1.03
Aluminium - 0.79
Wrought iron and carbon steel -0.61
Cast Iron -0.61
Stainless Steel Type 400 AISI (17% Cr) -0.57
Stainless Steel type 304 AISI (18% Gr, 18% Ni) -0.53
Less Active Rolled brass -0.40
Copper -0.36
Aluminium brass -0.32
Nickel -0.20
Titanium -0.15
Silver -0.13
Graphite 0.25
Platinum 0.26 V