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INDEX
S. No Topic Page No
Week 1
1 Introduction to corrosion - I 1
2 Introduction to corrosion - II 13
3 Types and forms of corrosion 29
4 Uniform and Galvanic corrosion 38
5 Crevice and Pitting corrosion 48
6 Forms of corrosion: Explanation with Examples 59
7 Electrochemical Nature of Corrosion and its Thermodynamics 70
8 Thermodynamics aspects of corrosion-I 79
9 Thermodynamics aspects of corrosion-II 89
Week 2
10 Thermodynamics aspects ofcorrosion-III 99
11 Relation Between Free Energy and Equilibrium Constant 109
12 Derivation of Nernst Equation 119
13 Standard Reduction Potential Series for Pure Metals 130
14 Reduction Potentials in Acidic and Neutral Solutions 140
Week 3
15 Nernst equation in terms of pH 149
16 Limitations of Standard Reduction Potential Series of Pure Metals 159
17 Concentration Cell Formation and Galvanic Series 167
18 Examples of Concentration cell and Spontaneity of Corrosion Process 177
19 Spontaneity of Corrosion Process and Introduction to Pourbaix Diagram 187
Week 4
20 Construction of Pourbaix Diagram 198
21 Construction of Pourbaix diagram for Ni-H2O system-I 207
22 Construction of Pourbaix diagram for Ni-H2O system-II 215
23 Construction of Pourbaix diagram for Ni-H2O system-III 224
24 Pourbaix diagram of Ni-H2O and AI-H2O 232
Week 5
25 Inferences from Pourbaix diagram of Fe-H2O and AI-H2O 242
26 Estimation of Corrosion Rate - I 253
27 Estimation of Corrosion Rate - II 262
28 Estimation of corrosion Rate -III 271
Week 6
29 Exchange current Density 280
30 Exchange current Density and Standard hydrogen electrode 290
31 Electrical Double Layer and Polarization 300
32 Correlation between Current Density and Overvoltage 308
Week 7
33 Introduction to Buttler-Volmer Equation 317
34 Derivation of Tafel Equation 329
35 Tafel Plot and Activation Polarization 339
36 Activation polarization, concentration polarization and total polarization 349
Week 8
Summary of concentration polarization (CP) and introduction to mixed
37 potential theory-I 359
38 Mixed potential theory-II 369
Understanding of mixed potential theory through the case studies and events
39 of corrosion-I 380
40 of corrosion-II 390
41 of corrosion-III 399
Corrosion - Part I
Prof. Kallol Mondal
Department of Materials Science Engineering
Indian Institute of Technology, Kanpur
Lecture – 01
Introduction to Corrosion – I
Hello everyone, today we will start our first lecture on this course Corrosion. This is a
MOOC course a 20hour course and a 8 week. This course will be this course lectures
should be floated. And I will be giving the lecturers and in addition to that there will be
three TA’s teaching assistants available to respond to your queries as well as the
problems what will be given to you, they will be the first interface with whom you will
be interacting for those solutions as well as if you have any queries they will respond and
then of course, I will be also be available all the time. This three TA’s are mister P. K.
Rai, mister N. K. Prasad and mister B. Bhushan and interestingly this all three TA’s are
in their advance stage of PhD and they are all doing in corrosion related topics.
Now, as I have mentioned in my introduction that corrosion is a very very important

subject. And it is to be understood carefully and we need to spend little time on this and
also we mentioned that there are scientific aspects of corrosion, were electrochemistry is
to be known, is to be understood. But there are many engineering aspects to this
materials corrosion, where you would be seeing that many other factors like
compositions of metals and alloys, design of components, then environmental factors
like oxygen concentrations and H2O presence; that means, moisture presence as well as
sometimes you would see that the stress also plays major role.
We will go gradually one by one two different aspects of corrosion, but today we will
have a kind of history that why we should study corrosion. And also you would find that
there are some aspects which lead to kind of catastrophe and if we do not understand
corrosion properly, we would not be able to protect our structures, which are made out of
metals and alloys from corrosion and finally, from premature failure. Now, before we go
into the subject, I would like to put up some of the corrosion books which are good
books, and of course, other books are available thousands of books are available, there
are materials available in internet you can Google anytime, and try to get as much as you
want from the literature as well as from internet.
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(Refer Slide Time: 03:33)
So, these books are just for reference, you can find any other books because, the aspects
of corrosion is same whether you follow this book or that book. It depends on how it is
presented in that particular book, but still I have put some books. In addition to that you
would find some of the lectures in YouTube as well as I mentioned that in this course we
will also explain some of the intricate matters related to corrosion.
Now, coming to the subject directly; this slide is actually if you see this slide this slide is
related to some of those is basically showing some of the common features of corrosion.
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Now in day to day life, every direction if you look at you would find examples of
corrosion. I start with let us say our utensils, our a household goods, you will find that
many a times household goods like scrubber or kind of a this spatulas those are corroded
heavily. Even for example, the first picture if you see the first picture this picture if you
see, this picture is related to the corrosion of bolt, you see this entire part is so heavily
corroded. This is the bolt part and this is the nut part, nut is also corroded, this is
commonly observed feature.
Now, another commonly observed feature is if you consider overhead structures beams,
this is the overhead structures and beams they are also heavily corroded. And corrosion
always it comes with the different colour most of the cases and many a cases you do not
find any signature of corrosion, but still it happens and those cases are more deadly than
any other cases, where you have a kind of signature in the form of colour change.
Here you have the basically red rust which is forming, which is a typical feature of iron
corrosion. These are either a hydrated ferric oxide the ferrous of ferric ions are
containing over there, and this is this happens because of the presence reaction with
oxygen and moisture in the environment, this is basically a atmospheric corrosion. Again
if you see this kind of structure, which is a basically a kind of beams as well as a kind of
bridge also you will find this kind of corrosion.
If you can see that the entire material is out, and the kind of thickness what it had this
being physical initially it was basically this much thickness and now it has reduced this
particular section has reduced. That means, initially it is to it was designed to carry some
load, now since the cross section has reduced of course, it will not be able to follow that
particular load it will not be able to carry that load at some point of time it will definitely
fail. And when this metallic structure fails, it fails catastrophically without giving any
signal that it is failing. Now, a typical corrosion features like this, if you see this is a kind
of pipeline. It also relates to the safety of people walking around that.
Now, if it is a pipeline, now if it carries oil and if suddenly this kind of failure happens, it
might catch fire or any other things and then it there could be explosions. Now kind of a
failure here if you see, this is a kind of pipeline which carries water. And then with the
pipeline corrodes and finally, it leaks before one could rectify and then finally stop that
leak you lose lot of water. And of course, if you see this kind of situation, where those
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corroded products even if the, if it is carrying some kind of a liquid which contains heavy
metals and other stuffs like what we have in chemical factories. If it leaks if that wall
leaks it will leave that particular liquid into the environment in the, into the soil and that
soil is contaminated.
For example, if some sections some in if for example, in Kanpur specially, in it is

basically a belt where lot of these tanneries are there. So, the tannery the this particular
(Refer Time: 08:38) this particular kind of liquids, it lead to the environment those liquid
contains lot of not so good metals. So, it is also leads to environmental hazards. So, this
kind of corrosion we can see these are all visible naked eyes; now, if you consider this
kind of corrosion, which is basically related to a corrosion of tooth filling. Tooth filling
this is also corroding, this is also not good if some metal is put up and then if it goes out
again it leads to a health hazard.
Now, this is a typical corrosion failure for example, in this zone, this is a kind of broken
bone which is locked which is connected by screwing and putting a rod. And now if a,
this corrosion product is accumulating; and when this kind of attachment is fixed to the
bone to the broken bone finally, it is function is to carry load. Now if there is a corrosion
product, it becomes weak, now it will no longer hold the load and it will fail. And when
it fails, again if the person has to go and sleep on the operation table ok. So, in other
invasive surgery and a kind of trauma and other things other pains those that person has
to be here for another time.
So, corrosion see these are actually some of the pictures I have taken from internet, but
in the internet you just put this particular buzz word corrosion and damage or corrosion
accidents, you will find thousands of example. Now, let me put up some small small
examples like you might find in the though it looks a little awkward, in the urinal you
will find that a, some kind of water connections, there you will find that the top this nuts
are little shiny, but the base of that particular metal with the connector is corroded
heavily. Now, the question is people always put nuts in the form of a kind of a better
metal, which has little bit of extra corrosion resistance.
And that particular connector the small rod connector connects this particular nut to the
main pipeline source is of a poorer grade metal I would say compared to that nut
material. Now, this I am telling poorer grade means with reference to the corrosion
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resistance of those metals. Now, that case a kind of corrosion happens which is called
galvanic corrosion, and there the connector which actually takes water pipeline to the to
the pipeline inside the bathroom that gets corroded and leakage happens. So, these kind
of stuff many a times happen in our day to day life.
And for example, another example I can sight let us say water sink this kitchen sink.
Kitchen sink sometimes we find that at the corners we do get little bit of a kind of small
small dots like appearance, which are nothing, but pits and over the time this pit grows
and then there is a leakage. Another example water storage tank; now water storage tank
the typical failure point is in the corner positions, at the at the bottom corner you would
find that leakage is taking place from there. So, that actually relates to another kind of
corrosion which is called crevice corrosion. So, those everywhere you will find
corrosion.
Now, some of the cases you would see if some construction is taking place. Sometimes
people do construction and then they form the beam and that beam is half cooked beam, I
would say that half is made the half is exposed; that means, all those reinforce bars are
exposed to the environment. And you would find that that beam during the rainy season
that beam will become a kind of reddish appearance, because that red rust what is
forming on the expose reinforce bars those are trickle down and then it will make the
beam colour reddish ok. This particular nature is always visible if you look around.
Now, coming to your house, sometimes if it is old house and if there is a problem of
seepage; You would see after little if you if you see a for a longer duration of time, the
corners or say where the seepage is more you would see that the cement is that particular
concrete structure as if it is swollen and you will see the peel off of that particular a
concrete pots. And after sometime you might find that the reinforce bar is also exposed.
And the, reinforce bar if you see carefully, it is a kind of a flect reinforce bar the
reinforce bar if you see in the raw condition you will find that it is nicely ripped a
reinforce bar with a little bit of red rust, but otherwise it is fine. But over the time inside
the concrete that red rust is forming and that red rust has got a higher volume than the
metal, so that means, that particular concrete reinforce rebar, which call reinforce bar the
rebar is confined in the concrete structure.
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So, when that corrosion is taking place in the rebar, it is getting swollen because of that
rust formation and rust has got higher volume it gives huge pressure on the concrete.
And since concrete has got a very very small elongation, so, at some point of time
concrete starts cracking and then it falls off. And in fact, that makes the structure
extremely vulnerable to failure; even it happens in bridges, old bridges you will find that
some places the rebar is exposed. Though it was initially confined in a concrete, but over
the time this concrete is getting spoiled off and then finally, the rebar is exposed. So,
those are kind of examples I am putting up.
So, these examples though you would not find that significant, but if we if we see some
of the data you will see that yes it is a significant and we need to see that how to stop
them. And in order to stop those we need to know how corrosion takes place. So, I when
we know the reason then we can attack some problem. So, let us see a kind of accidents
that can that have taken place due to corrosion.
So, these data I am I have put Aloha incident, Bhopal accident, Carlsbad pipeline
explosion all sort of examples I am putting. So, this you can also find out in this
particular website, it is basically called corrosion doctors dot org, there you can get the
history of this particular failures. There are other failures also, but here it is nicely
recorded.
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Now, in those cases the accidents many a times took life ok. Also if something breaks
something fails for example, a silver bridge 1967, it broke down and there are lot of
economy loss, life loss finally, the connection is lost and then again you have somebody
has to rebuild it so, those cost needs to be considered. And in fact, these particular
failures all of though cases the corrosion is one of the major causes major cause.
Now, if I see some of the pictures for example, this picture this is a kind of oil vessel
Erika, this failed due to corrosion. This is a major reason that this failed this broke into
half actually. Now this is the kind of failure I was talking about this is a silver bridge
silver bridge failure, and I think it is it happen in 1967. And again if you come to see this
part this particular situation, this is high temperature oxidation failure of aluminium steel
heater tubes.
Now, here also since steel heater tubes now, here also since it is mentioned as oxidation
later you will see that oxidation is also a kind of corrosion. So, this kind of failure I am
just giving an example for sake of understanding that yes it can lead to a serious
accident.
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Now, coming to cost ok we do see lot of losses. For example, the USA it is basically I
could find 1998 data, it says that the cost of corrosion means at the loss of money due to
direct as well as indirect loss. I will come to that direct as well as indirect loss 260 billion
dollar it is not a small money, it is 3.1 percent of GDP of that particular country.
Now, in India I have put two data, one is a this data which is 2012 data 2 lakh crore
rupees and this is in the form in rupees. Then in 2016 data this is a kind of a data what
we have the 6 lakh crore so; that means, 2012 to 2016, we have for the increase in loss of
money due to corrosion is of the order of around 300 percent it is a quite a bit actually.
Then it is also the 4 to 5 percent GDP of our country, which is almost 2 trillion dollar
economy. So, it is a quite up quite a bit of loss.
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Now, direct cost is basically US data infrastructure. Infrastructure when I am talking

about direct cost, this will be the failure of infrastructure bridge, buildings, utilities then
transportation of course, transportation railways. If you have noticed railways and also
you can find some of the pictures in the internet, that sometimes if you see the goods
train ok. In which vizag I will show later some of the pictures in vizag sometimes a one
picture I have I will show it later.
One goods train was stranded for almost 2 months there was waterfall. And that entire
boggie was full of with water and it was looking like a small swimming pool. So, now,
you imagine, if it stays for longer duration how much corrosion it can take place? And
then finally, what happens you have to throw that particular boggie and it is a loss of
money.
Then a production and manufacturing around 17.6 billion, government expenditure 20.1
billion, total around 137.9 billion. Indirect cost is a kind of cost of labour attributed
corrosion management activities. For example, let us say painting time to time we have
to paint the structures in the factory. So, for that you need to spend money on paint, you
need to spend money on the manpower because somebody is to be there, to paint that
particular structure.
Then cost of equipment required because the corrosion related activities ok. Of course,
corrosion related for example, there is one corrosion protection system which is called
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cathodic protection or anodic protection you need to monitor ok instruments that how
good is that particular corrosion protection. So, that also needs money.
Loss of revenue due to disruption in supply of product for example, the bridge is broken.
And once the bridge is broken then next at least 2-3 months the supply chain is broken.
So, it is also loss of money of course, the loss of cost of loss of reliability and it is not
mentioned here, there is nothing important other than life there will be life loss. So, this
is a kind of data what I am showing. So, we have to study corrosion.
Now, coming to as we have mentioned about all those losses, kind of accidents kind of
examples, what we have put for till now that there are corrosion incidents everywhere
every direction. Now, coming to material degradation, material degradation something
degrades and every structure everything what we have to do with the material.
Mechanisms of material degradation and the characteristics of the economically

significant forms of damage to the material are discussed in terms of the physically and
chemical process involved. Yes there will be physical features there will be chemical
process. For example, one particular example of physical features, let us say a kind of a
structure we have built. Now, if their for example, in a stormy areas, where we have lot
of storms. If there are sand particles and if that sand particles hits any structure it will
always erode it is not corrosion, but it erodes that is also a kind of loss of material is a
material degradation.
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Now, coming to railways ok, in the railways there is one form of loss of material is wear
because wear happens when two bodies are in contact, and due to friction some part of
the material is lost ok. So, there will be a thickness reduction and finally, you have to
discard that particular product particular material and you have to replace that material
with a new one.
So, by direct mechanical action of course, this wear; where you have kind of relative
action a between two bodies and which are in contact. Heat or radiation of course, heat
does play a major role. Radiation of course, for example, radiation damage one particular
radiation damage is in nuclear applications. Radiation does lead to a kind of a loss of a
material properties ok. We will come to that it can lead to a kind of void formation in
materials. By presence of chemical reagents yes there are chemical reactions there are
electro chemical reactions.
Now, we would concentrate on electrochemical reactions not chemical reactions of

course, when we talk about electrochemical reactions, we would also consider couple of
things. For example, if we try to see iron corrosion, and that iron corrosion you will see
that iron is corroding in the form of electrochemical reactions, but there could be other
aspects other reactions, which will be coming along with that electrochemical reactions.
So, our interest would be mainly in these particular sections.
Now, if we see all three by direct mechanical action, by heat or radiation, by presence of
chemical reagents, there could be combination of two or more or all three could be
present. For example, erosion corrosion, this is a classic example of combination of all
three; so, sometimes we for example, in heat exchanger. Heat exchanger the hot air is
being cooled by water. So, this water when it is flowing it takes the heat.
Now, when it flows, it could also lead to erosion on the pipeline and at the same time this
water also contains little bit of chemicals which can lead to chemical attack on the
surface in the form of chemical reaction or electrochemical reaction so, there will be
material loss. So, those kind of situation for example, mechanical action and chemical
reactions. Classic example is fritting action; in the fritting also we have mechanical
action as well as corrosion action.
So, this combination can also lead to material degradation fine. So, we would look at
more in a greater detail on this part electrochemical reactions or rather electro chemical
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degradation which is nothing, but corrosion. So, as we understand till now that, first of
all we need to study corrosion and when you need to study corrosion we have to also see
the features of corrosion, we also need to see the reasons of corrosion, we also need to
see how we can tackle corrosion. So, if we have all three combined then we can become
the successful corrosion engineer.
Thank you.
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Corrosion - Part I
Prof. Kallol Mondal
Lecture – 02
Introduction to Corrosion –II
Welcome back to lecture number 2. We would continue where we have left in our lecture
1. We have started talking about material degradation, and where we have seen that we
would look at the chemical or electrochemical route of material degradation where there
could be combination of mechanical action, as well as there could be combination of heat
or radiation.
Now, if we come to this slide if you see this slide, here it says that the material
degradation can be defined in terms of loss of performance of an engineering system. Of
course, loss of performance; it can be due to material loss, due to loss of colour, due to
loss of aesthetics, many aspects.
Now, loss of performance can be related to many other parameters, such as loss of
reflectivity in optical equipment due to fungal attack. This is also degradation and once it
happens then of course, we have to throw that for example, camera lenses.
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Loss of mechanical strength of a structural component exposed to corrosive medium.
This of course, we will attack this particular situation in our next series of lectures. Wear
can increase the clearance between piston ring and cylinder, hence incomplete
combustion of compression gas; this is also loss of performance. Now we would not look
at wear, but of course, the part of wear will be taken along with corrosion. In case of
erosion corrosion, we will take wear plus corrosion. Loss of efficiency of course, once
we have corrosion related damage, we do loose efficiency of that machine. Loss of
lifetime this is natural, once we have a degradation in the form of corrosion; that means,
a loss of materials then of course we have to replace that particular material prior to its
usual time duration. And of course, lastly extensive control component: this adds to the
cost of that particular corrosion.
Now, if we come to see the reasons or phenomena that can cause material degradation,
there could be anything which are available in environment. Because every time any
material we have to expose it to the environment for our purpose; like heat, light, short
wavelength, electromagnetic radiation, radioactive emission, chemical, mechanical stress
and interactions with bacteria, fungi or other life forms. So, all this factors they will be
the reasons for someway or other a material degradation. Hence, the classification of
material degradation according to its basic cause is it first step in any plan to protect a
specific material in a specific situation that is what we have been talking about.
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Now, coming to materials and environments interesting if I see materials, then first thing
what it comes to a material scientist is basically the material tetrahedron. And in the
material tetrahedron you will see for example; if i draw a material tetrahedron, this is a
kind of material tetrahedron we see where structure is one side then processing, then
performance and then properties. Now of course, when I talk about this material
tetrahedron in the structure we can also have one other more criteria, which is called
composition.
Now, for a particular composition the structure, properties, performances, processing all
are interrelated. So, this is a classic material tetrahedron. Now if I come to this particular
picture, this particular picture this material tetrahedron we have made some material for
performing some duties. For example, some cases we need to hold a particular load,
some cases we need to have a kind of a protection against a corrosion or we need to also
prepare material where wear can be protected, wear can be resisted all sort of things.
Now, if I consider materials this is coming under this. Alloying compositions it is

coming under compositions one particular field of material tetrahedron, microstructure
which is coming under structure again. Now the stress is basically a kind of factor, which
can come under processing or performance ok. So, processing sometimes we do use
rolling forging. So, you need to put stress performance means we do need to hold some
load, the stress part is coming up.
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Now, when this particular structure so that means, the structures is made out of this
particular material, alloying composition, microstructure, stress and with intended with
some properties, which will be needed for performing some details. Now this particular
material is exposed to the environment, and our environment is does have such things
which can degrade the material.
For example if i consider this part, this part, this section you see we have air and gas
environment, where temperature is a factor sorry for the spelling mistake. Temperature is
a factor, humidity which is nothing, but H2O content, PO2 of course, oxygen
concentration is there. Then of course, there could be another factor which is CO2. CO2
is also available. Now these kinds of gases and environments they have many a times
have negative effect on that material performance like atmospheric corrosion of iron
objects.
Now, coming to surface condition: yes, so I will come to that particular surface condition
little later, now coming to aqueous environment, many a times that particular material or
structure is either in the soil or in the water medium or in the chemicals so; that means,
that aqueous environment comes into play. And whenever we come to aqueous
environment we have temperature, we have of course, the H plus ion concentration or
OH minus ion concentration that time it will be called pOH. So, ph, pOH of course,
dissolve oxygen content chlorine ion. So, we have just given an example of chlorine ion
there could be halides. Other halides for example, fluoride all sort of halides they are
deadly towards the corrosion of metallic objects.
Now, flow velocity, this is also coming in the form of a kind of corrosion aspects you
might have heard of heard about cavitation. The cavitation is a serious kind of damage
happens due to a change in pressure in during operation of impellers, pumps all those
stuffs. So, their flow velocity also plays a role for example, a pipeline if the pipeline for
example, I am just giving an example, if a pipeline is like this pipeline is like this that
time if water is flowing like this and that water contains suspended particles this velocity
can create lot of force on this particular section. And then gradually this particular
section will get corroded in this corroded or eroded rather ok. Now this is a kind of
factor, which also leads to material degradation this is coming due to flow velocity.
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Conductivity of course, if something is placed in water and that water contains a very
little amount of conducting ions apart from of course, a little hydrogen ion on OH ion
that is present, because of the dissociation of H2O. Then that water the material would
corrode could to little less compared to the if that particular water contains little bit of
iron ion or chlorine ion there it will be a hugely corroded.
Now, coming to the soil, if we see the soil part there also moisture is important factor,
acidity is important factor, which is H plus ion concentration H plus ion concentration P
O2 partial pressure of oxygen even chlorine ion content there could be a possibility of
bacterial attack on the materials; so this surface condition. That means, now I am coming
to the surface condition, surface condition means if something is exposed to the gaseous
environment or air environment and below that if it is below the soil, within the soil or in
the water medium or any other chemicals liquid chemicals.
Now, coming to radiation this is also another factor, which can lead to problems on the
materials. So, this is a kind of a relation between materials and environments which is
not a kind of very friendly relations they are always trying to attack the materials.
Now, corrosion part.
So, if you see the corrosion before let us forget about corrosion for the time being, let us
say how do we get iron. The iron the first general we make it iron in blast furnace, in the
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blast furnace what you do? It’s a basically a reduction process, and in that reduction
process we reduce iron ore which is in the form of FeO, Fe3O4 or Fe2O3, these kind three
iron oxides are reduced by carbon that is what we always have iron containing iron
containing sorry containing carbon.
That carbon presents if it is below 2 percent or 1.8 percent we call it steel, and then
beyond 2 percent carbon of course, in weight percent it will be called as cast iron, but
this is coming from the production route which is blast furnace.
Now, there we refine this reduction and then after reduction we send it to another plant
which is called steel making plant where actually we do oxidation, because once we form
iron from blast furnace its generally called pig iron. That pig iron contains many
impurities and those impurities are to be taken care of or removed by oxidation. That
means, by oxidizing those particular impurities, we take we remove them from the metal
and then we get steel which contains low carbon. And then that steel is taken to a milling
process means either rolling mill or forged products will they get lot of iron objects.
Now, that those iron objects are exposed to environment in the form of structures, in the
form of utensils in the form of many other applications. And then we see that gradually
that iron is again turning into red rust and interestingly the red rust are nothing, but this
three oxides mainly these oxides Fe2O3.
So, what happening? It is basically coming from rust and then again we are turning to
rust. So, it is a natural process, we cannot stop corrosion because this rust formation; that
means, when the reaction happens with air moisture and oxygen then the rust forms, and
these process is thermodynamically a feasible process. In fact, this process we need to
spend lot of energy because thermodynamically this is stable phase. So, in order to get
iron from iron oxide we need to spend energy, we need to reduce we need to have lot of
other factors but from this to this is a natural process.
So, the corrosion is a natural process. So, natural process cannot be stopped it will
happen. So, what we can do? We can control it. So, when we control what do you mean
by control we mean control? That means, we can prevent corrosion, rather we can reduce
corrosion to a great extent. So, that is the essence of studying corrosion. So, we have to
reduce or we have to control corrosion, stopping corrosion is out of question.
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Now, coming to definition there are two definitions: one is practical definition. If we see
the practical definition the tendency of a metal to revert to its natural state, which relates
to if you see the previous slide. So, we are taking iron from iron oxide, now we are
reverting iron to iron oxide. So, the second process is natural process, the first process is
energy consuming process. So, this loss of and of course, when you do that when you
have this of course, there will be loss of mass and loss of money.
So, this is a practicality in it the tendency of a metal to revert to its native state. Native
state means what? Iron oxide or iron ions those are native states. Scientific definition yes
when you talk about scientific definition we have utter this word in some cases,
electrochemical degradation of metal as a result of reaction with its environment.
Now here interestingly, we are using electrochemical, we are not using chemical.
Remember that whenever we talk about corrosion related corrosion kind of degradation
corrosion is of course, a degradation wear is of course a degradation, but when we talk
about corrosion that time we must consider that the metal is reacting with its
environment electrochemically. That means, there is a formation of metal ions. So, metal
from metallic from atom it will go into the ions that is the scientific definition of
corrosion.
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Now, coming to definition of corrosion still continue, the destructive attack on a metal
by electrochemical reaction with its environment as we have mentioned. Corrosion
returns the metal to its oxidized state or combined state in chemical compounds, that are
similar or even identical to the materials from which the metals are extracted. So, in this
particular definition, we are combining both practicality as well as the scientific part of
it. The first part which is the attack on a metal by electrochemical reaction, with its
environment is the scientific part and the second part is basically the corrosion returns
the metal to its native condition. So, this actually combines both.
Now, since we have started talking about electrochemical reaction, gradually we will see
that we will getting into the electrochemistry.
So, now let us see this aqueous corrosion of zinc in HCl which is a dilute HCl.
20
Now I would go to let us get to the aspect of zinc corrosion let us say we start with this
particular thing, zinc corrosion in dilute HCl. Now if we have a kind of container and in
that container if we put a bar of zinc, bar of zinc this is zinc and we have HCl here, this is
dilute.
And once we put in zinc you will see that there are bubbles formation on the zinc
surface. So, those bubbles are coming out and there will be vigorous bubble formation.
And if we take this particular bubble for example, you encapsulate this particular section
and then take this bubble. And then finally, you burn a matchstick, you will see that it
gets burnt. So now, this particular gas which is coming out this gas is nothing, but H2
gas.
Now, if we see the reaction, the reaction is zinc plus HCl equal to zinc Cl2 plus H2 and if
we balance it this is the balanced one.
Now we wonder that where this electrochemistry taking place. That means, we have said
that electrochemical reaction might happen because zinc is this in metal condition
metallic condition. And now it is going in the form of zinc chloride and this zinc chloride
is actually zinc is dissolving in the form of zinc chloride, and zinc chloride will dissolve
in that particular solution and hydrogen gas is coming out.
21
But if we break this particular reaction into 2 parts, you would definitely see that yes
there are electrochemical reactions. Now if I look at zinc, now if we take 2 electron out
of zinc it goes to zinc 2 plus ions.
And now since this 2 electron is coming out from zinc atom, this 2 electrons need to be
taken up because charge cannot remain unbalanced. So, now, there are HCl in that HCl
you have H plus plus Cl minus if we dissociative HCl. So, these H plus will take up one
electron and form H, and if we consider 2H plus ion. So, it is plus H it is forming H2. So,
2 atomic hydrogen will combine each other and then from H2 gas.
Now, if I see this reaction this reaction is nothing, but anodic reaction or we call it
oxidation reaction. And this reaction we call it cathodic reaction and or reduction
reaction.
Now, whenever there is anodic reaction or oxidation reaction it talks about material
degradation so; that means, zinc atom is going into solution so; that means, this zinc rod
is gradually losing zinc. So, it is a degradation and this degradation is happening because
of this electrochemical reaction, because this reaction is electrochemical reaction. And
these 2 electrons which have been released by zinc they are taken up by 2 hydrogen atom
and forming hydrogen gas. So now, you see in this entire reaction we have 2
electrochemical reactions taking place, one is anodic another one is cathodic.
Now, question is these 2 electrons how would it move to the side of cathodic reaction.
Electron must flow through a conductor. So, it is flowing. So, for example, let us say the
small segment if I zoom it. So, this is the zoom part of this, and this side zinc plus plus
ion is forming.
So, the 2 electron this is the metal side and this is the solution side, 2 electron is released
to the metal. And now here let us say hydrogen is taking up electron and forming
hydrogen gas. So, these 2 electrons is flowing through this conductor, and in this
electrolyte which is also called solution we call it electrolyte. There zinc ion and there
are chlorine ion, there if combining and forming zinc chloride.
22
So, now in order to have this entire reaction we have four components; what are those
four components? One component is anodic reaction where anodic reaction happens we
call it anode, where cathodic reaction happens we call it cathode. So, these are 2
components this is second component then where the electron transfer is taking place, we
call it conductor, and of course there is one more component which is electrolyte. For
example, if there is no electrolyte these reactions cannot take place. So, this electrolyte is
this is third component, and this is fourth component.
So, now for this particular zinc corrosion through this electrochemical reactions, we must
satisfy this condition that there must be four parts, one part is anode, second part is
cathode, these two are forming electrodes and then one part is third part is conductor and
fourth part is electrolyte. So, this all four must be there.
Like that if I see the iron part now, iron corrosion, there iron of course, if it needs to
corrode it has to form ions. So now, how can it form ions? It can lose 2 electrons and
then go to plus 2 or 2 plus as we are putting this convention 2 plus.
So, this particular ion would then react with H2O and oxygen. So, now, then this will
form Fe(OH)2 and if we try to write the complete reaction then it becomes 2Fe(OH)2.
23
Now question is this anodic reaction is of course there now where is cathodic reaction
taking place we need to know that. And for that we need to also consider one more
cathodic reaction is O2 plus 2H2O plus 4e equal to 4OH minus.
So, this is anode or anodic reaction, this is cathodic reaction or cathode electrolyte is
nothing but this moisture becomes electrolyte these happens when a metal object iron
object is exposed to environment this H2O becomes electrolyte.
Now, question is this is cathodic reaction of course, the electron where it flows that
electron flow would happen; these happens on the anode these happens on the cathode
and electron flows through the iron object ok. That becomes conductor and this becomes
electrolyte.
Now, in the previous case also, we could see that zinc itself act is acting as cathode as
well as anode because the cathodic as well as anodic reactions are taking place on zinc
surface. Here also the anodic surface as well as cathodic surface, iron is behaving in the
same pattern if iron becomes cathode as well as anode. Now question is we will not be
able to tell specifically this part is cathode and this part is anode, because in the
beginning it will be all statistically distributed reactions. That means, cathode where only
we can say where the cathodic reactions happens, anode where the anodic reactions
happens.
So, but if I try to see the formation of this, it also follows the same route; that means,
electrochemistry. And iron is dissolving by forming iron ion, and there is a cathodic
reaction which is oxygen reduction this oxygen is reducing and of course, cathodic
reaction is nothing, but the reduction and in case of zinc zinc ion is forming anodic
reaction, and hydrogen ion is getting reduced and forming hydrogen. So, that becomes
my entire situation for iron corrosion as well as zinc corrosion we follow electrochemical
roots.
We would continue with these particular aspects that cathode anode electrode as well as
conductor and electrolyte this is the essence of or the backbone of corrosion subject.
Now before we end this lecture 2, I would like to just tell you that of course, corrosion is
deadly, but some cases corrosion of course, helps. Now let us give some examples you
24
would be surprised to see that some of the cases yes, the corrosion actually helps one
classic example is let us come to this battery.
Now, in the battery we of course, have corrosive reactions. Now carbon rod which is
acting as cathode zinc case casing is acting as anode. And then because zinc case is
corroding it is releasing electron and that electron is flowing through this particular
electro external circuit external conductor and that is what we are getting a glowing light.
So, battery is designed on the basis of corrosion because zinc is corroding that is what we
are getting electrons and that is available for glowing lights.
25
Now this is another example the microstructures which is the bread and butter of
material scientist, because this microstructures are needed to correlate property and
structures.
Now, another example is porous silver, there are porous gold which are very good
catalyst they are they are formed by dealloying. For example, zinc silver or gold silver if
we formalize then specifically, and then we can take out silver. In case of gold silver or
26
in we can take out zinc in case of silver zinc alloy, and then form porous network like
this.
And finally, I come to this example, which is called galvanic zinc application.
Galvanization is a popular method where we protect iron structures, this also is the
corrosion is the basis of galvanic corrosion galvanic galvanization or galvanic zinc
application. Zinc corrodes and zinc becomes my sacrificial anode and then iron is
protected iron becomes my cathode.
27
So, at the end let me end this lecture by saying our aim is to understand thermodynamics
and kinetics of corrosion, different forms and reasons of corrosion. And of course,
finally, we would look at protection and preventive mechanisms for corrosion. Thank
you very much let us stop today.
Thank you.
28
Corrosion - Part I
Prof. Kallol Mondal
Lecture – 03
Types and Forms of Corrosion
Hello everyone. Let us start our third lecture. As we have discussed in our first two
lectures on importance of studying corrosion, we have also given some examples, some
of the catastrophe, we have also mentioned. And finally, as we go ahead and then we
have seen that corrosion involves four parts and it also is directly associated with
electrochemistry. And the four parts are two electrodes which is; one is cathode, one is
anode. We have electrolyte, where ions will be flowing; and then we have conductor
where electron will be flowing. And then, we have a complete circuit and then corrosion
will go on. So, a corrosion is electrochemical in nature, that is what we have understood.
And we have also given two examples; one is zinc corrosion in dilute acid where on the
zinc plate, you have hydrogen bubble and this hydrogen bubble is forming due to
cathodic reaction which is hydrogen plus ion takes one electron and it converts to
hydrogen atom and then finally, two atoms joined together and forms hydrogen gas. And
that reaction happens on zinc surface itself. And this particular electron is coming from
formation of ions, formation of ions of zinc which goes into solution from the metal part
and that electron will be released into the metal and then metal acts as a conductor and
that electron comes to the place where hydrogen evolution reaction happens. So, that
way the complete circuit is, the circuit is complete and this zinc actually finally forms
zinc chloride because already you have chloride in that particular HCl medium and that
way zinc corrosion goes on.
We have also give an example of iron corrosion in atmosphere and if I go back and try to
see that particular slide
29
If you see that iron is actually going to iron plus 2 ion electrons are released and these
electrons are taken by cathodic reaction which is oxygen plus 2H2O plus 4e equal to
4OH minus. And here, we have seen that this particular ion reacts with this H2O plus O2
and goes to FeOH whole two. In fact, this particular reaction is anodic reaction and this
particular reaction is cathodic reaction which happens on the iron surface itself.
Now, this iron plus 2 reacts with OH minus and forms FeOH whole 2 which is same as
this reaction. Finally, this reaction is parallely taking place. This is also electrochemical
because this is anodic reaction, this is cathodic reaction. This anodic reaction happens on
the iron surface iron corrodes and cathodic reaction also happens on the iron surface
which takes care of that electron which are released by iron while formation of ions. This
is also electrochemistry.
Now, we will get to the thermodynamics of these reactions as well as how we can
explain this formation of ions at different levels of pH. And, we would basically consider
aqueous corrosion. Now, since I have mentioned aqueous corrosion, this corrosion can
be divided into two parts; one is wet corrosion and another one is dry corrosion. Now,
you must be wondering what is dry corrosion if we recall that we have mentioned that
oxidation is also a corrosion process. Now, whenever we talk about corrosion process,
we have to take, we have to see that whether this four parts of electrode that particular
cell corrosion cell is are being satisfied.
30
Now, let us get to as we have mentioned that corrosion can be wet and dry, wet and dry
corrosion. Now, in the wet corrosion, we see that where H2O is involved. We also call it
aqueous corrosion. And in case of dry corrosion, we are mentioning that oxidation,
oxidation of metal we are mentioning that this is also a corrosion. That means, it is also
electrochemical, aqueous corrosion from those two examples, it is very clear, it involves
oxygen, it involves water because in one case we are dipping zinc metal into dilute HCl
solution which is aqueous solution of HCl. And in second case, we are seeing that
corrosion of iron object in the environment in the atmosphere where we have moisture
which is again water; of course, there oxygen is also involved.
But in case of dry corrosion, let us just have a look at what happens at the interface of
metal when oxygen is involved because anyhow I am talking about oxidation of metal. If
we consider this particular reaction, O2 equal to half O2 MO, if I consider this oxidation
reaction, let us have a look at what happens at the interface.
This is metal surface. Let us say some oxide has formed, MO and then this is gas
medium. Now, in the beginning there was if we consider that there was nothing. So,
metal surface we are having M going to taking leaving two electron and then forming M
plus 2.
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And if I consider oxygen, half oxygen; that means, one oxygen atom, it takes care two
electron and forming O2 minus.
Since we are having this, this notation 2 plus and 2 minus, and if they combine, you see
M plus half O2 equal to M plus 2 O sorry M2 minus 2 plus 2 minus. This is nothing but
MO which is same as this reaction.
Now, interesting, let us look at carefully this. What is this reaction? This reaction is
nothing but anodic reaction, because it the metal atom is leaving two electrons, is
basically oxidation is taking place. In the sense that if we consider oxidation to be
electron when metal leaves electron, we call it oxidation. Now, if I consider this reaction,
this reaction is nothing but a reduction reaction, reduction or cathodic reaction and this is
oxidation reaction.
Now, question is two reactions are done; now since in the beginning we have only metal
surface, we have oxygen and then metal. So, if this place we have metal plus 2
formations, so two electrons are released here in the metal. So, these two electrons are
flowing through that conductor and here, half oxygen takes care two electron and
forming O2 minus, this is 2 minus. So, these two are reacting.
Now, you see this part acts as anode. So, one electrode this part act as cathode; second
electrode, this is conductor and here when this two reactions are this two reaction, this
half cell reaction, these are called half cell reactions, this half cell reactions are taking
place finally, metal 2 plus and oxygen 2 minus they are combining and forming metal
oxide. So, this metal oxide is forming on top of this metal surface. So, now, we have
situation like this. So, here metal surface, metal oxide and oxygen.
Now, once we have this, now question is whether this reaction would continue or not.
Now, still if I consider metal ion is forming. So, two electrons are here and these
electrons can go somewhere around this metal object because every metal part is
basically acting as conductor. And now this electron can flow through this because metal
oxide either it could be n type or p type. If it is n type, then this electron can flow
32
through this through the electronic area and then here can form 2 minus. Now, this ion
can also move like this. Now, when it moves like this, it comes here and then combine
with this and form metal oxide.
Now, if metal ion is moving on the outer side and there this particular thing can combine
and form metal oxide. Now interestingly, charge flow is taking place through this; for
example, here oxygen 2 minus is flowing or here metal 2 minus is flowing through this.
So, charge flow is taking through this MO. So now, MO becomes my electrolyte.
And in case where oxygen ion goes through the metal oxide and reaches to the metal
surface and at the interface of metal and metal oxide forms further oxide molecules are
forming, that case the oxide growth is taking place on the metal-metal oxide surface. So,
on the surface metal oxide growth is taking place. Now, in case metal ion is moving out
from the metal, metal oxide interface and coming to the metal oxide oxygen interface
and there it combines with the oxygen ion. Then the oxide growth is taking place on the
surface of or at the interface of metal oxide and gaseous oxygen.
So, here also you are seeing that the condition of corrosion cell is satisfying; that means,
we have cathode we have anode and in this case since this cathodic reaction is taking
place at this surface at this interface, this becomes my cathode and this particular
reaction is taking place at metal-metal oxide interface. This becomes my anode. An
electron flow is taking place through the metal surface or it can flow through the metal
oxide. So, metal oxide itself is acting as electrode, acting as a conductor as well as
electrolyte, because it also allows charge flow in the form of metal ion or oxygen ion. So,
this is also electrochemical reactions and here metal is oxidising. So, metal is losing in
the form of oxide, this is also corrosion.
So, but here we do not have moisture. So that means it is a dry corrosion. So, that is what
we have come to the condition of dry corrosion where we have oxidation. If we have
time, then we would definitely look into oxidation of metal little depth, but our primary
interest would be on this aqueous corrosion, primary interest. So, we will concentrate
more on this in our present set of lectures.
Now, before we go detail analysis that means, when I talk about analysis, we talk about
thermodynamics and kinetics of this electrochemical reactions either metal ion formation
or cathodic reactions where electron is being accepted by some species. It can be ion, it
33
can be metal again another metal or it can be another it can be oxygen. So, all those cases
we would try to see their thermodynamics and kinetics.
But for the time being, we would again go back and try to see some of the forms of
corrosion.
So, next topic is forms of corrosion.
For understanding these forms of corrosion I think near observation as well as a little bit
of the idea what we have already learnt from this two and half lectures you can say; that
means, that there would be electrochemical reaction; one is cathode, one is anode, one
would be anodic reaction, one would be cathodic reactions. On that basis, we would be
able to understand some of the forms means the kind of appearance I would say. So, let
us look at some of the appearances and then accordingly we would define the forms of
corrosion.
Now, when we come to the forms of corrosion, if we have a kind of observation rather
careful observation; one form is Uniform corrosion, second form Galvanic corrosion,
third Crevice, fourth Pitting, fifth Dealloying. We also call it in case of a dealloying or in
case of iron brass let us say we call it Dezincification like that then we have
intergranular, seventh Erosion corrosion where we have two special forms I would say
two special forms one is Fretting, another one is Cavitation. And finally, we have Stress
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assisted corrosion where we have three segments; one is stress corrosion, then Corrosion
fatigue and another one is Hydrogen embrittlement. And in case of hydrogen
embrittlement, we have few other forms; for example, hydrogen blistering is one form.
And this particular definition of this definitions of different forms are basically arriving
from the appearance like let us when for example, if we consider uniform corrosion as
we mean by uniform means it is homogeneous uniformly happening like one example let
me put up. If we see iron made sheet cover over a roof, one can find that after sometime
you will have a red rust formation over the entire surface. And if it is carefully looked at
add a little, carefully looked at the interface you would see that at different sections, we
would have almost about similar depth of attack. I would say depth of attack means the
corrosion is gradually progressing towards the depth direction of the metal surface. So, at
every sections, we would have almost about similar a depth of attack. So, that time we
call it uniform corrosion. So, it is a form; it is a appear, it is basically a appearance of
that particular mode.
Now, for example, pitting corrosion; when we talk about pitting corrosion, we know this
particular name pitting for example, on a surface as if from the appearance you would
see that there is no problem, because it is as shiny as it was obtained in the as received
condition when it was obtained first.
But the pitting can be extremely localized and again if we carefully look at and analyze,
we would see that at some positions the depth of attack is extremely localized. And it has
gone very far towards the depth direction of that metal surface, but rest of the surface
looks absolutely fine.
Similarly, crevice this is also appearance. For example, let us say crevice means
wherever we have a small opening in the metal structures or metal bodies and in that
small opening that opening should be enough. So, that it can allow solution to go in, but
the solution would remain stagnant into that particular metal opening. So, that case that
would create a kind of corrosion localized corrosion, rest of the surface would look
shiny, but in that localized portion, you will have red rust in case of iron I would if I
consider iron surface again appearance.
Now, dealloying interestingly, if we have a brass 70-30; 70 percent copper and 30

percent zinc and that brass if you dip it in HCl, dilute HCl solution after sometime we
35
would see that the colour generally in the beginning the colour of the brass is little
golden yellow. And then when you expose it to the acid after sometime you would say
the surface is becoming a bit a red coloured. And if we analyze it that for example, the
analysis tool is for example, SEM-EDS, if we do then we would see that the copper
content has gone up from 70 percent to even close to around 90 to 93 percent. So, now,
at the surface that means, copper is enriching and if we look at that copper surface under
the microscope, you would see that the copper surface is porous in nature.
So now here zinc where is then zinc because in the beginning it was 30 percent zinc. So
now, zinc contain has gone down to 1 or 2 percent in that particular copper enriched
region. So, the zinc has gone out in the solution and copper has been left out and that
forms a particular mode of corrosion which is called dealloying. Since, zinc is going out
that is what we call it dezincification. So like that, so those are basically appearance.
Now, if we try to analyze some of those all though of those variations, then we would
also see some interesting part that all those variations we will see that they are decided
by some factors. Generally, if we those factors we will categorise into a five major
sections; one is materials definitely material and when I talk about material that means, if
I consider this particular forms on a particular material, then material composition is
fixed. So, that time we talk about microstructures that time we talk about microstructure,
since we are fixing the composition.
Now, then we have environment, this environment is a very big thing and in nutshell we
can say that when we talk about aqueous corrosion, environment the influence could be
from oxygen, from moisture content, from SO2 content or there could be possibility of
presence of some metal ions; for example, Fe3 plus ion if somewhere it is there, this Fe3
plus is not good, because Fe3 plus allows a greater corrosion to happen in case of for
example, in we have given this example zinc dipped in dilute HCl, if we have little bit of
impurity FeCl3. That means, Fe plus 3 ion is there, so the corrosion rate of zinc would be
much higher than in the solution where FeCl3 is not there. So, thus metal ions.
Then of course, the other factors like temperature, those factors will come into picture.
Then we have of course, stress, stress is important when we talk about stress assisted
corrosion. One particular example we have put forth that is a silver bridge crumbling of
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silver bridge that people said that the reason behind that crumbling of silver bridge was a
stress corrosion and corrosion fatigue.
Then, we have this is 1, this is 2, 3 then of course, we have design factor makes a huge
impact. For example, if a smooth surface and rough surface smooth surface of course, it
will have a less corrosion effect then the rough surface, in general.
Finally, fifth it is a time. Of course, if something is exposed for longer duration of

course, there will be corrosion would be more. So, these five major factors are crucial.
So, in my next lecture, I would talk about this eight forms of corrosion in nutshell we
will not go greater depth into it into this particular corrosion mode, because that is not
our purpose our purpose is to understand the fundamentals of corrosion.
And then of course, on the way we will see that the effect of this five factors. Let us stop,
we will continue in our next lecture.
Thank you.
37
Corrosion - Part I
Prof. Kallol Mondal
Lecture – 04
Uniform and Galvanic Corrosion
Hello everyone. Let us start lecture 4. As we have seen from this particular slide, the
slide
We have discussed in our third lecture, forms of corrosion and we have said that it
basically based on the appearance of corrosion. So, we will just briefly discuss on these
eight forms and at the same time we would also discuss associated factors like
composition, metals, materials, microstructure, then environment. Of course, there will
be stress, design, design of components, and finally we have time, the time of exposure.
Now, when you talk about uniform corrosion, uniform corrosion
38
One example we have already discussed is basically the corrosion what we notice on the
steel sheet roof, we call it corrugated roof that roof if we notice that the corrosion is
uniform. For example, if this is my section the steel roof. And there if we call it uniform
that means, the depth of corrosion is more or less uniform. So, this is my depth of
corrosion is basically uniform throughout the cross section.
And this form of corrosion is in the sense good because we will see later that as well as
we have noticed that a corrosion cannot be stopped. It can be controlled of course, it can
be minimised, but we can never stop it because thermodynamically, corrosion is
thermodynamically more probable feasible possibility. That is what we always get metal
from metal ores. And then finally, we again return to metal ores due to corrosion. So,
when we have this uniform mode of corrosion, as we have mentioned that the see this is
good, because we do not have a preferential attack at any position. When we talk about
crevice and pitting you would see that, why this preferential attack is not good to the
structural integrity.
Now, if we have this, then we know that how long it would perform. Let us say we
would like to have we know that the rate of this corrosion is x, if we know that rate of
corrosion is x. Now if we want to work this particular structure for 10 years we can
calculate what should be the thickness so that I can operate safely and considering this
39
factor x thickness. So, we know that every year I have x amount of material loss and so, I
can easily calculate what should be the total loss after 10 years.
And also in this case the protection is also easy because in this case we can simply put
paints or a kind of organic coatings, it will work. And in this case, also the material
choice would be cheaper for example, mild steel would be much better low carbon steel
would be much better compared to the stainless steel, because if we want to protect it for
a longer duration. Let us say somebody chooses stainless steel then we are getting into
more and deadliest situations, because stainless steel has got a tendency of pitting or
localised attack.
Now, also we can also have a kind of protection method called cathodic protection. So,
in this uniform mode of corrosion, we have simple protection route, we have the material
requirement is not that exotic. We can work with the low grade steel; low grade steel
mean I mean to say that mild steel which is a very well commercially available cheaper
steel. But if we consider other forms of corrosion, so what we say that protection route
coating, then we can have painting, we can have cathodic protection, all those
possibilities are there and the main advantage is we can easily calculate life.
Let us come to some of those forms which show, which show localised attack; if I come
to galvanized, galvanic corrosion, in case of galvanic corrosion why this galvanic term
comes up. Let us say, we have metal 1 and metal 2, and if we individually we dip them
dip those particular metal pieces in acid dilute HCl solution let us say.
Then, both of them will corrode heavily, but once we connect them rather we weld them
let us say electrically we connect them. Then interestingly one metal does not corrode
much rather corrosion is minimized to a great extent, but the other metal corrodes
heavily and these happens when we have a joining between two metal parts and that time
one metal is poorer another metal is superior. This poorer and superior term is coming
from the point of activity in that particular solution. And when I talk about activity, we
talk about electrode potential and that time we one which will corrode heavily in the
joined condition, we call it anode or active part another part which will get less corrosion
because of this joining we call it cathodic or noble part.
Let us have an example, example is let us say iron and zinc. And when we have iron and
zinc, individually if we dip these pieces in dilute HCl solution, we would see that the
40
corrosion rate somewhat iron corrosion rate sometime it is more than zinc in HCl dilute
HCl solution. But if we connect them, let us say iron and zinc is connected and then if
we dip it, then we will see that the zinc part is corroding more and iron part is corroding
less. So, this section this section of zinc is getting corroded. This section of zinc is
corroded. So, this happens whenever this happens, we call this galvanic corrosion
galvanic corrosion. And since this is due to the connection of or joining of two different
metals, we also call it two metal corrosion.
Now, in this case, zinc is corroding that is what this becomes my Anode and, we also call
it Active and this one we call it Cathode, we call it Noble. Such example is amply
available in every corners of our day to day use. We will show some of those examples
later, we will talk about mix potential theory. For the time being, let us understand few
issues with this galvanic corrosion. This is very very important mode of corrosion.
Now, if we try to see this situation, this situation is also possible if we leave this
particular joining in atmosphere. There also zinc part corrodes more and then the iron. In
fact, iron gets protected due to the corrosion of zinc and we call it galvanic protection of
iron and that is what the great example of galvanic protection is zinc coating on iron
surface. So, zinc sacrifices itself, by corroding itself, by corroding and protects iron. So,
that is what we also call it sacrificial protection due to the sacrificial effect of zinc on
iron surface.
Now, here interestingly since we have talked about electrochemical reactions, there must
be cathodic and anodic reactions. Now, whenever we talk about cathode and anode; that
means, on the anode surface, anodic reaction should take place and cathode surface,
cathodic reaction would take place. Now, the question is whether cathodic surface we
have iron reduction, iron ion reduction. That is a crucial, crucial question. For example,
on the surface it is very clear that anodic reaction that means, zinc would release two
electron and form zinc plus plus ion.
Now, question is whether here we have iron plus plus plus 2e, it will form iron.
41
So, now, my question is this is right all the time, this would happen because if zinc has to
act as anode, but here do you think that we would have this reaction?
Now, let us analyze it.
Whenever we have this particular situation, let us say iron and zinc and we have water
pool let us say, this is a water pool or water droplet kind of thing. Now, when water
droplet falls on this particular joining, that droplet does not contained iron ions. So,
where would we get iron ions? So, the cathodic reaction is something different. It acts as
cathode, but the cathodic reaction here in the atmosphere, we have it a mildly acidic
generally, generally we consider to be neutral. And there the reaction, the cathodic
reaction that happens on the iron surface is oxygen plus H2O plus 4e equal to 4OH
minus.
Now, zinc corrodes in the form of zinc plus plus and then for this two electron, these two
electron will flow and it will come here.
So, in this particular metal object, this reaction happens on this surface and electron will
go like this, electron will go like this. And this two will react and form zinc hydroxide.
42
So, that way reaction is taking place. So, the cathode does not mean that that cathodic
reaction of that particular metal ion, cathode means where cathodic reaction takes place
and the cathodic reaction will be decided by the condition at this interface or the
environmental species what we have there.
For example, in acidic medium the cathodic reaction would be H plus. This happens in
HCl solution and interestingly, in the HCl solution, this reaction can happen if we have
Dearated solution. Dearated means, the dissolved oxygen content is very small. So, then
we have this reaction. So, that time cathodic reaction is this, but still it happens on the
iron surface. So, iron surface acts as cathode. So, remember, cathode indicates cathodic
reactions on that particular surface. Let us put for, write it down cathode, cathodic
reaction take place and anode of course, anodic reaction.
Now, interesting part is in this case, cathodic reaction could be hydrogen evolution,
could be oxygen reduction and could be metal ion reduction also but if some metal ion is
already present. Now, classic example let us say, we have in a solution, let us say I have
a zinc block and that case if it is containing HCl, that time the reaction cathodic and
anodic reaction would be H2.
These are the two cathodic and anodic reactions. But, if by chance if we have impurity
like FeCl3, then this there could be one more cathodic reaction that one more than
cathodic reaction is plus 3 plus e equal to Fe plus 2.
Now interestingly, we have to see in a corrosion cell that the total number of electrons
released and total number of electrons accepted, they should cancel out because charge
cannot stay individually they have to be balanced and on that basis the mixed potential
theory will be derived or will be established.
Now, if we see that when we do not have FeCl3, then we have one cathodic reaction, one
anodic reaction. But once we have FeCl3, we have two cathodic reactions and one anodic
reaction; so that case the corrosion rate of zinc would increase because these particular
43
anodic reactions need to take place more to supply more electrons for the requirement of
these two cathodic reactions.
So, here I am just giving example that metal ion can also reduce provided that particular
solution contains metal ions. For example, this particular system is if it is dipped in HCl
solution where we have little bit of FeCl3 contamination, then this reaction also can take
place and of course, zinc dissolution would increase in that couple.
So, this is a galvanic corrosion and in the galvanic corrosion, there are factors. Of course,
one factory is, important factor is distance effect.
Distance effect, let us say I have this couple and in that couple, if this is metal 2, this is
metal 1 and if metal 2 is active and metal 1 is noble. That time, the corrosion of metal 2
would take place preferentially, but the corrosion would be more at the interface rather
than away from this a joint interface. Because as we have a more and more distance from
this joint phase where the galvanic couple is joined couple that couple is formed, you
have more resistance for the electron flow as well as charge flow. That is the reason that
is where the corrosion rate reduces as we go away from the joint interface.
Now, in this regard, as we have mentioned that active and noble, this factor would come,
this will be pronounced if we have a polarity change. This is another factor. The polarity
change is serious. Sometimes, though we design the couple for galvanic protection of a
44
metal, if we do not look at seriously at what happens with the change in condition.
Sometimes the metal part which is active and which gives a sacrificial effect to protect
the other metal part, if polarity changes, the metal part which we want to protect would
corrode more than expected. So, how does it happen? And in order to know that, we have
to know another important factor, another important issue which is called Galvanic
series.
Galvanic series is a kind of we will talk more about this galvanic series, we will talk
when we talk about electrochemical series. This galvanic series is designed on the basis
of the current flow. Now, if we have a metal object M 1, if we have a metal object M 2
and if we connect them and then put up this one in electrolyte, a particular electrolyte let
us say a HCl solution, then we simply notice which way current is flowing in the external
circuit. In the external circuit, if current flows this way; that means, this is current flow
that means, electron is flowing this way. So then, this particular component becomes
active component and this particular component becomes noble components. And that
time, this one will be protected and this one will corrode. So that means, in the galvanic
series if I try to put them in a kind of sequence, then if I put the noble one at the top and
the active one at the bottom like this, I can put them in a series.
Similarly, I have M 2, M 3. Let us say this becomes my M 3 component and M 3 can

have a couple between these two or it can have couple between this two. Now, if M 3
lies and then of course, you will have a voltage difference also because whenever we
have this there will be voltage difference.
Now, this voltage if it is more that means, they are widely apart in that series and if this
voltage del V is less in that couple, they are closely placed. For example, if we have M 1,
M 2, then M 1, M 3 and then another couple we can have M 2, M 3. So, we need to see
the voltage difference between these two in that particular solution. This voltage is del
V12; this is del V13, this is del V23.
Now, if we see that del V12 is greater than del V13; sorry let us say del V13 is greater than
del V12. Then, this two would be lying close to this M 1. So, the series becomes like this
M 1, M 2, M 3. So, now, that time if I connect these two or if I connect this two, galvanic
effect will be more in case of M 1, M 3 rather than M 1, M 2. So, if I have a connection
between M 1 and M 3, M 1 would be better protected, because M 3 would corrode more.
45
And if I have this couple M 1 and M 2, the protection mode would be little less than M 1
and M 3. But in both cases M 1 and M 2 as well as M 3 individually, they will corrode.
So, like that so, if I have to design a better protection system for galvanic protection, I
would always try to choose M 1 and M 3 rather than M 1 and M 2.
Now, question is sometimes in order to design a component, we have to choose different

metal combinations, that time we have to be careful. So, that time we have to choose
those different metals in such a fashion that in that series, they should be closely spaced;
means for example, I can have a kind of component design where M 1 and M 2 would be
better because that time the galvanic effect is less. For protection of M 1, I should choose
go for M 3, but making a better ragged deign for a component that time I should where
the corrosion should be less for both the components that time I should go for M 1 and M
2 because. In fact, many times we should we will not be able to make the same that
component entire component with the same material like nuts and bolts.
In the nuts and bolts, the primary design criteria is the bolt should be stronger than this
nut, sorry the nut should be stronger than the metal parts which are being joined. For
example, if I have a metal joined this plate and another plate, this three plates are joined
or the fastened I would say fastened by a bolt nuts and bolts, this is a bolt and this is
become my this becomes my nut. So, that time this should be this material should be
stronger than the parts to be fastened. So, that time we should choose material, so that in
that galvanic series they are closely spaced.
Now, once we discuss this. Now we would understand the polarity change.
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Let us talk about zinc and iron. In case of zinc and iron, if the temperature goes beyond
60 degree Celsius that time on the zinc surface, there could be a formation of zinc oxide
and once there is a formation of zinc oxide, it becomes a deadly combination. Why
because in the beginning, in the galvanic series in that particular temperature and
solution that particular couple is exposed to, iron is on top, zinc is at bottom so; that
means, zinc is active and iron is noble. But once zinc oxide forms, zinc oxide has got
position which is above iron and ones that zinc oxide forms, zinc oxide becomes noble
part and iron becomes active part. So, that time iron would corrode and the zinc surface
will be protected because of the presence of zinc oxide. So, in that particular series, zinc
oxide stays above iron. So, zinc oxide would act as cathode and iron surface would act as
anode and that time iron would leave electron and they will form iron 2 plus ion. So, the
corrosion of iron would increase.
So, that is the deadly part of considering materials for galvanic protection, in case of
zinc, in case of galvanization. The galvanization is the process where zinc coating is
done on the metal surface iron surface. So, we should not operate beyond 60 degree. And
that time, zinc will not protect iron rather zinc surface metal oxide the zinc oxide would
form that would corrode iron, then my purpose is lost.
So, let us stop here. We will continue our discussion in our next lecture.
Thank you.
47
Corrosion - Part I
Prof. Kallol Mondal
Lecture – 05
Crevice and Pitting Corrosion
Hello everyone. Today, we have our 5th lecture. And in our last lecture, we started
talking on different forms of corrosion. And we completed uniform corrosion. And then
we started Galvanic corrosion. And we will continue with the galvanic corrosion, some
more information or a knowledge on galvanic corrosion. We talked about distance effect,
we talked about polarity effect that means, if we are trying to have a kind of protection of
steel by zinc, then zinc is active and iron is noble.
And that is what iron acts as cathode, where cathodic reaction takes place. And zinc of
course acts as anode and where anodic reaction takes place. But, we have seen a kind of
situation, where the temperature goes beyond 60 degree Celsius; then zinc converts to
zinc oxide due to the reaction with the species that are forming due to corrosion.
And this zinc oxide then acts as cathode, because zinc oxide position of zinc oxide in the
galvanic series is above iron. So, iron would then act as active component. So, iron
dissolution would happen, and zinc cathodic reaction would take place on zinc oxide
48
surface. So, we have to be careful while taking some metal for sacrificial protection just
like in case of iron and zinc.
Now, we also looked at a brief description of galvanic series. And we thought that we
would know better on this galvanic series, when we talk about electrochemical series that
will come little later. Now, in the galvanic corrosion, we have one more important issue,
which is area factor.
In case of area factor this is a very interesting aspect. For example, if you have two
copper plates and if you are trying to join them or rivet them with steel rivet. This is
made of iron and this is copper. This is a situation.
And when we have steel plates, now let us say this is iron plates, which are reverted by
brass. And the brass is nothing but copper zinc alloy, where copper is predominately
high. In these two cases, if we dip this two riveted object in HCl solution 3.5 percent in
HCl solution, we would see that in case of iron revert joining two copper plates would
lose would lose its strength quickly as compared to the brass rivet, which are fastening
two iron plates. And this there also the galvanic effect is active, in fact what happens in
case of this iron corrodes quickly, since, iron is active as compared to the copper plate.
And then, it the joint becomes lose.
And in this case, cathodic reaction happens on copper surface. And since it is a kind of
neutral solution if we have dissolved oxygen, then the cathodic reaction, which will take
place on copper surface would be oxygen plus 2H2O plus 4e equal to 4OH minus.
And since iron is corroding, so iron minus 2e anodic reaction would take place plus. So,
this is anodic reaction and it acts as anode.
Now, if we see the number of cathodic reactions that are taking place on copper surface,
since copper surface has got a huge area compared to the iron rivet surface. So, the total
number of cathodic reaction on the copper surface would be hugely, it is very large.
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And in order to supply the amount of electrons for this cathodic reaction, iron has to
dissolve quickly, because this electron would be supplied from this anodic reaction. Rate
of iron dissolution would be faster. And this is the concept of area factor in galvanic
corrosion.
So, the cathode area if cathode area is very large and anode area is small then the danger
of galvanic corrosion is very aggressively felt, just like this case. But, in this case it
would also lose, but the loosening would be a little this time to time for this loosening
effect would take place would be higher time, the longer time, the duration would be
longer, because here the brass is cathode and iron of course it will be anode.
Now, cathodic reaction would take place the same reaction would take place on the
cathode surface, which is basically the brass surface. And iron dissolution would take
place on the anode surface. And since the cathodic area is small, the number of cathodic
reactions would be small of course. So, in order to supply the electrons for cathodic
reaction, the total amount of iron dissolution would be less as compared to this situation.
So, the loosening effect would be hindered.
So, now from this idea, it is very clear that in order to design some joining material, we
have to make sure that the cathodic area should be small as compared to the and anodic
area should be large, so that case the galvanic effect would be felt less severely.
So, this is very important factor. And we would talk about this area effect, when we talk
about inter granular corrosion, there are also the area effect would be severely effect.
Now, once this particular galvanic corrosion again will touch upon, when I complete
explanation on, mix potential theory.
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Now, let us go to another form of corrosion, which is called crevice corrosion. Now,
when we talk about crevice corrosion, we have to understand what is crevice. Now, if we
have a plate surface on this, if we have a small dot particle, this is the small dot particle
and this is let us say iron plate. And this particular surface, if we have moisture, now of
course these particular region, these two region there could be possibility of water
ingress and these water ingress could be possible, if this opening is wide enough, so that
the water can take over the surface tension resistance to get into this particular sections.
So, this is a small region, so this region is a small gap, where moisture can sit or moisture
can enter. And interestingly in this gap, moisture once moisture goes in, still moisture
remains stationary or stagnant. And this is a particular example of crevice, this is also
crevice.
Another example of crevice is let us say, I have a bolt and this bolt is joining two plates.
And two plates these are joining, these are the threads. Now, when we have this bolt, we
also sometime put a rubber gasket, rubber small rubber thin, thin rubber a kind of sheet,
which will act as the gasket.
Now, this gasket what is the reason for this gasket, it will tighten it. Of course, one is it
will not allow this particular bolt to be loose. But interestingly, if this gasket is little
wide, then this gasket end could have this kind of appearance. And once, we have this
gasket appearance like this then it is also forming a crevice.
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And in that section again water can sip in, and it will remain stagnant there. This is
another crevice region. There could be formation of crevice in case of corners, for
example, in the metal corners like this. If this is a small metal tank, now this corner is
also acting like a crevice.
Here also, even if there is turbulent, turbulence in the water in the water storage
turbulence, but this corner region will be nearly stagnant. So, this is also crevice. Now,
we have been talking about two things. One is crevice, and second is water ingress in the
crevice.
When we talk about water ingress, we also talk about another thing, which is called
stagnant water that means, this gap should be this crevice gap should be wide enough
should be wide enough to get water inside. And second is this water inside crevice
should be stagnant.
When we have these two situation met, then the corrosion in the crevice region is
extremely high, that the rate at which the dissolution takes place in that region would be
so high, that the surrounding region might look very clean, but that region there could be
possibility of corrosion towards the depth direction, that means, in this case there could
be a small gap that is forming.
And that gap can that corrosion point can ingress towards the depth direction. So, if this
is my thickness of that wall at times, this wall can be punctured. And there could be
leakage. And this is the level of crevice corrosion that is possible. Here also there could
be possibility of crevice corrosion around this region.
So, the corrosion would be so fast, that even without giving any signature, it might leak
the container. Here also, since there is a crevice pole crevice and water moisture content
is there also this is stagnant. Here also the corrosion can take place, and then corrosion
attack can be like this. So, these are some of the deadly corrosion effects of crevice.
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And we have to make sure. And now as we have mentioned in the on the slides, if I go
back to that particular slide, if you see that on the right side, on the right side we have a
factor called design. Now, when we talk about electrochemical nature of corrosion the
design does not come into picture, because the electrochemistry does not talk about
design. It talks about the rate at which anodic and cathodic reactions are going on.
So, now when we talk about crevice, then the design factor would come very handy in
order to control this crevice attack. For example, in this case if we have a dirt content on
the bottom of steel container, it is always better to get rid of those dirt’s, that is what
water container time to time it is better to go for cleaning. And the cleaning would allow
theses dirt particles to get rid off and finally that will reduce the crevice attack.
For example, in this case this is a typical case, where we can have a design criteria which
will control the crevice. Now, when we control this crevice, that time we have to make
sure that the gap should increase, so that water would enter.
But when there is a flow relative flow between the water and the container then if we
increase this gap that would allow turbulence to take place. And that turbulence would
not maintain this stagnancy, because during crevice this stagnancy is very important
issue. If we have stagnant solution in the crevice, then only crevice attack is possible
very at a very high rate. So, if we have to take care of this stagnancy also, so that the
turbulence should be felt of course. Turbulence should not be, so high that it would lead
to another kind of corrosion, which is called erosion corrosion.
53
So, now we have to have a wider gap in the crevice region, even if we are not able to
remove the crevice, then we have to increase the gap, and to the allow this stagnancy to
break this stagnancy by introducing turbulence in the water. Now, in this case this
exactly can be done. So, now, instead of having a sharp corner, we can have kind of
container design like this. So, once we have a container design like this you see in this
portion I have avoided crevice. And now, if there is a flow in the water, so this flow in
the water is actually does not allow this stagnant solution to form in that region. So, this
is a typical example how we can improve design, so that we can avoid some deadliest
forms of forms of corrosion.
And in this case for example, we have to first try that there should not be any crevice. So,
one way is we can chop of these particular edges, which will allow this gasket not to
protrude out, so that the crevice is avoided. So, this is the design factor we can take it
think of. So, now this crevice corrosion itself is a wide subject. So, we are just giving
some sort of nutshell that what is the form of crevice corrosion.
Now, the next form is a before going into the next form I just would like to show some
of those common crevice attack that is possible. Now I have just giving one particular a
rod. This rod is very common is not it. You have seen all those in on the road itself, if
you see that these particular things are available, while construction is going on. This is
54
nothing but a reinforced bar. And this is also a ribbed bar, if you see this are ribbed, this
ribs are formed, because it will hold the cement better than the plain bar.
Now, if we see this, if we concentrate on this particular section, if I see from this; so, if I
see a kind of route of this particular rib, I am talking about the route of the rib, you will
see that the route of the rib has bit more red rust compared to the other portion the flat
portion. See you see this, this is the route, and in this route you have bit more red rust
than this flat regions, ok.
Now, let us take another example. For example, here if you see this, if you see this, the
route is having more red rust compared to the base regions ok. Now why does it happen?
Now if we see this, this is lying on the floor and rains are falling on this. Now, ones there
is a dry weather just after the rain from everywhere the water would be evaporated.
But, in the this is forming a kind of crevice the small crevice if you see this, small
crevice it is forming just at the root of at the base of this particular rib. And their water
can deposit and it would stay this is stagnant absolutely stacked water, and that would go
for a higher corrosion. So, that is what you are getting more red rust at the route of this
particular ribs other portions are relatively a red rust free ok. So, this is one typical
example that where you can see crevice corrosion.
55
Now, let us go to the fourth mode of corrosion. This is also a very deadly form of
corrosion, which is called pitting. The criteria for formation of crevice corrosion is
almost similar in case of pitting. In case of pitting also we need stagnant solution, and on
the surface. If water is flowing, if the water is stagnant, and if the metal, there are some
sort of weak regions. I mean to say that weak region means some of the active regions
like grain boundary. Grain boundary is a place, where the activity of that region is more
than the activity of the grain body.
Here, I am talking about electrochemical activity, so that regions if we place that

particular grain for example, if we have a microstructure like this. Now, the grain
boundaries after reaching we see the grain boundaries can be seen. And these grain
boundaries can be seen, because the grain boundaries are attacked more in the etchant
because the grain boundary is a very active region. So that means, grain boundary
potential if we compare the reduction potential of grain boundary, and grain body, the
grain body has a positive reduction potential as compared to the grain boundary
potential. So, that is why the grain boundary region acts as an anode, so it dissolves
more.
So, if we have weak places like this for example, another weak place where this the on
the metal surface the weak place is for example, iron. If it contains inclusions or
aluminium alloys, it can contain inclusions or magnesium alloys, it can contain
inclusions, those interface between inclusion and the matrix is another weak place. So,
those are the regions where pitting can initiate. So, the initiation of pit happens on weak
and active region of a metal.
And also crevice is another region where pitting can initiate. Now, once pit forms let us
say a kind of small pit forms on the surface, if we see this cross section wise, let us say
this spit forms as a small dot. But interestingly this pit may not grow like this it may not
grow like this. But interestingly pit growth can take place very rapidly, if we see the
depth wise very rapidly like this. And this pitting can be, so rapid that it can puncture a
plate steel plate, and for that stagnant solution is one of the criteria’s.
So, the mechanism of pitting and mechanism of crevice they are nearly similar. But we
are not going to discuss all those mechanism. But I am just saying that what is the form?
So this is the kind of form. For example, if we have a plate like this. So, this plates you
56
have the small dots. And these dots are nothing but pits. And around that dots you will
find little bit of red rust in case of iron and many a times it punchers the plate ok. And
why I am telling stagnant solution? Let us say, if we have a water and this is the metal
surface, if we have water flow, if the water flow is, less, the number of pits and the depth
of pits will be less, will be more it is just reverse and if there is a water flow then the pit
formation would be hindered.
Now, as we have mentioning that the pit can be so dangerous. I just would like to give
you one example. This is the plate. Let us look at this plate and this plate the material is
304 stainless steel and when we see this 304 stainless steel, we have a kind of idea that
stainless steel means it should be stainless that means, the corrosion would be
minimized.
And in fact, if you see this is a very old plate almost about 3 years old plate and this was
used for accelerated corrosion test of concrete rebar that means, this was dipped in the
solution and this was acting like a anode, anode material. Now, when we use this, after
sometime we could see that this is developing kind of small small holes.
And if we see this holes, if I would like you to look at this particular plate, if we see this
hole, I have just put little bit of light on the back of this particular plate. You can see that
gaps are there. And it these are looking like stars blinking; is not it? And this small small
57
holes, we have not formed. In the beginning, it was a flat plate without any small small
gaps, small small holes.
These holes are formed after use of this particular plate as an electrode in the electrolyte,
which contains NaCl and FeCl3. Now, these are called pits. So, now this is a rarely thick
plate, which is almost about 3 millimetre plate and 304 stainless steel. Around that pit
over all this is quite shiny, considering the fact that 3 years have spent. This particular
plate has spent 3 years in open atmosphere we have not protected it, but this pits are
formed. And this pits are so aggressive, that it has punctured this plates.
So, I am just talking about a kind of a structure which is made of some kind of material
like this. And this pits and then these structures are designed to hold some load. Now,
once we have load hole like this the cross section is decreasing. Now, the design stress
would be design load will be felt heavily on this smaller cross sections and then the
stress should go beyond yield point and then it will start yielding. And it may arise the
situation may arise that it will crumble into pieces, so that is what this pitting corrosion is
so dangerous that, it will not give you any signal before a fracture happens.
And though we are able to see, if we see though we are able to see these big holes,
sometimes, this holes are so microscopic, until unless you go under the microscope, you
will not be able to see it, but actually it is it has punctured. And now it has reduced the
cross section thickness. So, this is a kind of a severe mode of corrosion form, when we
talk about 8 forms of corrosion. So, let us stop for this lecture. And then, we will
continue this subject in our 6th lecture.
Thank you.
58
Corrosion - Part I
Prof. Kallol Mondal
Lecture - 06
Forms of corrosion: Explanation with examples
Hello everyone. Let us start our 6th lecture, and till 5th lecture, we completed pitting
Corrosion Mode. And we have seen that compared to uniform corrosion galvanic crevice
as well as pitting mode of forms of Corrosion, they are not; I would say they are a deadly
forms of corrosion compared to galvanic, I would say pitting as well as crevice they are
not at all desirable, because they degrade the durability of a component made out of a
metal or alloy. Now, we will continue our discussion on rest four forms.
So, we are left with four other forms one is dealloying. Dealloying a kind of corrosion
form, where one of the elements in an alloy preferentially dissolves. For example, if we
consider copper zinc alloy, if we consider 70 percent copper and 30 percent zinc which is
called alpha brass, there we do experience dealloying where zinc which is very active
component when copper and zinc are together.
So, zinc dissolves in the solution or in electrolyte copper stays back. So, if we have a
surface like this copper zinc surface, on this surface we have enriched copper. So, the
59
concentration of copper can go even up to 95 to 99 percent. Initially it was 70 percent,
now it has gone go 95 to 99 percent and of course, the zinc content would be 5 percent to
1 percent and it was 30 percent now it has reduced to 5 to 1 percent.
So, here we call it dezincification, it has got another name which is called selective
leaching. So, this dealloying can be observed in many other situations, like silver zinc,
like zirconium palladium alloy, like zirconium gold alloy. So, all those cases we do see
dealloying and in all cases for example, here zinc goes out and silver is left out. So,
silver enriched region is formed. These two are typically example of metallic glasses.
If we do little bit of if we do rapid solidification, they lose their crystal in structure and
they form, random arrangement of atoms just like what we see in liquid phase, but that is
in solid condition and that time we call it metallic glass. And if we leave this particular
two alloys in HCl solution, then zirconium, this is zirconium goes out. And in this case
we have Pd enrichment and in this case gold enrichment.
So, here also this is dealloying since zirconium is going out, this dealloying is not good
for some situations like brass. If we have a water pipeline designed for carrying portable
water, drinking water; the inner wall of the pipeline, they can experience dezincification,
the copper enrichment happens and these copper region is loosely stuck to the inner
surface.
Now, these copper region also is also porous. So, after sometime it might crack, it might
break, the pipe might break or pipe might leak. So, from the point of holding the
structure, this is not good. But interestingly has we have talked in the first lecture that
this dealloying can be used in the positive sense, like nowadays we are trying to make
porous structures and of course, nanoporous structures. The porosity size of the porosity
is in the nano metric range.
And when we have this, this porous structure can be used as a very good catalyst, or it
can be used for active surfaces for many other purposes like medicines and drug
deliveries and all those cases. For example, if we consider silver zinc, then zinc goes out
and it leads nanoporous silver.
60
For example, Au silver Ag goes out in the solution and it leads Nanoporous Au. So, these
things can be used as very good catalysts. So, this is the positive sense we can make use
of dealloying or selective leaching; this is another forms of corrosion.
Now, if we come to intergranular corrosion where from this name, it is very clear that
corrosion would take place along the grains. For example, if we have a structure like this,
where you have grain boundaries; the corrosion would go along the grain boundaries,
that is what this name intergranular corrosion. Classic example is 18-8 stainless steel. An
18 percent which is weight percent is chromium and 8 percent nickel, when we have 8
percent nickel that time the structure becomes austenitic; austenitic stainless steel. And
this austenitic stainless steel can be made at a very low carbon content or moderately
high carbon content for example, normal stainless steel contains 0.08 percent carbon.
And this is the typical 304 trade name of this particular steel.
Now, if it is this is 304; if it is 304 L that means, carbon content goes to 0.01 percent.
Now in this case, if we consider 304 which is containing 0.8 percent carbon. There if we
hold this particular steel in the temperature region around 450 to 650 degree Celsius hold
for a longer duration, then one peculiar thing happens.
Now, in case of stainless steel the stainless property is derived from this chromium
content. The chromium actually reacts with atmospheric oxygen and, then forms
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chromium oxide which is a thin layer on top of this stainless steel which gives the
stainless property. So, oxidation is not always bad. So, actually this because of the
chromium oxide it gives the stainless property to the stainless steel.
Now, when we hold this steel around this temperature region and if we have this grain
structures grain boundary structures, the chromium carbide nucleates along the grain
boundaries. These are chromium carbide and this is Cr23C6, this carbide nucleates on
these grain boundaries; in case if this steel. And when it nucleates occurs, there would be
surrounding regions the surrounding portions will be depleted with chromium. So, this is
depleted chromium region.
Since stainless property is derived from chromium oxide and interestingly here, also just
like zinc and zinc oxide, chromium oxide is also cathodic in nature compared to iron.
Now, in this region we have eighteen percent chromium. So, there we have a chromium
oxide layer. Now along the grain boundaries, we have higher chromium content, because
the chromium carbides are precipitated over there, because the grain boundary is active
place for the precipitation.
Now, there also we have chromium oxide. So, now, the typical situation is we have two
situations the centre region we have chromium oxide and then around this a region we
have chromium oxide, but in this region we do not have chromium oxide. And since the
chromium oxide is cathodic in nature; so, cathodic in nature is as compared to the iron
surface with the depleted chromium. So, cathodic reaction would happen on the
chromium oxide, wherever we have chromium oxide.
So, we have a huge area where cathodic reactions are taken place. And of course, if it is
dipped in NaCl solution which is neutral the cathodic reaction of course, here would be
O2 plus 2H2O plus 4e equal to 4OH minus.
So, these cathodic reactions happens on the huge chromium oxide covered regions, and
the small region this is this region which would act as anode. So, these are acting as
anode and this region acting as cathode.
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And since the anodic region is narrow, so, small area and the huge cathodic area so, the
anodic region would corrode at a very very fast rate compared to the very very fast rate
in this particular situations. So, galvanic effect is felt at the same time the area factor is
also governing this corrosion, very high rate of corrosion along the grain boundary. And
then what would be experienced? The attack would be along the grain boundary and that
is what it become intergranular corrosion.
This kind of corrosion attack is also possible in some aluminum alloys, in some nickel
base alloys, where we have also carbon, there was be also possibility of formation of
chromium carbide along the grain boundaries. So, there also we can have a these kind of
intergranular corrosion.
Now, just to continue on this how to stop them, the stopping character is this particular
chromium oxide is the culprit. So, somehow we have to stop this chromium carbide
formation along the grain boundary. How can we stop chromium carbide formation? One
route is of course, if we reduce carbon content. So, if we do not have carbon for the
precipitation of chromium carbide of course, chromium carbide would not precipitate.
So, the chromium would be distributed homogenously over the entire surface. So, there
will be no formation of a preferential anode and a large area cathode. So, we can avoid
intergranular corrosion.
Second part is of course, this temperature region. See, if we can avoid staying longer in
450 to 650 degree Celsius. And when you hold this steel in this temperature region and
when this chromium carbide forms along the grain boundary, we call this particular
phenomena sensitization. So, avoid now let us say we do not want to get rid off carbon.
Steel we would like to prevent sensitization, how can I do it? If we add niobium into it,
see the niobium has got a higher affinity towards carbon. So, it forms niobium carbide.
So, that the formation of chromium carbide is avoided because there is no more carbon
available for chromium carbide formation.
So, again this stabilize sensitization can be avoided and when we add this niobium kind
of higher affinity elements to the stainless steel, we call it stabilization. So, let us not go
ahead with this intergranular corrosion any more.
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So, let us go to the another form of corrosion which is erosion corrosion. In case of
erosion corrosion, as the name suggest that there would be a flow which we will involve
wear of this material and plus corrosion so; that means, erosion plus corrosion. So, like a
kind of pipeline, where we are flowing water and that water if it contains suspended
particles.
Then when it is moves, it will hit this particular region. So, when it hits, what it will try?
It will try to deform that regions locally, or it will try to remove material by wear
mechanism. So, when we have that kind of situation, the corrosion rate around this
region would be also high. So, then gradually if we keep having this particular flow at
some point of time these region, there could be a hole formation. This is a typical
example of erosion corrosion.
Now here also the designed part would definitely come into picture. Now, if we have a
design like this the pipeline design, the erosion corrosion tendency would be much fast,
much higher. It will be felt more, because the effect of turbulence here. Now, if we have
a flat section, we make gradual change in slope, or the corner then erosion effect would
be less because the turbulence is avoided it is a typical design aspects.
Now of course, the material is one aspect. We have to have a better material which will
have an inherent erosion corrosion resistance, just like instead of pearlitic steel, we can
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go for temper martensite and nowadays people are thinking of bainitic steel which would
have a much higher erosion corrosion resistance. These are all in the research regime.
Now, if we consider two definite two forms of erosion corrosion, which are typically
experienced like impeller corrosion or pump corrosion.
Now, many times if we go and look at the blades of the pump water pump, we see that
the edges of the blades are heavily corroded and many a times we see that the edges of
the blades are basically detached from the original shape original structure. These
happens because of a typical corrosion which is called cavitations. In case of cavitation
what happens? Because of the pressure change water bubbles forms and then when the
pressure increases, this water bubbles collapse on the metal surface.
So, this formation of bubble and collapse of the bubble during bubble for collapse, the
kind of shock waves it generates that shock waves goes towards, this towards the metal
side. And this shock waves can even deform the base deform the metal surface. So, once
we have deformation; that means, it is becoming active. So, once it becomes active; that
means, the corrosion rate is also increasing compared to the region where the bubbles are
not forming and then prolong corrosion of that region.
So, now, because of this bubble for collapse there is a small dent and once you have a
small dent, that we will nucleate another bubble around that region. So, another collapse
and then shockwave generation this will be deformed further and it will be corroded
further. So, like that way this goes on this is the kind of cavitation corrosion which is
bubble formation and, then collapse of the bubble because of the pressure change. So,
these also has got a scientific explanation to it, but we are not looking at that. So, I have
just giving some kind of eye views that this is a form of corrosion
And another corrosion special type of erosion corrosion is fretting corrosion. In case of
fretting corrosion, we do experience this fretting corrosion near the fish plate, you might
have seen fish plate. This is basically the two adjoining rails they have joined by fish
plate. So, you have a rail two rails are coming. So, this is a rail, another rail is like this;
this is a rail two rails. So, you have holes here. you have holes here; so, we and then you
have a plate which connects this two rails tightly and these is called fish plate and these
fish plate are tightened regular basis.
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Now, when a rail moves on the surface, there would be a small vibration around that fish
plate region, the vibration could be this way or it could be this way, because of
expansion and contraction. And these particular vibration is so small, this amplitude is so
small that it remains in the fretting region and, when this fretting happens this vibration
happens. Since they are tightened, there could be a formation of oxides in that interface
between fretting this fish plate of the steel of this particular rail.
And because of this fretting action for example, oxide forms this two surfaces. And there
is a small amplitude vibration and it is under load because the train is come falling on it.
So, then these regions might get dislodged. So, a kind of erosion is taking place or wear
is taking place. And now once the train goes out they might get oxidized, because also
the temperature goes up.
So, now, you can have oxidation first and then erosion, or you can have erosion first and
then oxidation and finally, you would see that in this particular small dips there could be
possibility of debris accumulation. So, this debris will act further during the next fretting
action when the train moves. So, this is the typical fretting corrosion. And interestingly
you might see that time to time some a railway person comes and tightened this fish
plates, because this fish plate loosens and this loosens, because of this fretting action ok.
And this here also we have a we have a kind of fear of crevice corrosion, because these
are also acting as a crevice connection; if waterfalls water stays, there it remains stagnant
the corrosion takes place.
So, in order to avoid this fretting corrosion why people do put grease kind of object a
lubricant, which will reduce this friction effect. And also this lubrication helps in
avoiding crevice effect, because it will not allow the water increase in to this crevice. So,
two ways it acts. So, like that there are cavitation, fretting, erosion, corrosion; there are
many examples. So, we are not looking at this, but this is kind of bird’s eye view that
what is erosion corrosion.
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And finally we have stress assisted corrosion. In case of stress assisted corrosion as the
name suggest again. So, we have corrosion and then stress is also helping or it can be
other way around, stress should be there corrosion would also aggravate the attack. Now,
stress associate corrosion. They can be divide into three parts: one is Stress Corrosion,
another one is Corrosion Fatigue and then, high we have Hydrogen Embrittlement.
In case of stress corrosion, if an object is component is under tensile stress and if it is

exposed to the corrosive, then if the stress is less than yield stress of the component and
if we combine corrosion, an interesting in this case this particular loading is stagnant. So,
we are not having alternate loading just like fatigue. So, that case the kind of stress
corrosion we experience we call it stress corrosion. We call it stress corrosion because it
is a stagnant form of corrosion along with the stress.
But incase for corrosion fatigue, we have a component and that time we have alternate
stress. So, it can go towards tensile component as well as compressive component and
that time you have a corrosive effect that particular failure would be considered as
corrosion fatigue. Just like what we have to experienced in case of silver bridge as we
have given example in the first lecture. So, people think that the corrosion stress
corrosion, as well as corrosion fatigue they are the two culprits for having catastrophe in
that bridge failure.
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And the another effect which is called hydrogen embrittlement. In many situations, if
they are acting if the component is in active hydrogen environment. Active hydrogen
means for example, there is some cathodic reaction plus e this reaction is taking place.
So, this hydrogen before it combines with another hydrogen, these hydrogen atomic
hydrogen is very very active and this hydrogen can react with hydrate forming elements
in present in steel like hydrate forming element like titanium, which will allow a
formation of brittle intermetallics in front of a crack tip and they will go for a brittle
mode of fracture.
So, this is hydrogen embrittlement there could be a possibility of hydrogen blister also.
These hydrogen elements; for example, in this hydrogen is going in inside the metal by
diffusion. And then around inside region hydrogen can combine each other from
hydrogen gas and they will form blister. So, those kind of diffuse can be possible. So,
these happens because when we have an existence of atomic hydrogen formation due to
some cathodic reaction; this cathodic reaction.
So, these particular forms stress corrosion, corrosion fatigue and hydrogen
embrittlement, they generally lead to catastrophic, or a kind of sudden failure of the
component. And those failures could be along the grain boundary for example, in case of
a sensitized stainless steel. If we have stress effect also, they will the corrosion and
stress, they will allow this particular material to fell along the grain boundaries. So, you
will have an inter granular corrosion and intergranular kind of stress corrosion in that
case.
It can be also transgranular nature. So, there are many theories for stress corrosion
fatigue and hydrogen embrittlement. So, we would not look at all those theories, but in a
nut shell, this is a kind of stress corrosion fatigue and hydrogen embrittlement. And these
leads to many a times catastrophe and this main thing is they will not give you any
signature that it is failing; it fails suddenly ok.
So, now, we have looked at different forms of corrosion. So, now, we would step into
our fundamentals aspects which are basically electrochemical nature of corrosion and its
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thermodynamics and kinetics and finally, we will relate the thermodynamics and kinetics
to understand the corrosion phenomena in metals, or alloys let us stop here.
Thank you
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Corrosion - Part I
Prof. Kallol Mondal
Lecture - 07
Electrochemical Nature of Corrosion of its Thermodynamics
Hello everyone. Let us begin 7th lecture. And in our 7th lecture, we will now start
looking at Electrochemical Nature of Corrosion and its Thermodynamics.
So, lecture 7 Electrochemical Corrosion and, its Thermodynamics. Now, when we talk
about this electrochemical nature, we will bring in the examples what we have already
discussed in our earlier lectures. The example is if we have a zinc plate dipped in dilute
HCl solution and this is a zinc plate let us say.
Now, once we putting that zinc plate, we see that the bubbles are forming on top of zinc
surface. And these bubbles are nothing, but hydrogen gas. Now, if we analyze this
particular reaction because these bubbles are forming, because of some reaction then will
see that one reaction is this one this is anodic reaction or we call it oxidation.
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Now, two electrons are released by zinc atom and it goes to zinc iron. Now, electrons
cannot remain free. It has to be balanced by some mechanism, because the total amount
of charge is constant in this universe. So, we call it charge conservation. So, these
electrons will be accepted by some other reaction. The other reaction is nothing, but H
plus plus 2e it goes to H2.
Now this is reduction reaction and we also call it cathodic and this is anodic. Now if we
combine them, then we will see that 2H plus plus Zn 2 electron this two are cancelling
each other so; that means, we are maintaining charge balance and then, also we are also
maintaining the conservation of charge concept. So, that becomes H2 plus Zn plus plus.
Now, this is the complete reaction. Now as we have understood before that when some
metal atom converts to metal iron. So, it goes into the solution and that one we call it
corrosion. This is nothing, but corrosion. So, oxidation is nothing but corrosion. Now, in
this case interestingly this is the complete reaction; this is the complete reaction, or if we
consider another species that is present in the solution which is chlorine ion.
Now, that chlorine ion will react with zinc plus plus, so it will form zinc chloride. So, the
complete reaction, we can also write in this form 2HCl plus Zn equal to Zn plus 2Cl
minus plus H2.
So, this is another way to write a cell reaction. So, here I am sorry that we missed 1 plus
sign here and finally, from this we can write this reaction.
Now, this is the complete cell reaction and in order to have this complete cell reaction,
we have to have two reactions; one is reduction, another one is oxidation. They are
running parallely. Now, interestingly if we see in the reduction if we take only the red
part and in the oxidation if you take only the ox part, if we connect them; then it becomes
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REDOX and when we have REDOX reaction, then only we have these complete
reactions.
So, for the complete cell reaction which is nothing, but the REDOX reaction, it has got
one reduction reaction and one oxidation reaction. And when we have this REDOX
reaction, we have the corrosion of zinc in the form of zinc plus plus iron. And this
REDOX reaction is important in the sense that only oxidation cannot take place or only
reduction cannot take place see. If there is one reduction reaction, there must be one
oxidation reaction, at least from this particular example it is very clear.
And then only we have complete cell reaction. And interestingly in the REDOX reaction,
we have the number of electrons accepted by reduction is equal to number of electrons
generated or released by oxidation reaction. This is very important aspect and that, we
maintains the charge balance and also the charge conservation
Now, this also reflects a kind of rate thing in rate kind of aspect; rate means per unit
time. Now, if we have this particular reduction reaction happening at a different rate,
than the second oxidation reaction, then there will be cumulative charge conservation
charge consumption cumulative charge consumption. This is nothing, but the
consumption and this is generation. So, what I am considering that if we have more
amount of the number of reactions of this first reaction which is reduction reaction,
happening at a much higher rate compared to the second reaction which is oxidation.
That means at any given time we have more amount of electron consumptions than the
generation. so, which will not maintain this charge conservation.
So, in order to maintain charge conservation so, consumption of electrons per unit time
should be equal to generation of electron per unit time. So, the rate of reduction should
be equal to rate of oxidation and since oxidation is nothing, but corrosion; so, it becomes
rate of corrosion this is extremely important concept. The rate of reduction is equal to
rate of oxidation or corrosion.
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Now, if we go to see some other considerations. For example, in this situation the
example, what we have considered in the previous case, you have zinc and same HCl
solution dilute. And in this if we have let us say, if we have little bit of FeCl3, a small
content it is considered as impurity, then the situation would be different.
Now, before considering this situation as we have seen that if the previous case, if this
particular condition; if it is happening at a particular temperature and pressure, if I we
maintain the temperature and pressure and if we make it a close system. So, this reaction
this particular reaction would reach to equilibrium. Now, when it reaches equilibrium
then this reaction it also reaches equilibrium.
So, now if we consider this particular reaction the forward reaction is nothing, but the
reduction reaction. So, this is reduction now if we remove this part so, then it becomes
only red. And interestingly reverse reaction is nothing, but oxidation and if we remove
this part, then also this becomes a REDOX reaction. So, combinedly it becomes another
REDOX reaction.
Now, in the beginning of course, hydrogen gas generation would be very fast rate. Now,
if we consider the rate criteria, time, rate in the beginning, we have huge amount of
hydrogen ions in the systems. So, the rate at which hydrogen gas will be generated will
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be very fast in the beginning and as we have a time lapses, then the rate will decrease and
it will be like this. It will flatten out; that means, thus it reaches a steady state
Now, when this particular thing is H plus plus 2 equal to H2;
now once we have a generation of hydrogen the reverse reaction would start happening.
So, the reverse reaction would take place, now that initially it was almost no hydrogen
gas. So, it will start with a 0 and then it will also merge with this particular rate. So, this
is H2 minus 2 equal to 2H plus.
So, this is the point where it reaches equilibrium. So, the rate of forward reaction is
exactly same as the rate of backward reaction. Similar situation can arise zinc plus plus
zinc can go to zinc plus plus here the forward reaction is OX and the backward reaction
is red reduction.
So, this is also a REDOX and it also reaches equilibrium when the system reaches
equilibrium.
Now, interestingly for this complete cell reaction 2H plus plus Zn equal to Zn plus plus
plus H2, it is combination of this reaction and this reaction these two reactions are
electrochemical in nature, because it involves electron acceptance or electron release and
they are called half cell reaction; so, this is half cell.
This is one half cell this is second half cell, which combines and then forms a complete
cell reaction.
Now, coming to these example when we have dilute HCl and we have little bit of FeCl3.
In the previous case we have one reduction on one oxidation. Now interestingly in this
case, there will be one additional reduction reaction. Now, let us see what is that
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additional reduction reaction, first in this case first reaction would be definitely 2H plus
plus 2e equal to H2 this is of the same has what was considered before.
Second reduction reaction which is Fe 3 plus accepts one electron and it goes to Fe plus
plus Fe 2 plus this is also a reduction reaction.
So, these are two reduction reaction and there would be only one oxidation reaction
which is zinc plus plus. This is oxidation reaction.
Now, as we have mentioned that there should be rate of reduction reaction should be
equal to the rate of oxidation reaction. Now, here we have two reduction reactions, so
you need more electron supply for those two reduction reactions. So, where from this
extra electron would come to take care of two reduction reactions; it has to come from
this reaction. So, the generation of or release of electron from zinc atom would increase,
or at the same time the rate of which zinc would release electron would also increase, it
means that the rate of zinc dissolution would also increase and finally, it suggests that the
corrosion rate of zinc increases.
So, we have a system where we have multiple number of reduction reactions. So, here
two reduction reactions 2 number and 1 oxidation and that would increase the rate of
corrosion. And exactly that is observed when you have zinc in a in the solution of dilute
HCl, where you have little bit of FeCl3 impurity and of course, temperature and pressure
both are same both are maintained same.
Now in this case, we can also have a consideration of dissolve oxygen. Now, if it is
containing dissolve oxygen dissolve oxygen would also allow another reduction reaction.
So, this reduction reaction for this case since its acidic medium; so, then the reduction
reaction involving oxygen would be this would be the reduction reaction and this is a
very strong reduction reaction. So, we are having one more reduction reaction.
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Now, in this system we have three reduction reactions and one oxidation reaction. So, in
order to maintain the electron supply for three reduction reactions, the number of atoms
of zinc going into solution by releasing electron for the reduction reactions would also
increase per unit time. So, the rate of oxidation or the rate of corrosion of zinc would
further increase. So, as we see these three examples that in a system, we can have one
reduction and one oxidation or there could be multiple reduction reactions and one
oxidation.
But the total number of electrons supplied by the oxidation reaction would also increase
because we have to maintain three reduction reactions, but at the end we have to
maintain the total rate of reduction should be equal to total rate of oxidation. So, these
particular concepts will be clear and it will be quantitatively understood when we talk
about mixed potential theory. So, this is consideration where we have one reduction
multiple reduction reactions and one oxidation reactions.
We can have a situation. so this particular thing we are having if we try to see a situation
so, multiple reduction reactions and one oxidation reaction all three examples. .
Now, we have example like where we have one reduction reaction, but there could be
multiple oxidation reaction. The classic example is if we have iron and zinc, this couple
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this galvanic couple is placed in acid. Let us say HCl acid the situation would be like
there would be two reduction two, one oxidation reaction and if this acid HCl is pure as
well as no dissolved oxygen. So, then we do not have any other reduction reaction except
hydrogen reduction.
So, this reduction reaction would take place, and two oxidation reactions are Fe, zinc;
these 2 oxidation reactions.
Now, interestingly when we have individual individually iron is dipped in HCl or zinc is
dipped in HCl, their corrosion rates are considerably high. But once we have this
situation a galvanic couple of iron and zinc are dipped in that couple is dipped in HCl,
then we have both this oxidation reactions going on and one reduction reaction. But
interestingly that time our observation after sometime if you take it out that couple and
try to analyze, we will see oxidation of iron is minimized in couple condition has
compared to when iron is immersed separately in the same acid.
But at the same time, if we see the zinc, oxidation of zinc would highly increase rather in
couple condition as compared to when zinc is immersed separately in the same acid. So,
what we are saying qualitatively, but when we talk about mix potential theory, we will
also quantify that how much would be the reduction of iron reduction of rate of oxidation
of iron or how much would be the increase of oxidation of zinc. Here the reduction
means I would say when how much would be the lowering or decreasing the oxidation
rate of iron and how much would be the increase in oxidation of zinc, when we have a
couple and that one is dipped in HCl solution and this is the very concept of sacrificial
effect of zinc.
And here also REDOX reactions are taking place. Here, REDOX reaction if we consider
REDOX reaction. In this case, we have 2 OX 1 red, but in our earlier situations this is 2
OX and 1 red or I would consider since we are talking about REDOX not OX red. So,
we can put it as 1 red 2 OX, this is the example couple of iron and zinc dipped in acid.
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And in the previous situation all three examples, this is example 4th example three was
zinc dipped in dilute HCl containing FeCl3 and dissolve oxygen where we have three red
plus 1 OX 2 zinc dipped in dilute HCl plus FeCl3, we have two red reaction reduction
and 1 OX reduction reaction and finally, in the first case where zinc dipped in dilute
HCl; we have 1 reduction and 1 OX. So, like that there could be number of oxidation
reactions and there could be number of reduction reactions in a particular cell. But finally
we have to make sure that we have to see that the rate of total reduction should be equal
to the rate of total oxidation. And because of that total rate of reduction and total rate of
oxidations are same in order to maintain charge conservation. So, in these three cases, we
have increase in zinc dissolution, as we go upward we have more and more zinc
dissolution. But in this case, we have a sacrificial effect of zinc iron dissolution
decreases or minimized and zinc corrosion increases and that is the very concept of
sacrificial anode nature of zinc on iron surface. So, let us stop here we will continue our
discussion on electrochemical nature of corrosion.
Thank you.
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Corrosion - Part I
Prof. Kallol Mondal
Lecture – 08
Thermodynamic aspects of corrosion-I
Let us start 8th lecture.
On Corrosion and today we will talk about the thermodynamics will now start getting
into the thermodynamics aspects of, thermodynamics aspects of corrosion. Now let us
look at a cell ok one of the very popular cells is galvanic cell of copper sulphate and zinc.
Now, the cell structure is like this if we have 2 containers and in this container we have
copper sulphate solution in this container we have zinc sulphate solution. And there we
dip a copper plate and here we dip a zinc plate. So, this is zinc this is copper now in
order to make it a complete cell. So, we have to have a salt bridge this is the salt bridge.
The salt bridge what it does, it connects 2 cells. So, that the charge transfer is possible
between these 2 electrolytes this copper sulphate and zinc sulphate. Both are electrolytes
it allows charge transfer. Now the external circuit we can connect it by a wire and once
we connect it we will see that current is flowing. And this current flow would be in this
direction so, this is the current flow direction.
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And once we have this complete cell. So, that time the cell notation becomes like this.
So, the complete cell notation would be copper, zinc.
So, these 2 are electrodes so, this is basically one electrodes this another electrode. Now
for the time being let us discontinue this external circuit this discontinue this external
circuit. And now let us look at what is going on in the individual beaker. And in this
beaker if we carefully notice and this beaker if we, for example, let us say this is the
beaker where we have copper sulphate and copper rod this is copper sulphate and this is
at a particular temperature pressure.
Now after some time, if we try to connect it to reference electrode. So, this reference is
nothing but the reference electrode. And this reference electrode will be able to measure
voltage. Now if we use hydrogen reference electrode and that hydrogen reference
electrode is maintained at one atmosphere pressure and 298 Kelvin temperature. Then
that time that hydrogen electrode reference potential is considered to be 0.
And then this with reference to this, if I measure this potential it is shows something
around some potential E1 and if this copper sulphate copper is maintained activity of
copper is 1, then this value would become 0.34 volt. Similarly, on the other side if we
have zinc plate, this is zinc sulphate and if maintains activity of zinc is maintained as 1.
Then after sometime if we try to connect it to a reference electrode again, and if that
reference electrode is happen is hydrogen reference electrode.
Then this potential it will also show some potential and that potential would be minus
0.76 volt. Now question is this is E2 question is these potential whether it is a reduction
potential or oxidation potential. For this course (Refer Time: 06:27) wherever we will
talk about some potential unless, it is not mentioned clearly we will always talk about
reduction potential.
So, this is nothing but reduction potential this is also reduction potential. Now these
reduction potential means we are measuring that potential consideration considering the
factor the reduction reaction is taking place. So, in this case the reduction reaction would
be, this is the reduction reaction and in this case. So, from this it is very clear since it is
potential reduction potential of this reaction is higher than the reduction potential of this
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reaction. So, the reduction ability of this copper plus plus ion is more than the reduction
ability of zinc plus plus ion.
So, the statement what I am saying is reduction ability of copper plus plus is more than
reduction ability of zinc plus plus. Once we have this situation then if we again complete
the circuit, it will show initially if we try to see the potential difference between these
two. These potential difference would come as E 1 minus E 2 equal to 0.34 minus minus
0.76 equal to 1.1 volt.
So, this is the voltage what the system would experience before any current flow. Once
we start this current flow; that means, once we short this entire circuit the reaction that
would take place on the copper terminal and the zinc terminal would be decided by this,
and this potentials; reduction potentials.
Now, let us see what is going on there cell. This is my salt bridge this is zinc plate, this is
zinc sulphate, this is copper sulphate, this is copper plate. So now, we have connected
them reactions are taking place. And we have seen that reduction potential of this
terminal is greater than reduction potential of this terminal and since current is flowing.
So, this terminal becomes positive terminal and this terminal becomes negative terminal.
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Since we know that the electron flows current flows from positive to negative electrode.
So, these are the sign of that 2 electrode, now what are the electrode reactions that are
taking place and on this side since copper plus plus has got higher reduction ability. So,
this reduction reaction would take place and in this case since zinc has got zinc plus plus
has got a lower reduction tendency. Now we have electron acceptance reaction; that
means, in this case electron is consumed for this reaction.
So now the reduction reaction would not take place on the other electrode because, for
this electron we have to have electron generation. And since the reduction ability of zinc
plus plus is less than copper plus plus or other way around oxidation tendency of zinc
plus plus zinc is higher than oxidation tendency of copper. So, the electron generation
would start on the other electron, where zinc would release 2 electron and it form zinc
plus plus ion.
So, the zinc would dissolve in this electrode and copper would deposit on this electrode.
So now, interestingly now let us see what is happening so, we let us this is reduction and
this is oxidation. So, if you add them we get this is the complete cell reaction and again if
we remove this part and if we remove this part again it is becoming redox.
So, this redox reaction again is taking place, and in that way we have a definite current
flow and that current flow would be utilized for glowing a light. Now interestingly as we
see that the current flow is in this direction that is what we could fix the terminal the sign
of the terminal, now here electron is flowing opposite to the current flow and that is what
it should be.
So, the electrons are generated on this electrode and these electrons are flowing through
this and then it is coming towards the copper electrode and those 2 electrons will be
consumed by this reduction process. So now, question is how the current flows through
the electrolyte. So now, current enters into the electrolyte through the zinc surface. So,
current enters in the electrolyte, through the zinc electrode.
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Now, when current enters into the through the zinc electrode to the electrolyte that time,
what process is going on this process is going on. And this is what oxidation or
corrosion. So, wherever corrosion is taking place remember, that current in that
particular circuit enters through that metal rod or metal electrode into the electrolyte. So;
that means, whenever current enters into the electrolyte through the metal we have
corrosion.
Now, through the charge transfer this particular salt bridge will allow charge transfer. So,
the through that particular salt bridge the charge is would go and the current would enter
into the copper electrode from. So, this is one and second part is current enters copper
electrode, from electrolyte. So, what is going on the other side cathodic reaction or
reduction reaction. And wherever current enters into the electrodes from the electrolyte
we do not get corrosion rather we are getting deposition.
And not any corrosion; these two concepts are the backbone of the concept of cathodic
protection. So, in the cathodic protection actually we have to device something. So that
the rod or the metal structure what we want to protect, the current should enter in to that
particular structure from the electrolyte to that system.
So, that is the sole criteria; the sole criteria is this one for cathodic protection. So the
cathodic protection; which is a basically a protection method from corrosion of any metal
objects so, the primary concept is we have to make sure that current enters into the metal
structure, what we want to protect from electrolyte. And remember wherever any system
anything wherever the corrosion is taking place since it has a electrochemical behavior
electrochemical nature and there should be a current flow and you would see that
wherever the corrosion is taking place there the current is actually entering into the
electrolyte from the metal.
So, from this concept of corrosion it talks about corrosion how to know that where the
corrosion is taking place and this is the concept of cathodic protection. So, 2 concepts we
would know from this. Now we see that the potential difference E2 minus E1 sorry is
basically E1 minus E2, we since we are taking about reduction potential is 1.1 volt
before we sort the circuit.
Now this volt is useful for doing some electrical work. Now we can connect this
electrical work with the free energy change and then that is the first step towards the
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consideration of thermodynamics in electro chemistry or for corrosion related aspects in
our in our the kind of thing what we are discussing. Now let us see that part that how we
can integrate free energy change with voltage difference.
Now, this free energy change since we are talking about a system, where we consider del
G this is the free energy change Gibbs free energy change. When we do all the
operations at one atmosphere so, the pressure we are maintaining fixed, and then we can
consider Gibbs free energy. We can have another free energy term which is called work
function which is A that will come when there is a constant volume process, but in case
of constant pressure process we generally have this kind of we consider Gibbs or the G.
Now, before we talk about this relation, let us see independently what is going on in case
of voltage difference and in case of free energy difference. Now there are 2 parts one is
electrical energy. Let say in a circuit I supply Q amount of charge and the voltage is del
E then the amount of work electrical work would be Q del E.
And let us say the situation the system is working reversibly means it is maintaining
dynamic equilibrium. And remember reversibility does not mean that it should come
back to it is original position it has more to it and for the time being let us consider the
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reversible process is a very very slow process and every state is a very very small
infinitesimal steps. So, that the dynamic equilibrium is maintained.
Now if we have some electrochemical reaction going on let us say m n plus ne this is the
reduction reaction.
And in this reduction reaction, for 1 mole of metal atom formation from metal ion we
need any number of electrons will be needed to convert 1 M n plus to M. And we know 1
Faraday is basically the charge of 1 mole of electron.
So, how many charge we need to supply to get 1 mole of M would be equal to nF. So,
this is the total charge, for 1 mole of M formation. So now, electrical work becomes is
equal to nF del E. So, this is the total charge which is Q. Or you can put it as Q.
Now this F we can find out from charge of electron which is nothing but 1.60 into10 to
the power I think 02 or something. 10 to the power minus 19 coulomb and N0 which is
an Avogadro number is 6.023 and 10 to the power 23.
Now, then we have F equal to so, charge of one mole electron. So, F equal to n 0 into
1.602 into minus 19. We will see that it will come 96483 something around that. So, this
is written as 96500 coulomb so, this is the value of 1 faraday.
Now, let us look at the other side. So, this is the amount of electrical work that would be
available to do for available from a galvanic cell, because in the galvanic cell we have
chemical reactions which leads to potential difference, which will be useful for electrical
work. Now on the other side if we consider G relation with H minus TS this is a famous
relation and then we can write it as U minus PV minus TS.
Now, if I consider change in G is equal to del U minus P del V minus V del P minus T
del S minus S del T I can write this. Now since it is a constant pressure process pressure
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is constant this goes to 0; temperature is constant this goes to 0. So, temperature and
pressure both are constant. So, we end up getting del U minus P del V minus T del S.
From the first law of thermodynamics we get del U equal to q minus W. Now in this case
this W is the total work. Now let us say the system does mechanical work which is again
some external pressure the volume expansion again some external pressure. So, it is
basically the mechanical work and also if it does electrical work. So, it has a 2
contribution so, q minus W prime plus W mechanical.
And W mechanical with this particular system can be also written as PdV.
So now, we have del G equal to q minus W prime this should be, sorry, we made great
mistake here it should be positive, it should be positive. So, H is nothing but H equal to
U plus P V. So, we made a mistake here. So, please correct it. So now, minus P del V
plus P del V minus T del S. And what is W prime? W prime is electrical work.
Now again these 2 are cancelling in case of when we have both the work so, then it
becomes del G equal to q minus W prime minus T del S.
Now what is T del S term; let us say the system is it is not specified whether the system
is going reversibly or irreversibly. Now if the system goes on reversibly. So, then q
reversible is nothing but T del S and now if the situation, then we can write equal to q
minus W prime minus q reversible.
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Now if we maintain that reversibility this q also is nothing but reversible q, reversible q.
So, in a system these 2 are same if it is happening reversibly. So, then we get to if we go
to the next slide.
We see that delta G equal to nothing but W prime and on the other side, what we have
received W prime which is electrical work is nothing but nF if we see this nF del E.
Here from the thermodynamics classical thermodynamics, we get del G equal to minus
W prime and from electrical work concept we are get this. So, if we combine this we get
delta G equal to minus nF del E.
Now in the situation of copper zinc cell we generated del E equal to 1.1 volt. So, the total
free energy change for the chemical reaction would be nothing but nF into 1.1 volt. So,
this is the free energy change that is possible in the system and that free energy change is
negative in nature. So, it leads to a formation it leads to do some electrical work
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So, one of the major concept what we are getting is delta G equal to minus nFE this. And
these del E is termed as E which is nothing but the difference. So, let us stop here will
continue discussing this particular unique relation in our subsequent lectures.
Thank you.
88
Corrosion - Part I
Prof. Kallol Mondal
Material Science Engineering
Lecture - 09
Thermodynamics Aspects of Corrosion-II
Hello everyone, today we have our 9th lecture.
And here we would continue our discussion on Thermodynamics Aspects of Corrosion

and in our last lecture we have come across relation which is nothing, but del G equal to
minus nFE, and this relation was obtained from the basic classical thermodynamics as
well as electrical work.
One side was classical thermodynamics which started from delta G equal to del H minus
T del S and finally, we have got to the situation which is delta G equal to q minus w
prime electrical minus q reversible.
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This is the relation we obtain and then finally, we consider reversible situation. In the
reversible situation q equal to q reversible. So, we got delta G equal to minus w prime
electrical. Whereas, on the other side we have tried to see the work done which is w
prime electrical if there is some charge flow across a potential difference and that goes to
nFE that one also we have seen.
And from this two conditions since this is this is one relation and this is another relation,
we got to this relation. Now, this is the work which is the maximum work that is possible
when we have one mole of substance either coming into the solution or getting deposited
on a metal surface. Now whether this is the maximum work or not that we can also prove
from this relation, let us say if it is irreversible process. Then irreversible process q is not
equal to q reversible and also we can see the q irreversible is if I put it as irreversible is
less than q reversible the heat for reversible heat is more than the irreversible heat.
Now, we are considering that the system is going irreversibly; that means there is a
spontaneous reaction a spontaneous process. Now once we have this relation, then delta
G is not equal to minus w prime electrical work. Rather if this is true then q irreversible,
minus q reversible and this q irreversible is nothing, but this in case of irreversible is
process is less than 0 because q reversible is more than q irreversible. If it is less than 0
then, we can get minus delta G is greater than w prime electrical.
What it means? That the amount of free energy that is available for doing work, that
work is that amount of free energy will not be able to produce the same amount of work
what we have noticed in this case which is reversible. So, in this case there would be
some loss. So, entire thing entire free energy will not be available for doing electrical
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work. Of course, we have seen that the mechanical work part gets cancelled when we
start from this.
So, this is the maximum work that is possible if the system goes reversibly. Now once
we see this, then we can also derive some useful relation in order to know some of the
thermodynamics parameters. Like for any reaction like what we have in our situation
which is copper plus plus plus zinc equal to zinc plus plus plus copper, which is the
relation, which is the reaction that takes place in galvanic cell which of this cell, this cell
and now we saw that the potential goes to potential difference goes to 1.1 volt provided
the concentration of copper plus plus is 1 or activity of copper plus plus is 1, and activity
of zinc plus plus is equal to 1 in the solution of copper sulphate as well as zinc sulphate
respectively.
This concentration has got huge importance, we will see later on that how the
concentration of oxygen in atmospheric condition affects the corrosion of iron, we will
later on when we talk about Nernst equation. Because the Nernst equation will tell us
why that kinds of situations arises if there is change in concentration of oxygen.
Now this reaction the complete reaction of course, copper sulphate plus zinc is equal to
zinc sulphates or copper.
And these reactions must have some enthalpy change, it also involves some entropy
change and then we know this relation this is nothing, but the free energy change for this
reaction and this free energy change actually give rise to a potential difference.
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So, is other relations that we know those are existing in classical thermodynamics. One
such classical thermodynamics relation is del G equal to del V dp minus del S dT this is
a very very useful relation. Now from this we can know that del delta G, dT constant
pressure is equal to minus del S.
Now, we know that delta G equal to minus nFE, then I can get nF because n and F both
are constant for a particular reaction, F is faraday one faraday which is constant this
becomes dT P minus equal to minus del S. So, I am replacing del G with minus nFE.
So, both sides this would get cancelled. So, this is the entropy change of a process. Now,
if we know the variation of potential with temperature for a particular cell we can also
get the entropy change for that particular reaction.
Now in the other hand we have this relation which is delta G equal to delta H minus T
del S, now we have found out a relation like this which will give me minus nFE equal to
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delta H minus T, which is of course, become nF dT at a concentration. So, del H we can
find out as minus nFE plus nF T del T p. So, this is the relation we can get.
Or we can so, get E equal to minus delta H nF plus T del E del T p this also we can get.
So, this is these are two important relations what we can obtain from our understanding
on classical thermodynamics, and from there we can also find out this for that particular
reaction. Now, we can have an example on this. The example what I would like to put up
the problem statement if I try to see that problems statement let us say at 25 degree
Celsius for a particular cell like this Agcl.
So, this is the cell if I consider, now if these many data are provided let say del E del T is
equal to 1.8 into the 10 to the power minus 4 volt per Kelvin,
and cell potential I can have the cell potential for the cell 0.49 volt, and then one can find
out entropy change for one mole of silver deposition. In this case on the right side there
will be deposition of silver, on the left side there will be formation of light electrolyte.
Now, we can also calculate the heat of formation of silver chloride, and the data another
data that is provided is del H of PbCl2 is equal to minus 359 480 joule.
So, now, first we gave to write down the cell reaction and the cell reaction is half Pb plus
AgCl equal to Ag plus half PbCl2 this is the relation.
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So, where I could see that this is plus this is 0. So, this is my reduction or cathodic and
here this is 0 this is plus 1 sorry plus 2 which goes to oxidation or anode. Now this silver
will be deposited on that silver silver chloride plate that interface. Now here we have
written this equation in such a fashion that I have one mole of Ag.
Now, when we have one mole of Ag the number of electrons that would be participating
in cathodic reaction is. So, this is 1 so, n would be 1 here, and accordingly it is adjusted
because once we need one electron. So, Pb minus 2e equal to Pb plus plus. So, if put half
so, this becomes 1. So, this two would get cancelled and now we see that the charge
conservation is followed.
Now once we have this, now let us go and find out delta G for this particular chemical
reaction, which gives me the potential difference that is 0.49 volt. So, this is equal to nF
E which is minus 1 into 96500 as we have understood from our previous class that one
faraday is equal to 96483 or something like that.
So, roughly it is considered as 96500 coulomb 1 faraday and into this much volt so,
which is equal to minus 472852 joule.
So, this much is basically my free energy change.
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Now once we know that, then we can calculate we have the data d E dT equal to 1.8 into
10 to the power minus 4 volt per kelvin from there we can calculate del S.
Del S equal to nF del E del T constant pressure. So, this becomes 196500 into minus 1.8
into 10 to the power minus 4, this is also joule per kelvin. So, this value would be minus
17.37 joule per kelvin.
So, heat of reaction for this particular reaction this particular reaction would be then delta
H would be, minus nFE plus T del S how come it comes? Delta G equal to delta H minus
t del S. So, delta H equal to delta G plus T del S and then delta G is equal to minus FE
plus T del S.
So, we can put those values this is minus 47285 since this value we have calculated from
this equation, delta G equal to minus n F E and we have found out that value to be minus
47285 plus and this T is 25 degree. So, which is 298 kelvin into del H we have found
95
which is minus 17.37 joule. So, this becomes joule. So, then in total if we try to calculate
then it would become 52461.3 joule.
And of course, here we are considering 1 mole of Ag deposition. So, per mole deposition
now we have to calculate. So, this is our problem statement was entropy change we have
found out entropy change, this is the entropy values then we have to find out second
problem heat of formation of AgCl. So, we have found the heat of reaction. So, heat of
reaction for any reaction for example, A plus B equal to C plus D this reaction if it goes
this way.
Because then our heat of reaction would be H of c plus H of D minus H of A minus H of

B. So, formation enthalpy of individual species reactants as well as products.
Now, if we have this particular relation so, then for this we can write as H Ag plus H half
of PbCl2 minus H of Pb of course, half because this half sign is there minus H of AgCl.
Now if we perform because this is happening at one atmosphere and 25 degree Celsius
and if we consider that these are pure substance those cases they can be written as
standard values. So, this super script 0 I am putting because, these are standard values
and as per convention if we have a pure metal the stable condition which is solid in case
of Pb as well as Ag at 298 kelvin and one atmosphere pressure is going to be 0.
So, this is a convention. Now we know this value which is sorry there was a minus sign
missing. So, minus 52461.3 this is the heat of reaction for that and then is equal to 0 this
is minus we know this value, this value was this. So, this is half into minus 359480
minus 0 minus H AgCl.
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We can also put 0, now then H 0 Agcl would be equal to which is nothing, but the
formation enthalpy. We can also put formation enthalpy which is equal to minus 5246.3
minus this would become plus and this would become this is 179740. So, this is the
value. So, equal to around this would become 7 8 this is 8 then. So, 179740 minus
52461.3. So, this becomes 127278.7.
So, this is the joule this is the value of enthalpy of formation of AgCl. So, here we can
see that we have not put del value here, we can also put del value because absolute
enthalpy we cannot calculate we have to calculate relative enthalpy which is the
difference. So, actually this is nothing, but del H 0 AgCl. So, this is the formation
enthalpy of AgCl.
So, we could see that from this relations we can have lot of informations on the
formation enthalpy of a species, entropy change for a particular reaction as well as we
can also calculate enthalpy change for a particular reaction. Because E is experimentally
determined E can be experimentally determined and as a function of temperature
constant pressure I can also find out this particular relation, dE d T we can also find out
say a then entire thing can be chopped out.
Now this is one example. So, we will have problems on this particular aspect and the TA
s will manage that and of course, I will be also interfering whenever there is a need
arising.
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Now, from these it is very clear that this particular relation delta G equal to minus nFE is
a basically a kind of fundamental relation in electrochemistry.
Now, we have not started looking at what would be that importance of that relation on
the corrosion aspects. Now before we talk about that we have also stated that the
concentration of solution is very important. This is very important until unless we have
some relation between E and concentration, we will not be able to quantify and that
quantification would be possible if we have a relation which is popularly known as
Nernst equation N e r n s t Nernst equation.
In that Nernst equation we can relate free energy with potential with Kp or the reaction
constant. So, this Nernst equation will enable us, we have understood this relation which
is delta G equal to minus nFE we have to understand the relation between this two, this
relation we have to understand. And then we will see that how this concentration comes
into that. Let us stop here will continue our discussion in our next lecture.
Thank you.
98
Corrosion - Part I
Prof. Kallol Mondal
Lecture - 10
Thermodynamics Aspects of Corrosion-III
Hello everyone. We will start our 10th lecture and in this lecture, we will get into the
relation between delta G and equilibrium constant. And then, over complete picture on
this electrochemical behavior of corrosion would be clear. So, we already know delta G
equal to minus nFE. So, before we get into this, I thought of discussing another issue,
which I forgot to discuss, when we talked about sign of sign convention of cathode and
anode.
If we get to the old lecture, we would see that we have started discussing on this
particular cell, where we have zinc and another side is copper; and here we have copper
sulphate and here we have zinc sulphate; we have a salt bridge. And now, this terminal
will get to plus, this terminal will go to minus. And if we connect them by an external
conductor, then the current will flow this way, and electron will flow this way, because
we know that here oxidation happens, here reduction happens.
99
Now, question is we know that current flows from positive terminal to negative terminal
that is what the sign becomes positive here on the copper side, and zinc side becomes
negative. And remember, we are considering the concentration here or in the form of
activity of ions activity of zinc, here copper plus plus, here zinc plus plus is 1. So, we
will see this importance of this activity to be 1 or if it is not 1, what could be the issue.
Now, from this, it is interesting. If we try to see that current flows from positive terminal
to negative terminal and of course electron would flow opposite to it. But, convention as
per electrically as per the convention, we have this positive terminal to be the side, where
from the current flows to the negative terminal in that external circuit or the conductor.
Now, would it mean that the cathode, so this side is cathode here, and this side is anode,
so would that mean, that the cathode would always be positive, and anode would always
be negative.
So, the question is would cathode be always positive or would anode be always negative;
we have to answer this. Now, this is a confusion that is always there in the students
mind. I think it is better to clarify here that how would you take up, whether it is a
cathode or anode; and whether cathode would always be positive or anode would always
be negative.
Now, for that we have to bring in concept of electrolysis. So, let us say one important
aspect is water electrolysis. In case of galvanic cell, the cell what we have mentioned
here, here the chemical energy actually gives rise to electrical energy or electrical work.
But, in case of water electrolysis, the reverse happens. The electrical energy gives rise to
chemical work or chemical energy. Now, in this case, this is very popular experiment in
our 10th standard, school days.
So, what we had, we had a cell, and then two platinum electrodes, and those platinum
electrodes are connected to one terminal is connected to positive, one terminal is
connected to negative. And then, this is negative; this is positive. And then, this here
hydrogen evolves the side, which is connected to negative terminal, here we get
hydrogen and the terminal, which is connected to positive terminal of that external
circuit external cell, we get oxygen. So, that way so H2O gives rise to O2 and H2.
100
So, if we balance it, this should be the balance. And this goes into positive terminal and
this goes to negative terminal. So, from this concept, I should see that the cathode should
be the positive terminal, but actually the cathode is here, this is cathode; and this is anode
here. Why is this difference, so that means, the terminal the sign has changed for cathode
and anode, so that means, it is not same. In case of cathode, we have we see that it is a
negative terminal. Why, because as per this convention, current flows from positive to
negative terminal. So, here current flows this way so, the current is flowing from positive
to negative terminal. Now, so this current flow is this way. So, the current is flowing
positive to negative terminal; with convention wise, this convention is (Refer Time:
07:42).
Now, in order to understand, why this positive terminal becomes anode and negative
terminal becomes cathode, we have to understand the cell reaction. And whenever, we
have water system, this water is very important, because now I am trying to say the four
reactions that could be possible in water provided, there are dissolved oxygens.
So, this four reactions let me point out H plus 2e equal to H2, 2nd is H2O plus 2e equal to
H2 plus OH minus 2OH minus, 3rd this is not considering any oxygen dissolve oxygen,
but if we have dissolve oxygen. So, oxygen plus 4H plus plus 4e equal to 2H2O 4,
oxygen plus 2H2O plus 4e equal to 4OH minus. So, these are four major reactions that
are possible in water system. And these are important, when in the with regard to the
corrosion of metals; we will see later on that these reactions are extremely important.
Now, if we see that this and this (Refer Time: 09:22) two reactions, these two reactions it
involves hydrogen ions. So, they are possible, when pH is less than 7, so that means,
acidic. Now, if I see these two these two are possible, since they are a there are no
hydrogen ions involved in this particular reactions, rather we have a generation of OH
minus ion. And these two reactions are possible, when pH is equal to or greater than 7.
So, neutral or basic medium, these two reactions are possible.
101
Now, we can have two sets of reactions, those are possible in case of electrolysis of
water; one set is H plus plus e equal to H2, and then we can have another reactions.
So, this is the cathodic reaction, cathodic reaction. And then, there should be an anodic
reaction, which is nothing but H2O minus 4e equal to O2 plus 4H plus plus sorry this, you
see that this is (Refer Time: 11:20).
So, what I have done, this particular reaction if you see this particular reaction, I have
written in the form of oxidation mode, because this is oxidation or it is anodic; we can
also say that or reduction and this is oxidation. Now, if I multiply this top equation by 2,
so it becomes 4; this is also 4; this is 2. So, if we add them, then it would become 4H
plus plus 2H2O minus 4e. So, 4e 4e, this would get cancelled equal to 2H2 plus O2 plus
4H plus, so these two gets canceled. So, finally, we get 2 H2O 2H2 plus O2. So, this is
another, this is the same one as we have mentioned here.
So, we can also have the same reaction derived from other two reaction that are possible
in water system, so that means, we can consider this one; and this one, and then also we
102
can have the same reaction products. But, interestingly now you see this is the cathodic
reaction and cathodic reaction always happens on cathode. Now, since this terminal is
negative so, hydrogen ion will go there and would get reduced. So, the cathodic reaction
is taking place on the cathode, but interestingly this terminal is negative.
On the other hand, water would lose electron and then get to this situation, which is and
this anodic reaction, this is anodic reaction, which can only happen on anode. So, the
terminal is positive here. So, positive and negative terminals will be decided by which
way current flows. But, whether the positive terminal is cathode or anode, it will be
decided by what sort of reaction is taking place.
If so remember if anodic reaction takes place on any electrode, it would be always anode,
irrespective of positive or negative sign of the terminal. Whenever, we talk about anodic
reaction, definitely we can also talk about oxidation reaction. Now, if cathodic reaction
takes place on any electrode, that will be considered as (Refer Time: 15:28) cathode,
irrespective of positive or negative terminal.
If we see this in case of galvanic cell, where one electrode corrodes and other electrode,
there would be some cathodic reaction; either it would be deposition like in case of
copper zinc system, copper deposits on the cathode. In the galvanic cell, cathode is
positive and anode is negative the sign of that electrode.
And in case of electrolysis, cathode negative, anode positive. Since cathodic reactions
and here also cathodic reaction so, here the cathodic reaction is copper plus plus plus 2 e
equal to copper and here anodic reaction, zinc 2 e equal to zinc plus plus and here the
cathodic reaction, H plus plus e H2. And anodic reaction, H2O 4e equal to O2 plus 4H
plus. So, this should be the basic fundamental the basic behind considering, which one
should be cathode, and which one should be anode.
Now, remember, corrosion is always corrosion does happen in the form of galvanic
fashion, so that means, the part which is corroding, which would always be anode and
the part which is not corroding, where cathodic reaction is taking place. That would be
always cathode, and the negative terminal in case of corrosion, would always be anode,
so that should be remembered.
103
But, in case of let us say kind of industrial practice, what we have is basically the coating
let us say electro deposition. They are definitely the part, which is to be coated is to be
made cathode, there the terminal sign should be negative, because then the deposition
should happen by taking electrons by the positively charged ions. So, once we know this
conventions now we should not have any problem with this convention, that which one
should be anode, and which one should be cathode. Not the sign part is important; is the
reaction part that is important.
Now, let us get to the concept what we have been talking about is the relation between
delta G K p. In order to do that, let us take a basic relation, any chemical reaction let us
say A plus B equal to C plus D. And now, let us say number of b atom, a atom, this is the
number of molecules that are involved in this reaction. Now, if this system reaches
equilibrium, let us say it does not reach equilibrium in the beginning, I do not know,
whether it has reached equilibrium or not.
Now for this reaction, if it is happening at a particular temperature and pressure and if
these are condensed system ok. So, those condense system, initially we will talk about
condense system; and then we will see what happens, if we have a kind of gaseous
104
system. There the situation would be little different, but in case of condensed system, we
start looking at free energy change for this reaction.
And if we see that the free energy change in this direction if we consider, then the free
energy change would be mu of C plus mu of D minus a mu A minus b mu B.
Now, question is what a mu and what is mu, mu is nothing but this is written in the form
of n i let us say i P, T, n j. Now, this is a kind of definition, what we have for the mu; mu
is considered as a chemical potential.
Now, as we know that if there is no composition change, then we can define any
thermodynamic system, rather we can define a state of a thermodynamic system by three
parameters and two independent parameters. So, if you have pressure, temperature and
volume, and let us say the composition is fixed. And if it is a closed system, then we can
either have P or T or P or V or T or V to define the system. And define the system
means, define the state. And state is nothing but the equilibrium position of that
particular system of that particular thermodynamics system.
Now, once we have the composition variation, then we have to introduce one more
parameter to define the state of the system. And that parameter is defined in the form of
chemical potential, because the composition becomes also another factor. So, when we
have, so that means, when we have a system like P, T, V and composition in order to
define the state of the system, then we need to have 3 out of 4 to define thermodynamic
and state.
Now, we have been talking about state, the state is nothing but the state of equilibrium
until or unless the system has gone to place itself at some position, where the all the
parameters are fixed, we cannot define the system. If the system is moving in that
particular space P, V, T space, we will not be able to define its system its state.
Now, for example, if we have a P, V, T P, V, T system for example, if it is here, now we

know, what is the what is the temperature of this particular point. So, this is basically a
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three-dimensional situation, where I need to find out the position of that coordinate of
that particular space; this is P 1, V 1, T 1. So, this coordinate we have to fix.
Now, in this case, we see that two parameter out of three 2 out of 3. Since, we have
equation of state in case of ideal system, for example, ideal system, we have equation of
state as PV equal to RT. So, now if we fix P if we fix V, so T is automatically fixed,
because this relation has to maintained so, now that means, my state is fixed. Now, in
this case, 3 out of 4 we have to fix, then the last one is automatically fixed by equation of
state. So, what is that equation of state, we have to find out ok.
So, if we try to see G as a function of P, T and number of components compositions, so

this n i, i varies from 1 to n let us say or n1 to j let us say varies from 1 to j. Then I can
write this partial I can write this equation n1 P, T, n2, n3 like this nj and dn1. So,
similarly I can write del G dnj P, T, 1, 2 j minus 1 j plus so j minus 1, because I see that
only up to j is available in the system.
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So, now if we fix P and T, then we get del G equal to so, this goes to 0, if we fix P and T.
So, this term goes to 0; this term goes to 0; so this is also 0. So, we are left with so ith 1
is missing, so then I can write ni minus 1 ni plus 1 dni. So, and here n varies from 1 to j.
So, chemical potential of i that means, chemical potential of that component in that
particular phase. This is talking about a particular phase; this is a phase.
In that particular phase, the variation of the rate of change of free energy if we add one
atom, one mole of ith component or if we take out one mole of ith component from that
particular phase, that particular change is termed as mu. So, this mu is also called at
chemical potential of i, ith component in that phase so, this is defined as j. And this is of
course is intensive property, because it does not depend upon the size of the system.
So, now getting back to this particular relation, so any reaction we can have reaction like
what we mentioned here, what we mentioned here. So, we can write the free energy
change as the product chemical potential of product minus chemical potential of reactant;
so, this is we can write.
Now, from that also we can convert this into the standard value, because chemical
potential also can be written as RT ln activity of that component.
Now, here I am putting activity, because we are seeing that this is a condense system, we
have said that it is a condense system. But, if it is a gas, then the situation would be little
different; we will come in our next lecture. But, for the time being, we will stop by
saying this particular equation that this equation will be put up in this equation, and then
subsequently we will progress and then see the relation between free energy and
equilibrium constant. So, let us stop here, we will continue in our next lecture.
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Thank you.
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Corrosion – Part I
Prof. Kallol Mondal
Department of Material Science Engineering
Lecture - 11
Relation between Free Energy and Equilibrium Constant
Hello everyone, today we will start our lecture 11. And we will continue our discussion
on Relation between Free Energy and Equilibrium Constant. This equilibrium constant
depending on whether we are taking mole fraction as our concentration of the species or
activity, accordingly it has got it is name Ka when we talk when we take care
concentration, activity of the species in a particular chemical reaction or Kx when we
take mole fraction to be our concentration of those species in the system.
Like that way we can have a different connotation for this equilibrium constant. And this
equilibrium constant is arising because, whatever process we are considering for the
corrosion; that means, a redox reaction this is also a chemical reaction though this is this
has electrochemistry associated with it, but it is also chemical reaction.
Now, as we talk about in our last lecture that delta G for a particular reaction a A plus b
B equal to c C plus d D this all those are number of moles associated with different
species. And actually if we take reaction is going towards this then we can write in this
form c chemical potential of c plus d chemical potential of D minus a chemical potential
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of A minus b chemical potential of B. Because, it is products chemical potential of
product minus chemical potential of or I would say summation of chemical potential of
product minus summation of chemical potential of reactants. So, that is what we have put
here this equation.
Now, from our discussion we have also seen the concept of chemical potential. The
chemical potential is nothing, but the change of free energy of the system or a system
means of a particular phase when we have a small quantity which is one mole of the a
particular component in that particular phase is added or taken out. This is a basically the
rate of change of free energy of the system.
And that is written as chemical potential equal to let us say I consider the ith component
in that particular system i0 plus RT lna of i. Here I am taking activity since we are
considering condensed system and there we are not assuming that it is a dilute solution or
something.
So, once we have this and now we have to understand this part. This is nothing, but
standard chemical potential of that particular phase and this indicates the chemical
potential of pure component at one atmosphere pressure and 298 Kelvin. This is a
standard value and when we talk about chemical potential it immediately points that ai is
equal to 1 and if we put ai to be 1 then of course, mu 1, mu i equal to mu i 0. So, this is
the standard chemical potential of that particular component.
Now, we can break this and then write accordingly delta G which is the free energy
change of the system for this particular reaction. And since we are considering in terms
of chemical potential and at the same time chemical potential is nothing, but delta G
delta ni constant pressure, constant temperature and all the components are kept fixed
except the ith component.
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So, that is what I would say that except ith component. So, this is the concept so, that is
what this is also P T because we are fixing pressure and temperature. Now, this becomes
c chemical potential of i 0 plus d chemical potential sorry this is C, this is D, 0 minus a
chemical potential of A minus b chemical potential of B, with their standard value this is
the one part.
See for example, if we write this mu C in terms of standard potential, chemical potential
of c which would be for example, mu C would be it is a nothing, but mu c0 plus RT ln
ac. So, accordingly we have broken all those chemical potentials into their respective
standard and the other part which contains the activity. And then the rest of the part
would be plus RT ln ac c because, when I am put c then it would become C chemical
potential c so it will turn into this, so then let me write accordingly RT ln ad D, minus
RT ln a A to the power a plus RT ln a B to the power b.
Next step we can write, I can write the entire term this entire term as delta G0 and then
plus RT ln aC c, aD to the power d, aA to the power a, aB to the power b. So, this is my
relation where delta G0 equal to c mu C0 plus d mu D0 minus a mu A0.
Now, question is when I write this particular equation I do not know the system whether
system has reached equilibrium or not. Now, when it reaches equilibrium then as per our
classical thermodynamics this goes to 0 or it has got another connotation that means, G
goes to minimum.
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For example, let us say I have reaction coordinate and G. So, if I try to see this graph a
schematic representation at this point I see that delta G, delta if I consider this axis to be
T would be equal to 0 so, this is the slope which is 0. But at the same time you see the
variation of G with temperature this point is minimum 2 so, this is the equilibrium. So,
then from this I can write delta G0 equal to RT minus becomes the relation we get this
relation in case of equilibrium.
Now, if we write the same equation once again, this term we can term it as Q which is
nothing but the reaction quotient. Now, when delta G PT equal to 0 then this term
becomes Q becomes K, which is the reaction equilibrium constant, so delta G0 equal to
minus RT ln K which is the equilibrium constant.
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Now, here we are talking about the standard state, before going to the next stage let us
put let us discuss little bit on the standard state remember standard state is nothing but
the reference state it is a reference nothing, but it is a reference. Now, what do you mean
by a reference? Let us have a crude example. So, if I try to measure height of this pillar
or length of this pillar so, if the length is let us say 6 feet, whenever I am talking about 6
feet the length of this pillar I always try to measure from a particular datum point; that
means, we have to take something as 0. So, this is let us say 0 point, which is the
reference point.
Now, if we change the reference point would there be any change in my actual length of
this particular pillar. Now, let us say I take reference point to be minus 1 so; this minus 1
feet which is going downwards is my new 0, new reference so, this becomes my 0 point.
So, now height becomes 7 feet but is that actual length of this particular object 7 feet?
No, it is 6 feet, but even if we take this new reference to be 0 point still we can get the
actual height of this particular pillar. Because, when I try to find the actual length of this
pillar what I will do, I will just do 7 minus 1 so, 6 feet, so this is my actual length. So,
whether I take my reference state to be this one or this one it does not matter the
difference would always be the same, because if I try to find out the difference between
difference of this particular length of this particular pillar would beside.
Same thing happens here when I talk about G which is a state function whether I take
one particular point to be 0 or different other point to be 0 finally, we cannot measure
absolute value of G. We always measure delta G which is the difference. So, once we get
this difference whether I take something to be 0 or other my other part to be 0, it does not
matter it will give me the same value. Now, let us see we can also have some connotation
with reference to classical thermodynamics.
Now, we have seen this particular relation. This is a very popular relation in
thermodynamics and there if I do this particular treatment at a constant temperature if T
equal to constant, then I do integration. So, it becomes G2, P equal to P2 temperature
minus G1 P equal to P1 temperature equal to and V if we take ideal gas then V would be
equal to RT P because PV equal to RT for one mole of gas. So, then it becomes RT ln P2
minus RT ln P1. So, this term, so this would be go to 0, because T is a constant.
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So, then we have to find out these difference. Now, when I try to find out this difference
I need to know P1 as well as P2 and then we will be able to find out. Now, question is
can you simplify this so, if we do it G2 P equal to P temperature and G1 P equal to 1
atmosphere and T then it will become RT ln P.
So, this P1 equal to 1, so this would also go to 0 this term. So, this particular quantity we
write in the term of we write as G0 plus RT ln P. Now, this G0 is basically the free
energy of a pure gas when the pressure is 1 atmosphere when pressure is 1 atmosphere
and then at any temperature could be anything.
So, now whenever we have the P equal to 1 atmosphere we take it as a superscript 0 is

put which is the standard value this is the standard or this is called reference. So,
standard is nothing but the reference now, it is up to you what you want to take it as
standard.
Now, this has there is an advantage, advantage is once you take P equal to 1 atmosphere
at any other temperature any temperature wherever you would like to put this as
standard. So, then you do not have to deal with one more pressure. So, only one pressure
the final pressure is important for you, the other pressure you do not have to worry
because already you fix that particular pressure.
Now, question is you can also take P to P1 to be 2 atmosphere, if you want to do that still
you will see the difference would become say if you consider P1 to be 3 atmosphere no
problem. So, it is up to you, but the convention is as per the convention everybody
follows pressure is considered to be one atmosphere so, that is what this is called
standard. So, pressure is important temperature I can have standard value at 273 Kelvin,
273 Kelvin, I can have standard value at 100 Kelvin, I can have standard value at 1000
Kelvin.
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That is what in text book you see that sometimes this G0 is put like this connotation
people do in textbooks G0, 1000 Kelvin equal to some value, ok. It means that the
standard value the pressure equal to 1 atmosphere at 1atmosphere free energy of that
particular phase at 1000 Kelvin is this much. So, that is the way one has to read for
example, enthalpy, enthalpy also has got standard value.
For example, in case of enthalpy we let us say aluminium in case of aluminium if we

take one atmosphere pressure and that case the solid is the stable form at 298 Kelvin or
25 degree Celsius stable form. So, at that temperature stable form of aluminium is solid
and then H aluminium is considered to be 0.
For example, iron H0 iron equal to 0, when we consider 298 Kelvin and 1 atmosphere
pressure. So, these are already some fix some value which we generally assigned to the
enthalpy value. So, until unless we assign this value to some particular value assign some
particular, this particular enthalpy at one atmosphere pressure we cannot calculate the
change in enthalpy.
For example, a gaseous system, in the gaseous system for example, oxygen, if it is a pure
oxygen at 25 degree Celsius the stable form is gaseous form. So, that case the enthalpy
of pure oxygen at 298 Kelvin one atmospheric pressure would be 0 so, that is the
convention.
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Now, in case of electrochemistry also we have some convention. The convention is
chemical potential or the standard free energy value of hydrogen ion is taken as 0, 1
atmosphere pressure and 25 degree Celsius.
So, this is a reference value we do not know whether actually this value the hydrogen ion
chemical potential of hydrogen ion is 0 at 25 degree Celsius, 1 atmosphere pressure, but
we already assign this value.
And this assignment helps us in finding the change in enthalpy or change in free energy
or change in entropy. So, that is about the standard state which is nothing, but the
reference state remember this and the pressure is very important we can have standard
state at any other temperature.
Even temperature we can change, but that part, that discussion is not part of this current
discussion just we thought that we should rebrush brush up this particular knowledge of
standard state. Now, coming back to this quantity since we have taken delta G0 equal to
minus RT ln K which is the equilibrium constant relation between equilibrium constant
and free energy change at standard condition.
Now, we also saw another relation delta G0 equal to minus nFE.
Now, this delta G is we have not specified whether it is a standard state or not. Now, if
you recall when we talk about this particular cell copper and this is basically my salt
bridge this is copper and here you have copper sulphate and here you have zinc sulphate
and this is zinc. So, that time we saw that if activity of zinc plus plus equal to activity of
copper plus plus equal to 1, then we saw the cell potential becomes 1.1 Volt at 1
atmosphere pressure and 25 degree Celsius.
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Now, this also we see that it is also standard value, this is standard value. Now, if we
change this temperature this will not become this will also be standard value, but it is at a
different temperature, but the pressure is one atmosphere. So, this standard value we can
have separately, for this particular cell standard value is plus 34 Volt copper side zinc
side is equal to 0.76 Volt minus. So, that is what we got E equal to E0 copper minus E0
zinc is equal to 1.1 Volt we have seen this.
Now, there another condition is since the activity is 1, so you will see later on that why
this activity part is important, when activity goes to 0, this will become this only then
this becomes this otherwise it will be a different value. Now, since we are taking
standard conditions we can also write this.
So, now, I can have a triangle, where I can put delta G0 at one side, K at one end and E
at one end, E0 at one end. So, we are talking about standard conditions. Now, let us see
the relation delta G0 equal to minus nFE0, here delta G0 equal to minus RT ln K and on
this side we can have nFE0 equal to RT ln K.
So, now, we have the relation between these two, relation between these two, and the
relation between these two. And this triangle would enable us to understand at what pH
or at what potential in aqueous medium I would get corrosion or I would get protection
or I would get there is one particular term first time you are listening which is called
passivity we will get passive region.
So, this triangle will be able to let us know where is corrosion zone, where is immune
zone and third is where is passive zone for a situation when metal is exposed to aqueous
medium of different pH. So, from this we would we are very clear that we have a relation
between free energy change with potential change or the cell potential as well as
117
equilibrium constant of the reaction that is taking place in the cell. So, we will stop here
we will continue in our next lecture.
Thank you.
118
Prof. Kallol Mondal
Lecture - 12
Derivation of Nernst Equation
Let us start lecture 12. In lecture 11 we have learnt this triangle delta G0, K and E0,
where this I can write minus nFE0 delta0 equal to minus RT ln K and this one would be
nFE0 equal to RT ln K.
So, this is the relation between all 3 quantities. Now, we will go ahead with this triangle
and try to see if we can have some sort of correlation between potential cell potential or
the redox reaction potential with the equilibrium constant.
Now, to start with since we are talking about n we are not fixing what is that value of n,
the n could be for example, Ag plus plus e equal to Ag, where n equal to 1, zinc plus plus
plus 2e equal to zinc, where n equal to 2 we can have Fe plus 3 plus e equal to Fe plus
plus where n equal to 1 again. Even we can have this relation where n equal to 4.
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And we have taken 4 reduction reaction and there is one more reduction reaction which
we call it H2, where n equal to 2 interestingly if I write this way then n equal to 1.
We will see later on that whether you take this reaction or that reaction whether you take
this reaction or this reaction it does not matter you will get the same potential value. But,
from the reaction since we had to electron is involved. So, that is what n becomes two
and here one electron is involved that is what n equal to 1, but both the cases if the
concentration of hydrogen ion remains fixed. And if the hydrogen ion hydrogen gas
pressure is maintained at one atmosphere pressure, then both the reactions it will lead to
same potential of that particular electrode. And this reaction is also called hydrogen
evolution reaction or it is shortly call at called as HER which is Hydrogen Evolution
Reaction. So, this is very important reaction in electrochemistry.
Now, let us start with this, ok since we cannot write K because, we are taking non
standard values that is what we write Q reaction quotient.
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And this will be standard when this goes to equilibrium and that time this K becomes 1,
K becomes this Q becomes Q and this becomes my standard change in free energy. Now,
we can write it as minus nFE equal to minus nFE0 plus RT ln activity of C to the power
c, activity of D to the power d activity of a b. Now, this is almost similar like now, where
c equal to 1, d equal to 1, a equal to 1 and b equal to 1 as well as that time C goes to
copper, D goes to zinc plus plus, A copper plus plus, B equal to zinc. So, like this aA
plus bB equal to cC plus dD, I am trying to correlate electrochemistry with the chemical
reaction.
Now, since we are not specifying here the number of electrons associated with this
particular process n equal to 2 why copper plus plus plus 2e equal to copper since our
convention is we will always take reduction reaction and zinc plus plus plus 2e equal to
zinc so, the n becomes 2.
And since we are taking n equal to n, so then my reaction pattern would be A n plus plus
B equal to A plus B n plus.
So, that case so exact this kind of similarity if you see this and this two and then of
course, this two they are quite similar only thing is the numbers are changing. So, if we
take this then we can write this equation.
121
Now, from this I can write E equal to E0 plus RT by nF ln. Now, since we are writing
with reference to this reaction a B n plus a A, ok so, this becomes like this. So, I have to
put minus here because, this minus minus would go and the minus would come here.
Now, if we take A and B are pure metal that case aA equal to aB I can write it as this.
So, my equation becomes E equal to E0 minus RT by nF ln a B n plus n plus. We can

write so, we are just changing this positive sign we are changing denominator and
numerator and then accordingly we can change it. So, this is a very important relation.
Now, from the look of this who have little idea you will say that this is nothing but
Nernst equation.
Now, we would look beyond this Nernst equation we would try to see, this is for the
overall reaction. Now, we would try to see what happens on the one beaker and what
happens on the other beaker. Now, if we write this thing in terms of copper and zinc
122
reaction, so then we can write E equal to E0 plus RT by 2F ln a copper plus plus zinc
plus plus so, that time n becomes 2 for this reaction.
Now, let me see two cell, this is my salt bridge; this is a copper terminal, zinc terminal,
copper sulphate, zinc sulphate. So, we have some activity of copper plus plus ion,
activity of zinc plus plus ion. Now, if I try to look at the reaction copper plus plus plus 2e
equal to copper this is also electrochemical reaction, for that also we can construct
equation like this.
So, that would become E equal to E0 plus RT by 2F ln a activity of copper plus plus
activity of copper.
Now, this is a relation for copper side and for the zinc side this is copper side and zinc
side I can write other relation reaction is zinc.
Now, both this, now look at this let me look at this. So, this relation if I see copper plus
plus is nothing but oxidant and then it goes to reductant how do I know that oxidant and
reductant because, again go back to hydrogen this relation and where we know that
hydrogen gas is a very good reducing agent. That is what in some cases when we try to
avoid oxidation of metal during sintering of some metal we do purge hydrogen gas. So,
the hydrogen gas actually reduces the oxides that are forming on the top surface of that
metal. So, hydrogen is a very good popular reducing agent so, this becomes my
reductant.
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So, reductant would always get oxidized so, reduction reductant minus e equal to H plus.
So, this becomes my oxidant so, this is oxidant. Similar way if you see that here the ion
is accepting electron and forming reductant so, the oxidant can only get reduced. So, our
convention is fine. Now, from this can I not write E since I am converting copper plus
plus to copper. So, I can write copper equal to E0 copper plus plus copper plus RT by 2F
ln a copper plus plus activity of copper.
In general, can I not also write, I can also write this this is a generalized form.
Now, instead of this I can also replace this with concentration of ox and concentration of
red if I see that the solution is dilute. So, in case of dilute solution a becomes
concentration, activity becomes concentration because that time activity quotient activity
coefficient goes to 1 in case of dilute solution. Dilute solution extremely dilute case of
course, but in general we can take it as a kind of simplification.
This is valid in case of ideal case, an ideal situation can arise when the system is dilute,
because the interaction between the molecules or the species could be minimised. And
what do you mean by dilute or ideal system? Ideal system is the interactions between the
spaces is nil, that means, there is no interactions. So, that is normal that is possible in
case of dilute medium.
124
So, I can write E equal to ox red equal to E ox red plus RT by 2F. Now, instead of 2 I
can generalize nF ln a ox red or I can write.
So, these two the generalized statement of Nernst equation, why you are writing ox and
red? See this is oxidant this is reductant which is copper and similarly we are writing this
and from this we are writing this and these are coming this is when we do not know
whether the system is dilute and this is when the system is dilute.
Now, similar pattern we can write in case of zinc side, zinc side we can write E zinc plus
zinc equal to E0 zinc plus zinc plus RT by 2F ln and the copper side is. Since we know
that copper is pure and zinc is also pure in the metal part this goes to 1, this goes to 1 so,
then we are getting only this term and only this term.
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Now, this side is positive, this side is negative, as per our observation that the current is
flowing from copper side to the zinc side.
So, then the potential difference would be which is nothing but E0 equal to not E0,
because we are not specifying that whether the system has reached a standard situation
because, the activity of copper plus plus and activity of zinc plus plus may not be 1. So,
then this becomes E which is nothing but or we can write; this is the same one what we
have seen here. So, we can also get to the same equation considering the individual cells
or the considering individual half-cell.
So, this relation will enable me to find out E as a function of concentration of copper
plus plus and zinc plus plus this is extremely important statement. The E cell would be
function of concentration of oxidant or reductant. Since this is a fixed quantity which is
25 degree Celsius, 1 atmosphere pressure in case of this copper zinc system we have this
to be 1.1 Volt. And the half cells are E0 copper plus plus copper equal to 0.34 and E0
zinc plus plus plus zinc equal to minus 0.76 Volt.
And as we have already mentioned that we would all the time talk about the reduction
process and these entire relations are on the basis of reduction because whenever I am
writing ox slash red. That means, ox is going to red it means that ox red it means that ox
going to red or we are having reduction this is important.
So, reduction potential on one half cell is this and reduction potential of other half cell is
this and also this relation tells me that the what would be the cell potential if we change
the concentration. Now, if we make it 1, this goes to 1, this goes to 1 then of course, E
becomes my E0 cell, which is the standard potential difference.
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This also becomes delta G0 because, we are considering the standard value. Once we
know this now, we have to look at the value the quantification.
Now, in order to quantify since we have already told that G0 H plus or we can tell it as
mu 0 H plus equal to 0, 25 degree Celsius one atmosphere pressure.
Then let us look at hydrogen evolution reaction. Now, in this case let us say the
hydrogen gas which is evolving from this reaction is maintained at 1 atmosphere and this
is also following this route, can write E H plus half H2 dilute and if we considered to be
that concentration of H plus ion and pressure of H2.
Since we have considered this is to be 1, 1 atmosphere, so this turns out to be plus H

plus.
127
We have to find out this quantity since we know this another convention is 1 atmosphere
pressure 25 degree Celsius. So, if we both the quantities are 0 then for this reaction free
energy change delta G0 would be mu half H2 minus mu 0 H plus equal to 0.
Now, delta G0 equal to minus nFE0, n equal to 1 for this reaction n equal to 1 F is equal
to 96500 into E0. So, this is 0, so, E0 equal to 0, this is interesting the standard reduction
potential of hydrogen evolution reaction is here.
So, this goes to E H2 equal to 0 plus RT F ln H plus.
Now, ln H plus I can write in this form minus RT ok, into 2.303 by F log H plus, I can
write 8.314, 298 Kelvin 2.303, 96500. So, I am taking minus here in the bracket. So, I
am taking another minus so, if you remove the bracket it would become plus.
So, E H plus half H2 equal to this. So, if I calculate this let me calculate 8.314 into 298
into 2.303 divided by 96500 equal to this becomes this.
Now, interestingly minus log H plus is nothing but pH. So, I can remove this term I can
have pH this is a crucial relation also we will use this relation. Now, interestingly if we
have this reaction would there be any change in this reaction for in this particular
equation.
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Let us see so, that time E H plus H2 equal to E0 2H plus H2 plus RT by 2F ln H plus
square pH 2 so, this becomes pH 2, this is 1. So, it becomes this should be also 0 because
in this case this half term will go off and then finally, you will see that E0 becomes 0. So,
this is 0 plus RT by 2 F and this 2 I can take it out ln H plus. So, this 2 2 gets cancelled
finally, we get again if we put those values 0.0591 pH.
So, this reaction and this equation both the equations are same. So, if we go and look at
this we said that both the reactions have the same electrochemical potential. So, it is also
showing that they are same electrochemical potential and their slopes are also same. So,
let us stop here we will continue our discussion on electrochemical nature of corrosion
and also the associated thermodynamics of corrosion.
Thank you.
129
Corrosion - Part I
Prof. Kallol Mondal
Lecture – 13
Standard Reduction Potential Series for Pure Metals
Hello everyone. Let us start lecture 13, in our previous lectures we have come across this
triangle where RT ln K equal to nFE0, delta G0 equal to minus nFE0 and delta G0 equal
to minus RT ln K.
At the same time have come across this Nernst equation where E ox red equal to E0 ox
red plus RT by nF ln activity of ox, activity of red, for this reaction ox plus ne equal to
red. So, this is the Nernst equation what we have for reduction.
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At the same time this activity part can be written in terms of molar concentration ox, red
when we considered dilute solution and also the ideality.
Means activity equal to activity coefficient this is the activity coefficient and this is the
concentration in molar concentration.
Now, this activity coefficient will be 1, when we considered very dilute solution where
ideality is maintained, that time I can write this. Now, this particular is called standard
reduction potential and when we achieve this standard reduction potential which is 25
degree Celsius, 1 atmosphere pressure and activity of ox, activity of red equal to 1 that
time we get this equal to red.
Now, once we have this particular knowledge then also we have looked at this hydrogen
evolution as well as; and we saw that both these reactions both these reduction reactions
are basically same reaction only thing is in the Nernst equation in case of n in this case n
equal to 1, in this case n equal to 2. But finally, we would come across this would be
equal to E H plus half H2 plus RT by F ln activity of H plus and pH 2 half would be
equal to E and you would see that both the cases the equations would remain same.
Now, also we have try to find out the value of this and for example, for this reaction we
get delta G0 is equal to mu 0 H2 half minus mu 0 H plus since we are considering half.
And then from that this is considered this is the as per convention this is 0, this is also 0
in standard state then we would get 0. So, delta 0 0 equal to 0 equal to minus n equal to 1
FE0, so E0 it becomes 0. Similarly, you would get the same value E0 equal to 0 this is
what we have learnt from our previous lectures.
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Now, let us see whether this we can find out E0 for other reduction process.
And initially we would consider pure element and pure element ions of pure element;
that means, in a particular solution we have the ions of that particular atom that particular
element and that element is getting that ions are getting reduced.
So, now, for example, if I consider Ni plus plus plus 2e equal to Ni this reduction process
if you consider.
we consider the reduction of ions of pure element and then try to find out E0 Mn plus M
so; that means, the reaction would be n plus plus ne equal to M. So, M is equal to M is
nothing but pure element.
Now, if I consider this as we can also find out E0 for this process. Now, mu Ni plus plus
0 it has a value of minus 48250 Joule per mole whereas, mu 0 at standard state that was
25 degree Celsius, 1 atmosphere and solid as we have said that the in case of solid if it is
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pure and the stable state in this at this particular conditions where we consider; for
example, oxygen. At this temperature one atmosphere it is gas, so it is a stable form
therefor the mu 0 of oxygen gas would be 0. Here also this is solid nickel which is the
stable condition at 25 degree Celsius and 1 atmosphere pressure. So, then also it is
assigned as 0.
So, now, we can find out delta G0 equal to mu 0 Ni minus mu 0 Ni plus plus then it
becomes plus 48250 which is nothing, but minus 2FE0 Ni plus plus Ni.
Remember since we are considering reduction process that is what we are writing the
reduction free energy change, the nickel from this reaction. So, once we have this then
we can find out E0 equal to plus plus Ni equal to 48 minus 250 by 2 into 96500 F which
is the one faraday it is nothing but 96500 coulomb. So, you know how we get it is
basically charge of Avogadro number of electrons. So, if you multiply Avogadro number
into the charge of an electron you get this number. It is not going to be exactly this 96500
rather it will be 96488, something around that. So, it is rounded off and then we get
96500 coulomb. So, now, you will get this value to be around 0.25 minus Volt.
Similarly, this is reaction this is one example this let us say example 2. So, we can have
example 2 as aluminium let us say aluminium 3 plus plus 3 electron equal to aluminium.
Here also mu 0 aluminium in standard state is considered as 0 and mu 0 al plus 3 plus
equal to minus 481200 Joule per mole.
So, I can again get the same thing mu 0 Al, Al minus mu 0 Al 3 plus equal to plus
481200 equal to minus 3 FE0 aluminium.
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So, every time I am writing ox by red; that means, this is oxidant this is reductant this is
oxidant, this is reductant. So, now, from this we can also get E0 Al 3 plus aluminium
equal to 481200 by 3 into 96500 would be equal to minus 1.662 Volt.
So, we can also get like that we can also get for zinc where mu 0 zinc solid equal to 0 in
standard state and mu 0 zinc plus plus in solution aqueous solution it becomes minus
147030 Joule per mole. So, again we get so this becomes like that we get it.
Now, let us see some other thing. For example, if we consider Ag which is silver plus e
equal to Ag again mu 0 Ag solid in standard state equal to 0 and mu 0 Ag plus equal to
minus 77120. So, then this is plus, this is plus Joule per mole, so then we get delta G0 is
equal to minus 77120 equal to minus 1 into FE0. So, I get volt; so here I am getting a
very positive voltage.
Now, we know that hydrogen is E0 hydrogen is 0 Volt. Now, you see from these
calculations that pure metals in case of pure metal the reduction of ions pure metal, we
can have reduction potential these are the all standard reduction potential. Now, we can
also place them with reference to hydrogen electrode.
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Now, if we try to place all those values. Now, if I see that this is a particular line and.
Now, hydrogen is here this is in volt unit this is hydrogen, this is hydrogen. Now, if I try
to place nickel in the same scale then it is minus 0.25 which is E0 nickel plus plus nickel.
If I try to place zinc which is minus 0.76 E0 zinc plus plus zinc and then I can also put
Ag which is plus 0.80 around that which is around this is E0 Ag plus plus Ag. Like that
we can calculate for all the other metals and we can distribute in this particular scale
scale.
Now, interestingly if we have let us say as we have seen that zinc if you put a zinc plate
in HCl we see that hydrogen bubble hydrogen, bubble formation and that time our
reduction reaction is H2 and oxidation reaction is plus plus.
Now, let us see is there any correlation between these reactions, and the kind of scale
what we are getting or kind of distribution of reduction potential and the standard
reduction potential in this particular plot, in this particular plot.
Now, see this 0 value is lying on top of this minus 0.76 Volt and here also you are seeing
that this is cathodic, and this is anodic, that means, if we have a connection between
these two I could see that which one is behaving as a noble which one is behaving as a as
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an active element. Now, in this case zinc corrodes so; that means, it becomes active in
HCl solution and hydrogen gas evolves. So, this is acting as a noble part in that particular
two half cell reactions and the complete cell reactions.
Similarly, if we connect these two, we could see that nickel reduction will be nickel ion
reduction would be preferred and zinc would dissolve. So, again I could see that in this
particular reaction nickel plus plus nickel zinc zinc plus plus.
So, I would say this should be written like this. So, here this would be acting as positive
this should be acting as negative, if we have unit activities of those ions of those nickel
as well as zinc ions, so then this would be noble this would be active component of that
particular cell.
So, now, from this particular and for example, Ag and zinc if we connect Ag and zinc
you would also see the similar behaviour; that means, Ag would deposit because of the
reduction process of Ag plus and zinc would dissolve because of this active nature of
zinc because its reduction potential is way below the reduction potential of zinc plus Ag
plus Ag. Now, like that we when we distribute all the standard reduction potentials we
call it as standard reduction potential series and in this we in order to construct this the
criteria is activity of metal ion should be one, metal should be pure. So, and also since
this is a standard reduction potential the temperature 25 degree Celsius and 1
atmosphere. So, this is the criteria to have this series.
And in fact, we can calculate this potential this E0 with reference to some with reference
to hydrogen standard reduction hydrogen potential rather standard hydrogen cell we can
measure this because here the potentially E0 H plus H2 is maintained as 0. So, we can
calculate these potentials with reference to this. Also we can calculate once we know the
thermodynamic data; that means, the chemical potential of ions as well because the
chemical potential of the pure component is considered as 0 if it is a standard state; that
means, it is in a standard and this is stable state at 25 degree Celsius and 1 atmosphere
pressure. So, this is standard reduction potential series.
And this series what information it can give? One information is, one is active and noble
part in a cell we can get to know; for example, the example what we have provided this
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even this even for silver and zinc. For your information if you start with a silver zinc
alloy and then expose it to HCl solution then you would see that if you start for example,
zinc 75, Ag 25 and if you put it in HCl, dilute HCl solution after sometime you will see
that the cell this particle even if you say start with the particle small particle this particle
would have several small small porEs.
And those ports if we analyze this composition again you would see that zinc has gone
down to 75 percent of that composition initial composition, the zinc concentration would
be very low in that remaining porous particle and silver concentration would increase
more than 25 percent. So, this happens because in this condition this particular standard
reduction potential is pretty high as well as this one is pretty low and then if we compare
these two reactions then this zinc plus zinc would corrode zinc would dissolve and silver
would remain or silver would deposit back if at all there is silver in the system and then
we have this kind of situations.
So, silver would act as a cathode and zinc would act as an anode ok. So, the zinc
becomes your active component and silver becomes your noble component know. So,
that information we can definitely get. Now, let us continue with our discussion. Now,
we see that in case of pure metal ion reduction we can calculate the standard reduction
potential.
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Now, we have been talking about one reaction which is O2 plus 2H2O plus 4e equal to
4OH minus or we have also mentioned about another reaction 4H plus plus 4e equal to
2H2.
So, these two reactions can happen in aqueous medium when we have dissolve oxygen.
Now, in addition to that depending on the pH we can have two more reactions in aqueous
medium which is these two or we can have H plus plus 2e equal to H2.
So, this 4 reactions that are important in aqueous medium or the water medium and we
have already talked about this 4 reactions before we just mentioned. Now, this is also a
reduction process, this is reduction, this is reduction, this is reduction.
Now, we can also have standard reduction potential for those reduction processes and
that case definitely in this case in this two situations we have to consider again 25 degree
Celsius, 1 atmosphere pressure pO2 should be 1, activity H2O should be 1, activity H
plus should be 1, ok. And, here also similarly these three conditions rather in this 3
condition should be prevailing here and here we have pH2 should be 1, H2O would be 1,
activity OH should be 1, an activity H plus should be 1.
So, then we can get standard reduction potential for these reactions. We have already
seen the standard reduction potential for this we have seen this.
Now, let us calculate one of those oxygen reduction and you will see this is 0 oxidation
number and that goes to minus 2. So, it takes basically reduction. So, we have to see this
particular situation. Now, in this case definitely we can also calculate delta G0 equal to
mu 0 to mu 0 2H2O plus minus mu 0 H plus minus mu 0 O2 and then we can equate it to
minus nFE0 oxygen and I can put it like this. So, this is 2; now here n equal to 4 E equal
to 96500.
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Now, I can have the value of mu 0 H2O equal to minus 236964.2 Joule per mole. So,
then I get delta G0 equal to minus 2 into 236964.2. Now, you see this one is already 0
and this one is also 0 because this is a gas and this is the standard state. So, its value is 0.
So, then this is equal to minus 4 into 96500 into E0 oxygen 2H2O. So, then we get E0
oxygen 2H2O equal to 2 into 236964.2 divided by 4 into 96500. So, it becomes 2 into 2
(Refer Time: 28:08) so it becomes 1.227 volt. So, we can also calculate the standard
reduction potential for this reaction. So, this is the value. So, like that we can calculate
for other reactions.
So, let us stop here. So, we will continue our discussion in our next lecture.
Thank you.
139
Prof. Kallol Mondal
Materials Science Engineering
Lecture -14
Calculation of Reduction Potential in Acidic and Neutral solution
Let us begin lecture 14. As we have seen in last lecture that we can have a series, which
is also called standard reduction potential series for pure metals, where the condition is
the ions of pure metals will reduce, and there will be no other elements. Now, at the
same time, we have also noticed that some of the reduction processes like oxygen
reduction or hydrogen reduction in case of water system aqueous system.
We can also have a concept of standard reduction potential like; what we have calculated
in case of this reaction, which is oxygen reduction in acidic medium Because, you see we
have hydrogen ion and there is no OH minus sign that is what it is basically considered
to be the reaction happening in acid medium or the PH, when the pH is less than 7 and
we got this value.
Now, if we try to write standard this Nernst equation for this reaction, so we can have a
Nernst equation plus RT by nF since n is 4 here, so I can write 4 ln activity of ox. Now,
here ox is the entire the top part, so this entire thing becomes my ox. So, this is O2 or
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activity of O2, I can write in terms of pressure and activity of H plus 4 to the power 4 and
activity of H2O, which is the reduction reductant.
Now, if we maintain this is to be 1, and this is to be 1 as well as this is to be 1, then we

get this standard reduction potential for this reaction. Now, if we keep maintaining PO2
equal to 1 and H2 if we considered to be pure, and it is in the liquid, so then still we can
consider activity H2 equal to 1, then this equation becomes E0 O2 plus and if it is
standard state that means, RT by F, it becomes 0.0591.
We have already calculate, because a calculated this 314 into 298 divided 96500, it goes
to 0.0591. So, by 4 ln, so that time into 2.303. So, we are considering the log conversion
so, this becomes my log activity of H plus 4 so, this becomes E0 O2 2H2O plus 0.0591
into log of activity of H plus.
Now, I can if it is ideal system, so I can write E0 O2 2H2O minus 0.0591 pH. So, here log
minus H plus equal to pH and we have also considered the dial ideal solution. So,
activity of H plus equal to concentration of H plus, where activity coefficient equal to 1,
so that case we get this equation. So, similar so this equation will be very critical, when
we try to find out the stability of a particular metal in aqueous system.
The stability in the sense that whether in for example, what a metal is dipped in water of
certain pH whether that metal would dissolve or it would not at all dissolve or it would
dissolve initially and then finally, it will passive it. All three conditions can be judged
from a diagram, which is called pourbaix diagram that while drawing that pourbaix
diagram, this equation would be very critical.
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Now, coming to so now if we try to see the other reaction, O2 plus 2H2O plus 4e equal to
4OH minus, this is another reduction reaction.
Here also we can calculate delta G0 equal to mu 0 OH minus mu 0 sorry, this is 4 and
minus mu 0 O2. So, this is 0 as per our convention, because standard state oxygen
chemical potential of pure oxygen is 0. So, this we can calculate 4 into mu OH minus
equal to minus 157147.1 joule per mole.
And we know mu 0 H2 equal to minus 236964.2 joule per mole. So, then this becomes
minus 157147.1 minus 2 into minus 236964.2. So, this becomes if I try to find out those
values, so 2 into 236964.2 equal to plus 473928.4 minus 4 into 157147.1 6285 88.4, so
this minus 473928.4 equal to minus 154660. So, this is equal to nothing but minus nFE0
O2 OH minus.
So, E0 n equal to 4 here, so, E0 equal to 154660 divided by 4 into 96500 equal to 0.401
volt. So, this is 4OH minus, because this is my reductant, this is my oxidant.
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So, we get this and also if we try to write the Nernst equation, so we can write RT by 4F
ln activity instead of activity in case of oxygen we can write pO2, then we can write
activity of H2O 2 divided by activity of OH minus 4 to the power 4.
So, this we can simplify, if we simplify this part only, so this part becomes 0.0591 by 4.
So, this is 1, this is we keep it 1 and when this activity of OH minus is all 1, then this
becomes this. This potential of the cell becomes half-cell becomes the standard reduction
potential. So, now if this is not equal to 1, then we can have and if it is a dilute solution,
because in the dilute solution ideality can be maintained, so then log 1 by 4. So, this we
can write it as 0.0591 by 4 into 4 log 1 by OH minus. So, I can still write it like 0.0591
minus log of OH minus or I can write pOH.
Since, the definition of pOH equal to minus log of OH minus this is the definition.
So, I can write this, so this equation becomes E O2 for OH minus equal to E0 O2 4OH
minus plus 0.0591 pOH.
Now, if I consider H2O the water, I can write this the dissociation of water and in that
case, we can write the dissociation constant is nothing but 10 to the power minus 14. So
that case I can write delta G equal to minus RT ln K ok. So, I can write this, when the
system riches equilibrium and since k is 10 to the power minus 14.
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So, I can write activity in terms of concentration if I would like to write, H plus OH
minus equal to divided by H2O equal to 10 to the power minus 14.
Now, if I take logarithm of this, so log H plus log OH minus equal to minus 14, which I
can write in the form of pH plus pOH equal to minus 14. Since, this is nothing but minus
pH, this is nothing but minus pOH. So, this pOH becomes 14 minus pH.
So, we have this equation so, I can start with this since pH equal to 14 minus pOH. And
also we know O2 4OH minus equal to E0 O2 4OH minus plus 0.0591 pOH would be
equal to E0 O2 4OH minus plus 0.0591 14 minus pH equal to this value is as we have
calculated 0.401 plus 0.0591 into 14 minus 0591 pH. So, if I try to find out this value, so
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0.0591 into 14 equal to 401 plus 0.827 minus 591 pH equal to 8212 minus. So, we get
this which is if we try to compare the value, what we have obtained here in this case. So,
this is the reaction number where acidic media, so which I can write it as 1.227 minus
0.0591 pH, so that means, I can see that this is for this reaction.
And if I try to see, now you could see that these two reactions are almost similar with a
little bit difference on the third digit after decimal, but this difference is not going to be
there.
If we take exact value of all the parameters for calculating this quantity or this quantity
ok, so finally we can say that these are equivalent reactions, I can say equivalent
reactions.
For example, let us say I would like to plot them on pH versus E0 sorry, E potential is a
reduction potential, now when pH is equal to 0, both the potentials are almost on the
same point. This is this, and this is this so, thus both are one the same point. And the
slope of the reaction is nothing but this is the slope minus 0.0591. So, and if this is my 7,
so if I try to extend this 7 pH so, I know that this reaction happens, when pH is less than
7. So, then up to that if we extend this, this is the slope is minus 0.0591 with the pH so,
this reaction happen over this plot.
Now, in the basic medium, because it involves OH minus and also in the neutral case
these reactions happens, so that time the plot would be and if you see this particular
region. Where we can also see that this reaction, this particular plot for this reactions, it
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is also on the same line because, this would be lying on the same plot, and then it will be
extending.
So, this reaction happens in this zone, but actually they are lying on the same line. Only
difference is oxygen reduction in acidic medium happens, when pH is less than 7. And
oxygen reduction in basic or neutral medium happens, when pH equal to 7 or greater
than 7. So, these happens, when pH greater than or equal to 7 and these happens pH, less
than 7. So, this is only difference, but they are falling on the same plot.
Now, my interest is now you see that here also, we can find a reduction standard
reduction potential. And in the previous case also, we could find the standard reduction
potential here is this one. This is the standard reduction potential for the oxygen
reduction in acidic medium. So, this particular diagram will you will come again for
discussion, when we start talking about pourbix diagram, but from this at least we are
clear that both the reactions are falling on the same slope line.
Now, if we have to see the another reaction, which is 2H2O plus 2e equal to H2 plus 2OH
minus, this is also a reaction in aqueous medium.
Here also, we can calculate E0 that time this would be I can say that this is H2. So, this is
the reduction process, because this is reduction I can calculate this. So, how do I
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calculate, again I have to find out delta G0 equal to mu 0 H2 plus 2 mu 0 OH minus mu 0
2H2O.
So, I can put those values, this is 0 plus 2 minus 157147.1 plus 2 into 236964.2. So, I can
calculate this value, this becomes 236964.2 minus so this becomes minus plus 159634.2,
which is equal to minus nFE0 H2 n equal to here 2, so this is the 2 electrons. So, E0 equal
to 159634.2 by 2 into 96500 equal to minus 0.827 volt.
Now, if I write it in terms of Nernst equation, now here this particular part we can
simplify, so this becomes 0.0591 by 2. So, this is 1, this is 1 over atmosphere, if we
maintain that and if this goes to OH minus square, so that means it is a dilute solution.
And also ideality is maintained, then this goes to log OH minus O2, which is 0.0591 pOH
with a minus sign with minus sign definitely yes, so, this is becomes this becomes 0591
by 2 into log OH minus ion, so this pOH.
And now again, I can have pOH equal to 14 minus pH so, then I can write ok, so here we
see that we have committed a mistake, because here we have put ox here. Actually, ox
should be here and this part should be here. So, in order to write it again, so I can cancel
it I can cancel this part, and write RT by 2F ln a H2O pH 2. So, now this 1 this goes to 1
and this I can write it as OH minus square.
So, everything is all right, only thing is I have to put a minus sign here. So, then it
becomes plus, because this was done with reference to this numerator and denominator
would be exchanged, so this becomes minus. And finally, it becomes plus pOH. So, then
I can write 14 minus pH, so E equal to 2H2O H2 equal to E0 2H2 H2 plus 0.0591 into 14
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minus 0591 pH, so this is minus 0.827. We have also calculated before this is 0.827
minus 0.0591 pH. So, this so finally this becomes minus 0.0591 pH.
Now, you see this relation and for this what was the relation, so these are also similar.
So, it means that this reaction and this reaction, they will also fall on the same line with
the same slope. But, one equation would be valid for in case of the acidic medium,
another equation would be valid for basic medium. This should be basic or neutral, this
would be valid, when pH greater than equal to 7. And this would be valid, when pH less
than equal to less than 7. So we stop here, we will continue our discussion on these
equations, and then standard reduction potentials in our next lecture.
Thank you.
148
Prof. Kallol Mondal
Materials Science Engineering
Lecture - 15
Nernst Equation in terms of pH.
In lecture 13 and 14, we have discussed standard reduction potential series. And
accordingly, we have notice that hydrogen standard reduction potential is considered as 0
and the potential standard reduction potentials of metals which are greater than 0 are
considered to be noble. And if the metals which are having standard reduction potential
below 0 value, they are considered as active components.
Now, then we started looking at different reactions that are possible involving oxygen,
hydrogen ion, OH ion and H2O. And then we started looking at how to calculate standard
reduction potential for those four major cathodic reactions. And in lecture 15, we will
continue our discussion on that on those four reactions. And then we started looking at
cathodic reactions, which are possible in water medium considering oxygen, water, as
well as hydrogen ion.
And then we saw that there are four reactions. And those four reactions, one set is
oxygen plus 4H plus 4e equal to 2H2O; another one as O2 plus 2H2O plus 4e 4OH minus.
And interestingly the Nernst equation in terms of pH, it boils down to E0 O2 H2O, we
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can write straight away this value, it is coming close to 1.227, I can write it this one I can
write 1.23 minus 0.0591 pH.
Similarly, this Nernst equation for this one also it boils down to 1.23 minus 0.0591 pH.
So, I can I am writing 1.23, because the value what we obtained was 1.228, so I can write
as 1.23.
So, you see the equation, if we try to have a plot between potential and pH, they will fall
on the same line. But, the occurrence of first reaction will happen, when we have pH less
than 7 and occurrence of second reaction would happen, when pH greater than equal to
7. So that is this is this happen in neutral or basic medium and this happens in acidic
medium, because this involves hydrogen ion and this involves water. And then finally,
we get to OH minus, so it would increase the basicity of the solution.
Similarly, we had discussed on two more reactions, which is 2H plus plus 2e equal to H2
as well as H2O plus 2e equal to H2 plus 2OH minus. This is as we have mentioned that
the Nernst equation 2H plus H2 equal to minus 0.0591pH. In terms of pH, so this also we
saw that, it goes to so, I can write instead of this, I can write E ox by red for this reaction
equal to minus 0.0591 pH same equation.
And if we plot them on E versus pH plot, they will lie on the same line, but this will be
valid for pH less than 7 and this would be valid when pH greater than equal to 7. So, here
also it will be valid in neutral or basic medium or this will be valid in acidic medium.
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Now, as we try to draw for pH and E and remember these potential we are measuring
with reference to one standard hydrogen reduction standard hydrogen electrode SHE, we
call it SHE, which is called Standard Hydrogen Electrode. So, there the potential value is
0 at 25 degree Celsius and 1 atmosphere pressure of hydrogen gas.
So, we will talk about the standard electrode little later. And we will discuss two
important or three important standard electrodes; one is standard hydrogen electrode Ag
AgCl electrode, and standard calomel electrode. There we will see that how those
constructions happened, and what are the benefits for different levels of standard
electrodes.
Now, if we try to plot them, so if this is let us say 1.23, when pH equal to 0. So, now if
we see these two reaction, they are actually if this is the plot, then if this is the pH equal
to 7, so first reaction will be up to this. This is the first reactions, if we consider this is to
be 1, this is to be 2, this is to be 3 and this is to be 4. So, this is the 1st one, because the
pH is 7 and the 2nd one if we consider this, the 2nd one starts from this, and then it
continues, so this is 7. So, this is 1st reaction, this is 2nd reaction.
Now, if I try to see the variation for these two reactions, so then again we can have
another plot let us say this is 0 volt, this is in volt, 1.23 volt is this point. So, now again
this will be parallel line to this. And again, this point is pH equal to this line is pH equal
to 7. So, the 3rd equation will be valid here and 4th equation will be valid here.
So, this is the plot and in fact, in between we have H2O, above that we have O2, and
below that we have H2 generation. So, we will talk about this again when we talk about
stability lines of water, these are basically, two stability lines and in between water is
stable.
Now, if I continue our discussion on this on the same line, now we see that even if it is
not involving pure metal and also it involves water, hydrogen ion as well as oxygen, then
also we get to see a standard reduction potential. This is basically the standard reduction
potential values for these two reduction reactions. And sorry for this the standard
reduction potential we found out I think if we remember, this value was 0.401 volt and
here the standard reduction potential was 1.23 volt. So, we do have standard reduction
potential for reactions involving several other constituents other than metal ions.
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Now, here also we can constitute standard reduction potential series for other reduction
reactions, where hydrogen of course, will be sitting at 0 point. And then above 0, it will
be we can call it as strong reduction reactions and below hydrogen we have oxidation
reactions, because if in comparison to hydrogen I would say.
Now, if I look at the series some of the series for example, one series is let us look at
this, this is standard reduction potential series for potential series for metals as well as
pure elements. So, now you see gold, this is here, which is 1.50 is of highly positive
standard reduction potential. And if I compare hydrogen, hydrogen is here so, if we have
a combination between gold and hydrogen, I always get hydrogen evolution. And if there
are any gold ions present in the solution, gold will in gold will immediately deposit back.
Similarly, if I compare gold and silver, so gold is standard reduction potential is 1.50,
and it is 0.80, so that means, gold is highly noble as compared to silver. So, now if you
have gold silver alloy, then if we dip it in acid medium, then gold will remain, silver
would dissolve and then we can have a porous gold structure.
And those porosity could be in a nanometric range, so that is what we call it nonporous
material. So, this is usual route of making nonporous gold, because once we have a
combination of gold and silver, the active component would become silver, so silver
would dissolve. And since, gold has got a very high standard reduction potential, so it
would try to get reduced or it would try to try to stay back.
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Now, if I roll down and then go to whole screen again now, here I have placed hydrogen
here now this is hydrogen part. Now, if I try to look at zinc, this is zinc. So, zinc
reduction potential is negative, where hydrogen reduction potential is 0, so that is what
when you have enough acid medium if you have zinc plate, so that is what you have
immediate hydrogen evolution, because the hydrogen ion would get immediately
reduced and zinc would dissolve quickly.
Similarly, if we see this and this, so there also we could see that iron would dissolve and
hydrogen would hydrogen ion would get reduced, and then form hydrogen gas. There
also the iron would dissolve quickly, because iron has got a lower reduction potential as
compared to hydrogen.
Now, if you compare iron and zinc, iron is minus 0.44 and zinc is minus 0.76. So, there
also I could see that if we have a couple between iron and zinc, iron has got a higher
reduction potential as compared to zinc. So, the possibility would be iron would deposit
or stay back, and zinc would dissolve.
So, now you can see that if we choose any of those any of those particular series a series
any of those pure elements and then if we club it with another element, where the
reduction potential is below the earlier one, then the earlier one will act noble and the
bottom one will act active in that particular couple. So that information definitely we can
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get from this but, in remember this is for pure metal, we do not have we are not talking
about alloys, this is completely 100 percent pure situation.
Now, if I go back to other cases, like the way I have told you that there could be
situation, where you can have reaction, which are not considered in pure elements rather
there could be several species. Here also I can have a plot like this if I go to full screen, if
you see this, hydrogen again it is staying here hydrogen.
Now, the reaction we what we considered in our in our case was this one. If you see this
one, so this is oxygen reduction in neutral or basic medium, the standard reduction
potential of was 0.401, so here it is written 0.40 and hydrogen is 00. So, if we have a
combination between these two, then definitely this will be preferred as a reduction
potential, the other one would be oxidation reactions.
Now, similarly if I try to see 1.23, this reaction sorry, this reaction, which is the oxygen
reduction in water medium in acidic condition, it is highly positive as compared to the
hydrogen. So, this will be a preferred reduction reaction, if we have acidic medium and
dissolve oxygen.
Now, if we compare iron and this, so these two if we compare let us say in acidic
solution, we have dissolve oxygen. and there we dip in sorry not this one not this one, if I
see let us say I have I can put in here itself, it be noted down. If we see iron plus plus 2e
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equal to iron, their reduction potential standard reduction potential is 0.44 volt so, it is
lying below this below hydrogen. So, there if I have iron in acidic medium, then of
course, this is one cathodic reaction and this is another cathodic reaction, both the
cathodic reactions can be a possibility. So, iron would dissolve, and these are the
cathodic reactions.
So, like that way we can go down. So, like for example, these reactions if I consider this
reaction, these are not considering any metal ion metal deposition, rather here we are
considering the reduction of ferric iron and it is going to Fe2 plus. And we see that the
reduction potential is 0.77 volt, which is of course, standard reduction potential, because
here you see E0 is mentioned. Now, this is a very strong reduction reaction.
So, now in as we have mentioned in case of zinc dissolution or zinc corrosion in acidic
medium, we said that if we have a pure HCl, then reduction reaction is already single one
which is hydrogen evolution. But, once we have little bit of ferric iron in it which is
considered as impurity, then this reduction reaction can also take place, so which is a
very strong reduction reaction. So, then the dissolution rate of zinc would increase.
Now, there was another example, where we consider three reduction reactions. For
example, in the acidic medium, we dip zinc and then there we have ferric iron and as
well as we have dissolve oxygen, then this reaction can also happen. So, you have three
reduction reactions; this one, this one this one, as well as this one, so they would
definitely increase the rate of dissolutions.
So, from this an interestingly, whenever we are talking about E0, even if the reactions
contain only ions like the example what we have given here. Remember, the activities of
those ions in that aqueous medium will be will be 1, so that is what that in that Nernst
equation.
So, if I write that Nernst equation E equal to E0 plus ox by red plus RT by nF lna ox red.
So, in this case, this one and this one will always be 1, when we talk about standard
reduction potential. So, there also for example, if I consider this particular situation, the
activity of this and activity of this will be 1, then only we can achieve this potential.
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So these are table for example, if I scroll down and then again go to the full screen. You
see now here we have hydrogen here; this is hydrogen. Now, the other reactions if we
consider this, so this was the reactions we considered for basic or neutral medium. So,
this is pH greater than equal to 7, this happens pH less than 7. So, now this is a very
strong oxidation reactions, when we compare with this.
Similarly, we have this, which is minus 0.44 zinc, if I go to zinc, zinc is minus 0.76 even
aluminium, it is minus 1.66. And magnesium if you see the magnesium is this so, why I
have I am putting importance on aluminium and magnesium as well as zinc, if I say this
zinc. So, now these elements zinc, magnesium and aluminium these are very active
elements and magnesium of course, is a is highly active element.
And you might have a you might come across that magnesium is a very very popular
sacrificial anode, even zinc and is also used as a very popular sacrificial anode.
Aluminium is a problem, though it we can be used, if we maintain the active nature of it.
But, the aluminium has got a problem, they has aluminium has got in has got in inherent
tendency to get passivated, so it passivates. And when it passivates, so it forms
aluminium oxide on the surface so, then it will no longer remain as active component.
So, aluminium has a problem so, we will discuss that thing later also. But, for the time
being you see that if I compare the because most of the engineering applications we still
use iron. So, in order to stop this reaction, when we try to stop these reactions or
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minimise these reactions, we have to have a counter anodic reactions, so which will
supply electrons for this reactions. So, iron dissolution will be minimised, but of course,
zinc dissolution would increase. As well as if we club iron and magnesium, magnesium
dissolution would increase, so that is what magnesium and zinc they are used as a
sacrificial anode for protecting iron object.
So, from this, now we get back to this importance of this series. As we have mentioned
that the series are constructed on the basis of thermodynamic values as well as the
inherent criteria is they have to be standard state. Those ions and species are to be in
standard states, and activities should always be 1 and in case of metals, it is a pure metal
condition.
And from this, we can definitely make out that which one would act as noble one and
which one would act as active. So, active metal, noble metal can be just from this by
looking at this series or active reaction or cathodic reaction can be just from these series.
This is the series, where I can see which reaction is going to be cathodic reaction, which
reaction is going to be anodic reactions that also we can make out.
But, interestingly this will not be able to tell few things. For example, metals, in most of
the practical applications, we have alloys, but this table will not be suitable for alloys,
because there the activity of ions may not be 1 or activity of metal in the metallic part,
since it is an alloy, the activity may not be 1 also. For example, let us say silver zinc,
silver is 50, iron is zinc is 50, so that case zinc activity may not be 1 is not 1 in that alloy,
so that case this particular series will not come into purpose.
Now, secondly we assume that in that solution we have those species in order to have
cathodic or anodic reactions. But, most of the situations, you would see that if there is
anodic reactions, then definitely those ions are forming. But, there may not be the
cathodic that ions which are there ions of that particular metal available in the system,
which we would try to get reduced, rather the reduction reaction would be something
different.
So, those informations also we cannot make out, so that is what this series is a theoretical
series, more practical purpose series is galvanic series. We will continue our discussion
on these two series in our next lecture so, let us stop here.
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Thank you.
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Prof. Kallol Mondal
Lecture – 16
Limitations of Standard Reduction Potential Series of Pure Metals
Well, let us begin lecture 16. In last lecture, we have seen two series. One is based on
elements, and of course pure elements. The most of the cases in the first series we saw
that metal ions are reducing and then going to a metal with the oxidation number 0. In
the second series we saw that some of the reduction reactions are distributed. And one of
the reduction reactions in hydrogen reduction as well as oxygen reduction, we saw that
they are also positioned in that particular series. We had also reduction of metal ion to
another metal ion, which is nothing but the reduction of the ferric ions to ferrous.
So, those reduction reactions are mentioned in the second series. And both the series are
based on our theoretical situations, where we have activity we can find out that value
from chemical potentials of those species involved in that reduction reaction. We have
calculated for some metals as well as for four reactions that could possible that could be
possible in water system. And those E0 values for both the series are valid when the
activities of ions as well as metal are maintained at 1.
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Now, after that we started talking about the benefits as well as some of the issues with
standard reduction potential series. So, benefit definitely we have benefit for example,
when we have metal ions present, and we can definitely decide, which one is going to get
deposited, which one is going to dissolve. For example, in case of this cell where we
have copper and copper plus plus, copper sulphate solution and this is zinc and zinc
sulphate solution.
In both the cases, now if we connect them, and then also we connect them with a salt
bridge; since, this particular solution contains copper plus plus ion, and here also it
contains copper plus plus sorry zinc plus plus ions. And if activity is 1 and here activity
is 1, then definitely we can achieve standard reduction potential. And then if we join
them, this reduction reaction E0 for this equal to 0.34 and E0 for zinc plus and zinc equal
to minus 0.76. So, this here on this side, we have cathodic reaction; and this side we have
anodic reaction ok. This side we have cathodic, and this side we have anodic reaction.
So, also we can see that this part this side is noble and this side is active. So, these two
informations definitely we can get. At the same time, it also gives an idea that let us say
silver zinc alloy, silver zinc alloy if we put it in HCl, then we can get to know that even
there are no ions of silver and zinc in the beginning in the HCl, but since Ag plus plus e
equal to Ag this reaction we have E0 equal to 0.80 volt. And zinc plus plus plus 2e equal
to zinc plus plus sorry zinc E0 equal to zinc plus plus zinc equal to minus 0.76 volt.
And since it is acidic medium we have another reaction E0 0 volt.
From the standard reduction potentials we can make out that this one is lying in between.
So, I can have this reaction and this reaction. So, we can have H2 evolution and zinc
dissolution. This information can also be obtained, but of course silver dissolution is
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impossible or rather I should not mention impossible, because the de alloying mechanism
we have different situations, but at least we can say that silver dissolution by looking at
these 3 reduction potentials, minimum feasibility, minimum occurrence. So, once we see
the zinc dissolution is taking place that is what this particular situation gives rise to
nanoporous silver.
So, silver remains in the is not dissolving rather zinc dissolves, and that makes this
particular alloy enriched with silver. And of course you will see hydrogen evolution
reactions on the surface of that particular zinc silver alloy, that information also we can
snatch out from this. So, here I have written minimum feasibility.
So, there are reasons for this actually the modern mechanism for de alloying in silver
zinc system, there are several proposals or several mechanisms some people say that zinc
and silver both dissolve in the beginning and then silver deposits back, because of its
higher reduction potential and zinc iron stays back so that option is also there. But finally
after the formation of nanoporous silver we get to see there in the solution silver content
is as minimum as possible. So, this information can also we make out. One thing of
course we know what is active and what is noble so these are the benefits.
And on the second series what we have seen at least we can tell that what reactions are
going to happen. For example, if we have our acid medium HCl, and there if we have a
silver plate a zinc plate sorry zinc plate and if we have pure, Fe contain Fe plus plus ion,
and Fe content dissolved oxygen, the dissolution rate of zinc would increase, because the
reduction potential is E0 for Fe plus 3 Fe 3 plus plus 2 equal to 0.77.
Here since it is an acidic medium, so E0 oxygen red it becomes 1.23. If we have unit
activities of oxygen this is E0, and hydrogen ion 0 volt these are all in volt, but if we
compare zinc plus plus zinc E0 equal to minus 0.76 volt. So, this is highly active, this
zinc would behave active, and other all three reactions have got higher standard
reduction potentials. So, we can make out that yes zinc would dissolve, and there could
be possibility of all those 3 reactions, and that would actually increase the zinc
dissolution rate or zinc corrosion.
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So, this information we can also snatch out from this. Of course, the quantification is
difficult we cannot say that how much zinc would dissolve by looking at this standard
reduction potential. We cannot have for that we need to get into the kinetics part, but
from thermodynamic concept, because E0 is a thermodynamic quantity, why E0 is a
thermodynamic quantity, because E0 equal to minus delta G0 by nF.
So, this, and this is a thermodynamic state function change, which is the Gibbs free
energy change in the standard condition; n is the number of electrons associated with that
reduction process. And F is the 1 faraday. So, this is at least from this we can tell that
thermodynamically zinc dissolution would happen, and other reduction process would
take place, but there are limitations.
So, the limitations one is of course actual system cannot happen for pure metal, and
metal ion of activity 1. Actual system does not happen like that for example let us let us
say if I considered alloy if I consider M and N alloy these are two metals. So, M activity
of M in the alloy would not be 1 And also activity of N will not be would not be 1 so that
case if I try to find out E0 M n plus M or I can put it as n plus M, we cannot find out,
because if I try to see the Nernst equation provided, we have these reactions that time
this is not equal to 1, since it is an alloy, and this also not equal to 1, so that case we
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cannot find out this so we cannot find out this, so that case this standard reduction
potential would not exist.
Now, similarly in some situations we may not have in the beginning we may not have
metal ion present. For example, a classic example is the corrosion of iron in atmosphere.
So, we would have few case studies on this corrosion of iron in atmosphere. So, first case
studies let us say we have an iron object. Now, we have a moisture. Let us say this is a
moisture layer there is a small moisture. This is iron object. And we do see on the on the
in our localities that iron object have red rust on top of a iron object, so that is the
corrosion product.
Now, there in the beginning, and even if we take a pure iron. So, in the beginning in the
water system we do not have iron ions. And later it of course it comes from iron by this
reaction these reactions. So, the standard reduction potential we cannot calculate,
because this activity of this in the beginning is not 1. Rather activity of this iron ion in
the beginning where water does not contain any iron is 0 there is nothing.
Now, if we, but there are oxygen dissolved oxygen as well as water, and since if the
atmospheric water is mildly acidic, so we can consider it to be neutral. So, the neutral
medium we know that there is a possibility of this reduction process. See if we have this
reduction then this oxidation reaction must happen in order to supply electron for this
reduction reactions. And then we have combination of to form whole 3, and later it goes
to it again gets oxidized. So, FeOH whole 2 plus half O2 plus H2O equal to Fe OH whole
3. If I try to balance it, so if I put 2 here 2 here so, then 6 oxygen ion, so this is 4, this is
half, this is half hydrogen ion there are 6 also 2 and 4 yes this is balanced. So, we have
this ferric hydroxide which is nothing but the red rust.
So, then we have formation of corrosion product and the corrosion of iron, but here also
we do not see the possibility of attainment of standard reduction potential, because the
iron ion activity will not reach 1, because as it is trying to reach 1. This product is
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forming, and this product is this product precipitates out. So, it would further reduce the
concentration of iron ion. If there is a possibility of equilibrium, will be decided by the
dissociation of this ferric hydroxide or ferrous hydroxide sorry this is 2 sorry I put 3.
So, ferrous hydroxide or ferric hydroxide this also has a very low solubility. So, the iron
ion activity may not reach or will not reach 1. So, we cannot have standard reduction
potential development or standard reduction potential. So, there we have to see as we
have earlier discussed the potential difference between this and this. So, if the potential
difference for example, here we can have a reduction potential developed.
And here also this is E1 and here also we have a potential developed. So, if E1 less than
E2 greater than 0, then we can say that iron corrosion would be a possibility. And then
since it has got a higher potential, this particular reaction has got a higher potential, this
is having higher potential than this. See if we distribute E1 and E2, so E1 would be since
it has higher potential, it will be lying on top of it. So, this would be noble then and this
would be active.
And the cathodic reaction would be this and anodic reaction would be this. So, these
series what we have discussed before is basically nothing but galvanic series. Here we do
not mention potential. We just distribute a potential as per the difference in potential we
distribute those reduction processes like the way we have distributed these two reactions.
And then we try to see that whether one reduction one is on top of other.
So, if one is on top of other the one which is below will act as active and one which is
above will act as noble. And now if this gap is very wide say let us say this E1, E2
position is here. So, this gap is huge so that means there is a possibility of higher degree
of corrosion or higher degree of reduction and as well as oxidation reactions. So, here we
only have a distribution of cathodic reactions. We do not have any potential value, but in
case of reduction standard reduction potential series we do have a potential values
mentioned there, but here we do not have to have potential values mentioned. So, we will
talk about this finally but, one thing is there for example, E1. So, when we try to find out
E1 definitely we have to get the help of Nernst equation.
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And now if you see the Nernst equation for this reaction oxygen plus 2H2O plus 4e equal
to 4H minus, so there E0. I am just writing E ox red equal to E0 ox red minus 0.0591 pH
or if I write plus RT by 4F ln, PO2 activity of H2O divided by activity of OH minus to the
power 4. So, this is the potential we are trying to see there with reference to the standard
reduction potential for this reaction.
And again for iron here also we are writing E0 ox red equal to E0 ox red plus RT by 2F
ln activity of Fe plus plus activity of Fe. So here also we are making use of this standard
reduction potential, but we are seeing the difference between this is nothing but E2 and
this is nothing but E1.
So, we are seeing the difference between E1 and E2 that is what we are constructing
galvanic series. So, this one would stay above and this one would stay below. So, if we
have a couple between these two. So, this is the series, so here we mention O2 plus 2H2O
plus 4e is equal to 4H minus, and here we mention Fe plus plus 2e equal to Fe. So, this is
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the position of those two. Now, we can have a position of zinc also zinc here. So, there
are also we could see that we can have a position. So, we are not mentioning the
potential.
We will see a galvanic series in our next lecture. And there we will discuss it more on
that, but before that if we see this particular reaction again, this particular reaction again
O2 this particular reaction. Now, interestingly Eox, so this is basically ox part this is the
red part. So, ox by red equal to E0 I am not writing those individuals species plus RT by
4F ln pO2. And if we try to see that the concentration of activity of H2O of course, since
it is a pure water we can consider it to be one. And if we maintain this activity of OH
minus a same in two situations where in one case pO2 is high, and another case pO2 plus
E0 ox red; so, now if I consider pO2 1 greater than pO2 2.
What could be the situation? Now, here the assumptions are activity of H2O is 1, and
activity of OH minus in case 1 equal to activity of OH minus in case 2. See if we have
this situation this then we have in an interesting situation, which is originated from a
concept called concentration cell, and that concentration cell would be able to explain the
corrosion of iron if there is one small droplet of water on top of it. So, we will discuss
that part in our next lecture. And next lecture, we will also look at the galvanic series in
little bit detailed manner.
So, today let us stop here. We will continue our discussion in the next lecture.
Thank you.
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Prof. Kallol Mondal
Lecture – 17
Concentration Cell Formation and Galvanic Series
Hello everyone let us begin lecture 17.
In lecture 16, at the end we started talking on concentration cell, let us discuss this
concentration Cell little bit and then we try to understand some of the corrosion
phenomena related to concentration cell development. So, when we talk about
concentration cell; that means, that it is actually talking about difference in concentration
of the ions that are forming in the solution or electrolyte or one of the species that are
taking part in those electrochemical reactions.
Let us consider one particular reaction which is copper plus plus plus 2e this is copper
this is a cathodic reaction.
Now this is cathodic or reduction, the backward reaction is nothing, but oxidation or
anodic. Now here I can see this is a copper pure metal and if it deposits; so, the activity I
can consider to be 1. So, when we talk about concentration cell for this cathodic or
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anodic reaction, for this particular half cell reaction we have to consider the
concentration difference of this particular species.
Now let us construct a cell; so if we construct a cell let us say. So, now when we talked
about the concentration difference that lead to a galvanic couple, which lead to a cell
called concentration cell. Now, if we construct the cell let us say this is a copper sulphate
and we have a copper electrode with activity of copper plus plus is equal to let say equal
to a1.
And then we have another cell another half cell we can construct same solution, but here
activity of copper plus plus is equal to a2; temperature and pressure are constant; that
means, they are not changing. And then because of this activity a1 and a2; they will
develop a potential.
So, the potential that would developed here would be E copper plus plus copper same as
ox slash red; that means, oxidant slash reductant equal to E0 copper plus plus copper
plus RT by 2F ln a of copper plus plus by a of copper. Because in this reaction if we see
this is oxidant and this is reductant; now since we are considering this is to be 1 because
it is depositing. So, we are left with only this part this one; so now, instead of a plus plus
we can write a1, similarly this is for this cell.
Similarly, for this cell we can write E copper plus plus copper equal to E0 copper plus
plus plus slash copper plus RT by 2F ln a2; similar way we can have this Nernst
equation.
So, here activity equal to a1 here activity equal to a2. Now the potential; that means, the
potential developed at this electrode respective 2 cell; 2 half cells, we can have a relation
between these two; that means, whether E copper plus plus copper a1; greater than E
copper plus plus copper a2; that means, a1 and a2 they are basically the activities of
those copper of the copper ions in this respective half cells.
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When it is true? When a1 greater than a2 because these 2 are same for both the cases. So,
now, once we have a difference in concentration of copper plus plus in both the half
cells; then we see that the potential at this electrode which is E copper plus plus copper a
1; that means, the activity of copper ion and E copper plus plus copper a 2; this becomes
positive compared to this, this becomes positive. So, now, if we have a series in the
series if we try to plot them this is E copper plus plus copper a equal to a1, this is E
copper plus plus copper a equal to a2.
So, of course, then this would become my positive electrode, this would become my
negative electrode because once we complete this cell by connecting a salt bridge; this is
my salt bridge. And then if we connect this 2 electrode then will definitely see that since
this one this potential lies on top of this potential, then we have a current flow from left
side to the right side.
So, the left side whenever we have a current flow then the current always flows from the
positive electrode to the negative electrode. So, this would become my positive this
would become my negative and electron would flow this way. Cathodic reaction would
take place in this electrode which is nothing, but copper plus plus 2e equal to copper.
And anodic reaction would take place on this electrode which is copper minus 2e; minus
2e equal to copper plus plus.
Now we see that because of the concentration difference of Cu plus plus ion; we have
developed a potential difference and that potential difference is leading to current flow.
And also this current flow it relates to the galvanic series, galvanic difference galvanic
potential difference between these 2 half cells; so, this is the concept of concentration
cell. Now the concentration cell what we see here the same concentration cell can be
developed in atmospheric corrosion of iron.
Now, whenever we try to talk about atmospheric corrosion of iron; this sometime
happens due to differential aerated cell formation, due to difference in oxygen partial
pressure. So, let us look at this part little more carefully.
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And when we try to look at before that let us see in the atmosphere what is that cathodic
reaction that happens involving oxygen and moisture? Generally in atmosphere we have
a situation where the system can be considered, the electrolyte can be considered as of a
kind of neutral system. So, if we have a neutral system then we have this reaction; this
reaction is possible and this reaction can be considered as cathodic. So, if forward
direction we consider then it is cathodic; if we consider backward direction, this is
anodic. And depending on the partial pressure of oxygen, we have a different
concentration cell development.
Now, if we try to write Nernst equation for this; now instead of writing all those pieces
here this and this these are basically the oxidant part and this is my reductant part. So,
now, we write only ox by red; if we go back to earlier lectures you can see that we can
write it as oxygen slash OH minus; that means, oxygen is basically the oxidant and OH
minus becomes my reductant. So, this one I can write it as E0 ox red plus RT by 4F,
since here 4 electrons are involved; so, ln pO2 activity of H2O activity of OH minus to
the power 4; so, this is my Nernst equation for this.
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Now when we have iron corrosion; then we have this reaction, this is the oxidation
reaction that take place. Now if we put multiply by 2; so then it becomes 4 and this
becomes 2.
Now this is my anodic reaction and cathodic reaction; is this one. So, then if we add
them this is 1, if we consider this is 2 then if we add them then we get oxygen iron plus
oxygen plus 2H2O equal to 2 FeOH whole 2.
Now even after that we can have Fe plus 2, it can also go for another oxidation reaction
of Fe plus plus 3 plus; this is another reduction process that can take place.
Now whenever we are having Fe plus plus; that means, we are considering Fe plus plus
along with OH minus. So, if we consider 2 Fe plus plus; that means, we considered 2; 4
OH minus ion along with that; so, it also have OH minus 4 OH minus. Now the same
reduction reaction if we multiplied by half, then H2O plus 2e, so, this is multiplied by 2;
so, the 2 equal to 2 OH minus.
Now, if we add them again; so, this equation and this equation these two if we add; then
we get 2 FeOH whole 2 plus half O2 plus H2O equal to; so because this 2 will get
cancelled; so, you get 2 FeOH whole 3.
So, this is this has and these 2 these 2 have very low solubility constant. So, we call it
kSP; so that means, solubility constant because that is what they precipitate. Once they
precipitate we can assume that they are going into the activity state 1 because when they
are precipitating we are assuming that, they are precipitating in the form of pure form.
So, if we consider the kSP; kSP for this reaction this, this, this one. So, equal to Fe plus
plus ion or in the form of activity; I can write a Fe plus plus a OH minus 2 by a FeOH
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whole 2, because we are considering FeOH whole 2 Fe plus plus plus 2 OH minus. So,
now, this is 1; so then all the thing kSP equal to activity of a plus plus into activity of OH
minus square.
Because we are considering because they are different same thing we can construct for
this. Now you see this OH minus percentage is decided by the kSP of that particular phase
that is forming due to the reaction with oxygen and moisture. So; that means, at a
particular temperature and pressure if we have this particular thing and mostly
temperature because this particular equilibrium constant depends on the temperature. So,
then we can have this one to be fixed because the activity of OH minus will be fixed
because that is decided by the solubility product of both the insoluble faces or partially
soluble faces.
And since they have a very low solubility product that we can then say that they are
partially soluble; so, this activity of OH minus we can consider to be fixed in this
particular situation. And activity of H2O if it is a pure then it can be also considered as 1.
So, now, entire thing boils down to this particular reaction or equation boils down to plus
RT by 4F ln pO2 the partial pressure of oxygen.
So, now, once we have this relation; we see that if we have a difference in this quantity
in at two places. For example, if we consider place 1 and this place 2, place 1 and place 2
and if we have pO2 1 and pO2 2; then if this is greater than this; then automatically we
have E ox red 1 greater than E ox red I can put 2 here. So; that means, we see that
because of the pressure difference of dissolved oxygen difference in two places, which
are electrically connected we see that there is a difference in potential.
And since they are electrically connected; so that means, the place where the oxygen
pressure is more than the place where oxygen partial pressure is less; then this place
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would act as positive electrode and this place would act as negative electrode. So, this
becomes cathode and this becomes anode. So, then we see that the concentration cell is
developing again. Now this particular concept can be used to understand some of the
corrosion phenomena; as we see commonly happen in our day to day life if you see that.
So, let us understand some of these corrosion phenomena; first let us understand the
corrosion phenomena what happens if we have a raindrop.
Let us say when the raindrop happens the raindrop is small raindrop and that actually
stays on the surface of that metallic object; depending on the contact angle, depending on
the nature of the surface, it can have this or it can have this or it can have appearance like
this. So, this becomes my hydrophobic, this looks like better hydrophobic because the
contact angle becomes this is a contact angle.
This contact angle becomes more than 90 degree and this is hydrophilic because it is
trying to absorb water and this is in between this is in between. So, contact angle is this
is the contact angle theta. So, here the contact angle is more than 90; here it is more than
this angle. So, this is hydrophilic this is hydrophobic this is in between and that is what
we have super hydrophobic surface where the contact angle is generally around more
than 140 or 145 degree.
And one of the super hydrophobic surfaces basically the lotus leaf; there we if we put a
water droplet it bounces on that particular surface and that is what water at this that is
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what; it actually helps in cleaning the particular surface; that means the lotus leaf
because when we tilt it the water falls down and that way it takes those dirt particles
along with it and then gets rinsed.
Now if we try to see this particular situation; now I can make it a bigger picture like this
I zoom it this particular situation I zoom it. So, if I zoom it; so, then this is my H2O and
if I see the surrounding area, they are in contact with air and this is my iron surface; so,
this is my iron surface. So, let me remove that part; so now, once we have this situation
then since this is electrolyte, this H2O becomes my electrolyte and we have iron and also
oxygen.
So, immediately we start having this reaction; as well as Fe plus plus minus E equal to
Fe 3 plus. So, these are anodic reactions and this is cathodic.
So, initially the partial pressure or the initially the oxygen concentration throughout this
water droplet, this water droplet this throughout this droplet; we have almost similar
concentration level. So, in the beginning both those reactions will happen statistically
uniformly over the surface.
So, now if I consider this section; at this section in the beginning we have both the all 3
reactions and these are actually forming FeOH whole 2 as well as FeOH whole 3. Now
due to the reaction this oxygen is getting consumed. So, once we have consumed oxygen
then of course, there is a from this plane to this particular centre position; we have a
concentration difference.
Why that concentration difference is coming? Because the oxygen that is being
consumed here or here that is getting replenished by the oxygen diffusion that is coming
from air. Because these section this peripheral sections are under direct contact with the
air. So, oxygen content in this section remain almost same from the starting of the
reaction as well as during continuation of the reaction.
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But at this zone the oxygen is consumed because since is a diffusion process that oxygen
has to diffuse through this layer; go to this even though it is a small droplet, still it takes
time for the oxygen to reach to that particular section. So, now here we have oxygen
deficiency and here we have almost similar oxygen. So, now, if I see the plot of oxygen
concentration; so now, if I see the plot; so, from this to this if I try to see the oxygen plot
between oxygen. So, this is the distance and this is oxygen content, if I see the
concentration or activity of oxygen; then at this place the activity would be the
maximum.
And then as we go from this to this as the reactions are progressing; we are relaxing
time. So, then the oxygen content in this zone would get will get depleted in this zone
there will be supply of oxygen from surrounding air; so, oxygen concentration gradually
goes down. So, this particular line it may have its own plot depending on the diffusivity
of the temperature of the atmosphere.
So, even though this water droplet remains momentarily, but still this situation can arise.
So; that means, we see the concentration activity of oxygen here this is 2; let us say and
this is activity of oxygen this is one position, we have difference in concentration. Once
we have difference in concentration if I try to see the E ox red position 1 and this is the
position E ox red position 2.
So, this becomes higher than this; so, this becomes positive this becomes negative or this
becomes cathodic and this becomes anodic. So, finally, this here we have anodic reaction
and here we have cathodic reaction. And we must say that these are basically
predominantly cathodic and here we have predominantly anodic reactions. Now for the
anodic reactions we can have anodic reactions like this, but for that we have to have
supply of oxygen or this OH minus should get decomposed and then form oxygen, but
there are 2 more strong oxidation reactions which are these two.
So, in the cathodic zone we have this cathodic zone we have cathodic reactions. So, this
becomes cathodic reaction zone and this become cathode, this become anode and here
the cathodic reaction would be Fe minus 2e equal to Fe plus plus Fe plus plus minus e
equal to Fe plus 3 plus. And whereas, here we will have oxygen plus 2H2O plus 4e equal
to 4H minus. So, in this zone we have cathodic reaction and in this zone we have
reactions.
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The cathodic reaction is this one and anodic reactions are these two. So, whenever we
have Fe plus plus and Fe 3 plus; so, they would try to form FeOH whole 2 and FeOH
whole 3 and they will try to deposit. So, this is the deposit if I consider; so, now,
corrosion; that means, this iron is dissolving. So, the iron is dissolving preferentially in
this zone; in this zone in the centre part because the centre part becomes my anode. And
those iron ions will form OH minus that is forming in this particular reaction and they
will form a deposit around this zone, around on this zone.
So, these are my deposit of ferric oxide ferric hydroxide or feroxide oxide. So, the
corrosion is taking place in the centre part and the cathode regions or these regions will
have very little corrosion because the preferentially cathodic reactions are taking place
and why it becomes cathodic? Because we have these situations; so, it becomes a
concentration cell and where this is negative part and this is positive and this is positive.
So, this is a typical corrosion phenomenon when have it corrosion phenomena happening
inside a water droplet; even though it is a momentarily staying of this water droplet is
staying momentarily, but still these corrosion reactions can take place. And with time
you would see that there could be a small if we see carefully under the microscope we
will see that yes this zone has got attack more than the surrounding zone the annular
zone.
So, this is the effect due to concentration cell or the differential aeration cell that is
forming because of the concentration of oxygen or the dissolved oxygen in the water or
in the electrolyte; so, this is basically we call it a rainwater corrosion.
So, we will stop at this moment. Now, we will continue our discussion in our next
lecture.
Thank you.
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Prof. Kallol Mondal
Lecture - 18
Examples of Concentration Cell and Spontaneity of Corrosion Process
Let us begin lecture 18.
We discussed concentration cell in brief and then we attacked a problem on corrosion

under rain water droplet. And then we explained that at the centre position after
sometime at the centre position becomes preferentially anode and the annular portion
becomes preferentially cathode because we have more oxygen there.
So, there cathodic reaction should happen and they would act as cathode in the centre
portion anodic reactions that iron would go into iron plus bus as well as iron plus 3. And
those iron plus 3 as well as plus 2, they will combine with OH which minus that is the
product for this product in the reduction reactions of oxygen in in combination with
water. So, they will form ferric hydroxide or ferrous hydroxide and they will deposit
around that centre positions.
Now, you might have seen that in some cases if let us say some handle the metallic
handle is fixed on a wooden block on the door or some places in the window. And you
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might see that if you after sometime after some years; if you take that particular block
particular the metal block out, the portion where screwing has been done. And if you
watch the screw carefully or the nail carefully, you would see a nice observation if you
are if you have observed before.
I have brought 2 samples let us see whether we can see something and then we can have
a direct correlation on this concentration cell and that differential aeration cell that
develops due to the difference in oxygen concentration. Now first example I am showing
this one if you see this is a broken wood then it was nailed here; this was fixed on a
particular, this particular broken wood was fixed on an another block with this nail this
was a nail or rather it is a screw this is a screw if you see this cut you can see this cut.
So, let me put (Refer Time: 03:03) put a pen and then if you see this cut. So, this is the
cut so; that means, it is a screw it is a screw and see the top part top part of the screw its
corroded there are red rust is the signature of red rest. But once you see this the rest of
the part which are going inside the wood; let us say this part if I see this part; this part if I
carefully see let me put light on this; so, then you will it will be clear, if you see this let
us see this you can see it carefully can you please zoom it little more, is it possible to
zoom?
So, I am talking about this nail this nail this nail part, this is the nail I am talking about
the rest of the screw part it is seriously corroded. But top part which is exposed to the
atmosphere is corroded, but that not serious; this also can be explained from difference in
oxygen content. Now, let us see another one; if we see this one this is more severe this is
the metal object and there are screws here, there are 2 screws here and one screw here.
So, almost similar type of screw one screw is missing because when I pulled it up and
then once screw got missing. But if you see this particular segment this screw top there
are corrosions I am not saying that there are not no corrosion, there are corrosion, but
interestingly if you see the other part, if you see this you see it is a kind of exfoliation
this screw the rest of the screw has swelled. And this swelling has happened because of
this iron hydroxide and iron hydroxide formation these are rust these are basically the red
rust.
And if you see this one some part has vanished because the corrosion was so severe that
some part has vanished because it got lost into the atmosphere not into that particular
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remain in that particular wooden part because it was fixed like this on the on a wood. So,
this is a wood and this was fixed like this. So, now, why there is a little bit of corrosion
on top, but the part which has entered into the wood there we see lot of corrosions. So
why? So, this can also be explained by using this concentration cell.
Now, if I see this top part, if I see this top part the top part is exposed to the environment.
Yes there are moisture there are oxygen, but the bottom part which has entered into the
wood; though we assume that the wood also the wood is of pervious because there are
fibres that fibres can have moisture or even the moisture can enter into the wood over the
time.
And, but the oxygen content on top and the so; that means, we have electrolyte that the
they are basically electrically connected. Because here also we have moisture here also
we have moisture because the wood contains moisture all over the time the moisture can
sweep in and this part of course, we have moisture. At the same time we have oxygen
here, but the oxygen content in this zone will be very less. So, here we have a maximum
oxygen, but as we go towards depth the oxygen content would reduce drastically.
So; that means, these zone the at the extreme part wood be anode, but the top part where
we have more oxygen; so, cathodic reaction which is oxygen reduction in neutral media.
So, that reaction would happen onto this entire surface, but the bottom part where we do
not have oxygen that becomes my anode. And since iron dissolution, iron goes into iron
ions they are strong anodic reactions those reactions would happen here. And then those
iron ions that are forming they will combine with this OH minus that are forming and
they form red rust or hydroxide or a hydrated oxides of iron.
So, this is again can be explained from the point of concentration difference of oxygen.
So, this is a classic example you might also see at several locations such kind of things
happen. So, now this is what I wanted to say that concentration cell is a serious
consequence even crevice or pitting corrosions. These two are very serious forms of
corrosion as we have explained before because they are localised extremely localised and
they are also related to the concentration difference of oxygen.
So, in the crevice part there would be oxygen depletion and the away from the crevice
part; we have still oxygen. So, the crevice part becomes preferentially anode and the
crevice section away from the crevice section, they will act as cathode. So, the crevice
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part would corrode; the cathodic part the rest of the part would corrode less. Similarly
pitting also, in the pitting zone we have preferentially anode and preferentially anodic
reactions or iron dissolution and then formation of iron oxide or iron hydroxide they
would form and the rest of the part would remain as cathode because there we have more
oxygen. So, these are the kind of examples what we find in our day to day corrosion
phenomenon.
Now in lecture 18; we will look at that see these corrosions are taking place because of
the ions formation. And then we have a concentration cell development and oxygen
effect (Refer Time: 09:21) oxygen content, it can change in a short region and then we
can have cathode and anode all those examples we have put. Now final we have to see
that when a metal oxidizes or corrodes in a particular aqueous medium.
Now, when we talk about aqueous medium; in the beginning we concentrate on a

presence of moisture or water. And when we talk about moisture or water we have to talk
about pH level or pOH level. So, now, we will consider the presence of metal ions,
metal, pH and water. So, when we have this kind of system which are commonly
observed. So, there we have to see at what condition we have corrosion of that particular
metal. Now when we talk about this what condition that initially we talk about the
thermodynamics part; that means, initially we have to see whether the free energy
change for that corrosion process is negative or not.
When the corrosion process free energy change is negative, we say that the corrosion is
spontaneous. Otherwise if we see that the free energy change becomes positive then we
may say that we have we will say that the corrosion process is not spontaneous rather it
is difficult; rather thermodynamically we will say that it is not feasible. So, let us have
some examples for before that we see this particular plot.
This particular plot is a serious plot and I want you to understand this plot and time to
time this plot has come in this particular set of lectures. So, we see delta G0; E0 and K,
K is the basically equilibrium constant. So, now, relation between these arms basically ln
K equal to nFE0 and here it will be delta G0 equal to minus RT ln K and here delta G0
equal to minus nFE0; so, these are the relations between the arms.
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Now, if we try to see let us say delta G0 equal to 0; now for a particular equilibrium
reaction let us say this is my equilibrium reaction, I am considering M ne equal to Mn
plus; so, this is the reaction what we talk about. Then if we consider the standard free
energy change delta G0; that means, P equal to 1 atmosphere T equal to 298 Kelvin; then
K would be 1; so, K is nothing, but activity of Mn plus by activity of M.
Now, when we have this one to be 0; then we see E0 ox red equal to 0; now if delta G0
less than 1 so; that means, there is a quite a lot of spontaneity in this particular reaction;
that means, by that time we consider this reaction; that means, the forward reaction is
taking place. So for a forward reaction; for the forward reaction; so that case K becomes
greater than 0; that means, K becomes positive. So, more amount of product will form
and that time E0 ox red also greater than 0; sorry here we made a mistake because when
it is 0 that time 1. So, it is more than 1 and when this is equal to this is less than 1; so,
this becomes greater than 0.
Now, K greater than 1 and K equal to 1 means; so both forward and backward reactions
they are equally possible, but when K greater than 1; it means that the preferentially
forward reaction is taking place. And that is what when this becomes less than delta G0
is less than 1; so, this condition holds true; so, there is a positive potential gradient; so
current would flow.
Now, if delta G0 greater than 1 then for forward reaction. So, that case K less than 1 and
E0 less than 0; so that means, the forward reaction would be less probable and the
backward reaction; that means, this reaction becomes more probable if we have this
situation and that time we have this so; that means, the potential would go towards
negative. That means, the cathodic so, we so; that means, we have less amount of this
reaction so; that means, metal ion would not be formed rather metal ion would get
reduced.
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So, when we say that metal ion would get reduced; it means that the corrosion process
that mean ion formation process would not be a probability, rather deposition becomes
my probability that case we might say that the corrosion is controlled or corrosion is
minimised. But in this case corrosion is maximized and in this case its equilibrium. So,
the corrosion as well as metal deposition they are happening at a same rate. So, these 3
situations this is situation I, this is situation II and this is situation III. In fact, situation II
and III would guide us whether the corrosion would take place or not.
Now, when we talk about normal system; that means, let us say nickel in H2O of certain
pH. So, nickel might get oxidized; that means, nickel can form nickel ion so; that means,
it is a corrosion or it can go back and form nickel. So, that becomes my cathodic reaction
or less corrosion and that time; since these are all the standard states; that means, E0 as
well as G0, we are talking about standard state and in the actual system we may not
maintain standard state.
So, the nickel concentration in water may not be 1 that activity of nickel ion may not be
1; so, that times we have to consider non standard situation. In the non standard situation,
we have the similar kind of analysis. So, that time we have to consider this equation it is
Q or the activity quotient. So, Q can be written in the form of activity of n plus activity
of M; so, we are talking with reference to this reaction.
So, there we are having a non standard free energy change and then we have to consider
this value. We have to if we see this goes to is greater than 0; that means, the forward
reaction or corrosion reaction is not feasible.
And if delta G less than 0; that means, corrosion process is and here we are considering
with reference to the corrosion; so, that case this would be a feasible process. Now our
interest would be to find out with the data set what we can generate from this to see
whether this is greater than 0 or this is less than 0 at that particular condition. So, in order
to know this we have to have a numerical problem and then we would be really clear that
yes if we have this condition; that means, this is the pH level, this is the temperature, this
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is the pressure level; then we can decide that whether a particular metal would corrode in
that particular solution.
And when we talk about corrode in that particular solution; that means, the corrosion
process becomes spontaneous. And when we talk about spontaneity we have to consider
free energy change and we have to say this condition is met.
Now, in order to do that we will take up a problem; that problem I am taking from a
book which is a very good book Principles of Corrosion Engineering and Corrosion
Control by Zaki Ahmad; you can read this book this is a fantastic book, I will just take
one problem from that.
So, the problem statement says that calculate the theoretical tendency of nickel to
corrode in deaerated solution, deaerated water where pH equal to 8. And I assume the
corrosion potential; corrosion products are H2 and NiOH whole 2. Data given kSP for
NiOH whole 2 equal to 1.6 into 10 to the power minus 16, E0 Ni plus Ni equal to minus
0.25 volt. Temperature of course, is 298 Kelvin, pressure equal to 1 atmosphere.
So, now it is saying theoretical tendency; so, theoretical tendency whenever we are
talking about theoretical tendency; we first consider that nickel is corroding. So, nickel
2e equal to nickel plus plus this reaction is taking place. And then we will see that if this
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reaction happens then we have to find delta G0 for the entire system should be less than
0.
So, then we would say that the nickel corrosion is spontaneous; so this is corrosion. But
if we find delta G0 delta G greater than 0; then we will say that this is non spontaneous
and this is spontaneous, we are talking about corrosion of nickel. Now, we are talking
about; so when we say that entire system; so not for this particular reaction. So, we have
to see the another reaction which takes place because this is my anodic reaction; so, we
have to have a cathodic reaction.
So, cathodic reaction is this; so now, if I do this; so, if I add them. So, then it becomes Ni
plus 2 H plus it goes to Ni plus plus H2. So, this is my the total this is my overall system
reaction; that means, there is a equivalent cathodic as well as anodic reactions; so this is
my cathodic reaction.
But in addition to this we see that Ni(OH)2 is forming and it has got a very low solubility
product. So; that means, these Ni plus plus; this Ni plus plus will react with OH minus
that is there in the water system already. Because water we can also dissociate H2O; it
goes to H plus plus OH minus; so this reaction we can consider. So, when we consider
this reaction then we have to also take care of kSP of this H2O. So, the kSP of a (Refer
Time: 24:54) 10 to the power minus 14. So, this 10 to the power minus 14 we can write
H plus into OH minus equal to 10 to the power minus 14.
So, if we take log; so log of H plus plus log of OH minus equal to minus 14. So, if we
take minus log of H plus and minus of log of OH minus equal to 14; since we have one
more, one H plus and one OH minus. So, we can assume that the number of H plus and
number of OH minus should be equal. So, then this and this they would have equal
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contribution to this 14. So, I can say that and this is nothing, but pH plus this is nothing,
but pOH equal to 14.
Now, if we have 7 and 7; then it becomes 14 and we have if we have a neutral solution
that time the pH is 7. So, that is what we have pOH is also 7; now here we have pH; pH
equal to 8. So; that means, H plus concentration is nothing, but 10 to the power minus 8;
since minus log of H plus equal to 8 and that is what the concentration of H plus I can
find out.
So, now if I find out H plus then I can find out OH minus into H plus equal to 10 to the
power minus 14. So, I know what is the concentration of H plus ion; so, I can find 10 to
the power minus 14 equal to 10 to the power minus 8 in to 10 to the power minus 6; so, I
know the concentration of OH minus.
Now, once we find out OH minus now these OH is available to react with; this OH is
available to react with Ni plus plus and when they react; they form whole 2.
So, now it will also have its own equilibrium; now there the amount of nickel plus plus
that is available in the system would be decided by the kSP of NiOH whole 2. Because
once NiOH whole 2 forms, the limited solubility of NiOH whole 2 would allow little bit
of nickel plus plus ion to be present in the solution and once we know the concentration
of nickel plus plus in the solution; then we can find out what is the potential that would
generate for this particular reaction, for this particular reaction in that particular solution
and also we know pH.
So, we also can find out E1 and E2 and then we can have a difference between these 2
potentials and that would lead to finding out these 2 situations. So, we will discuss this
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same problem in our next lecture; for the time being we know that we have to go through
this route to find out the nickel concentration, nickel ion concentration in the solution.
Let us stop here; we will continue this lecture in our next class.
Thank you.
186
Prof. Kallol Mondal
Lecture - 19
Spontaneity of Corrosion Process and Introduction to Pourbaix Diagram
Let us begin lectures 19.
So, in last lecture the end we started discussing nickel corrosion; I we would like to say
that it is whether that nickel would corrode in a particular solution.
187
And the problem statement was; if you see the problem statement, this was the problem
statement. We need to calculate theoretical tendency of nickel to corrode in deaerated
water pH 8. Assume that the corrosion products are H2 and NiOH whole 2 and we have
the data temperature pressure 298 Kelvin and 1 atmosphere. Solubility product of nickel
hydroxide is 1.6 into 10 to the power minus 16 and standard reduction potential of nickel
is minus 0.25 volt.
And we did these calculations, you can just go back and then see these calculations; we
just wanted to see what is the concentration of nickel ion that could be present in the
solution, when we have this NiOH whole 2 product formation. And when we have NiOH
whole 2 and this NiOH whole 2 would dissociate into Ni plus plus and OH minus ions.
And we know the pH of the solution and from the pH we can calculate what is the
concentration of hydrogen ion and then accordingly we can also calculate the
concentration of OH minus ion. And that concentration will be in equilibrium as set by
the solubility product of NiOH whole 2. Now if you see that since the pH is 8; so, you
know the hydrogen ion concentration is 10 to the power minus 8.
And since hydrogen ion concentration the product of H plus and OH minus ion
concentration is 10 to the power minus 14. So, we get OH minus concentration was OH
minus ion concentration to be 10 to the power minus 6. And now we have to look at this
particular equation which talks about the equilibrium between Ni plus plus and OH
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minus. And it is forming NiOH whole 2 and this Ni OH whole 2 has got its own
dissociation constant; so, we start from here. Now if we see this NiOH whole 2, it can
have equilibrium between Ni plus plus plus 2OH minus. Now we know that OH minus
ion concentration in the solution is 10 to the power minus 6.
Now, from kSP consideration would be equal to concentration of NiOH 2 OH whole 2

divided by whole 2. So, now, this is a solid product which is precipitating out. So, we
can consider to be 1 and then we get to Ni plus plus ion concentration which is kSP
divided by OH ion whole 2. So, here it should be we made a mistake; so, this 2 should be
here square because we are considering the dissociation constant.
So, now, if we know this we know kSP 1.6 into 10 to the power minus 16 and here 10 to
the power minus 6 square. So, it ends of 1.6 into 10 to the power minus 4.
So, I am just putting unit concentration unit which could be mole per centimeter cube.
Now, once we have this then initially we are assuming that nickel is corroding. So, if we
have an electrode, if we see these two electrode; one side is hydrogen electrode and one
side is nickel electrode.
And when nickel is dissolving and that is of course, forming NiOH whole 2. Now since
nickel is dissolving and hydrogen is evolving; so, this is H2 is evolving. So, hydrogen
plus plus plus 2e equal to H2; this cathodic reaction is taking place on this particular
electrode.
Now if we have a connection like this with the salt bridge; then if we connect them, the
current should flow from this way to this way. So, this is positive end this is my negative
end; so, this would be my cathode and this will be my anode.
189
So, this cell is also replicating the situation here; how it is replicating? Because in this
case I have a solution with a pH 8 and in that we have a nickel piece. So, this nickel
piece is forming a half cell which is similar like this and hydrogen evolution on the
surface of the nickel piece is mimicking the hydrogen electrode on the other side. So, this
is the solution and this is the solution; here these are these two half electrodes have been
electrodes have been broken. So, the entire reaction is broken into two half; that means,
two half cell reactions which is one side is Ni minus 2 equal to Ni plus plus another side
is this one.
Now, when we have this situation because we are assuming there is a nickel is corroding.
So, then this side should be always positive; this side should be always negative. So,
now, the potential E1 which is setup on this right side should be greater than the potential
on the left side and this potential of course, for our convention is we will take reduction
potential.
So, E1 which is a reduction potential for H plus going to H2 and E2 reduction potential
for Ni plus plus going to Ni. And in order to have nickel going into Ni plus plus; so this
E1 should be E2 and if E1 is greater than E2; so, the cell potential which is del E is
nothing, but E1 minus E2 should be positive. And if it is positive then we see that since
we know del G for the reaction is equal to nothing, but minus nF delE over the cell
potential.
And if this is positive, so del G would be negative and once we get del G to be negative
then we can say that the reaction is spontaneous. And since we are considering nickel is
dissolving; so, nickel dissolution is spontaneous or corrosion is nickel corrosion is
spontaneous. Now then our main interest should be to find out the reduction potential on
this side and the reduction potential on that side; so, let us find out.
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Now, we have all the ideas all the data because nickel ion concentration we know which
is 1.6 into 10 to the power minus 4 unit; we can consider mole molar unit sorry, we can
consider molar unit. So, now, H plus is equal to 10 to the power minus 8; now let us see
what potential it would get.
So, E2 equal to nothing, but ENi plus plus Ni equal to E0 Ni plus plus Ni plus RT by 2 F;
since 2 electrons are involved for this reduction reaction lnNi plus plus ion concentration
which is oxidant and nickel ion concentration nickel concentration which is the nickel
metal.
So, this we know minus 0.25 volt and if it is 298 Kelvin and 1 atmosphere pressure. So,
then this particular quantity becomes 0.0591; we have calculated before, 2 and this
becomes then log because when we take log say 2.303 that conversion factor from ln to
log need to be multiplied with RT by F factor. So, this becomes minus 0.25 plus 0.0591
by 2 log 1.6 into 10 to the power minus 4. So, we get the value; so the value becomes; so
this becomes divided by 2 into 0.0591 by 2 minus 0.25 minus 0.112 volt equal to minus
0.362 volt; so, E2 is nothing, but this much.
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Now, we can calculate E1 which is this side nothing, but E H2 equal to minus 0.0591 pH.
We have done it this particular calculation before because E0 H plus H2 equal to 0. So,
E1 becomes minus 0.0591 into 8; so this becomes minus 0.473 volt. So, del E would be
equal to E1 minus E2 which is minus 0.473 minus 0.362 plus would be equal to 0.111
volt with a minus sign, this is a minus sign here.
So, del G for the overall free energy change for the system and the overall reaction is Ni
plus 2H plus equal to Ni plus plus plus H2; this is the overall reaction.
So, for that the change would be minus nF delE and here n is equal to 2; so 2 into 96500
into 0.111 volt and since there is a minus sign here. So, it becomes plus into equal to plus
21384.4 joule and remember this is a plus sign.
So, for a spontaneous process del G should have been less than 0; as we have seen before
if we see this part you see this is the section I am talking about. So, del G negative means
spontaneous del G positive is non spontaneous. So, now here we are getting spontaneous
and del G positive non spontaneous and here we are getting del G positive. So, it
becomes definitely the; this particular process becomes non spontaneous; means the
assumption we had that the nickel would corrode that assumption does not hold true.
So, if this particular process is non-spontaneous then the reverse process should be
spontaneous. So, the nickel ion rather would get reduced; so nickel corrosion is not
feasible in the present condition. Now let us see; so this is the in order to find out
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whether the nickel would corrode or not; we are doing the calculations and all those
consideration starting from here.
If you see this section this particular slide we see that entire lot of calculations and
finally, our primary interest is to find whether del G is negative for the process or del G
is positive for the process.
Now, let us see if we maintain all other this particular NiOH whole 2 that is forming and
if the temperature is fix. So, if we maintain this particular kSP constant of Ni OH whole 2
is not changing. So, it still 1.6 into 10 to the power minus 16 and if we change pH; let us
say pH becomes 3, let us see what happens.
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So, if pH becomes 3; then I can find out H plus ion concentration or I can do a different
route. Since we have seen pH plus pOH equal to 14; so, pH is equal to 3 plus pOH equal
to 14. So, pOH equal to fourteen minus 3 equal to 11.
So, this can give me the concentration of pOH minus ion is equal to 10 to the power
minus 11.
Now kSP remains same; so Ni plus plus OH minus whole 2 equal to kSP equal to 1.6 into
10 to the power minus 16. So, that time nickel ion concentration becomes 1.6 into 10 to
the power minus 16 divided by 10 to the power minus 11 ; 2 is going to be 1.6 into 10 to
the power minus 22 minus 16 equal to 1.6 into 10 to the power 6; this is the
concentration level of nickel ion concentration in that solution.
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So, we can have again calculate E2; E0 which is minus 0.25 plus 0.0591 by 2 log Ni plus
plus ion concentration and this side becomes into pH is equal to 3. So, I would get
0.0591 into 3; it goes to minus 0.1773 or I can just simply say 0.1 volt and this side
becomes plus. So, that consultation becomes 1.6 into 6; 0.183; so this becomes minus
0.25; 0.07 volt.
Now, if I try to find out del E is equal to E1 minus E2. So, that becomes ok; so, we can
find out del E again and then del E becomes 0.177 minus or which will become 0.07
which goes to 0.107.
So, I still see that I get a negative del E value. So, even at a pH of 3; which is highly
acidic I could see if this data other data holds; other data hold other data are just like the
way we have considered, still we could see that the del E becomes negative. So, del E
becomes negative means del G becomes positive. So, then again it becomes non
spontaneous non spontaneous.
So; that means, we have to do a entire lot of calculations in order to see whether del G
becomes negative or positive. Just like that we can have other calculations, but instead of
doing this; these entire calculations to see whether the del G becomes negative for a
particular corrosion process, we can also have another route to understand whether the
system or the metal would corrode in the water system or not; when it is dipped in
atmosphere with certain pH level. So, that information can be obtained from a particular
diagram which is called Pourbaix diagram.
So, this Pourbaix diagram is nothing, but plot between pH and potential. When a metal is
exposed to aqueous medium and whenever we are talking about a metal is exposed to
aqueous medium; we take following species, oxygen, H2O, H plus ion, OH minus ion
and of course, metal and metal plus plus ion or rather if we do not know what is the
oxidation number; we can consider n plus ion. So, Mn plus this M is nothing, but the
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metal; now whenever we have existence of metal ion then there could be possibility of
formation of m oxygen n this oxide can form or MOH whole n, this hydroxide can form.
So, generally these oxides or hydroxides they have very low solubility product and that is
what they tend to settle down. So, now, whenever we expose a metal in this particular
system containing such ions; there could be possibility that oxygen is not present, but
hydrogen ion would always be there. Now there could be possibility of presence of
oxygen and of course, you once you have a metal there could be possibility of formation
of metal ion and if the system situation permits we can have oxide or hydroxide.
So, that time we can have the stability of different phases for example, this phase this
phase or this phase and this phase even this one. All those phases we can have some
information from that diagram and we are also we are forgetting another important
species which is hydrogen H2. So, there could be possibility of hydrogen evolution also
when a metal is dipped in an aqueous medium; just like zinc when it is exposed to dilute
HCl, where we have pH less than 7 its acidic then we see that hydrogen bubble forms
and of course, Ni plus plus ion also forms. So, this is a stability diagram between pH and
potential.
So, these diagram has two axes one axis becomes this pH, another axis becomes
potential which is in volt and this is in pH which is a number.
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Now, there we can have a kind of if you see a Pourbaix diagram of certain metal; we can
see certain kind of this kind of diagram or we can have a diagram like this, we can have a
diagram like this is E versus pH also. So, this diagram if we see carefully, then we will
see that this is metal, this is metal ion and this is metal hydroxide n or M2On; so, this
kind of boundary we can have.
Now from this diagram without going for that calculation; detail calculations that
whether del G becomes negative or not to understand whether the corrosion would take
place or not. If we look at this diagram, then immediately we can make out that whether
the metal would corrode or not; so, this is the benefit of this diagram.
So, the our next level of understanding would be how to construct this diagram and what
are the informations we can snatch out of this diagram? And remember this diagram
plays a very very important role in electrochemistry and specially in corrosion because in
corrosion sometimes you will hear that the metal is passivating and this diagram can also
tell you whether the metal would actually passivate or not.
So, those informations definitely we can we can snatch out from this diagram and it
would also enable us to find out the tendency of the metal to remain as metal or metal
ion; that means, corrosion or passivating state; without going for detailed calculation the
way we have done for nickel. So, our next topic would be Pourbaix diagram; let us stop
here, we will continue our discussion in our next lecture.
Thank you.
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Corrosion - Part I
Prof. Kallol Mondal
Lecture – 20
Construction of Pourbaix Diagram
See in next couple of lectures we will be discussing Pourbaix diagram, we have already
started looking at Pourbaix diagram because it is an important aspect important feature in
electrochemistry. And when you look at the corrosion then this understanding of
Pourbaix diagram is very very essential. Now, as we have told that the Pourbaix diagram
is nothing, but the stability plot between of different phases between in the plot of E
versus pH, this is the Pourbaix diagram, this is basically stability diagram.
Now, whenever we talk about Pourbaix diagram we must understand certain facts, and
what are those facts? 1, we would only consider reactions involving oxygen, H2O, H
plus, OH minus, metal ion, metal-metal ion, metal hydroxide or metal oxide. So, here we
are talking about only this kind that would be several complex oxides involving these
many species and remember we will not consider any other species.
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Second part, we would consider reactions and those reactions can be categorised into 4
major reaction stages one reaction of course, will not consider, but that indirectly affects
the pH of the system, but that will not be plotted on the Pourbaix diagram. And certain
reaction only involve metal and metal ion, certain reaction would involve hydrogen ion,
H2O; that means, what a metal, metal ion or an hydroxide metal hydroxide on metal
oxide. And certain reactions would involve metal, H2O, hydrogen ion and metal
hydroxide or metal oxide, but between these two last two cases one case we would see
that there is no electrons involve for those particular reaction, but other case we have
electrons involvement of electron.
So, let us categorised those reaction, let us categorise those reactions one reaction for
example, in water we sometime we have dissolve of carbon dioxide that can react with
H2O and form H2CO3.
So, as I have told that this reaction cannot be plotted in Pourbaix diagram of a metal, but
actually whenever we have this is an acid, this acid would have this is the weak acid, but
still it would lead to set certain pH of the system that can affect the corrosion stage. And,
this is a typical acid that affects the corrosion of rebar; that means, reinforce bar in the
which is basically embedded in concrete mixture.
But this particular reaction if you see, it does not involve any metal, no involvement of
metal. So, this is kind of type-I I can say this is type-I reaction. Now type - II reaction for
example, metal I can have n plus plus ne equal to M, M is the metal and now since I do
not know what is the oxidation number then n plus
For example, if it is a copper copper plus plus going to copper n becomes 2 Fe plus 3
going to Fe n becomes 3 like that way we can have the value of n. So, n is basically
nothing, but the oxidation number.
So, this is this particular reaction if you see carefully it depends on potential why
because this reaction can be expressed with in terms of Nernst equation, but this
particular reaction does not involve any H plus ion. So, this H plus ion is not involved so,
then the pH of this particular for this particular reaction would have no effect. So, it we
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can say that this is function of potential, but it is not a function of hydrogen ion
concentration. So, this is the function of E, but not a function of hydrogen ion or not a
function of pH. So, whenever we have hydrogen ion presence we can express in terms of
pH this we call it type- II.
We can have another reaction for example, let us say I can have M which can react with
2H2O it can go to MOH whole 2 plus 2H plus plus 2 e and that time n is basically 2.
This is another reaction we can consider that can happen in water when a metal is expose
to moisture or water atmospheric. So, now, here we see that it is we have it here also we
can express this particular reaction in terms of Nernst equation RT by 2F since number
of electrons involve for this reduction processes 2F 2 ln activity of oxidant.
Now here the oxidant part is this part and reductant part is this part so, I can write this
particular reaction in reverse; so, MOH whole 2 plus 2 H plus plus 2 e equal to M plus 2
H2O. So, now, here M has got 2 plus so, the 2 plus going to 0. So, it is a reduction so,
this reduction process we can express in terms of a MOH whole 2 aH plus to the power
2, aM aH2O this a is nothing, but the activity I can express this in this form.
Now, interestingly this particular equation once we express in terms of Nernst equation it
becomes a function of potential. But here if we consider these particular hydroxide to
deposit back to or to settle down that may because of it is very low solubility product
solubility constant. So, this particular thing if it is we consider to be pure and solid. So, I
can consider activity to be 1 and if we considered it is a pure water it comes activity 1
metal of course, it is pure an activity 1.
So, then this equation we can write in terms of E0 plus RT by 2F ln activity of H plus we
can write. So, we can express this reaction through this Nernst equation. So, you see that
it is function of potential at the same time it a it is a function of H plus ion presents or
function of pH. So, this reaction becomes the type - III category. Now we have one more
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reaction that is also possible where let us say this is 1, this is 2, this is 3, now we have
one more, which is M2 plus plus 2H2O it can go to MOH whole 2 plus 2H plus.
So, this reaction we can also have, where you see that it does not involve any electron.
So, if there is no involvement of electrons we cannot express the equilibrium for this
particular reaction in terms of potential we cannot express, but this is the chemical
reaction.
So, this chemical reaction can be expressed in terms of equilibrium constant which is
nothing, but activity of product; so, activities MOH whole 2H plus square activity of M2
plus an activity of H2O square. So, if we see this reaction, this reaction so, if we consider
the forward reaction. So, I can express K to be like this whether forward or backward it
does not matter because it is a equilibrium constant so, I can write this.
Now once we write this then we can also simplify this equation, this equation can be
written log K equal to as we have mentioned MOH settle down. So, it is a solid and that
too pure. So, MOH whole 2 we can consider 1, a H2O still we can consider 1 because it
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is a pure water, then it goes to the equation boils to log activity of H plus, activity of M2
plus this.
So, I can write if I convert activity into concentration assuming that it is maintaining
ideal solution. So, in case of ideal solution activity becomes concentration so, that case I
can write log 2 minus log 2 plus. Now we see that in this final equation becomes I can
put it as pH because this is nothing, but minus of pH with a 2 sign because 2 would come
here minus log of M plus 2 plus concentration. So, this is an equation which can decide
the stability of M2 plus and stability of MOH whole 2.
But this particular reaction does not contain potential. So, the potential cannot decide this
particular reaction, potential cannot tell me the stability of this particular reaction
because it does not involve any electron acceptance or electron if the system is not also
giving away electrons. So, no cathodic or anodic reactions are taking place in this entire
reaction. So, it is pH dependent function of pH because here we have pH, but it is not a
function of potential. So, this is type – IV. So, this equation becomes type – IV. So, the
type- IV equation can be expressed with this.
Now, whenever we are having these equations for example, equations like this, equation
like this and finally, we are boiling with 2 we are getting to this particular equations or
equations like this, these equations would enable us to plot Pourbaix diagram and also
enable us to find out the stability of M2 plus M or M hydroxide because here we are only
considering hydroxide we can also have set of reactions involving oxides also metal
oxides.
Now, as I told you that the first one was this many species are considered depending on
the possibility of formation of this species or this species and the possibility of having
dissolve oxygen or deaerated and then second part was we can have 4 types of reactions,
but mainly we are considering type - III to type – IV. So, these reactions we are
considering to happen in the aqueous system and that would lead to the plotting of E
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versus p H and that too that would give us the Pourbaix diagram. Now interestingly the
Pourbaix diagram will not be complete, if we do not consider 4 reactions involving only
oxygen, dissolve oxygen of course, hydrogen, hydrogen ion and 2 other species which
are OH minus and H2O.
So, now, we can have 4 more reactions involving H plus, OH minus, O2, H2O, H2. So,
these 5 species can have following reactions: 1. H plus plus 2e equal to H2, 2. O2 plus 4H
plus plus 4e equal to 2H2O, 3. O2 plus 2H2O plus 4e equal 4 OH minus and 4. H2O plus
2e equal to H2 plus 2H minus.
Now you see all 4 reactions we have already discussed before these 2 reactions are
possible in p H less than 7; that means, acidic medium and these 2 reactions are possible
when p H is greater than equal to 7 neutral or basic medium.
Now, all 4 reactions you see that the electrons are involved and all 4 reactions we have H
plus ion presence in this 2 cases and OH minus ion presence. Now whether we have H
plus or OH minus we can express Nernst equation in terms of potential as well as pH. So,
now, all 4 reactions are function of potential and function of pH. So, in these 2 cases it is
a function of pOH which can be written in the form of pH now these calculations we
have done it before you just go back. And, then see some of the earlier lectures you will
see that all 4 reactions we have try to find out the reduction potential as a function of
standard reduction potential and the pH of the solution and also we have try to plot those
reactions as a function of pH we if you go back you can have a look at it again.
So, but these 4 reactions also R function of potential and function of H so; that means,
logically we have 2 types of reactions one which involves 3 types, one which involve
potential so; that means, 3 type, type-I only potential dependent, but pH independent,
second type potential dependent and pH dependent and third type potential independent
and pH dependent. So, these 3 would allow us to find out a Pourbaix diagram.
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Now in addition to that we can have the third criteria condition. So, these Pourbaix
diagrams are basically a thermodynamic stability diagram, it does not involve any
kinetics.
Now, from this diagram we will not be able to tell at what rate if there is any corrosion of
a metal in the aqueous medium, what rate it is going we cannot be able to tell from this
Pourbaix diagram, because it is a thermodynamic stability diagram why. In order to find
a Pourbaix diagram we have to find out those equations the equations like what we have
shown. So, this equation like this one or this one or this one and then finally, of course,
this equation and the equations related to all 4 reactions involving hydrogen ion, oxygen,
water, hydroxide and hydrogen we have to get the information about standard chemical
potential. And whenever we talk about standard chemical potential of a species that
indicates that there in their activity 1 and whenever we talking about activity 1 we
assume that they are pure state.
So, since we have understood that what are the species that are possible in combination
of course, we have chemical potential of metal, chemical potential of metal ion, chemical
potential of oxygen, chemical potential of hydrogen, chemical potential of metal
hydroxide, chemical potential of metal oxide, H2O, OH minus are we missing anything.
So, metal ion oxygen, hydrogen plus, metal hydroxide, metal oxide, H2O, OH minus and
of course, H2. We have to make use of the standard chemical potentials of all the species
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in a particular reactions, particular set of reactions we have to consider those chemical
potentials.
Now, how do we get it for example, K if I consider the activity this equilibrium constant
is nothing, but delta G0 with the negative sign here. Now delta G0 we can write as we
have done it before the summation of chemical potential of standard chemical potential
of product minus summation of chemical potential of reactant. So, this will give us free
energy change from that we can calculate activity this equilibrium constant.
And similarly we have another reaction nFE0 equal to delta G0 which is similar like this,
we can have product minus summation of product of this chemical potential standard
chemical potential of all the species that are involved in the reaction and the summation
of chemical standard chemical potential of reactance in that particular reactions.
For example M2 plus plus ne equal to M, here we have this chemical species this species
and of course, sorry here we are considering 2; that means, instead of n we can put 2e.
So, here this is we have to consider chemical potential of 2 plus we have to consider
chemical potential of M and of course, we can consider the chemical potential of electron
also that chemical potential will be used up in 2F. So, you have a relation for this we are
not getting the detail of that relation, but this one contributes to this 2F delta G0 comes
from chemical potential of M minus chemical potential of M2 plus. So, this is delta G0
minus 2 FE0.
So, this 2F is related to this 2 electron and of course, that is also related to chemical
potential of electron as we have said that we are not going detail derivation of this
particular election for reaction relation from the chemical potential of all the species
involving electron also. But, for our understanding we can see that this one this electron
is contributing this part and this one is can be found out from this relation and this comes
from this.
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So, we see that these are all thermodynamic data, these are all thermodynamic data and
this thermodynamic data will be used up to find out reaction equilibrium constant or the
chemical or the standard reduction potential and this equilibrium constant will be used
for type - IV type of this particular reactions. And in this case K equal to delta G0 RT
and in this case E0 equal to delta G0 nF minus. So, there we have application of delta G
0 or the application of standard chemical potential of the species.
In addition to that so, we have to calculate this K or E0 from standard chemical potential
data, but sometimes we do experience ion activity to be not to be 1. So, that case we have
to make use of Nernst equation where we also have contribution from the ions of metals.
So, then finally, we would construct Pourbaix diagram. So, these are the basic
consideration on which this diagram will be better.
So, in our next lecture, we will try to find out one example in the nickel system nickel
H2O system we will try to see the Pourbaix diagram. And, we will start from the
chemical potential of different species and we will end up getting the diagram and then
we will see that yes, in this position if I am then I will get metal remaining as metal. In
this position if I go I will get metal ion formation or corrosion or at certain region you
might get metal hydroxide which will settle down. So, we considered it to be a
passivating zone. So, let us stop here, we will continue our discussion in our next lecture
while we start with the Pourbaix diagram calculation in case of nickel H2O system.
Thank you.
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Prof. Kallol Mondal
Indian Institute of Technology Kanpur
Lecture – 21
Construction of Pourbaix diagram for Ni-H2O System-I
Let us start lecture 21, as we have ended lecture 20 saying that we would construct a
simple Pourbaix diagram and we will take an example with nickel H2O system. So, our
job today is to find diagram of nickel or nickel H2O system. So, for that we have to see
what are the reactions that are possible for nickel in H2O system and we can see that all
the reactions can be categorised in terms of type 1 type 2 type 3 as we have discussed in
our last lecture. So, the first type what we can think of is basically the type 1 reaction,
which is nickel plus plus 2e nickel this reaction which is function of potential.
But not a function of pH since there is no hydrogen ion formed in this reaction and in
order to find an equation which will give an idea about this reaction which is a Nernst
equation E Ni equal to E0 Ni plus RT by 2F ln activity of Ni plus plus activity of Ni; see
it we will follow ox by slash red and we will consider 25 degree Celsius 1 atmosphere
pressure. So, this quantity and then if we convert this one to log, then we will get
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following factor log of 0.0591 by 2. Here 2 is coming from 2 electrons that is involved in
this reduction reaction.
Now the next step is we have to find out this quantity and in order to find out we have to
find out delta G0, which is nothing but chemical potential where the standard chemical
potential of product minus standard chemical potential of Ni plus plus. And, we can we
have the knowledge of chemical potential of standard chemical potential of nickel as
well as Ni plus plus ion and Ni equal to 0 mu 0 Ni plus plus is equal to 48250 joule per
mole.
So, we get so there is a minus sign 0 minus, so minus and this minus should become plus
48250. So, which is to be equated to minus 2FE0 and in this case E0 is this. So, we get E
0 equal to 48250 2 into 96500 equal to 0.25 volt and then we can modify this equation
instead of this quantity we can put this 0 point with a minus sign 0.25. So, we can have a
plot for this equation, for this equation on E versus pH, so here unit is volt now this is
minus 0.25 volt.
When activity of when the conditions let us say let us put several condition, condition 1
activity of Ni plus plus equal to 1 and since activity of Ni is 1, then E equal to this
condition E equal to minus 0.25.
So, it will be a parallel line parallel to pH axis so we get this line. So, at all the pH values
we can have we can plot this equation E equal to minus 0.25 and that time condition is
activity of activity is equal to 1. So, here I am putting activity or a1 the condition 1 I
would say condition 1, so ai equal to 1.
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Now let us see what happens if we have a Ni plus plus equal to 0.5 and of course aNi
equal to 1 since it is a solid pure solid. So, E Ni plus plus Ni would become minus 0.25
minus plus 0.0591 by 2 log of 0.5 which eventually becomes minus 0.26.
So, if I give it a colour so this becomes my a2 equal to 0.5. Now we can have another set
aNi plus plus equal to 0.1 and that time a Ni equal to 1, so that case E Ni plus plus Ni
equal to minus 0.25 plus 0.0591 by 2 log of 0.1 so it becomes minus 0.28 volt. So, this is
also volt so here also we will have a plot which is a3 equal to 0.1.
So, for each activity of nickel ion in the solution, we see that we can construct a line to
indicate this reaction, this reaction on E verses pH plot and this line will be parallel to pH
axis because, since there is no pH term in this equation. So, now question is whenever
we have this line we have to also see the stability of two species, the here the stability
means this one and this one this two species are there. Now, question is which side
would be my nickel and which side would be Ni plus plus, for that let us assume that for
a particular solution we can measure the concentration of ions because, once we have
nickel in water we will see that nickel plus plus ion is forming.
Now, let us say 10 to the power minus 6 that is the concentration, that is a limit up to
which we can measure the activity of Ni plus plus. But once the activity of nickel ion is
less than 10 to the power minus 6, then we will not be able to detect anything what does
it mean. So, if we if we cannot detect anything so you would say that as if there is no
nickel ion. So, then if there is no nickel ion, that means the nickel is present only no ion
base present this is one part, second part is we see that as the activity of nickel ion
concentration is decreasing.
That means as we see that it is decreasing we are saying that this lines these 1 2 3 lines
you see the lines are dropping down, so they are going down so. That means, if we go for
10 to the power minus 6 it will it will go further down, so you can also calculate what
could be that potential. So, that potential would be definitely E Ni plus plus Ni equal to
0.25 plus 0.0591 by 2 log of activity of nickel ion is 10 to the power minus 6 we can find
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out some value. So, it will be further down so for that we can have another plot, so this
could be let us say here where a is equal to 10 to the power minus 6.
So, that means, but question is if we go further down if let us say activity is less than 10
to the power minus 6. So, what could be the potential, so that potential would be less
than the potential at 10 to the power minus 6. Now we see that 10 to the power minus 6
is my limit to measure nickel ion concentration, then of course when we achieve this
situation we would only see nickel. Now if I redraw that particular diagram this is pH
this is E volt, so we get this is a equal to 1 this is a equal to 10 to the power minus 6 and
now some a less than 10 to the power minus 6.
How do we measure this concentration? We would have potential here at this point, but
here we are not able to measure nickel ion so that means nickel is only there. What does
it mean, that below this line we have nickel because, we are not able to detect any
concentration below 10 to the power minus 6. Now let us say we assume that we cannot
measure a concentration a if it is 10 to the power minus 4, if we say that activity below
this we will now we are not able to detect any nickel ion. So, we would definitely say the
below this activity 10 to the power minus 4 there would be all the things will be nickel.
So, what does it mean, that means line below this only nickel is present.
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So, what happens on top of it? So, on top of it definitely we have nickel ion, so this is
nickel ion and here it is nickel. So, if I try to see again so any line which indicates that
reduction reaction for nickel ion reduction, which is parallel to pH axis below that line
we have nickel and above that line we have nickel plus plus. Now interestingly as we
decrease the activity we are actually pushing, we are actually extending the nickel ion
stability. So, this is activity equal to 1 and then if this is the activity equal to 0.1.
Like that way as we are decreasing activity of nickel ion or detectable nickel ion we are
extending the nickel ion region and contracting the nickel region. So then of course, the
bottom part would be a bottom part of this line would be bottom part of this line would
be definitely nickel and top part would definitely be Ni plus plus. So, now we are clear
that which side is nickel and which side is nickel plus plus.
So, this is the situation for the first reaction which is type 1 type where we have potential
dependency but it is pH independent, we can now we have two species one is nickel, one
is nickel plus plus. So, the nickel ion can react with H2O and then form NiO these
reaction is possible and these reactions you see that whenever nickel is forming nickel
ion is first forming and then that would again react with H2O to form NiO. Interestingly
if we see the forward reaction it is an oxidation reaction, but if you see the backward
reaction it is a reduction reaction.
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So, since we always consider the reduction reaction in order to find out potential, so we
can write this entire reaction reverse. So, it becomes nickel oxide 2H plus plus 2e equal
to Ni plus H2O, so this side is oxidant and this side becomes reductant
And similarly for nickel ion we can also react with H2O and then form nickel OH whole
2 plus 2H plus we can have this reaction.
Now, interestingly you see that these reaction is type II and this reaction is type III. Now
we can also construct another nickel plus H2O it can form NiOH whole 2 plus 2H plus
plus 2e or we can reverse we can write reverse NiOH whole 2 plus 2H plus plus 2e equal
to Ni plus 2H2O, this is also type II.
So that means, we see that we again have 2 types of reaction one is type II another is
type III, this reaction is pH as well as potential dependent, this is only function of pH and
no not a function of potential. Since here only we have H plus ion presence but no
electrons are involved in this reaction and but here we have electron involvement as well
as hydrogen ion involvement. Now first look at this type of reaction, so first consider this
is a simple type let us consider that.
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So, when I consider that so NiO plus 2H plus plus 2e equal to Ni plus H2O, now we have
to find out a Nernst equation for this. So, Nernst equation so I am not writing ox and
reduct like that, so this is the oxidation the left side is oxidation part and right side is
basically the redactor part; so, E0 plus RT by 2F ln activity of NiO activity of H plus
square activity of Ni and activity of H2O.
Now, since this is a solid and it is a pure solid so it is 0 this is 0 this is also pure 0, so we
are left with aH plus; now if we assume that the system is maintaining ideality. So, a H
plus we can consider with the concentration and then if we convert ln to log, so we can
write the entire this particular stuff in addition to this we can write E0 plus 0.0591 by 2
into 2 log of H plus or E 0 minus 0.0591 pH since minus log of H plus equal to pH.
So, we can plot this reaction this equation on a E versus pH plot. So, definitely this is a
negative slope see if I try to see E versus pH, so that pH 0, I would get E 0 and then as
the pH is changing. So, the there would be a straight line this is a plot of a straight line
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with a slope minus 0.0591. So, we have to find out E0, so E0 is nothing but nF and here
nF is 2F because, there are 2 electrons involved delta G0 is equal to summation of
chemical potential it should be product reactant then mu of nickel mu 0 mu 0 of H2O
minus mu 0 of NiO minus 2 mu 0 of H plus.
So, again we know that mu 0 Ni equal to 0 mu 0 H plus equal to 0 these are convention,
Now, mu 0 H2O is equal to minus 236964.2 joule per mole and mu 0 NiO equal to minus
215729.8 joule per mole. Then minus 236964.2 plus 215729.8 is equal to minus 21234.4.
Therefore, E0 be equal to minus 21234.4 divided by 2 into 96500 is equal to 0.11 volt.
So, for this line this point would be 0.11 volt; since when pH is equal to this equal to 0
then E equal to E0. So, you do get a plot, now which side would be nickel and which
side would be NiO, definitely this side would be nickel and this side would be NiO. Now
we see that this side we have said that this side is nickel and this side is nickel oxide, in
our next lecture we will understand why the below this line we have nickel and above
this line we have nickel oxide.
So, let us stop here, we will continue our discussion on Pourbaix diagram of nickel in our
next lecture.
Thank you.
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Prof. Kallol Mondal
Lecture - 22
Construction of Pourbaix diagram for Ni-H2O system-II
Let us start the lecture 22.
So, we will continue our discussion on Pourbaix diagram of nickel hydroxide nickel H2O
system. Now we have plotted nickel plus plus this we have then calculations for simple
nickel ion reduction to nickel and then we have gotten another plot this is type 1 and then
another plot was like this with a slope minus 0.0591. And here it was 0.11 volt and here
it was 0.25 volt with a minus sign. See this two, type 1 and type 2 one of the type two
reactions we have considered and then try to plot them.
Now, we have seen we have told that this side is nickel and this side is nickel oxide and
here the reaction is nickel oxide plus 2 plus 2 equal to Ni plus H2O and this is Ni plus
plus 2e equal to Ni. Now let us see whether this side right side would be Ni oxide NiO.
So, let us have a parallel line and I am changing the pH; this is pH 1, this is pH 2 and the
potential remains same and this is the so we see that left side let us see that when it is pH
1 what is the hydrogen ion concentration. So, the pH 1 hydrogen ion concentration is this
let us say 1 and here H plus 2.
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Now, if we increase pH concentration of H plus ion decreases, since pH is equal to
negative log of H plus ion concentration. Now for this reaction, we can consider reaction
equilibrium constant which is K, so this K can be written as Ni or in terms of
concentration so we can write this what this chemical reaction. Now you see that K is
constant at this point K is constant, because we have attained equilibrium. Now if we
increase H plus ion concentration, then the system should go this way in order to
maintain the reaction equilibrium constant.
And if we decrease H plus ion concentration the system should go this way. So, this is H
plus ion concentration increasing and on this side is decreasing. So, now, if we increase
pH if we have this point if we increase pH, so if we go to this point I am reducing H plus
ion concentration.
So, here H plus ion concentration if I try to have a relation between these two, so this
should be this and now once we have this situation then if I go from this point to this
point because at this point this equilibrium has set up. So, H plus ion concentration is
decreasing so then of course, then reverse reaction so this reverse reaction should take
place reverse reactions should take place. So, that time nickel should get oxidised to
form nickel oxidize nickel oxide so that means, this side definitely should then be NiO.
Now, if I go to pH 1, then I see that H plus ion concentration is decreasing in comparison

to of course, this one this was also having some pH level. So, this pH at this point is
more than the pH at this point, so at this point pH plus ion concentration would be more
than the H plus ion concentration what is there at this point. So, which is indicating the
pH level at on the line of that e verses pH plot, so once we see the hydrogen ion
concentration is increasing. So, in order to maintain this equilibrium constant we have to
go to the other side that means this side. So, then this region definitely should be nickel
and this region should definitely be NiO.
Now, can we combine these two? So definitely we can combine. Now once we combine
let us see what situation is arising. So, this is E, this is pH, so first draw dotted line and
then we have this. So, now, we can have two different colours this is for type one
reaction this is for type two reactions.
Now for type one we know this is nickel side this is nickel plus plus side and for type
two this is nickel side this is nickel oxide side. Now already we know if we consider this
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is the connection between these two this connection point can be found out by simply
solving two equations what we have already found out one equation is for the type 1 is
minus 0.25 plus 0.0591 by 2 log of Ni plus plus. So, instead of activity we are writing in
the form of a Ni plus plus and this is type 1 and E type two is equal to 0.11 minus 0591
pH.
So, these two equations if you solve for a particular nickel ion activity or concentration
we can get to know the potential as well as pH value. Remember for that case we have to
fix certain concentration of nickel ion or activity of nickel ion. Let us say we fix this
nickel ion activity to be one let us say. So, then this point would definitely by would be
minus 0.25. Now that case this equation this type one equation would simply be this.
This is type one this is two so then we can get at this point these two equations are equal
so minus 2.5 equal to 0.11 minus 0.0591 pH. So, we get pH is equal to 2.37 is so the pH
this pH value is nothing, but 2.37 if we solve this we can definitely get to a sorry I think
we made a mistake in the calculation. So, it should be 0.25 plus 0.11 equal to divided by
0.0591 equal to 6.09.
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So, this is this value is 6.09 this is the PH level and potential of course, it will be minus
0.25 if we consider activity to be 1. Now, we have to decide whether some of the parts of
these 09 lines can be possible on the stability region of three species. Now where we are
having stability of Ni plus plus as well as Ni and NiO. Now we know this region is this
left to this is Ni right to this is NiO below this is Ni above this is Ni plus plus so right to
this NiO.
Now we see that in this zone we have no confusion because here we are not having any
Ni plus plus or NiO, but if we consider this zone on top of this particular line we see that
Ni plus plus is stable and below this line we should see Ni, but actually Ni Ni plus plus
stability line indicates that this region should be Ni plus plus.
So, this particular line this particular line we cannot definitely say that it should exist
completely because we do not know what is the relation between Ni plus plus and NiO
for that reason we have to go for the type three reaction. And similarly if we see this part
right top of it should be NiO Ni plus plus and bottom side it should be nickel, but already
we know that on the right side of this line it should be NiO. So, nickel should not be
present on the on top of this line. So, this particular region of the line it should not exist
because that line indicating the equilibrium between Ni and Ni plus plus, but we see that
in this zone we have in this particular zone we have NiO after seeing the type two
reaction.
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Finally, if we club it if we see the clubbing, so it should be it should be like this. So, we
know this is Ni this is NiO this is Ni plus plus, but we have no idea what is going on here
in order to do that we have to consider another reaction which is type 3 type.
It indicates equilibrium between Ni plus plus and NiO.
Now from this reaction we see that there is no involvement of electron if we don’t have
no involvement of electron. So, as per this triangle we see only this region we can work
with see if we work with that particular region then we can find out K value. In order to
find that we have to find out a relation between we know the relation between delta G0
and where K is the equilibrium constant for this reaction.
So, delta G0 would be again then summation of product minus summation of sorry mu 0
mu 0 of reactant.
Now we can see from this reaction mu 0 of product is this is the reaction equation we are
getting we have already known this value this is 0 this is 0 point this is this value
becomes minus 257, 215729.8 this value is it will become plus because this value is
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minus 48250. This would also become plus because the value of mu 0 H2O is 236 minus
236964.2 so 236964.2.
So, if we get this value this becomes 69484.4 so k becomes or rather RT ln k is equal to
minus 69484.4 we can do little bit of juggling with this k. So, instead of RT lnk I can
write 2.303 into 8.314 into 298 Kelvin since we are considering 25 degree Celsius this is
R value universal gas constant and log since we are converting log ln to a log. So, that is
what this multiplication factor 2.303 is coming up.
And then so far this k case if we consider in terms of concentration NiO or we can write
since we are writing in terms of activity; activity of NiO and activity of H plus activity of
Ni plus plus H2O. So, these two goes to one because these are pure substance and now
this equal to minus 69484.2. So, log of minus log of equal to minus 69484.2 by 2.303
into 8.314 so this value becomes of course, into 298 it becomes minus 12.18 therefore,
this is nothing, but minus if I consider activity to be concentration of H plus ion
considering that the interaction parameter is one or activity coefficient is one rather.
So, this becomes minus pH minus log of a Ni plus plus equal to minus 12.18. So, I can
simplify pH plus log of a Ni plus plus equal to 12.18 this is the equation we are getting to
indicate the equilibrium for this particular reaction. Now once we know this equation
then we can also plot this on E verses pH for a particular concentration of or activity of
Ni plus plus ion. So, this is pH axis this is potential since here we are not having any
potential value definitely this particular reaction would be parallel to potential axis
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because it is becoming potential independent reaction. So, it will be like a parallel line
parallel to potential axis and where of course, the activity of nickel plus plus ion is to be
mentioned.
Now, if we mention that I think we made a small mistake here so there should be two
here 2 pH because this power 2 would come. So, now, if we consider this is to be one
then the pH value at which this particular equation would be valid pH would be 12.18 by
2 equal to 6.09, so this pH would be 6.09 this is the point. Now here we can definitely
say which side is nickel plus plus and which side is nickel oxide because this is reaction
which is equilibrium between nickel plus plus and NiO. So, if we draw a parallel line to
PH axis this is the pH where the system has reached equilibrium. Now if I go to pH level
pH 1 the pH 1 the concentration of H plus ion is definitely more than the value what is
there when the pH is 6.09.
Because if we have decrease in pH value the activity of H plus ion increases or the
concentration of H plus ion increases, so that time since I am increasing this H plus ion
concentration. So, in order to maintain the equilibrium constant the system should go this
way reverse way. So, the Ni plus plus ion should form so this side is Ni plus plus. Now if
I go at this point which is pH 2 where the hydrogen ion concentration should be
definitely less than a the pH at this point which is the equilibrium pH.
So, in order to maintain the equilibrium since the hydrogen ion concentration has
decreases at this point. So, system should go forward direction in order to maintain the
hydrogen ion concentration and that is what the, if it goes to forward direction NiO
should form, so this side would be definitely NiO. Now, interestingly we have three
plots.
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One is type one another one is type two another one is type three which is this; this is pH
this is pH and here we see that this is Ni this is Ni plus plus this is Ni NiO Ni plus plus
NiO. If activity of nickel plus plus equal to 1 this is 0.25 and that time this value goes to
as we have calculated before 6.09, when activity is Ni plus plus equal to 1 and this is also
6.09 when activity of Ni plus plus equal to 1.
Now we can club these two now here we can club these two lines since we have seen
that this particular extended line should not exist because it is the region of NiO. But we
are not sure whether this particular line would exist because we are not sure whether it is
a nickel plus plus it is a mixture of nickel plus plus and NiO zone.
So, now if we try to solve equation this one and this one let us see what happens what is
the point we can achieve. So, if we this is line and this line rather I would say that this is
nickel plus plus NiO Ni now I would like to find out this point. So, we can definitely find
this point by solving E equal to 0.11 minus 0.0591 PH and 2 PH plus log of activity of Ni
plus plus equal to 12.18 and since we are considering this to be 1. So, then 2 PH equal to
12.18 so PH equal to 6.09 so if I put this here E is equal to minus 0.25 volt.
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So, you see that this point the potential also becoming minus 0.25 and here also it was
minus 0.25 volt the connection between this line this line and this line was this and when
I try to see the connection between this and this. So, there are also the same point we are
getting the same co-ordinate we are getting on E verses pH plot. So, we would get a plot
like this now we combine all three reactions, this is reaction 1. Now we see that this
reaction also should go through the same coordinate which is minus 0.25 and pH equal to
6.09 and also this line should also continue like this; this is 0.11 0.25 6.09 this is activity
of Ni plus plus equal to 1 activity of Ni plus plus equal to 1 this side is nickel nickel plus
plus nickel oxide.
Now, interestingly last time we saw that this particular portion of the line should not
exist we were not sure about this particular line. Now once we get to this particular line
for the type three we know the left of this line should be Ni plus plus then if it is done on
on top of this we should have Ni Ni plus plus. So, this entire zone should be Ni plus plus
and what about this line now we know below this line its Ni left to this particular line is
Ni, so this entire zone should be Ni so this portion should not exist.
So, if I draw the final region whatever is not able to exist whatever line that portion we
will draw with a dotted line and then we can plot the regions Ni plus plus Ni and this is E
this is pH. So, we see that we can distinctively specify the stability regions of three
species this species this one and this one. So, in nickel H2O system we have consider
three simple reactions and then, try to see the stability regions in E verses PH plot. So,
we will have more on this Pourbaix diagram we will stop here for the time being and
next class we will start with four important reactions which are pH as well as potential
dependent that involves those involve no metal or metalize rather those involve oxygen
H plus OH minus and H2O let us stop here.
Thank you.
223
Corrosion - Part I
Prof. Kallol Mondal
Lecture - 23
Construction of Pourbaix diagram for Ni – H2O system – III
Welcome back to the course corrosion, today we are going to have our lecture number
23.
So, in last lecture we started discussing, we discussing on nickel H2O system and then
we could draw a Pourbaix diagram involving nickel; nickel plus plus and an NiO and the
diagram look like. So, this is pH axis this is E in volt unit this region was nickel, this was
nickel plus plus and this region was this was NiO where if we extend this line; this line if
we extend.
The point would be 0.11 volt and this was minus 0.25 volt and this pH was 6.09 and we
could also see why different regions how can we make sure that this region belongs to
nickel, this region belongs to NiO and this region belongs to Ni plus plus. And this also
talks about the stability of those phases in those regions in that E verses pH diagram,
moreover each line indicates the equilibrium between Ni plus plus. For example, this line
indicates Ni plus plus and Ni, this line indicates Ni and NiO and this line indicates Ni
plus plus and NiO; moreover we could also see that some lines are potential independent.
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For example, this line belongs to potential independent then we have one line which is
parallel to the PH axis that means, it becomes potential a pH independent, but potential
dependent. As we have seen that this was drawn as a when nickel ion concentration was
1 this is also belong to Ni plus plus activity equal to 1 then only we could get 0.25 volt
and we would see that if we change the activity of nickel plus plus from 1 to 10 to the
power minus 1 10 to the power minus 2 like that.
So, this line would go down an interestingly another important aspect is when we draw
these lines according to the reactions what we have stated earlier, we have to fix a nickel
ion concentration. Now, if we fix this activity to be 1 then for this line we have to also
see the activity of nickel ion concentration should be 1. Now if we change it to 10 to the
power minus 6 then this line also needs to be change to 10 to the power minus 6. So, it
will be valid for a particular nickel ion concentration, so this has to be fixed first and
then we need to draw all three lines.
Now, here if we could see that if we put it in a red colour, let us say let me choose a
colour let us say this red colour, if we choose that colour. So, this region I could see
nickel plus plus we could or we can get nickel plus plus if we remain any potential and
voltage potential and pH coordinate in this particular section; this particular section
covered by this particular boundary.
We would at any coordinates for example, any coordinate Ni plus plus and Ni plus plus
formation this nothing, but corrosion. That means ions, if we get ions of that particular
metal then it is actually dissolving in the solution water base solution because its
containing H2O and that means, corrosion. Now if we consider a boundary let us say if
we have this boundary there we get nickel and as per our convention in this region we
have least presence of Ni plus plus that means, nickel remains as nickel.
So, we call this particular zone as immune zone and now the earlier zone we used to call
it corrosion zone. Now there is one more zone which is covered by this zone where we
have a NiO and interestingly we had a problem where we tried to see what is the, what is
basically the tendency of nickel to get corroded in the water system, there we considered
NiOH, but here it is NiO. Now interestingly NiO if we take NiO and H2O NiO plus H2O
equal to NiOH whole 2.
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This also settles down, this also settles down because they have very low solubility
product. Now when it settles down that time if that if it settles down on the nickel
substrate then we have a covering of the nickel surface for the time being let us put in
this fashion that if you have a nickel substrate on that substrate you we have this
particular phase formation or this particular phase formation we get a covering of that
particular nickel surface. And then the nickel surface exposed to the water system, water
or electrolyte will be limited. So, the corrosion tendency of nickel will be sluggish.
Though nickel corrosion is taking place depending on the solubility of nickel plus plus
ion and 2OH minus ion. So, depending on that the solubility will decide how much
nickel plus plus ion exist in the solution, but that solubility would be so low so the nickel
ion presence should be so low. So, that time we call it as passivation, so we call it
passivation. So, this zone we call it passive zone. So, this is immune and this zone is
corrosion, so we have three zones specified according to the calculations what we have,
in this zone we have immune.
That means, nickel remains as nickel no corrosion would take place in this zone we have
that means, we could say from this diagram that the corrosion of nickel would be a
spontaneous process that means, more and more nickel ion would form. And here NiO or
NiOH when it forms that time they try to make a deposit on the nickel substrate and the
solubility of that particular deposit we will decide the nickel ion dissolution rate, nickel
dissolution rate and that dissolution rate would be much lower than the dissolution rate
what we can experience in this particular zone.
So, we call it a passive zone, so we decide three zones immune, corrosion and passive. In
fact, we can have such diagrams for many other metals when coming to this particular
phase since we have done the calculation on the basis of chemical potential of NiO we
can have also the same plot if we consider NiOH. So, that time you have to take two
more equations that time we will not consider NiO formation Ni plus 2H2O equal to
NiOH whole 2 plus 2H plus plus 2e 1 reaction.
And if we do the calculation we would see that the calculation would generate the same
line what we see here, the same line it will generate the same line if we fix the
concentration of nickel ion, now here the nickel ion is not coming into picture. So, only
226
thing is it will be decided by potential which will be E0 plus RT by 2F ln ox by red. So,
this is activity of ox activity or red and here ox is nothing, but NiOH whole 2 activity and
activity of H plus square and this one would be equal to activity of Ni activity of H2O
square.
And if you do the same calculations because if you take the chemical potential value of
NiOH whole 2 which is nothing, but minus 452694 joule per mole you will generate the
same equation what we had for this reaction.
So, then here we had if we go back you will see that this value would be 0.11 minus
0.0591 pH here also you will get the same value let us do that calculation. So, that time
delta G0 would be mu 0 because we have to consider this way because we have to write
ox plus E equal to red mu 0 Ni plus 2 mu 0 H2O minus mu 0 NiOH whole 2 minus mu 0
H plus and 2 electrons are involved. So, this is 0 this is minus 2 into 236 964.2 this is this
will become plus 452694 this going to be; this is going to be minus. So, E0 would be
equal to so here this is minus 212234.4 n is equal 2 and F equal to 96400 and with a
minus sign so this becomes 0.111 volt.
So, you for this reaction you get E0 like this and E would become 0.11 minus if you do
the simplification these goes to 1, these goes to 1 these goes to 1 so you are left with this
quantity, so these 2 2 will get cancelled. So, finally, you would get the same pH same
equation. So, these 2 are getting the same equation so that means, this line would be
similar to NiOH whole 2, if we form NiOH whole 2 instead of NiO and if we you want
to do calculation for the vertical line.
227
So, if you draw the, if you try to see the vertical line also this is NiOH whole 2 and Ni
this line gives the E equal to 0.11 minus 0.0591 pH and this line would be same as for
this reaction. So, if you try to d try to see the vertical line.
So, the new reaction would be Ni plus plus plus 2H2O equal to NiOH whole 2 plus 2H
plus it will give you the same equations. Let us get back to the equation you will get the
same equation like this minus 2 pH 2 pH plus log a Ni plus plus, you will get the same
equation what we gotten for this reaction for this reaction we got the same equation.
I want you to try it out from the K so you have to find out K value. So, the log K equal to
0 delta G0 by 2.303 into R into T. So, if you follow that and you have to find out delta
G0 for this reaction. So, delta G0 you find out from mu 0 NiOH whole 2 plus 2 mu 0 H
plus minus mu 0 Ni plus plus minus 2 mu 0 H2O you would get the same equation.
So that means, whether you write NiO or NiOH these lines would be same because
provided you are fixing the Ni plus plus and concentration you have to fix that. So, that
is what you are getting main cruxes, you are trying to plot the corrosion zone, immunity
zone and passive zone, but this Pourbiax diagram is not complete if you do not put the
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equations or the reactions which involve no metals rather than oxygen, dissolve oxygen,
hydrogen evolution, hydrogen H2 H plus and OH minus of course, there will be water.
So, I mean to say that this particular phase this diagram this E verses PH diagram this
should be complete once we include water reaction involving O2, H2, H plus OH minus
and H2O so let us do that. In fact, we have seen before if you see the earlier lectures we
have done it, now we will just mention those equations and then accordingly we try to
plot them.
Now, if we write down those equations first is acidic and then neutral or basic, so this is
pH less than 7 and here pH greater than equal to 7. So, there are two types of reactions
one is an in that two types we have two reactions each one is H plus plus 2e equal to H2
where the real equation would be minus 0.059 pH where E0 equal to 0, two O2 plus 4H
plus plus 4e equal to 2H2O and here you see that only H plus ions are involved. So, there
E equal to 1.227 minus 0.059 pH.
And on the other side we have 2H2O plus 2e equal to H2 plus 2OH minus and for this E
equal to minus 0.827 minus plus 0.059 pOH. Why this term is coming for this reaction if
you do the calculation delta G0 would be mu 0 H2 plus 2 mu 0 OH minus minus 2 mu 0
H2O and then here to electrons are involved. So, E0 would be delta G0 minus 2 into
96500, if you do that calculation because already you know the values of this you just go
back earlier lectures and then find out what is the values. So, let me iterate the same
value once again.
So, mu 0 OH minus equal to minus 157147.1 joule and mu 0 H2O equal to minus
236964.2 joule per mole and of course, this quantity is 0 and you get minus 0.827. Now
interestingly here it is pOH because E equal to E 0 plus 0.0591 by 2 and then activity of
that log H2O, if we put it in concentration term pH2O and O H minus whole 2.
229
So, this is maintain at one atmosphere the pressure of hydrogen gas is one atmosphere
this is one a pure substance. And so it becomes E equal to E0 plus 059 minus log of OH
minus is nothing, but E0 plus 059 pOH. Where pOH equal to minus log of O H minus
ion, then if you do the simplification then you would get E equal to E 0 minus 0.0591 14
minus pH.
So, where pH plus pOH equal to 14 so E equal to 0.827 minus sorry this was plus, this
should be class because plus 0.0591 pOH, so pOH equal to 14 minus pH. So, that is what
you have put here this becomes plus 0.0591 into 14 minus 0.0591 pH you will see that
these two quantities could cancel so it become 0.0591 pH. So, now, this acidic side, basic
side this was a basic side where pH equal to greater than 7, but on the basics acid side
this is the basic and neutral side less than 7 for the first reaction we had the same
equation.
230
So that means, they will be lying on the same line, but one starts from 7 on the right side
in the pH axis, one starts one this reaction would start below 7 pH and this reaction come
involving H2O this reaction would start when pH is equal to or greater than 7. Now we
had another reaction which is O2 plus 4H plus plus 4e equal to 2H2O there the equation
1.227 minus 0.0591 pH.
And here this side also here another reaction involving oxygen plus 2H2O plus 4e equal
to 4OH minus. In this case the equation would become E0 plus 0.0591 pOH if you
follow the same philosophy what we have done for this equation then you convert this
we have this particular value would be 0.401 and then 0.0591 into 14 minus 0.0591 pH.
So, if you add them you would get the value which is 227 roughly minus 0.0591 pH. So,
you have the same equation what we had for the acidic reactions now if you would like
to plot all those two reactions.
So, in this Pourbiax diagram E verses pH this value is 0 and then up to 7 pH we have H2,
and then if we extend it that time it will be 2H2O plus 2e equal to H2 plus OH minus 2.
Similarly if we consider this reaction this is 7 pH they will be parallel because both the
cases the slope is 0.0591. So, 1.227 volt and then on the right side they should be third
equation for this would be O2 plus 2H2O plus 4e equal to OH 4OH minus and on this
side it will be 2H2O. Now, this particular 4 lines are to be clubed with the nickel
Pourbiax diagram
231
Prof. Kallol Mondal
Lecture - 24
Construction of Pourbaix diagram for Ni-H2O system and AI-H2O system
Let us start lecture 24. In the last lecture we ended with that discussion on plotting water
lines, if we go back to our last lecture we saw 2 lines one belongs to lines involving O2
and one involved H2 rather evolution of H2. Now, we see that this is one line, this is
second line, third, fourth and both the lines all 4 lines for example, this 2 line are
merging because they have the same slope minus 0.0591, here also they are merging in
the same line this one as well as this one.
So, here also slope was minus 0.0591 is basically slope this is also slope. Now as we
have said that these 4 lines are equally important and these 4 lines are to be merged with
nickel those 3 lines what we have drawn as well as the stability regions of those phases,
here what will do?
232
We will try to merge them. So, this was nickel this is pH and we are trying with. So, we
saw that the slope was also minus 0.0591 slope this is NiO or NiOH whole 2. Rather I
put it like this because they are they are basically belonging to the same family. So, H
this is Ni plus plus region and this is Ni, this is 0.25 and if we extend this line, this will
be 0.11 volt. This is one set the another set is reactions involving this is 0, let us say this
is 0 slope was 0.0591. Of course, we have a pH 7 and here the pH is 6.09 when activity
of nickel plus plus equal to 1 and there is one more line which is the slope 0.0591 with a
minus sign.
Of course we have seen that below this line acidic reactions, those are reactions for the
acidic part would happen and on the right side basic reactions would happen and then if
we club them. So, let me draw the water lines this is 0 let us say this is 0, this region is
Ni plus plus this is Ni and now before this beyond this, and then here also we get this
reaction, on the left side this line H2. Now we know the regions in nickel system Ni plus
plus Ni NiO or NiOH whole 2.
But we have to also see the regions this is 1.227 volt, this is 0 volt this is 0 volt. We have
also see that on the right side for example, if we consider this particular pH, right side of
it and left side of it what are the phases that could be stable or that would be the
continuity. Similarly, here also if we see the right side and left side we have to see for
example, if we reach to this position and this position what are the phases is that could be
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possible, that would be decided by the reaction equilibrium at that point because this
particular diagram also talks about the equilibrium between different phases.
So, let us consider and that is what we once we finalize what are the phases that are
possible, then we can also finalize what are the phases that would be existing between
this line and this line as well as what could be possible above this line and below this line
as well as here above this line or below this. So, in order to do that we have to see the
reactions; first for example, consider what reactions is possible at this point, which is the
equilibrium point. Now, the reaction that is possible is O2 plus 4H plus plus 4e equal to
2H2O.
Now once it reaches equilibrium. So, since I am not changing the potential I am
changing the pH. So, if we are here and if we are here both the cases the pH values are
different. Now if I consider that oxygen partial pressure remains 1 atmosphere and H2O
definitely it will be always considered to be pure and then it does not its activity is
considered to be 1, then depending on OH values this pH values I can get different
concentration of H plus ion. So, left side pH is less, but OH and sorry this should be H
plus ion; H plus ion concentration is more.
And here we have pH is more. So, H plus ion concentration is less. So, they are inversely
proportional because there is a minus minus log of H plus ion concentration is nothing,
but the pH. So, now, at this position if we have high amount of H plus in order to
maintain equilibrium, the reaction should move this way. So, if we move this way. So,
left side of this particular point will always have H2O and similarly on the right side
since pH is more. So, H plus ion concentration is less, in order to maintain equilibrium
the reaction should move this way.
So, beyond at this point we have oxygen evolution ok. So, more amount of oxygen
would generate. Similarly if we have if we consider this; so, at this point similarly on the
neutral or basic region also depending on the pH for example, here we have pH more, H
plus ion concentration is less here pH less H plus ion concentration is more; now here is
a problem. The problem is we cannot though we see that this particular situation holding
true, but here when the pH is more than 7 we do not have the existence of H plus ion.
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So, we have the existence of OH minus ion. So, if we have H plus ion to be less. So, OH
mine ion concentration would be more and here H plus ion concentration is more. So,
OH minus ion concentration would be less and when the pH is more than 7, the reaction
is H plus plus 2H2O plus 4e equal to 4OH minus.
Now at this point, we see that the OH minus ion concentration is less sorry we put a
wrong connotation here. So, pH is less the H plus ion concentration is more.
So, we see that this point we have higher OH minus ion concentration compared to this
point. So, if you have higher OH minus the reaction would move this way so, will have
oxygen generation oxygen generation. And so, the oxygen generation would be always
on top of this line, this line and below that we have H2O ok. So, now, let us see what
happens for the reactions which are not involving oxygen rather H plus and OH minus.
And of course, on the line right side of 7 we have H2O involved.
But interesting if we consider this point again just I forgot to mention that, we have less
amount of OH minus. So, then the reaction should go this way; so, would which would
increase the pH level of the system. So; that means, it will also increase the OH minus
ion concentration trying to increase the OH minus ion concentration. Now let us come
back to these 2 points, now here pH is more and pH is less here. So, H plus ion
concentration is more and H plus ion concentration is less here. So, now, we consider
this reaction.
So, then at this position since the H plus ion concentration is more. So, the reaction
would this way go turn the right side. So, gaseous hydrogen would generate below this
line. Now if I consider this point there H plus ion concentration is less. So, the reaction
would try to go this way. So, we have more and more H plus ion concentration, and then
it will increase the acidity of the water system. Now, similarly we can have similar
argument here this.
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And this point we can have pH high sorry pH is less H plus ion concentration is more,
OH minus ion concentration is less and here pH is high H plus ion concentration is less
and OH minus ion concentration is more because pH and pOH are inversely
proportional. So, I can say sorry not pH and pOH rather H plus ion concentration is
inversely proportional to 1 minus. So, this is the relation we have so, that is what we
have these particular correlations. Now if I take these things in these particular equations,
if we consider at this point first their H plus OH minus concentration is less. So, this
concentration is less.
So, the in order to maintain that concentration, the reaction should go on the right side.
So, hydrogen evolution again starts. So, below this line we have hydrogen evolution and
at this point, we have H plus OH minus concentration is more. So, this concentration is
more. So, the reaction should go this way. So, water we will get water so; that means,
below this line we have H2 gas and above this point above this line, this water line we
have O2 evolution and within this zone we have H2O.
So, this is the basic mode of constructing this Pourbaix diagram, now what is the
importance of specifying that which one would be O2 and which one would be where
would we get O2 gas evolution and where would we get hydrogen gas evolution, that
would be decided by the potential p H coordinate during polarization. So, will talk about
polarization later on, polarization for the time being let us understand this polarization.
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Polarization is nothing, but the shift in potential from any stable potential. Now here we
are talking about equilibrium so, it is basically the equilibrium potential.
Now, if we somehow I am here and I am here, now at this point my potential pH is this
and at this point my potential pH is this. Now here once since the pH I am not changing.
So, I am changing the potential once I go from lower to higher potential, once I cross this
particular line then we would get oxygen evolution and we do get bubbling when we do
experiment during polarization. Polarization means if this is my stable potential, this
point is stable potential or the equilibrium potential if I go to positive side we call it
anodic anodic polarization, if we go to negative side we get cathodic polarization.
So, during cathodic polarization, in this case we get water and if we do anodic
polarization from the equilibrium polar potential, we get oxygen evolution. Similarly
here if you see this is the equilibrium potential at that pH value, this is the pH value. So,
now, if we go anodic polarization; that means, the polarization is taking place from the
positive side from the on the positive side from the equilibrium potential. So, then we get
water and if we go below that then we get hydrogen evolution that is what happened
during polarization.
So, will talk about that later on; so, for the time being that is what we have to make sure
that which region is water lined water and which region is gas. So, on top of this
particular line where it involves oxygen, we have oxygen evolution and that these line
which involves H2 evolution. So, below this line we get H2 or the gas evolution H2 gas
evolution.
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So, the final diagram we have to do it this way, this is pH this is E. Let me do the
hydrogen line, this is basically hydrogen line. So, below this line we have hydrogen
evolution and this we call it oxygen line, above that we have oxygen evolution and
between this. So, let me draw it with between this we get H2O and this zone this zone is
NiO NiOH whole 2, this zone is Ni plus plus and this 1 is Ni. So, this is my complete
Pourbiax diagram for or we can say for nickel. So, it is basically indicating H2O system
fine. So, we have done this is basically the simplified version.
In nickel there are other reactions involved, and we can call it as corrosion zone, this is
immune, this is passive. Now let us take one more example. So, here I will not draw the
diagrams, I will not to the do the calculations I leave it to you to the, to do the
calculation, but there is a small cracks here. So, I will discuss that cracks here. Because
whenever we do take equilibrium we have to club it into 2 segments is basically we have
to see those equations the reactions, and accordingly will choose we block them actually
we will segregate them into according to the reaction species that are involved in those
reactions. So, best example is aluminium.
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So, in aluminium system we can have following reactions and here I am taking one extra
species, then you will understand why I am saying that, that reactions after looking at the
reactions you have to block them you have to segregate them in segments. So,
aluminium these are the reactions you can consider, then 3 Al I am just writing the
equations first and then of course, we have water equations.
So, we have written all those equations, now you see that this 1, 2, 3 these three
equations that be can be clubbed together, because here we see three products 1 3 species
rather 1 2 and then 3. So, this H plus and H2 we are not considering the species here,
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because we have to see the metal reactions first the way we have seen in case of nickel
and then will talk about water reactions. These 3 can be clubbed. This is club number 1
and the another clubbing that is possible if we see 4 5 the clubbing could be this 2.
Now, first we see that aluminium and Al plus 3 and Al2O3 are the reactants or the
products that involve aluminium. And in the second set we see aluminium Al2O3 and
AlO2 minus these 3 species are involved involving aluminium. So, second set we do not
have Al plus 3 and the first set we do not have AlO2 minus. So that means, the first set
whenever we see those phase boundaries or rather stability diagrams, then that will
involve only those equilibrium between all 3 phases like Al 3 plus Al and Al2O3.
And the second set would involve equilibrium between Al, Al2O3 and AlO2 minus. And
then you can have those data you already have the water data then all you need to have
mu of Al 3 plus equal to minus 481200 joule per mole then mu 0 0 Al2O3 equal to minus
1608900 joule per mole and mu 0 AlO2 minus equal to minus 839800 joule per mole and
remember mu 0 Al would be 0.
So, once we have data and then H2O mu 0 H2O you can find out from previous lectures,
mu 0 H plus as well as mu 0 OH minus you can find it out from the previous lectures.
Now, if we draw the Pourbiax diagram, you will see that the first 3 set will have diagram
like this. So, here it is Al 3 plus Al and Al2O3 and the second set we will have diagram.
You will have this diagram. So, you see that this indicates this line this one indicates this
line and this one indicates this line. And, here this one is nothing, but this one is nothing,
but this and this one is nothing, but this. So, if we club them you will see that the plot
will come here minus and of course, you will have diagram for these four reactions. So,
those diagrams in this will be much below, this is a very highly negative from this value
you can find out; we will see the this would be hydrogen line and then oxygen line would
be above that this would be oxygen line.
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So, this is the complete Pourbiax diagram for aluminium H2O system. Only thing is you
need to find out these values from these data and then plot it by doing this clubbing this 2
clubbing, you should get it. And another important aspect is here you will see the slope is
decided by the number of electrons and number of hydrogen that are participating in the
reaction, which involves up potential and pH.
So, let us stop here, we will continue our discussion in our next lecture.
Thank you.
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Corrosion - Part I
Prof. Kallol Mondal
Materials Science Engineering.
Lecture - 25
Inferences from Pourbaix Diagrams of Ni-H2O and Al-H2O system, Pourbaix
Diagram of Fe-H2O system, and Advantages and Limitations of Pourbaix Diagram
Let us start lecture 25 so, today we will finish our discussion on Pourbaix Diagram and
then we will get to the kinetics of corrosion. In the last lecture we ended with schematic
phase diagram for aluminium. We have given all the reactions as well as standard
chemical potential for all the species active in the in those reactions. And from that you
need to calculate that phase diagram, but the schematic will be the like what we have
shown in the previous lecture.
The schematic phase diagram for aluminium would be this one where this is Al plus 3
this is Al, Al2O3 and then this becomes AlO2 minus and this is potential axis, pH axis.
Now, if we recall a Pourbaix diagram for nickel diagram was like this, this is pH, E volt.
This is also schematic where this region was nickel, this is nickel plus plus and here
either nickel oxide or NiOH whole 2. That time we indicated this region to be immune
zone. This region was passive and this region was corrosion. Since, nickel ion is forming
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and whenever ion forms nickel dissolves that is what we are talking about the corrosion
region.
Now, here nickel remains as nickel and that is what this zone is immune zone and then
we have a passive zone. Considering the fact that these products are forming on top of
nickel surface and they are actually giving a protective nature for further corrosion of
nickel. And the nickel corrosion is still there, but there the amount of corrosion is less
because, the amount of corrosion of nickel would be decided by the solubility product of
these two products. We call it as passive zone because, the corrosion of nickel is limited
because of the formation of this passive layer on top the of the nickel.
But, similar comparison can be drawn in case of aluminium only at one place we will
have little difference. Now, aluminium this zone is aluminium so, definitely this is
immune zone this is Al plus 3 so, this is corrosion zone and of course, here we are
forming Al2O3 that is what this is passive zone. Where aluminium oxide form some on
top of aluminium and then it actually gives protection to the aluminium and aluminium
corrosion is limited.
Now, there is one more phase or one may one more stability zone which is decided by
this particular phase which is AlO2 minus. So, this is a complex aluminium ion which is
in the form of AlO2 minus so, these dissolves easily in water. So, when it dissolves; that
means, it is also taking away aluminium from the aluminium substrate. So in fact, it is
corrosion it is corroding this aluminium is corroding in the form of AlO2 minus so, this is
also a corrosion zone.
Now, the only interesting fact is in case of nickel system if you increase the pH; that
means, if you increase the basicity of the aqueous medium we get to achieve passivity.
But in case of aluminium system of course, if you increase the pH level or basicity you
for example, you are here or you are if you are here let us say this zone. And now if you
increase the pH level you reach to this zone so, you are going to get passivity, but if you
increase the pH farther once it come to this zone, you are going to achieve no passivity
rather corrosion will again start.
So, that is what this Pourbaix diagram it is actually giving an idea that what could be the
stability of the reaction products and what could be the spontaneity of corrosion. So, here
corrosion is spontaneous, in this zone corrosion is limited, in this zone again the
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corrosion becomes spontaneous. And if we are here let us say then of course, where the
corrosion becomes very limited because, it is actually remaining as aluminium immune
zone. Now, these information is very critical.
For example, in case of aluminium we know that it is a very passive metal because in
aqueous system it gets to the passivity. Now, if we increase pH level the passivity will be
broken and then it will form AlO2 minus ion if we increase pH level to certain extent and
if we reach to the stability zone of AlO2 minus the corrosion will further start. This
similar situation arises in case of iron and we need to talk about iron because iron
constitutes almost about 80 percent of our structural bodies rather.
So, now we talk about iron Pourbaix diagram little bit, here also we will give some
equations and those equations if you follow if you see the book by Pourbaix there is a
famous book on Pourbaix diagram. I will give the data later on my ts will give you the
data for those chemical potentials as well as chemical potential of the all the of all the
species which are taking part in different reactions. In order to understand the stability
zone of different phases in iron H2O system and you can construct that iron Pourbaix
diagram.
So, let us talk about Pourbaix diagram of iron. Now, here also we can have several such
reactions, reactions patterns are let by let us keep in keeps seeing that reactions, this is 1
reaction, 2nd Fe, 3rd, 4rth. So, I am just writing down all the possible reaction that could
take place when iron is exposed to aqueous medium Fe plus I am just writing down all
the reactions.
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So, let us get to these equations there are such equations available and another equation
which is HFeO2 minus plus H2O equal to.
So, these are the reactions I have noted, there are other reactions possible for example,
one important phase in case of iron system, this could be available in the form of alpha
or in the form of gamma, in the form of beta. So, these allotropes are possible for this
particular phase and these phrases are important in the sense that they give a different
levels of passivity of iron surface.
Now, if I try to see the schematic diagram of iron system, let us get to the schematic
diagram would look like. So, this is the diagram what it looks like if this is Fe, Fe plus 2,
this is Fe plus 3, FeOH whole 2 and this region is FeOH this is FeOH whole 3 whole 2
and this is HFeO2 minus. Now, here also this phase and this phase they are insoluble
phase with a very low solubility product, rather this is very this has very low solubility
product.
Now, when they form they try to form on iron surface and they try to passive it, but here
this is remaining as iron. So, this region is definitely immune zone this is Fe plus 2 so,
this is corrosion. This is also Fe plus 3 so, this is also corrosion; that means, whenever
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we have ion, ion formation in the stability this diagram this Pourbaix diagram we have to
say that metal iron is forming. So, corrosion is taking place, this is passive, this is also
passive zone.
Now, interestingly just like in case of aluminium we have one complex iron ion which is
HFeO2 minus this also dissolves in water easily. So, again these zone definitely will be
corrosion zone.
And then if I try to indicate with schematic for example, here also I can note down those
reactions. For example, this is if I note down with different colour red colour let us say
this is reaction 1, I simply right with the bracket 1, this is reaction 2, this is this line is
FeOH whole 2. So, this is 3, this is 4, this is 5, this is 6, this one is 7, this one is 8, this
reaction is 9 and this one we can write it as 10.
So, if you go back and see all those reactions if you see 1, 2, 3, 4, 1 to 10 we have
indicated those for example, this line if I see that this line is basically pH independent,
this is also pH independent, this is potential independent, pH dependant, this is also pH
dependent. This line and this 3 lines are all pH as well as potential dependent and of
course, this one also pH independent.
And if we see those reactions definitely I can simply write in this fashion function of E,
function of E I can write function of E and pH. This is also function of E and pH, this is
function of pH, function of E and pH, this is function of pH because here no electron is
involved. If you follow the Pourbaix diagram for nickel you can easily understand this is
function of E and pH, this is definitely a function of pH, this is function of potential.
So, it is very clear that this will be parallel to x axis, this will be vertical to x axis, this
would be at an angle to the x axis, this will be parallel to x axis, this is at an angle to x
axis. That means, pH axis, this is at an angle to pH axis, this is perpendicular to potential
axis, this is at an angle to pH axis, this is also this is perpendicular to pH axis or parallel
to E axis, potential axis. So, we are very clear and that is what our diagrams also
confirming to that.
Now, here also we are saying that there is an immune zone there are 2 corrosion zones
rather 3 corrosion zones 1, 2, 3, three corrosion zones and this is passive zone, this is also
passive zone. Now, if I try see schematically how it looks it will look like this ok. So,
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both the zones are this zone and this zone both the zones are corrosion and then now here
we have this one and then this is passive this is corrosion, immune and corrosion.
So, this is a typical diagram, some book you might looks like this type, where this is
passive, this is corrosion, this is immune and this is of course, corrosion. Now, these 2
lines these 2 lines merge together depending on the phases what where we are
considering. So, this is about Pourbaix diagram for iron schematic drawing, then
aluminium we have also given the reactions as well as chemical potential data, in case of
iron we have just given reactions chemical potential will be provided to you. And then in
case of nickel we have complete formation of Pourbaix diagram.
Now, here one thing is you have to do that is we have to also indicate your water
reactions, water, this is hydrogen reaction and this is let us say oxygen reaction lines so,
then it becomes complete. At the end we would like to see the advantages and
disadvantages or the limitations of Pourbaix diagram. So, we have done a quite detailed
analysis on Pourbaix diagrams so; first see what are the advantages.
The advantages first thing, it indicates without going for detailed calculation it indicates
the stability region of different phases forms different phases formed when a metal is
exposed to H2O with or without oxygen and different pH level. So, that is what we are
saying that we are finding corrosion zone, we are finding immune zone, passive zone and
corrosion zone further on the right side of on the on the higher pH side. This is one
important information we do get once we do this thermodynamic calculations and find
out this diagram.
Second part it somehow predicts spontaneity spontaneous phase formation as a function

of E and pH. Definitely, it can predict for example, if I am here it will be iron if I am
here it will be a Fe plus here it will be FeOH whole 3 like that way we can decide what
could be the spontaneous phase, when a metal is exposed to the water system.
Now, 3rd point if I see the 3rd point indicates that it allows us to find out whether a
system would passivate or not or corrode that information would definitely get, we
definitely get. Now, interestingly in order to do that we need to just see the iron see in
case of iron and aluminium system if I see the aluminium Pourbaix diagram.
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This is aluminium Pourbaix diagram, if we see that when the pH level is 8.6 this is if I do
see the cursor. So, this 8.6 beyond that we do get AlO2 minus and then it would corrode,
but when the pH is between 3.9 to 8.6 and if the potential is within this region Al2O3
region we do get a passivity.
But, in case of iron situation is different, so, this is iron Pourbaix diagram what we have
shown in the schematic this is the exactly the same and here if you see that this particular
zone this FeOH whole 2 as well FeOH whole 3 these zones we do get passivity. And if
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you see the pH level varies from 9 to almost about 13. So, generally in case of rebar we
maintained atmosphere. So, pH is maintained at around 12.5 to around close to 12 and
12.5. So, at that high pH the iron passivates within in that concrete system, rebar when
the rebar is placed in a concrete medium.
So, if it passivates dissolution becomes very limited in when we have this 12.5, but 12.5
is not suitable for aluminium. Because, when we go for 12.5 we might get to the
corrosion zone which is AlO2 minus. So, these informations definitely we can gather
from Pourbaix diagram.
If I get to another important information for example, when we have a metal mixtures for
example, let us say a particular system particular potential and pH level, we need to see
that which metal would corrode and which metal would not corrode, that information can
also be obtained let us see it one such example.
If I try to see this diagram so, this diagram is Pourbaix diagram for aluminium and this
diagram is for silver and zinc system separately they are drawn. And if I try to see the
two potential values and pH value this is one and this is this is one point and this is
another point ok.
So, now, if I am here, that time silver is in immune zone because it is maintained in the
Ag which is solid silver; that means, the potential and very low pH; that means, very
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acidic medium; that means, this is 2 normal HCl. So, the silver would not like to come
out as a in the form of ions in the in the aqueous medium, which is of course, very acidic.
But, if I try to push the pH to 12 and the potential if we try to get it here there also I
could see that silver is maintaining immunity. But, when I look at the silver zinc system
when I am looking at the pH and potential of this particular section which is this one here
in case of zinc system it is in the zinc plus plus which is corrosion zone.
So, if we maintain the pH and potential at this point silver would not corrode, but zinc
would definitely corrode, but when I go to this point where silver is not corroding as well
as it is maintaining immunity, but when I look at this point in case of zinc Pourbaix
diagram it is in the zinc oxide region. So, if it is in zinc oxide region then it of course, it
would like to passivate. So, these informations we would definitely get if I try to
carefully analyse our Pourbaix diagrams.
Now, these are some of the advantages what are the information what we get, but there
are many things what we do not get from Pourbaix diagram. Now, what are the
limitations?
The if I try to see the limitation a first limitation is this is definitely a thermodynamic
plot. So, you need to have only chemical potential ok. So, whenever a thermodynamic
plot is given it cannot give you any information about rate of reaction. So, now, you will
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not be able to tell what could be the corrosion rate if I am in the corrosion zone. So, the
corrosion zone can tell me yes, there will be corrosion, but we will not be able to tell
what is the rate at which the corrosion is taking place and many a times the rate becomes
crucial even if there is a spontaneity. So, we have spontaneity because it is in the
corrosion zone, but the rate may be very slow. So, we might say that the corrosion is
very low.
Now, second part so, we do not have any information on kinetics of corrosion and
second part if I try to look at so, if I look at the passivity region. So, whenever we are
looking at the passivity zone so, we are saying that we are assuming that particular phase
would form on top of it. So, but it is not guaranteed why it is not guaranteed because,
sometimes those phases may not form on the surface of the metal rather they might be
very loose, they might contain lot of porosities and they would not give much of
protection. So, that time it may not be the actual passivation though the Pourbaix
diagram predicts that it is passivation.
So, actual passivation cannot be told. Third point is for example, this is only for metal
pure metal system; we are not looking at the alloy system. So, in case of alloy system
predicting the phases and predicting what sort of regions we will choose would be
difficult. So, this is not applicable to alloy system.
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Now, fourth, now another point what we can indicate is what is not possible from
Pourbaix diagram is other conditions like; velocity of the velocity or the turbulence of
the medium, velocity or turbulence of water. Then, if there are other things like dirts,
foreign material those informations cannot be obtained from Pourbaix diagram. So; that
means, it is very clear that though Pourbaix diagram gives lot of information about the
possibilities, but it cannot give us any information about the actual happening.
So, in order to know the actual happening we need to understand the kinetics of
corrosion. So, now, we end our Pourbaix diagram now we would shift to kinetics of
corrosion from the next lecture onwards, let me stop here.
Thank you very much.
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Corrosion - Part I
Prof. Kallol Mondal
Lecture - 26
Estimation of Corrosion Rate –I
Let us start lecture 26.
Till now, we have looked at thermodynamics of corrosion and then while talking on
thermodynamics of corrosion or rather the possibility of corrosion in a particular solution
of certain pH, we discuss we have discussed Pourbaix diagram in that context. Now,
Pourbaix diagram as we have mentioned that it tells us the stability of different phases in
water or aqueous medium. But, it cannot tell us one of the important aspects of corrosion
what is that is called the rate of corrosion or the kinetics of corrosion.
So, now onwards we will start talking on the kinetics of corrosion or rate. So, while
talking on the rate of corrosion; that means, we are talking about the rate of dissolution
of metal and of course, while we talk about dissolution of metal we have to consider
electrochemical mode or electrochemical mode of dissolution of metal or loss of metal.
So, dissolution we can also consider it to be loss of metal. Now, when we talk about loss
of metal; that means, it is a basically loss of mass of that metal. For example, we have a
beaker and we have taken let us say deaerated HCl solution deaerated.
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And there if we put a small zinc piece let us say a commercially pure zinc which is let us
say 99 percent pure zinc and then we will see that there will be bubble formation on top
of it. And after some time if we take this zinc piece out and then measure the weight we
will see that there is a loss of weight; that means, let us say the at 0 time, now weight
was w1 and let us say t time the weight is w2 we see that w2 is less than w1.
So, the rate of loss is nothing, but w2 w1 minus w2 divided by t. This is the rate of
dissolution or weight loss. Now, this is also rate means there is a per unit time part is
coming there. Now, question is we have to see that where the reactions are taking place.
If you see the reactions, the reactions are always taking place on the surface of that
metal. It is not that entire body of that particular metal piece; that means the bulk of the
metal piece is also reacting only the surface the hydrogen evolution is taking place.
And the reaction of course; zinc going to zinc plus and 2e and hydrogen will take care of
this 2 electron and then form H2. So, this gas will generate and then this Zn Z plus plus
will react with cl 2. So, it will form Zncl2, this is the reaction and these entire reactions
are taking place on the surface of the metal.
Now, let us have one situation if we consider that these reactions are taking place at a
particular temperature, pressure and then concentration of this acid is something like let
us say C1 mole per cubic meter. And then we consider that the zinc has some purity
which is 99 percent.
And now if we consider that the entire processing parameters or the surrounding
parameters are same, so, we have 2 beakers; one beaker we have a small zinc piece,
another beaker. We have a big zinc piece both of the same quality. Rather you have a
zinc piece of 99 percent purity we take out 2 cubes out of it, one cube is smaller cube,
another cube is much bigger cube. And then we are exposing them to HCl solution of
same concentration and also the pressure and temperature both are same.
So, then we will notice that the weight loss or del w this is nothing, but del w by t which
is nothing, but the rate of corrosion. So, del w1 this is let us say set 1, this is set 2 and del
w2. For a particular time, interval let us say the time is t for both the cases we would see
that in this case and in this case these two are different. And we would see that this is
greater than this, this will be much more greater than this. Because, here the zinc piece is
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much bigger than the zinc piece what we have here and the quality of every other
parameter are same.
Now, then the rate of corrosion would be this or the rate of dissolution or the rate of
weight loss. Now, we see that if the zinc piece is same and if the parameters are also
same then we should expect that the both the rate should be same. Now, here this rate 1
is equal to rate 2 that should be the situation because it is the same zinc piece and all the
other factors like temperature pressure concentration all are similar.
So, but it is not like that because you see this quantity and this quantity they are different.
Now where is the problem? The problem is since we are considering that the surface
reactions are taking place and the bulk of the system is not participating in the reactions.
So, we have to normalize with area, when you normalize with area because only the area
is taking part and here it has got much higher area than this particular situation.
So, that for the weight loss should be also higher and when we divided by the same time
duration that this particular factor would become much higher. Now, once we divided by
A1 so, this is A2 and this is A1 and A1 and A2 the relation is like this and these are
nothing, but area over which reactions are taking place ok.
So, now, whenever we consider this normalized factor area we would see that these
twoare equal which was not there before, but now after this is without considering area.
Now, once we consider area, then we will see that rate 1 equal to rate 2. So; that means,
the corrosion rate or the dissolution rate of that particular metal per unit area they are
equal.
So; that means, this area is extremely important factor while we consider that the rate of
corrosion. And we have to consider that the corrosion is nothing, but rate of metal
dissolution or loss of weight per unit area. This is extremely crucial factor and; that
means, our formula would be del w by At or you can say mass per unit area per unit
time.
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Hence, the rate corrosion can be considered as like if we consider the unit part, we can
consider as milligram per meter square per year or milligram per meter square per
second or milligram per centimeter square per second like that anything we can consider
only thing is we have to consider in the form of loss of metal or loss of weight per unit
area per unit time.
Now, there are some units available to express rate of corrosion those units are GMD, we
considered as gram per meter square per day these are some of the expressions or the
units that are available in order to express rate of corrosion. mdd we call it as milligram
per decimeter square per day. So, these are the 2 rates that are available.
Now, when we talk about these rates let us seek a which at some point of time whether
these particular way of expressing rate of corrosion would give us suitable corrosion rate
or not or suitable information about corrosion.
Now, when we talk about this let us say we have 2 surfaces, 2 metal block one is M1,
one is M2 they are exposed to that say NaCl solution. Now, after some time we might
experience that in one case if we see the if we analyze we will see that dissolution has
been more or less uniform over the entire cross sections or surfaces of surfaces available
for that particular metal exposed to the NaCl solution. So, this is the situation so, these
pink color regions are basically the loss of metal. So, that much amount of metal has
dissolved in the particular solution after some time some particular duration.
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Now, in the other case we might notice that macroscopically there is nothing on the
surface, the surface looks absolutely clean. But, if we see microscopically we can see
that in some portions some cases the dissolution has gone deep into the material so, like
this.
So, we did not have the situation what we faced here the dissolution was overall uniform;
that means, the thickness reduction for the particular block is uniform over the entire area
or the surfaces that are exposed to NaCl. But here, we see that the surface has not
changed much, rather surface character, surface nature or surface appearance does not
look different after dissolution study. Rather than if we see microscopically, we see that
there are pits these are called through depth through depth pits.
Now, these pits are basically progressing through the depth and the surface thickness has
not changed much. Now, would it be fine if we express this one as mdd and at the same
time this one also mdd. By looking at this data let us say this is 10 mdd and this is 2 mdd
by looking at these two data can anybody understand that the character of corrosion is
different? No, nobody would understand.
Now, in this case it is not about uniform dissolution it is basically localized dissolution.
And in order to understand the localized dissolution we have to understand the what is
the depth that has penetrated for that solution that has penetrated into the material.
So, here the unit should have been depth penetrated per unit time. So, that case mdd may
not give us the actual information. So, now, in that case we have to consider a different
unit and that time it is basically depth some unit let us say meter or centimeter or inch or
milli inch, milli inch and then time we can consider it to be second, we can consider it to
be day, we can consider it to be year.
So, here the unit becomes either meter per second, meter per year, millimeter, year, milli
inch per meter and these are all this dimension is nothing, but the depth that is basically
up to which the solution has progressed into the material. And here two units are popular,
one is millimeter per year, another one is milli inch per year which were we call it as
mpy.
So, when it is uniform corrosion we can express the corrosion rate in the form of mdd or
GMD. We can express like the situation what we have seen here. But, in case of
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localized we have to consider we can consider as millimeter per year or mpy means milli
inch per year fine.
So, these are two different rates now, question is we have the information about weight
loss per unit area per unit time. Now, we have to convert this one into depth by time.
How can we do it? Now, it is very easy if we know the density of that particular material.
Now, this is del w by area which in the form of let us say L square, this is mass and then
we have time in the form of second and then if we divided by density which is rho this is
M divided by L cube these are the dimensions.
So, now, if we see that so, it comes about L by second or distance penetrated per unit
time or we can call it as depth is not it. So, it is simply the dividing the mdd by the
density of that material so then we will convert the uniform mode of corrosion to
localized mode of corrosion. Now, one example I we can cite that is you have also seen it
we have shown one stainless steel plate you might have noticed that that stainless steel
plates have got lot of pits and those are true pits.
And the surface looks absolutely fine not much of corrosion product, but it has it has got
perforated because of the corrosion attack localized corrosion attack. So, that case it is
better to express the corrosion rate in the form of depth penetrated or the distance
penetrated into the material by time. But, in case of zinc when it is dissolving in HCl, we
can definitely consider it to be more or less uniform dissolution that time we can express
the corrosion rate in the form of mass loss per unit area per unit time. We can express the
unit in the form of GMD or mdd.
So, this is one important aspect while we talk about kinetics of corrosion or the rate of
corrosion. How to express the rate? What should be the best unit we should put to
understand at least by looking at the unit? What should what is basically the mode of
corrosion attack? Whether it is a localized or it is uniform. Now, there are another aspect,
when you talk about the loss of metal we are considering that every time there will be a
loss of after for example, the example what we have cited is HCl medium and we have
two zinc piece, one big one small and then after some time we are taking it out and then
measuring the weight.
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. And we could see that there is a loss of weight because, it is dissolution when it
dissolves the zinc does not form any corrosion product on the surface. It actually the, it
produces zinc chloride also it has got a very high solubility. So, it dissolves in the
solution.
So, when you take it out we do see the weight loss, now this is in HCL and it is also HCl.
So, this is uniform water corrosion, but many a times for example, in case of atmospheric
corrosion of iron we do not see that actually if we start from 0 time and after spending
certain days if you take out that particular metal space without disturbing the surface
conditions. That means, you are carefully taking the sample without disturbing the
surface and weighing the weighing the particular small item or the plate if you have a
exposed it to the environment, you might see that there is weight gain rather than weight
loss.
So, in certain cases we see that this is weight loss and it becomes straight forward, but
when we have weight gain then we have to have to mention that it is basically no
corrosion is taking place? No, it is not like that for example, in case of iron let us say iron
piece the example what we have provided if you have expose it to the environment; that
means, atmospheric corrosion if you led that atmospheric corrosion to happen. Let us say
some one month you have expose it and then you measure the weight and that time you
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also spray a little bit of NaCl solution. You would see that the weight loss is not there,
rather there is a weight gain.
So, now we are confused, but actually it is there is no point in getting confused, rather
there is also corrosion. Here, the particular block is covering with a kind of surface layer,
surface layer. Only the center part remains to be the iron and the rest of the iron let us
say you have started with this is the size, initial size and then it has grown in size, but
actual metal piece is nothing, but the center part. Rest of the layer is nothing, but oxides
or hydroxides of iron.
And since it is Fe2O3 or FeOH whole 3 or FeOH whole 2, now one mole of iron if it
forms oxide or hydroxide the weight will be increasing if they are not getting detached
from the surface.
Now, how do you get the corrosion rate then? In those cases you have to carefully
remove the outside layer of the surface layer. And that removal should be done so,
carefully that the inner part which is the metal part should not get damaged or should not
get removed. So, that is what we have some standards, how to remove the oxide layer
which is mostly done chemically and then after removal we are left with this much small
piece and that what we have to take the weight. So, this is w2 and here the weight was
w1. Now, and this one is w prime so, w prime greater than w1, but w2 is less than w1.
So, now we have to consider this one after removal of the oxide layer and then we have
to find out the corrosion rate. Now, this area should be the area what was initially
considered ok. So, the area of this particular block should be considered because the
dynamic change in area it was very difficult to understand what could be the dynamic
change in area.
Because, it may not happen completely uniformly there could be some localized attack
or there could be some uniform attack. So, it is a mixture of things so, that is what it is
always better to consider the initial area in order to consider the corrosion rate. So, this
should be my corrosion rate.
Fine so; that means, we have what we have gained from this particular lecture is we need
to consider corrosion rate in the form of loss of metal per unit area per unit time and area
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is important factor for the normalization because the surface reactions are leading to the
dissolution of metal, not the bulk of the system.
This is one part, second part is whenever there are 2 ways of expressing corrosion rate,
one is uniform corrosion mode where we can consider weight loss per unit area per unit
time. And there is one more way to express corrosion rate is basically the depth
penetrated or the distance penetrated into the metal or in the basically depth directions of
that particular metal or the perpendicular to the surface.
We have to put in the form of depth per unit time or the and the units are one case
uniform case we can consider GMD gram per meter square per day or mdd milligram per
decimeter square per day. And in the other case where we consider depth penetration that
time we have to consider the unit in the form of mpy or millimeter per year mpy is
nothing, but the milli inch per year. So, these are the usual practice the way we have to
express the corrosion rate.
Now, in the second part we have to consider. So, these are basically the experiments we
have to do; that means, in this experiment the kind of experiments what shown here is
basically nothing, but the immersion experiment and this is basically exposure or
experiment.
So, now, other than that we have to also look at the electrochemical nature of this
particular dissolution or the electrochemical nature of the corrosion rate. So, in the next
lecture we will talk about the electrochemical nature of this corrosion rate thank you very
much let us stop here.
Thank you.
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Prof. Kallol Mondal
Lecture – 27
Estimation of Corrosion Rate–II
Here we will continue our discussion on Kinetics of Corrosion. Now, in the last lecture
we talked about expressing corrosion rate in the form of either mdd or GMD, means
gram per meter square per day, milligram per decimeter square per day, or there are one
more section which is basically mm per year or mpy. So, now, mpy, and mpy is nothing
but milli inch per year. This is we talk about uniform corrosion and this one is nothing
but localized corrosion.
Now, then we thought that we would get into the electrochemical mode of corrosion
expressing corrosion rate in the form of current. Because you would see in a while that
current is nothing but the rate of charge transfer, and for corrosion is nothing but the
anodic reactions or the formation of metal ion from metal, and then electron will be
released and that electron will be taken up by some cathodic reactions.
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Now, sometimes we have to see that these units are interchangeable. Let us say the we
know that what is the amount of metal loss and then calculate the corrosion rate in the
form of mass loss per area per unit time. And then after that we see the surface and then
see that the surface does not change much. So, then we have to convert it into the another
unit which is nothing but the depth attacked or the depth penetrated per unit time. So,
that conversion is quite straightforward only thing is we have to divide it by the density.
And in addition to that while we change the units there could be some conversion factor.
So, like one conversion factor which is very popular is mpy is considered as 534 into del
W by area by time by density or the rho, the rho is density of the metal, where del W is
expressed in the form of milligram, A is inch square, time is hour and rho is gram per
centimeter cube.
Now, this is the convention people have used. So, I think from the first when it was first
understood that time this particular expression existed. But now I would say that you do
not bother about this expression only I am showing it that how to why this conversion
factor 534 comes in. I just would like to mention that, otherwise you simply consider the
units after taking mass loss area time and density whichever way would like to consider
but it should yield milli inch per year. So, then you would get different conversion factor.
But at least let us see how this 534 arrives.
Now, when we talk about del W A t rho, let us say somebody expressed these are the
considerations that weight loss was taken in milligram area was taken in inch square,
time is in hour and rho is in gram per centimeter cube. Now, if that value is let us say 10
unit of this, now we have to consider in terms of mpy.
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So, if we consider this part milligram per, area is in inch square then we are taking time
in hour, then we are taking in gram per centimeter cube. So, unit milligram I am just
doing the conversion in order to arrive to this particular mpy, so I have to make it in the
form of milli inch per unit area per unit per unit year or rather milli inch penetration in a
year.
So, inch should be converted into centimeter square or I could say centimeter should be
converted into milli inch. This inch square, so I just simply keep it inch square first, and
then hour should be converted into year. So, this should be 24 into 365 year because 1
year equal to 24 into 365 hour. So, from that I can write 1 hour is nothing but 1 by 24
into 365.
And then gram I can convert into milligram since this is a milligram, so 1000 into
milligram, 1000 milligram divided by inch centimeter I can convert it to inch. So, 1
centimeter equal to rather 1 inch is equal to 2.54 centimeter. So, 1 centimeter is nothing
but 1 by 2.54 cube, inch cube now then I can write it as, so this one would get cancelled.
So, this part would get cancelled, and then this one would go to 24 into 365 divided by
1000 into 2.54 inch per year, this should be cube.
Now, in order to convert inch into milli inch, I can multiply with 1000 so this would
become milli inch. Now, if you calculate this then you would see that it is coming about
534; roughly it is coming about 534 that it will come around 535, close to 535
something. So, you can roughly consider it as 534. So, that is what if I consider 10 of this
particular amount, then this should become into 10 into 534, this much milli inch. So,
this would be equivalent to milli inch. So, this is coming about 5340. So, you understand
that how this 534 comes up.
It is basically converting these units these units in the form of the units what we desire or
what we want here it is mpy. And if we consider all those parameters in the form of these
units then there should be a multiplication factor of 534, and this is coming because
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when we convert those units we have to see all those conversion and then finally, we
achieve 534 that is the multiplication factor. So, like that way you can convert any unit
into any other unit.
For example, if we consider let us say millimeter per year I have to convert into mpy or
vice versa. So, then also it can be done like, let us say I want to convert mpy into
millimeter per year. So, mpy is nothing but milli inch per year. So, this is coming out to
be, this is and then we have to make it in terms of millimeter, so 1 inch equal to 2.54
centimeter is equal to nothing but 25.4 millimeter.
So, it this becomes 10 to the power minus 3 inch per year. So, this, so it was 10 to the
power minus 3 into 25.4 divided by year, so 1 by 100 divided by 2.54 millimeter. So, this
becomes millimeter now the top part year. So, equal to 1 by 39.37. So, 1 millimeter per
year equal to 39.37 mpy. So, this is another conversion. So, you can see that you can
convert one into unit to another with some conversion factor. So, that factor is decided
by what is the unit we are considering.
Now, let us get to the electrochemical ways of expressing corrosion rate or we would
now consider the current flow for the corrosion rate. Now, when we talk about current
flow as the measure of the corrosion rate we have to see that why this current flow
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should give us corrosion rate. Now, let us say the metal dissolution. So, metal is going to
n plus ne, and where n is basically the oxidation number, oxidation number. So, when we
consider one atom of that particular metal is coming into the solution in the form of ion.
So, then we are seeing that any number of electrons are released.
Now, if we keep seeing this particular conversion from metal to metal ions that means,
we are seeing that the loss of metal is continuing and then we are also saying the number
of electrons are also released that number is also increasing. Now, the rate at which these
metal ions are forming that would also be related to the rate at which electrons are
getting released from that particular metal ion atom.
So that means, rate of metal dissolved in the form of metal ions. So, that is also
somewhat equivalent to rate of electrons generated. So, and when we consider rate of
electrons generated and we also know that rate of charge flow is nothing but current. So
that means, this is nothing but current. Of course, the current could be different current
could be anodic current could be cathodic, and here since we are considering anodic
reactions this current is nothing but the anodic current. So, it looks like that the current
flow is guiding the rate of dissolution, or if we can have the knowledge of that current
which can be easily measured with an ammeter so we can know what is the rate of
corrosion.
Now, when we talk about the rate of corrosion is related to the current or the flow of
charge per unit time, then we have to take care of we have to consider the faradays laws
of electrochemistry or popularly the laws of electrochemistry. So, this is very important
when you consider the rate of corrosion in the form of current flow. So, let us see what
are those two laws of electrochemistry, these are exact laws.
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Now, first it says the amount of chemical change which occurs at any electrode is strictly
proportional to the quantity of electricity passed through to the electrolyte.
Now, when we talk about electrolysis let us say, if we send let us say we are taking
AgNO3 that is the solution aqueous solution of AgNO3. And then if we send current, and
if we send current let us say I then we would see that this is positive electrode, this is
negative electrode, here Ag will deposit since these reaction takes place.
Now, if I send Q amount of charge. So, then we would see that the weight that is
deposited in the cathode is proportional to Q or simply write W is proportional to Q. And
the proportionality constant this Z is nothing but electrochemical equivalent. This is the
electrochemical equivalent of that particular metal. Here it is silver.
And this we can convert into Z I t, since Q is equal to nothing but dQ dt is equal to I. So,
Q is equal to I t. Now, Z, the definition of Z would be if I equal to 1 ampere and t is
equal to 1 second, then Z is equal to W.
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Now, if we consider the second law of electrochemistry, it says that if the same amount
or the same quantity of electricity is passed through different electrolyte, the different
amount of chemical changes produced are all chemically equivalent.
Now, let us see the, what it says. Let us say we have two cells, one is the cell what we
have shown there this is two electrodes and then here AgNO3 and another cell where we
are supplying current and here it is NaCl aqueous solution, both are aqueous solution.
And if we supply 1 faraday of charge, if we supply 1 faraday of charge which is nothing
but 96500 coulomb, then the amount of metal that will be deposited on this surface here
it will be Ag plus plus e equal to Ag. So, this will be deposited. And that amount would
be this amount if we send 1 faraday if we way that it would become 107.88 gram which
is basically 1 faraday charge.
Now, on the anode, this is my anode I will have this reaction and then we will generate
oxygen and that time the amount of oxygen anode for the supply of 1 faraday of
electricity is also equal to 8 gram.
Now, if we see this Ag and O2, Ag has got oxidation number 1, so 107.88 gram is
nothing but 1 mole or 1 gram equivalent, because since Ag the oxidation number which
is n is 1 here.
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But if we consider oxygen on anode its n is equal to 2 since we have to consider oxygen
ion, so the 1 faraday is equal to 8 gram of oxygen which is nothing but 16 by 2, 16 is
basically the molecular weight of oxygen is equal to 8 or this is nothing but 1 gram
equivalent.
Now, the chemical product that will be formed here is so, 1 gram equivalent of oxygen.
Now, similarly if we see the NaCl here on the cathode you would get following reaction,
where 2H2O it will react with it will accept 2 electrons and then forms H2 plus 2OH
minus and anode it will be equal to here Cl minus will release 1 electron or 2 Cl2. So, this
H2 gas will generate on cathode and chlorine gas will generate on anode.
Now, here also you will see that if we sent 1 faraday of charge on cathode it is 1 gram of,
roughly 1 gram of H2 and anode it is around 35 gram of chlorine. So, these are also their
gram equivalent. So, now, what we see that if we send the same electricity or same
charge we are getting similar amount of the equivalence the chemical equivalents
amount of products that means, if we send 1 faraday of electricity we are getting 1 gram
equivalent of that product. So, 1 gram equivalent of silver, 1 gram equivalent of oxygen,
1 gram equivalent of chlorine and H2 in those two cases, so that means, the second law is
validated.
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So, now that means, E1 by E2 should be equal to z1 by z2; so E1 and E2 are the
chemical equivalent for two substances and z1 and z2 are basically the electrochemical
equivalent for those two substances, and then second law says that they are equal; if the
ratios are equal. If you send similar amount of charge. So, we will get same amount of
chemical product which is chemically equivalent.
So, let us stop here. So, we will continue our discussion on this and try to get some
relation with the current and corrosion rate.
Thank you.
270
Corrosion - Part I
Prof. Kallol Mondal
Lecture - 28
Estimation of Corrosion Rate – III
Today we will have lecture 28.
We will continue our discussion on kinetics of corrosion and in the last lecture, we just
started looking at the corrosion rate in terms of current flow since for corrosion. That
means, the metal ion formation we have to have electron generation and per unit time if
we see that electron generation, we can get some idea about the corrosion rate and some
correlation with the current flow during corrosion. Now, while doing that we started
looking at laws of electrochemistry and the first law says that w is proportional to Q and
where we finally we got W equal to zIt. This should be capital I which is the current in
ampere. So, this is electro chemical equivalent and I is current in ampere, ampere t is
time in second.
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Now, there we saw that z is nothing, but the value of W when I equal to 1 t equal to 1.
Now, then in order to find out z, we started looking at second law. It says that E which is
the chemical equivalent is proportional to z. Why? Because we saw that we had taken
two examples. One was electrolysis of aqueous NaCl solution and another one is the
electrolysis of aqueous AgNO3 and we saw that in case of NaCl, we had chlorine gas on
the positive electrode that is the anode and on the negative electrode we had hydrogen
generation that was basically H2O reduction of water reduction and then, in case of
AgNO3 we had silver deposition on cathode. That means the negative electrode and
oxygen evolution on the anode and this oxygen evolution is coming because of OH
minus oxidation.
Now, when we saw that and then, finally we realized that if we send 1 Faraday of
electricity or the charge chemical reaction or the deposition or the evolution of gases on
the cathode or anode, they are all equal to chemical equivalent or the gram equivalent of
that particular substance. For example, in case of AgNO3 we had 118 where around
107.88 gram of silver deposition because of the because of that 1 Faraday of charge flow
in that particular circuit as well as around 8 gram of oxygen on the anode. So, we see that
every time this 1 Faraday of electricity or the charge is nothing, but equal to the chemical
equivalent or the gram equivalent of that particular substance. Now, if we say that E is
proportional to z that then E equal to Fz. So, F is basically 1 Faraday and z is
electrochemical equivalent.
Now, this equation can enable us and E is nothing, but the chemical equivalent as we
have said, this equation will enable us to find out the z value. So, in case of silver, we
can find out z is equal to E divided by F which is E is nothing, but 1 gram equivalent
which is same as the molar atomic weight of that particular silver because it has got the
atomic this oxidation number to be 1. So, 107.88 divided by 965500 gram and this is
coming out to be 000.00118 rather 1118. If we check this yes it is 0.001118 gram per
coulomb now.
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So, with the help of second law we can find out the value of z. Now, we try to
understand this importance of these two equations on corrosion rate. Now, whenever we
talk about M going to Mn plus plus ne that time it’s gram equivalent would be AM which
is the atomic weight of that particular metal divided by n. This is equal to gram
equivalent, fine.
Now, when you see that, then we could see that whether it is this way or this way. If I
send 1 faraday of electricity or 1 faraday of charge, that means 96500 coulomb of charge.
It will always liberate when it transforms to metal ion or well, it will also deposit the
metal of this amount which is AM divided by n. That means, this is E value of metal or
chemical equivalent of this metal. Now, if the deposition is in the chemical equivalent if
I send 1 faraday of electricity on the other way, the dissolution of metal ion would be
same as the deposition. That means, 1 faraday would be equivalent to this gram of metal
dissolution. Is not it? So, that much gram of metal dissolution would take place if I send
1 faraday of electricity. Now, electricity or 1 faraday of charge now if I take this
particular concept to understand if we send Q amount of charge, what would be my, the
amount of mass that will be lost in the form of ions into the solution; so, that we can
easily find out.
Now, let us see if I try to put it in the form of differential mode.
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Let us say 1 faraday of electricity is equivalent to AM divided by n. This is basically
amount of metal that will be dissolving. Now, if I send nF amount of charge or coulomb,
so it will be equivalent to 1 mole of that substance. Why? Because this is nothing, but
AM gram of metal or the weight, the atomic weight of that particular metal. So, one
particular atomic weight, so this much of metal ion if it forms, then we would definitely
have 1 mole of metal dissolution. So, if we send dQ amount, so it will be simply 1 by n F
dQ, so this much of mole that dissolves.
So, now you see if we send dQ amount of charge, we get this much, this much of mole,
loss of mole of that particular metal that is dissolving in the solution. Now, if this dQ
charge is sent for del t time or dt time which is a very small miniscale time, then we can
find out what is the number of mole dissolved per unit time. So, let us say this value is
the number of mole would be then w or this if I note it down as n prime which is the
number of moles that is dissolving, so this mole it is equivalent to n minus mole. So, n
minus divided by t is nothing, but the rate of number of moles of metal dissolved per unit
per unit time which is same as because n prime is nothing, but dQ by nF.
Now, nF is a constant, n is nothing the oxidation number for this particular reaction.
Now, F is 1 faraday which is also constant. So, now I can write this. Now, if I see this
quantity, this quantity is nothing, but I. So, I can write this 1 equal to I divided by nF.
Now, when I write this, it says the rate of I can rate of number of moles of metal
dissolved or in that case I do not have to mention this per unit time because when I am
using this rate, time is taken care of. Now, this particular is also indicating the corrosion
rate only in the form of number of moles dissolved per unit time, but it is not taking care
of the area because area is very important as we have discussed in our last lecture
because whenever corrosion happens, it is basically surface phenomena. So, the exposed
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area on top of it, this reaction will take place not in the bulk of the system or the bulk of
the metal. So, until unless we normalize it with area; we will not be able to get the proper
indication or proper expression for the corrosion rate.
So, in order to do that, we have to divide it with area. So, let us say small a is basically
area this is area. So, I can put it as n prime a dt equal to I by nFa.
So, now it becomes number of moles of metal dissolved per unit time per unit area. So,
this is the proper indications. Now, it is in the number of moles. Now, we can convert
this into grams per unit area per unit time. So, in order to do that n prime is basically the
number of moles. So, this w if w prime is the amount of metal that has dissolved divided
by A which is basically AM rather is AM is the atomic weight divided by AM adt is equal
to I by nFa.
I can write this way, where w prime is the weight of the metal or the mass of that metal
coming into solution formed and then, w and AM is nothing, but equal to n prime or the
number of moles, then w prime adt equal to IAM by nFa.
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So, finally we are getting the corrosion rate is equal to gram or I could say in the form of
weight divided by area divided by time equal to I AM.
This is the expression. What we are getting, now we can simplify this one AM I by a n F
and I divided by a is written in the form of i small i which is nothing, but ampere per
centimeter square.
I can mention in this fashion ampere per centimeter square which is nothing, but the
current density. So, corrosion rate is equal to inF. Now, AM for a particular metal n and F
for M equal to M n plus plus ne, they are all constant.
So, now corrosion rate I would say is proportional to I or the current density.
Interestingly it is not proportional to the current flow, rather it is proportional to the
current density because if we take current, then we are actually not considering the area
that is exposed to the solution for the corrosion reactions to happen on the on the metal
surface, but current density will look when we consider it actually takes care of this area
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that is actually on top of which the reaction the corrosion reaction is taking place. So,
hence the corrosion rate is directly proportional to the current density not I, but we get
this particular information by using this electrochemistry, of the laws of
electrochemistry. Now, once we get this idea, we can see that it is basically in the form
of weight loss or I can say weight loss per unit area per unit time.
Now, this we have seen that in those cases where the dissolution pattern is localized, we
have to use a different way, different way of expressing corrosion rate which is nothing,
but the depth penetration depth divided by time. So, we can convert this particular
expression in the form of the depth penetrated per unit time by simply dividing this
corrosion rate with density of that particular metal. So, the corrosion rate in the form of
depth per unit time we can put it as iAM by nF rho where rho is basically density. So, we
get another expression like this which is equivalent to weight loss area time density.
Now, we see that we have a very good idea that corrosion rate is electro chemical in
nature and by using laws of electrochemistry; we can relate the current flow in the form
of current density with the corrosion rate. Now, before we get to the details of this
current density part because we have to now get to the exchange current density which is
exchange current density is basically i0 which is a very fundamental aspect in
electrochemistry as well as in corrosion because while explaining corrosion in more
scientific fashion, we have to use make use of a mix potential theory and there this i0 will
be extremely needed and this is a fundamental parameter fundamental parameter. So,
before we get to this i0 which is exchange current density, let us use this particular
formulas and let us see whether we can find out the corrosion rate in different units and
express them in different units.
So, let us solve some numericals. We are just giving some examples of those numericals
TAs will give you many more problems on these two formulas and then, you can solve
them and practice.
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So, the first problem let us let us say a tin immersed in sea water shows what is the rate
of corrosion in mdd and mpy? Now, in this particular problem we have used a corrosion
current density. Now, if we go back and see this particular formula, here the corrosion
current density is nothing, but the current density at which the dissolution is taking place.
So, this is nothing, but the corrosion current density this is nothing, but the corrosion
current density. So, we will start expressing this or mass loss divided by area and time
which is nothing, but i Asn tin is nothing, but the Sn divided by n is 2 here and F 96500
coulomb where Asn is nothing, but 118.71 gram and Sn is going into the solution as Sn
plus 2 plus 2e. So, that means n becomes 2 and i is nothing, but in ampere per centimeter
square Asn is nothing, but in gram 118 gram divided by and here I can put this value
2.45 into 10 to the power minus 6, n is equal to 2 into 96500 coulomb.
Now, this quantity I can write in this way 2.45 into 10 to the power minus 6 coulomb per
unit time per unit area because i is i is nothing, but I divided by area or coulomb per
second per unit centimeter square.
So, then I can write this time as second area in centimeter square 118.71 gram and this
becomes 2 into 96500 coulomb. So, this coulomb would get cancelled and then, 2.45 into
10 to the power minus 6 divided by 2 into 96500 and now, I will convert the units
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because it is in mdd which is milligram per decimeter square per day. So, this becomes
gram. So, I have to convert this gram into milligram. So, 1000 milligram divided by
second, I have to convert into days. So, the second becomes 1 divided by because one
day is equal to 24 hours 60 into 60 second. So, one divided by 24 into 60 into 60 day
divided by centimeter should be in decimeter. So, 1 centimeter is equal to 10 to the
power minus 1 decimeter. So, it should be 10 to the power minus 2 decimeter square.
So, final expression would come as 2.45 into 10 to the power minus 6 2 into 96500 into 1
1. Sorry I miss this amount of gram 8.71 into 1000 into 100 into 24 into 60 into 60 this
much milligram per decimeter square per day. So, finally this value would be 13.01 mdd.
So, this is the corrosion rate.
So, we will solve the other part which is in the mpy in our next lecture. Let us stop here.
We will continue our discussion on Kinetics of Corrosion.
Thank you.
279
Prof. Kallol Mondal
Lecture – 29
Exchange Current Density
Let us continue our discussion on kinetics of corrosion.
And today we will have lecture 29 and we will continue our discussion on kinetics of
corrosion.
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Now, if I recall our last lecture we started this problem and then there we address the
first part, we had to calculate the corrosion rate in the form of mdd by using the
corrosion current density, what is provided to us. And then we found out and we have
actually did little bit of conversion of the units and then we got the value which is 13.01
mdd.
Now, we have to find out the corrosion in the form of mpy there are two ways one is you
once you know mdd you can convert that mdd into milli inch per year or you can start
with the basic equation, which is corrosion rate is equal to i AM here M is nothing, but
the Sn, nF into rho Sn and rho is the density ASn is basically the atomic weight of tin and
then we can write it as 2 .45 into 10 to the power minus 6 it is basically ampere per
centimeter square.
Now, I will write it directly in terms of coulomb per second per centimeter square. So,
this is coulomb per second per centimeter square weight is atomic weight is 118.71 gram
and n is equal to 2, F is equal to 96500 coulomb into rho the rho of Sn is equal to 7.31
gram per cc or centimeter cube so, 7.31 gram per centimeter cube.
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Now, I could see that this one will get we can cancel out coulomb coulomb can be
cancelled out and this gram gram also would get cancelled out. So, you are left with 2.45
into 10 to the power minus 6 divided by into 118.71 divided by 2 into 96500 into 7.31
gram per second.
Now, we have to convert this gram per second into milli inch per year. So, 1 second
equal to 365 a year consists of 365 days each day consists of 24 hours and then 60
minutes and each minute 60 seconds so, this much year. Now, 1 centimeter we can
convert 1 inch equal to 2.54 centimeter.
So, 1 centimeter equal to 1 divided by 2.54 I can make it milli inch by putting here 1000
because 1 inch is equal to 1000 milli inch. So, now, I will put these values here so, 2.45
into 10 to the power minus 6 into 118.71 into divided by 2 into 96500 into 7.31 into 1000
sorry, we made a mistake here it should be centimeter because only this part is left out.
So, 1000 by 2.54 so, that is 1 centimeter equal to 1000 by 2.5 for milli inch. And then 1
second is equal to this much here so, per second so that means, this will be multiplied
here so, this much inch per year.
So, this becomes milli inch per year or so, we could see that we can express the corrosion
rate by using the corrosion current density and then we can convert it into either mdd that
is gram per area per weight loss per area per unit time and also we can converted into
mpy which is milli inch per unit per year. So, we can convert it into uniform as well as
localized depending on the surface nature of that particular metal in that particular
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corrosion corrosive environment. So, now let us get into little deeper into the current
density part.
Now we have already started mentioning this particular term called i0 which is nothing,
but exchange current density and this has a relation with i. Now, if I try to look at this
particular reaction and if it reaches equilibrium and before it reaches equilibrium so, then
this is anodic this is cathodic.
So, this direction we have cathodic reaction and this reaction sorry we have just reverses
this would be cathodic and this side would be anodic. Now, this is reduction the forward
reaction and the backward reaction is the oxidation reaction or corrosion reaction. Now,
if I see the cathodic part the rate at, which electrons are consumed if we express that we
can convert it in the term of Ic or the current per unit time or equal to charge it is not
current it is basically charge per unit time is equal to current and this current is involving
cathodic reaction. So, that what we call it as cathodic current.
Now, if we divide these particular reactions let us say this is the metal surface on top of
which the cathodic reaction is taking place. So, we can divide this area and then we will
get or a is nothing, but area divided by area a. So, I get cathodic current density.
Similarly, on the anodic side we can get anodic current or charge in the form of electrons
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generated divided by time and then if I divide it by area of the anodic surface we get
anodic current density, we will try to term it as ic and this one would be ia.
Now, this is ia, this is ic now we will talk in terms of current density only because we
have seen the rate at which this deposition or dissolution that will be directly
proportional to the their mass loss per unit area per unit time or mass gain per unit time
mass deposited per unit time per unit area that we have already noticed. Not in the form
of current because current will not give us the actual information because, it does not
involve the area into does not take the area into consideration.
Now, so, this reactions Mn plus plus ne M this reaction is taking place simultaneously
and then they will reach equilibrium. So, ic ia now if I consider this particular direction
the current density to be ia so, the reverse direction which is cathodic reaction rate is we
shall mention it in the form of minus ic. Now, this minus sign indicates the direction this
negative sign indicates direction only of current flow. It does not tell that current density
is actually negative magnitude is positive, but negative means it is flowing opposite to
the anodic current.
So, whichever you take to be positive the other one should be negative, but our what we
will take it ia we will take it as a positive current and ic we will take it as a negative
current so; that means, its flowing opposite to the anodic current.
Now, when they reach and also we see that this is proportional to the deposition rate per
unit area, per unit time and this is proportional to dissolution rate per unit area per unit
time. So, the rate of corrosion rate, since they are taking place at a particular temperature
and pressure and they will reach equilibrium because, if we consider time and the rate
and if we tell this rate in the form of i then initially, if we consider if we say that our
particular solution has Mn plus ion. So, once I dip this particular metal into that solution
at a particular temperature pressure see this metal will start depositing and at the same
time opposite process would also start.
So, now if I consider that this is the initial concentration of initial rate because, since
metal ion concentration is very high in the beginning when we dip that particular metal
into that solution containing metal plus plus n plus ion. So, there are lot of supply of
metal in class so, the rate at which the deposition would happen would be very high rate.
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So, and then gradually this one would deplete gradually, but at the same time there
would be a dissolution also the metal ion will form from metal surface and these two
opposing process will try to equilibrant or they will try to reach to a particular rate,
where the rate of deposition and the rate of dissolution would be equal. So, initially this
is the rate which is let us say ic and I am on putting a minus sign because, I am
considering the direction of flow of that particular current and it is a deposition.
Now, the opposite current would also start immediately after putting that particular metal
into that solution. So, this is ia and then after reaching the same value they will maintain
that value if we do not disturb that particular solution. So, if you do not change the
temperature pressure that metal surface quality is same solution is same so, it will
maintain that particular rate. So, this indicates these particular value indicates i0, which is
the exchange current density.
Now, interestingly and whenever we are reaching to this equilibrium in that particular
situation do we get the dissolution or deposition to be different no they are same. And in
fact, that situation is called non corroding system so; that means, the metal is not
dissolving preferentially or the deposition is not going on preferentially. So, both are
happening same rate so, whatever metal is dissolving that particular that amount is again
going back and depositing on the metal surface.
So, that is called non corroding system and that time we see the rate of deposition or ic
with a minus sign because, I am considering it to be the opposite to the anodic current
flow is equal to rate of dissolution, which is ia and that particular situation this is called i0
or exchange current density.
So, this exchange current density is the unique situation at a particular temperature or
pressure on a metal surface for that particular reduction or the half cell reaction. So,
remember this is for half cell reaction because, whenever we are considering this rate of
deposition and rate of dissolution we are not taking into consideration of other species
dissolving or depositing or other reaction which is either reduction or oxidation.
So, it is the same metal ion and metal these two species one is this depositing one is
dissolving. So, one is reduction another one is oxidation this is basically with reference
to the half cell reaction. If we consider that in a particular cell the two situations are
taking place one is preferentially reduction, one is preferentially oxidation. Then we say
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that the one part becomes half cell because this these are because the full cell consists of
two half cells that what we have understood. So, this is related to the one single electrode
system or the single reduction or oxidation process.
Now, before we go deep into this discussion, I would like to just state the importance of
this rather current density. If we recall we saw that in case of galvanic corrosion, if we
have a copper this is copper plate, this is copper plate and if we have a kind of iron rivet
which is connecting these two copper plates.
And if we put it in NaCl solution and according to the galvanic corrosion this one will
dissolve quickly and then finally, the rivet would lose it’s strength joint strength. So, this
is the example what we have put in while discussing the galvanic corrosion and that to
we that time we consider the area effect.
So, we analyze this particular area effect saying that if we have a higher cathodic area in
connection to a smaller anodic area then the rate at which, the anodic area would
dissolve or the dissolution would be faster in case of that situation rather than a situation
where anodic area is larger than the cathodic area. And we said that the number of
cathodic reactions, that are taking place on cathode area will be so high in order to meet
that much of electrons supply we need to have a more and more metal ion that should
form from the anodic region and the dissolution becomes faster.
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Now, can we prove it through i which is current density small i we can do that. So, this is
a circuit let us say this is a circuit so, you have a copper and you have an iron. So, now,
you have this is the closed circuit let us say this is copper. So, here the current flow is
taking place, this is positive this is negative because, this is anode in case of galvanic cell
this will form definitely a galvanic cell, this is cathode. And this is through the metal this
current through the metal and this is through the solution. That way the total circuit is
complete.
Now, if we see the area the total area of copper is so large. So, assume let us assume that
100 oxidation cathodic reactions are taking place, some number arbitrary number were
taking cathodic reactions. And the cathodic reaction is nothing, but O2 plus 2H2O plus 4e
equal to 4OH minus and in order to see this cathodic reactions you have to meet this
number of cathodic reactions we need 100 into 4 number of electrons.
Similarly, on the anodic side we have to meet this total number of electrons. So, we have
to create into 4 number of electrons so, this should be created by anodic reaction and
here it should consumed for this cathodic reactions and here the anodic reaction is Fe Fe
plus plus plus 2e. Now, you see in order to meet this so, now, I see that here also the
charge is 400 charge and here it is equal to 400 charge in the form of electron of course.
Now, in order to meet that, we have to so, this is let us say per unit time. So, that means
the current this is c equal to Ia which is anodic reactions and now in order to maintain
that we just mentioned it as mod Ic which is the I am taking the we I am taking care of
that negative sign.
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Now, this is Ic equal to Ia now we have to take care of that area factor. So, the area of
cathode and area of anode is very large. Now, we know that current flow if we see this
circuit this circuit the current is same entering into the metal or going out through the
metal from the metal. So, this is same, but when I try to understand the rate at which this
cathodic and anodic reactions are taking place so, I have to divide Ic with Ac and Ia with
Aa. So, these are area of anode and this is area of cathode.
Now, since Ac which is the copper area in this particular situation you see the area that is
exposed to the solution this is the cathodic area copper behaves as a cathode in that
situation, that case area of cathode is very large. Now, if we see this ratio then as per the
ratio this should be like this because, Ac is much greater than Aa. So, then ia should be
greater than ic or I would say cathodic rate reaction rate is much lesser than the anodic
reaction rate. Now, if Ac equal to Aa then I would say that ia equal to ic or ic equal to ia
and if Ac is less than less than Aa, ic would be greater than greater than ia.
Now, interesting is in this situation we are saying that the anodic current density is very
high as compared to the situation what we have considered here. So, the dissolution rate
of that anode would be so fast if we have a larger cathode area compared to the anodic
area. So, the anode will dissolve in order to meet that many electrons requirement for the
anodic cathodic reactions to happen on the cathode surface.
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So, this is one interesting fact is when we see that current density we are able to analyze
or understand this particular phenomena more clearly or more better and scientifically it
is more intriguing rather than considering from analytical point of view so; that means,
this ic or the current density is extremely important consideration. So, let us stop here we
will continue our discussion on this very topic in our next lecture.
Thank you.
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Prof. Kallol Mondal
Lecture - 30
Exchange Current Density and Standard Hydrogen Electrode
And will continue our discussion on kinetics of corrosion and we have been discussing
on current density and we saw the concept of i0 also which is called exchange current
density, which appears when for a particular redox reaction. For this particular redox
reaction when it reaches equilibrium.
So; that means, then this is a kind of situation which is reversible as well as this is non
corroding. Why it is non corroding? Because, when a metal is dipped in an aqueous
medium the metal ion comes out from the metal surface as well as the reverse reaction
which is the metal ion gets reduced to metal.
These 2 processes happen at the same rate and that is the condition when we have the
exchange current density, the metal ion formation which is M goes to Mn plus plus ne
this is corrosion or we can take it as anodic reaction or oxidation reaction. And then this
backward reaction which is reduction or cathodic reaction or deposition reaction both
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this process happens happen at a very same rate and the rate is termed in terms of i which
is the exchange current which is basically the current density.
Since, we have seen that i A divided by nF is nothing, but the rate of metal dissolved in
ground per unit area and per unit time. Where A is nothing, but atomic weight of that
particular metal, n is the number of electrons that participate for this reduction reaction
or oxidation reaction F is 1 faraday.
So, this particular term we call it as ic and this one as ia; ia is nothing but the corrosion
current density. And in order to indicate the direction of flow of these two currents we
have put a negative sign in front of ic, these negative sign does not indicate that the value
of current is current density is negative. It indicates that it flows opposite to the anodic
current or the corrosion current density.
Now, when they reach equilibrium we come across i0 which is the exchange current
density and that is basically the reversible condition and non corroding situation because,
whatever metal ion forms that metal and goes and deposit on the metal surface.
Now, once we know this i0 we need to look at little bit carefully on this i0 because, this is
i0 is a very very strong and fundamental kinetic parameter. And this parameter would
have a huge importance on the corrosion of a particular metal in a particular medium.
And that will see little later when we start discussing on mix potential theory.
Now, if you see this i0, this i0 we have said that this is specific to a particular redox
reaction. It is not for the complete cell reaction, this is for a half cell reaction I would
say. For example, if we take this consideration like zinc plus HCl equal to zinc chloride
plus H2. For this reaction it can be broken into two half cells, one is zinc minus 2e equal
to zinc plus plus and 2H plus plus 2e equal to H2 this is the gas that forms on the zinc
surface.
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So, it is experimentally we have seen that when zinc is dipped in HCl, let us say that HCl
is pure HCl and it does not contain any oxygen so; that means, it is a deaerated solution
that time we have these two half cell reactions. So, for each half cell reaction we will
have corresponding i0 and in this case how do I how do I denote this? It should be
denoted like this. This is i0, this is also i0 for H plus H2.
So, for the reduction, reaction we are considering this is the notation would use and now
question is this i0 indicate some equilibrium reaction of that particular metal ion
disposition or dissolution or hydrogen ion formation or hydrogen gas formation.
Now, those reactions happen on a particular surface and in order to indicate that this is
taking place on that on a particular surface we have to also indicate on which surface this
is taking place. So, in the bracket we have to mention zinc because, on the zinc surface
only that zinc dissolution takes place as well as hydrogen evolution also takes place on
the zinc surface so, zinc.
So, now, exchange current density i0 on a metal surface and then. So, this is the notation
and now this particular redox reaction which is half cell reaction. So, for examples this is
for a half cell so, this is for a half cell and they are combination they are may constituting
one complete full cell reaction. Now, this particular reaction might change it could be
metal dissolution or it could be any other cathodic or anodic reactions that are taking
place on this metal surface.
For example, in this zinc case the zinc dissolution is taking place on zinc surface and that
is what we are considering i0 for zinc dissolution on zinc as well as hydrogen evolution is
also taking on taking place on zinc surface, that is what we are considering hydrogen
evolution exchange current density on zinc surface also.
Now, when we consider this another important aspect is since we are considering the
material aspect. So, of course, this exchange current density would depend on materials.
Similarly, it would also depend on the surface condition. So, these are two important
issues we would like to consider. So, one is metal surface and of course, a kind of metal.
So, let us put it in 2 ways, one is metal, which is type depending on zinc platinum or
palladium or gold this i0 would change for a particular reaction. Second is metal surface
so, the metal surface condition would also change the i0 for a particular reaction. So, this
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is surface condition I would say, surface morphology morphology. So, let us look at this
2 situations, one case is metal surface depending on the type of metal. Let us say we
consider this reaction, this hydrogen evolution reaction state, this we call it HER,
Hydrogen Evolution Reaction.
Now, depending on this reaction we can constitute a cell which is called Standard
Hydrogen Electrode, which we in short we call it as SHE. And when we talk about
standard electrode, standard hydrogen electrode we need to also see the how it how what
is the importance of the standard hydrogen electrode as well as it is constitution.
So, it looks like this, symmetrically you have acid solution where you can make it as
H2SO4 where H plus ion concentration is maintained at 1 molar 1 mole.
Now, this is the glass, simple a glass electrode where this is a metal wire which is
connecting a platinum plate which is dipped in acid medium and through this route we
send hydrogen gas and that pressure is maintained as 1 atmosphere.
And when you do that that time we get potential would be E0 plus RT by 2F ln OX by
red, which is E0 and if we consider 25 degree Celsius and 1 atmosphere pressure. So,
then this quantity would become 0.0591 divided by 2 and that time this quantity this is be
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in terms of log instead of log and then OX is nothing, but H plus ion concentration
square and pH 2 the reaction is H2.
Now, this is maintained at 1 atmosphere. So, it will become this is 0 minus 0.0591 pH.
So, these 2 they will get canceled so, this is the equation. So, finally, we are getting E
equal to minus like this. And I would like to put this 0 value.
Now, when this is maintained at 1 mole 1 molar solution so, then this goes to 0 so, E
equal to 0 volt. So, now, once we maintain this E0 so, if it is connected to let us say
another cell with a salt bridge, this is the salt bridge. And if we have a zinc rod here, see
if we connect like this is zinc sulfate we would see some voltage here and this voltage is
the difference between the electrode voltage between this 1 and this 2.
So, here we have electrode voltage which is E2 now if we maintain this situation 1 molar
as well as 1 atmosphere hydrogen pressure, then E2 would be always 0 and that is what
the E1 is nothing, but E1 minus E2 which is the difference between these 2 electrodes is
equal to E1. So, now, this becomes my unknown electrode potential isn’t it? So, that is
the use of the standard hydrogen electrode.
And why we are calling standard because, we are maintaining 1 atmosphere pressure and
25 degree Celsius and the activity or the concentration of hydrogen ion is also
maintained at 1. So, now, in order to maintain so, we have to make sure that this
particular cell stays at 0 volt all the time; that means that standard reduction potential for
this reaction in this particular hydrogen electrode is to be maintained at 0 volt. In order to
do that, we have to maintain those concentration as well as pressure.
Now, if it and this is taken as platinum now if we take some metal and why we take
platinum? Because, the on platinum surface it is around 10 to the power minus 1 to 10 to
the power rather 10 to the minus 2 to minus 3 ampere per centimeter square, which is
considered to be very very high current density.
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Now, what is why we should choose rather we should choose some particular metal
where this hydrogen reduction exchange current density should be very very high. Now,
what do you mean by very very high and what is the advantage of very very high value
of i0 for this particular hydrogen reduction reaction or hydrogen reaction which is the
half cell reaction?
Now, when you have this, then if we see the rate part, let us say this is the time and this
is the rate, once the metal is introduced in a solution. So, this metal ion would form or
other way around if we have the solution maintained at with the metal ion concentration
in maintain with some metal ion presence there. So, then there could be reduction
reaction as well as oxidation reaction. So, reduction reaction is nothing, but Mn plus plus
ne equal to M or oxidation reaction M minus ne equal to Mn plus. So, these two reaction
would happen.
Now, let us say initially the reduction reaction would be very high because we have
already the presence of Mn plus, depending on it is reduction potential Mn plus would
try to reduce and then form M. And as this reaction is starting this reaction would also
start, but they will be sluggish in the beginning, but as the time passes on they will pick
up the rate will pick up.
So, and the forward reaction which is this reaction the rate would reduce. So, Mn plus
plus ne M this rate initially would be very high because, already they are Mn plus ion
presence and then initially this particular reverse reaction which is M going to Mn plus
would be less because initially if I assume that the first the Mn plus would ion would get
reduced first and then metal would release electron and then form metal ion.
So, this is rate 1 and this is rate 2. So, rate 1 is nothing, but ic because this is the cathodic
reaction and rate 2 is ia in terms of current density if we like would like to express them.
So, the ic, the first rate is this one and then second rate this is rate 2, this is rate 1. Now,
at some time after some time they will reach equal and then they maintain if we do not
disturb the equilibrium because they would reach equilibrium.
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So, this is the condition which is basically the equilibrium rate and or i0. This is ic, this is
ia. And now interestingly you see this i0 is arriving at this time, this is the time let us say
t0 and this of course, happens in a metal surface that is for same metal surface. So, this is
for this particular redox reaction. So, similarly, if we can consider this hydrogen reaction
here also this forward reaction and backward reaction they will reach equilibrium after
some time on a particular metal surface let us say metal 1.
Now, this on metal 2, this is i0 on metal 1, i0 on metal 2 and when we talk and consider
about i0 metal 2. If i0 metal 1 is less than i0 metal 2, it means that equilibrium on metal 2
for this reduction reaction or that this particular half cell reaction would arrive at a much
fast time. So, means it will arrive here so; that means, this is my new i0, you see the i0
this is on metal 1, this is metal 2 so; that means, i0 in case of metal 2 arrives at a much
faster time this is let us say t1.
Now, what it indicates? It indicates that that the equilibrium achieves or is arrived at
much quickly in case of higher exchange current density.
So, higher exchange current density indicates early. Now, early equilibrium also
indicates, this particular early equilibrium also indicates now let us say somehow on this
metal 2 surface we disturb the equilibrium because of some situation. And since it has
got a higher i0 like the situation what we have seen higher i0 so, the equilibrium will be
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reestablished much quickly. Now, interestingly when equilibrium reestablishes quickly it
indicates if E is disturbed.
So, higher exchange current density it indicates early equilibrium and early equilibrium
indicates that if the equilibrium is disturbed by some means it will reestablish quickly.
What is the importance of that part? Now, this particular cell is basically a reference cell
which is the hydrogen reduction, hydrogen standard hydrogen electrode.
And in case of standard hydrogen electrode we have to maintain this voltage which
should be known beforehand, otherwise we cannot know the potential of the unknown
electrode. So, in order to know that, in order to maintain this particular potential all the
time similar potential and known potential we have to also see that potential is stable.
And in order to make it stable, we have to also see that the equilibrium is reached
quickly because, these potential is actually condition of indicating a condition of
equilibrium.
This also indicates a condition of equilibrium. So, and; that means, indirectly it also
indicates that it has to have a non corroding reversible condition and when it is a non
corroding reversible condition; that means, it is also related to i0. So, higher i0 means, the
condition equilibrium condition of equilibrium is established and if there is a disturbance
then higher i0 also indicates that condition of equilibrium will be reestablished quickly.
So, all the time we can maintain this standard reduction or standard potential or standard
reduction potential to be at the known potential. So, it will help us in determining the
reduction potential or the electrode potential of some unknown cell. And there could be
possibilities that that equilibrium is disturbed some by some means, during the
experimentation during measurement of this unknown electrode potential measurement.
And since platinum has got a very very high reduction exchange current density of
hydrogen reaction, it will reestablish the equilibrium and so, we are we will be with this
reference electrode.
Now, if I try to see platinum as well as zinc, now in that case on zinc for this particular
reaction i0 is of the order of 10 to the power minus 11 to 10 to the minus 13 ampere per
centimeter square. And here it is as we have mentioned is equal to 10 to the power minus
2 to 10 to the power minus 3.
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And also if I try to see other values of i0 on top of let us say if iron it is of the order of 10
to the power minus 6 ampere per centimeter square i0 of hydrogen reaction on nickel is
of the order of 10 to the power minus 7 ampere per centimeter square.
So, these are the values; that means, on platinum surface hydrogen reaction would
achieve equilibrium quickly compared to zinc surface it will take much longer time. And
when it takes much longer time; that means, if we make some standard reduction,
standard for cell with by using zinc it will not be a good practice. Because, it will take
long time to reestablish to establish equilibrium and then if somehow equilibrium is
disturbed it will also take long time to reestablish that equilibrium.
So, that is what the platinum is very much preferred electrode for hydrogen cell
hydrogen standard electrode. Now, instead sometimes we use platinized platinum and in
case of platinized platinum. So, i0 for this hydrogen reaction is much higher than i0 on
platinum, see the when it is platinized on platinum platinum is plated. So, when platinum
is plated it is actually forms a very rough surface and it means that if we have a particular
area of platinum and if it is platinized platinum. So, then the actual area increases if we
see this one from cross section so, it would be look like this. So, this is the cross section
from the side if you look at.
So, actual area increases this so, here actual area increases which lead to much higher
hydrogen reaction or i0 increases. It suggests that if we use platinized platina in place of
platinum, standard hydrogen electrode would be much better compared to if we use
platinum. Because, in case of platinized is platina i0 is higher so, the equilibrium would
be much stable equilibrium or if we disturb this it will come back to the equilibrium
quickly. So, that helps us to maintain this standard potential of that hydrogen electrode
so that we can measure the another potential of an electrode with certainty or surety. So,
this is about the effect of different electrodes, different metals as well as the surface
conditions.
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So, now, there are other factors on which this exchange current density depends. It
depends on as we have said metals type, morphology of the surface, then we have
temperature, environment. Why environment because sometimes we have a situation like
in one place we have higher salt content or in other place we have less salt content. Then
for example, in seashore area salt content is very high and if we go to Himalayan belt the
salt content would definitely be less.
So, in those 2 cases even we use the same temperature and pressure and the same metal
and solution we would have a difference exchange current density of a particular
reaction. And then we have solution concentration, this would definitely change the
exchange current density also. So, these are the some of the factors on which density. So,
will talk about exchange current density more in our next lecture so, let us stop here.
Thank you.
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Prof. Kallol Mondal
Lecture – 31
Electrical Double Layer and Polarization
Let us begin lecture 31 and we will continue on Kinetics of Corrosion. So, we have seen
i0 on metal surface for this. So, like that we have i0 for everything every reaction and that
time we have to mention the metal surface because that reaction is taking place on the
metal surface.
Now, let us look at this from this classical rate theory. This classical rate theory says that
there would be jump of metal atom from one surface to another and this is a thermally
activated process. So, that is what it has to have a barrier which is called as activation
barrier and then, once it crosses that barrier it goes to the other surface. And, this barrier
height decides the rate at which this metal would go from one surface to another.
When we dip a metal in a solution aqueous solution this is metal the metal ion forms
metal ions forms. Now, these metal ions would keep forming, but at the same time when
it released to the solution it will leave negative charges on the metal surface. So, you are
having a situation this is metal surface metal ions would go to the solution or instead of
Mn plus let us put in the form of positive charge. So, we have positive charge formation
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positive charge formation and then we have to maintain the neutrality. So, the negative
charges will be left to the metal surface and these two would try to balance each other.
Now, when this forms then of course, the reverse reaction also forms.
Now, after some time they reach equilibrium or reversible or I would say that it
establishes i0 and then because of this electrostatic interactions are positive and negative
charges they would form a kind of surface on metal surface as well as on the solution
surface very close vicinity to the metal surface and that time we have two boundaries and
that boundaries or two surfaces this is one surface and this is another surface these two
surfaces will be in close vicinity and they will try to cancel out the charge they would try
to balance the charges each other.
And, these two layers are called electric double layer electric double layer and this was
the very first concept of electric double layer and it is termed as Helmholtz double layer.
And, the inside part is called IHP and out one outer one is called OHP and then IHP is
nothing, but inner double layer inner Helmholtz plane and OHP outer Helmholtz plane
and when this double layer forms it is associated with a capacitor capacitance. And since
they are charged surfaces, we have a potential difference creation and these potential
differences nothing, but the electrode potential or the potential on that metal surface for
the reduction reaction.
Now, these two planes this is a very primitive concept of electric double layer and then
later on this has been modified and now when these metal ions forms they get solvated
because water is a polar molecule and because of that polar molecule presence this
positive charge is solvated by water molecule and on the metal surface since there are
negative charges the water molecule would get attracted depending on what charges are
there on the metal surface. If it is negative charge in the case what we have considered
here, the water molecule will be distributed like this. Sorry, this is plus, this is plus and
this side would be negative charges.
So, like this rearrangement of water molecules take place takes place. Now, the center of
this particular water molecules which are close proximity to the charged metal surface
and the center of this positive ion solvated vapors solvated ions positive ions close
vicinity to the water molecules which are arranged close to the charged metal surface
that becomes my OHP and this is my IHP and because of this situation the double layer
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this is becoming my double layer and that also leads to a potential difference and also
finally, it would lead to electrode potential.
But, this is an advanced level of consideration of the surface we would stay on this
preliminary consideration of double layer which is Helmholtz double layer where we do
not consider this salvation as well as water molecule polar molecules distributing close to
the charged metal surface depending on the charge of the metal surface. And, if it for
example, if it is positive charge, then this becomes. So, this water molecule would be like
this instead of positive charge is close to the metal surface negative side of the polar
molecule would be close vicinity would be directing towards the metal surface.
So, now, if we consider this particular situation we can constitute like this is IHP and this
is OHP and this is metal and this is n plus. Or we can call it as reductant or we can call it
as red and this is nothing, but oxidant or ox. So, Mn plus ne equal to M or ox plus ne
equal to red and when this metal goes to metal ion or metal ion goes to metal they would
not go straight way like this.
Since it is a thermally activated process, they will go over an energy barrier and this they
are on the same value if we consider G free energy with distance. So, they will be on the
same plane when i equal to i0. Why, because if I consider the rate forward rate and
backward rate. So, let us say this is my forward and this is my backward. So, rate r in
terms of if we consider rate or we simply say r forward equal to we can consider it to be
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same as r backward and when this situation arrives it reaches equilibrium or it calls it we
can call it as r0 and rate of if we consider rate in terms of moles per unit area per unit
time. So, this would be equal to i divided by nF, we have already seen this particular
formula.
So, this turns out to be i forward is nothing, but ic backward is nothing, but ia, ic divided
by nF equal to ia divided by nF equal to i0nF. So, then it terms out to be ic equal to ia
equal to i0.
So, that means, the rate at which forward direction reaction happens the similar rate the
backward reaction also happens. Now, if this is this barrier is nothing, but delta G star
and if we consider N1 or N prime or I would say N1 let us put it as capital N1 in order to
differentiate between this n and this N.
This is N1, this is N2; this N1 and N2, N1 is number of moles per unit area on metal
surface or rather IHP and N2 is equal to number of moles per unit area on OHP; that
means, the center of the metal ion align in front of the metal surface f1 is nothing, but or
the fraction N1 goes to OHP from IHP. So, this is nothing, but oxidation, f2 is the
fraction of N2 goes to IHP from OHP and nu 1 is vibrational frequency of metal atom
and nu 2 is vibrational frequency of metal ion.
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Then we can write this r forward equal to N1 nu 1 f1 exponential minus delta G star by
RT why?
So, this is as per classical rate theory and then multiplication of these quantities this is
basically this entire equation indicates the rate of metal number of moles of metal atom;
metal going to ion formation and this is basically a thermally activated process. It
indicates that metal atom should jump over this barrier and then should go to the OHP.
Similar the backward reaction rB would be N2 nu 2 f2 exponential minus delta G star by
RT.
Now, if I consider that whatever metal atom goes to the metal ion surface everything gets
it gets absorbed there or the metal ions which are getting reduced they all will deposit on
the metal surface. So, then f1 equal to f2 equal to 1; so, since this is a fraction, so, this
becomes 1 because whatever metal ions are forming they are going to the OHP or
whatever metal ions are reducing they are going onto the IHP.
Now, nu 1 equal to nu 2 is of the order of 10 to the power 13 per second and N1 and N2
what we have decided let us say N1 equal to N2 equal to N which is number of moles of
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metal ions or either the metal atom, metal those are converting to either metal or metal
ions. So, that means, for both the situation going to Mn plus or Mn plus going to M both
the cases this becomes similar number because we have assumed that whatever metal
ions are forming they are getting absorbed on the metal ion surface which is OHP or
whatever metal ions are producing they are also becoming part of IHP.
So, then I can write rF equal to rB equal to N f nu exponential minus delta G star RT
now we know from the previous discussion as we have seen here we can use this
equation. So, we know rF equal to rB equal to r0 equal to i0 by nF. Now, since we are
considering that they are they are jumping over the same barrier this is same this all
factors are same that is what they can be equated. So, this equal to i0 by nF; so, i0 equal
to i0 by nF; so, i0 becomes n F N f nu exponential minus delta G star by RT and here f is
considered as 1. So, I can remove this f. So, it becomes n F N nu.
This is an important derivation because this will be used up when we talk about
polarization. So, we have an expression of i0 with reference to the activation barrier
which is delta G star. Now, we have already termed and then you see this is also
becoming moles, this is current density our current density we can relate it to corrosion
rate or deposition rate. So, this is not same as corrosion rate, but it can be related to.
Now, we have used one term called polarization. So, when we talk about polarization it
means that it is a shift from the stable value. Now, we see that when Mn plus ne M this is
reaching equilibrium. So, we have a potential which is of course, giving a situation of i0
which is exchange current density and if we have maintain standard value it would be E0
so; that means, activity of Mn plus equal to 1, temperature equal to 25 degree Celsius
and pressure equal to 1 atmosphere pressure. So, then it becomes E0.
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So, if this equilibrium is disturbed and how can we disturb this is ic this is ia with a
negative sign. Let us say I supply little extra negative current this negative means we are
supplying little extra cathodic current which is opposite to the anodic current. So, then
this reaction would happen at higher rate. So, if it happens at a higher rate; that means,
this reduction process happens at a higher rate in order to maintain that reduction current
density it means that the electrode potential would switch to the negative side.
So, why negative side because when it switches to the negative side this metal surface is
becoming more and more negative and that is why the electrons supply of electron to this
reduction process would become easy. So, then it potential becomes let us say E1, now
the polarization would be this is called polarized electrode and that time the value of the
polarization would be E0 because now we have switched from E0 to E1. This is also
negative since the potential goes to the negative side and this is the value of polarization
or we call it eta c; c is nothing, but the cathodic.
Similarly, if we supply anodic current then the potential this anodic reduction, anodic
process will be at higher rate. The way we have discussed here the electrode potential
would increase from the standard value or the equilibrium value and we also call it as
polarized electrode. And that time if the potential goes to E2. So, E2 minus E0 is the
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positive quantity since the potential has moved on the positive side because we are
actually taking this oxidation process at a much higher rate.
So, this becomes the value of polarization and when we have seen when we see that the
potential increases from the reduction potential at that equilibrium condition, we call it
anodic polarization. And when it is termed as eta a and when we have this situation we
call it cathodic polarization and potential drops from the equilibrium value and the entire
this polarized situation arrives because of polarization and this ƞc or ƞa. They are the
measure of polarization or or we call it over voltage and this unit is nothing, but in volt.
So, from this particular information or the discussion what we see that the polarization
happens because of the supply of extra current either in the positive side or negative side
or either extra cathodic current or extra anodic current. And if we send extra cathodic
current the potential drops from the equilibrium potential which is E0 here and when we
send extra positive current or we call it anodic current, then the potential increases from
the equilibrium potential which is E0 here also. And the difference in that potential we
call it the measure of potential and in this case it is cathodic over polarization in this case
it is anodic polarization.
And, now in the next lecture we would get into this polarization part and then try to see
the relation between this over voltage and current density. Let us stop here.
Thank you.
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Prof. Kallol Mondal
Lecture – 32
Correlation between Current Density and Overvoltage
And, we will continue our discussion on kinetics of corrosion. In the last class we
started discussing on polarization and there we have noticed that for this particular
reaction. We have negative current which is minus ic or at a current density which
indicates the rate at which cathodic reaction takes place and we have anodic current
density which is the rate at which the metal ion forms from metal.
And now then we notice that if we supply negative current to this; that means, if we
supply more and more electrons then I can increase the ic value if we see the mod value
of ic; that means, we are not considering the negative term which is actually the direction
of the flow of current is greater than ia then the rate of forward reaction increases because
it indicates the rate nothing, but the rate of forward reaction.
So, if the rate of forward reaction increases the potential shifts to the negative side, that
what we have noticed. We have said in the last lecture and then if we had the equilibrium
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potential before having this condition or when ic equal to ia equal to i0; that means, the
reversible condition, non-corroding situation we have E0 potential. Now, once we have
this ic greater than ia; that means, we more and more electrons supply or more and more
negative current, then it leads to the potential a new potential which is the manifestation
of this current flow and the new potential let us say E1. Then my the polarization then
we say that the electrode has polarized and then the polarization quantity of polarization
will indicate by n eta and the c means the superscript c means the cathodic equal to final
potential which is E1 minus initial potential.
This is the value of polarization and you see this is a negative and we are also seeing if
we send negative current then definitely the potential would go to the negative side. So,
this is called cathodic over voltage and it is unit is in V and this is due to cathodic
polarization.
Similarly, if we have a situation ia greater than ic then actually I am increasing the rate of
backward reaction or the rate of metal ion formation reaction and that case the potential
would switch to positive side in comparison to this equilibrium potential. And that time
we also say that the material has that electrode has polarized and that polarization we call
it as anodic polarization and the measure of that polarization is n eta anode equal to E2
minus E0, where E2 is the potential, the new potential after anodic polarization and this
is you see that this is also unit volt and this is also anodic over voltage this is due to
anodic polarization.
Now, interestingly this potential change in the case of cathodic polarization the potential
drops from the equilibrium potential or in case of anodic polarization the potential goes
up from the equilibrium potential this is due to the excess current flow. This is
interesting, when this excess current flow is taking place in this case preferentially
cathodic current density is increasing and in this case anodic current density is
increasing. In case of anodic polarization and in case of cathodic polarization ic is more
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than ia; that means, this polarization is the manifestation of current flow or manifestation
of net current flow.
Since, once we have this situation then I would say that ic minus ia is basically i applied
or the i external. Similarly, here ia minus ic is equal to i applied, which is basically the
external current what we are providing or we are sending, this is the difference between
these two current densities.
Now, if we try to look at the evolution of i0 the way we have looked at it is basically we
have considered IHP and OHP and this is the metal side and this is the metal ion side and
both are at the same level energy level and we have high energy barrier and this barrier is
delta G star. And, then we have noticed that this particular flow of metal to metal line is
ia and then the backward current is ic with a negative sign. Then at condition of
equilibrium when ia equal to ic equal to i0 and we have found out an expression for i0
which is n F N nu f exponential minus delta G star by RT. This we have noticed and we
have said that if f is equal to one this can be brought down to n F N nu exponential minus
delta G star by RT. We can write this one or this one anyone would be ok.
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In this case f is 1; that means, whatever metal ions are coming from the OHP to IHP they
are all getting accommodated after reduction and whatever metal atom is going to the
OHP from IHP they are also accommodated on OHP surface. N is the number of moles
per unit area and this area we are considering this area and this area and both are if we
have a cathodic reaction on top of it and then anodic reaction is also taking place on the
same area because this is a reversible reaction. It is happening on the same area F is 1
faraday n is the number of electrons participating in this redox reaction or half cell
reaction.
Now, interestingly when we are saying that ic is greater than ia or ia greater than ic; that
means, rate of forward and backward reactions are also changing. In this case both ia and
ic they are experiencing the same barrier, activation barrier. Now, once we have this two
situation the activation barrier would change. How would be the change? Now, in case of
condition like this let us see what happens. In this case we have IHP and OHP and
interestingly this is reaction coordinate in this case I can considered as distance. Now,
here also distance between the double layer.
Now, in the beginning it was on the same level because we are having i0; that means,
they are on they are equilibrium their free energies are also similar and equilibrium
concept is says that when a system reaches equilibrium first condition del G PT equal to
0, second condition G PT goes to minimum. This is equilibrium and that is what you see
these two regions are these two energy tropes are basically the minimum point and they
are at the same plane, so, that means, they are also same. So, both the conditions are
meeting. So, this is the condition of equilibrium.
Now, if I send extra negative current or ic; that means, the rate at which this particular
backward reaction happens in this case would be faster than the forward reaction and that
means, definitely in this case delta G which is let us see the new delta G c. That means,
the jump activation barrier for metal ion to metal should be lesser than the jump
activation barrier to be less than jump activation barrier for anodic process. The cathodic
process then would be faster. Why? Because if we try to see that or ic equal to n F.
Now, this one I can simplify simply I put exponential minus delta G star by RT. A is
basically the part considered here. Now ic equal to i0 equal to a prime exponential minus
delta G star by RT in this situation.
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Now, in second situation when we have this particular condition, so that the rate at which
backward reaction happens is faster than the forward reaction then this would become a
prime exponential minus delta Gc by RT and ia should be a prime exponential minus
delta Ga by RT.
Now, delta Gc is equal to activation barrier, new activation barrier for cathodic process
and delta Ga equal to new activation barrier for anodic process. So, now, in order to have
this situation where delta Ga equal to delta Gc is less than delta Ga then this should move
up, this plane and this should go down.
Now, let us see if we have some situation here. Let us say we put a different color green
color. So, if you have a situation like this, let us see how the activation barriers are
changing. So, in this case now this is the new delta Gc and this is the new delta Ga and in
this situation I could see that this particular condition is met. So, the rate since the
activation barrier height has gone down in case of cathodic reaction the rate at which
cathodic reaction would take place as compared to the anodic reaction would be faster
than anodic reaction. So, in this case we have higher rate of cathodic reaction.
Now, what happens a situation when we have this that case the equation pattern would
be same, but only change would be if we put it in a blue color only change would be that
case delta Ga be greater than would be less than delta Gc when ia greater than ic. How the
situation changes let us see that is it that case this one will move up and this one will go
down. So, this go down this will go down and this will go up. So, how it would look
like? So, you see now what is the new barrier for anodic reaction? This is my new barrier
for anodic reaction which is delta Ga let us say prime and new barrier for cathodic
reaction would be delta Gc prime let us say.
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Now, you see the length of this activation area or the height of this activation barrier has
decreased even compared to i0 and the height of this delta Gc which is the new activation
for barrier for cathodic reaction has increased enormously as compared to even i0 and if
you see the height difference between delta Ga prime and delta Gc prime this condition
is met. So, ia is greater than ic. So, that case anodic process would be faster. So, in this
case this is the situation; this is the situation when I will have preferential cathodic
process and in this case we would have preferential anodic process.
Now, we can also indicate this that in this case it will be potential E would go down or
cathodic polarization in this case we will have E goes up. So, the new potential would be
higher than the equilibrium potential sorry, we made a mistake here it should be standard
is E0 make a make an amendment this would be E superscript 0, this is also E superscript
0. Now, here also this will be less than E0 and this should be more than E0.
So, now, you could see that how the energy barriers are changing and accordingly we
have preferential cathodic and preferential anodic reactions. Now, once we know this
situation, this particular situation energy barrier situation. Since it is a thermally
activated process we can have a correlation between this current density of a cathodic
and anodic with activation barrier and finally, we can have a correlation between over
voltage. We can have the correlations let us look at that correlation.
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So, now our intention is to find out the correlation between this basically current and
overvoltage. So, our intention would be to find out this particular correlation and then we
would see that; that would enable us to understand mix potential theory. So, that is what
I am trying to concentrate more on this correlation.
Now, when we see this particular this is M surface, this is Mn surface initially it was on
the same plane because it was equilibrium and then we are switching from because in
this case we are assuming that ia is higher than ic we can have this kind of situation.
Now, we have to understand that whenever we have this; that means, we have a net
current flow ia minus ic I applied this net current flow would lead to an over voltage
which is neta. Now, we have to understand that out of this neta how much would be
required to change this energy barrier for this side and how much would be required to
change this barrier to this side. And in order to know this we have to understand a
particular concept which is called symmetry factor and this is termed as alpha.
Now, in order to know symmetry factor which decides that how much fraction of this
neta will be used up for changing the activation barrier on the anodic side and how much
will be used up to change the activation barrier on the cathodic side. Now, we can also
put it in this fashion, this is reductant, this is oxidant or we can simply put it as R and O.
These are some notation this is reductant this is oxidant or we simply put as capital O
and capital R. Now, in order to understand symmetry factor we have to look at the rate
constant. Now when we have a kind of reaction like this A goes to B or in the same in
this case O plus ne equal to R that time the forward reaction rate I can put it as kc and the
backward is ka and c and a is basically cathodic and this is anodic.
So, kc into the concentration of ox oxidant, so, I can put it as C0 equal to rc; rc is
nothing, but the rate of the forward reaction. Similarly, ra which is the rate of backward
reaction is nothing like nothing, but ka which is the rate constant and concentration of R.
Now, at equilibrium both these rates are equal kc C0 equal to ka Cr. Since this is an
electrochemical process and this is going for equilibrium and this is reaching equilibrium
and this is the condition for equilibrium then I would have a potential developed which is
E equal to E0 plus RT by nF concentration of O ln and concentration of R concentration
of oxidant and concentration of reductant.
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So, RT by nF ln C0 by CR equal to E minus E0 and interestingly these two constants are
also dependent on potential and the dependency looks like this.
This is let us say E it is increasing, now this is k; when kc which is the rate constant for
the forward reaction or the reduction reaction, when it increases that time the potential
drops from the standard reduction potential. So, it should have opposite reaction with
respect to the potential increase.
So, the reaction this is if this is kc, so, as the kc increases then potential goes to the left
side. Similarly, in case of ka as the k increases; that means, the oxidation process
increases the potential goes to the positive side as per the polarization concept. So, we
have positive direction variation of ka. Now, at this condition both are equal. So, we
have this equilibrium situation and then we can take logarithm on both sides. So, ln kc
plus ln C0 equal to ln ka plus ln CR, we can simplify this is ln ka minus ln kc equal to ln
C0 by CR. Or we can simply write it as ln k a plus ln 1 by kc equal to ln C0 by CR and
interestingly ln C0 and CR I can write in the form of potential which is E minus E0 nF
by RT.
So, this is one important formula what we have derived by seeing looking at the
equilibrium condition. Now, this will be our starting point for the next lecture where we
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will try to see the symmetry factor. Let us stop here. We will continue our discussion on
this symmetry factor from this equation onwards.
Thank you.
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Prof. Kallol Mondal
Lecture – 33
Introduction to Butler-Volmer Equation
Let us start lecture 33. And we will continue our discussion on kinetics of corrosion.
Now in the last lecture at the end we have come to a situation where if we consider a
single half cell redox reaction O plus ne equal to R and then we try to see the equilibrium
condition which is kc O concentration of O equal to ka concentration of R and then we
have taken logarithm on both sides ln kc plus ln CO equal to ln ka plus ln CR. And after
distribution we are getting ln ka plus ln 1 by kc equal to ln CO by CR and we also know
that E minus E0 equal to RT by nF ln CO by CR which is the concentration of ox divided
by concentration of R and then we can put this one with reference to potential E minus
E0 nF by RT.
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Now, if we differentiate both the sides with reference to E potential since ka as well as
kc both are potential dependent. So, then we get d and if we consider that n is 1; that
means, for this particular reaction the number of electrons participating to reduce 1
oxidant to 1 atom of 1 molar 1 particular ion of oxidant is going to the reductant in case
of Mn plus plus ne equal to M is basically 1 on ion of M n plus we are reducing to M
which is reductant.
So, then this n goes to 1 we can write RT by F d dE ln ka plus RT by F and this side
definitely when we are doing dE then this would become this is constant. So, it will go
out since, this is taking place this reaction is taking place a constant temperature and this
is one faraday which is constant this is a constant. So, it would become 1. So, this E so
del del E of E is equal to 1. So, this goes to 1. So, then would be equal to 1.
Now, this quantity and this quantity this is called alpha which is the cathodic or a
reducive symmetry factor and this we can term it as alpha prime, which is oxidative
symmetry factor. Now if I try to look at this quantity this is nothing, but the slope of 1 by
kc for a particular plot of kc and E. So, if we see this quantity only RT I am just
considering d dE ln 1 by kc if I try to look at this then we have already noticed that if
potential is this and kc is this.
So, this would be like variation would be like this because once kc increases potential
drops from the standard equilibrium potential which is cathodic polarization so, 1 by kc
would be just opposite to it. So, 1 by kc and the slope of that point which is so d dE ln 1
by kc so, if we take log of this and then try to plot them again and then we have to take
the logarithm of that 1 by kc and then we differentiate with reference to with respect to E
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then this quantity with the multiplication factor RT by F is nothing, but alpha reductive
symmetry factor and of course, the other part this is the oxidated symmetry factor which
is talking about the talking about oxidation ka value which is the equilibrium the rate
constant.
Now, we have to have some sort of clear cut picture on this alpha, which is the symmetry
factor. which we can explain by drawing some semantics, let us say if alpha equal to 0.5
and if we consider two planes let us say these are the two planes and this is distance. This
is G axis this is IHP and this is OHP then initially they are at the same plane because
they are at equilibrium and then we have the energy axis distribution; energy distribution
is like this and here it is R and here it is ox or oxidant metal ion surface and metal
surface.
Now, if we see that oxidation process becomes faster then there will be change in the
activation energy as we have noticed earlier. So, the new position of the activation
barrier would be this one. So, you could see that activation energy is going down for the
oxidation process this is oxidation process or ia. So, the ia increases and for the reduction
process the activation energy increases from the earlier one this is for this is delta Gc and
this is delta Ga and when it happens symmetrically; that means, maintaining that equal
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distribution of the total polarization or over voltage if this is my over voltage value neta.
So, then in this case Mn plus plus ne equal to M for this particular half cell reaction, the
free energy change would be nF eta this is my free energy change due to polarization and
of course, thus is the over voltage in volt.
So, out of that alpha this amount will be the amount which will be the change in
activation energy for anodic side or delta Ga and then the rest of that particular fraction 1
minus alpha nF neta would be the change in activation energy for cathodic side, which
will lead to a change in delta Gc. Now since alpha is 0.5 so the contribution of this total
over voltage and thus the change in free energy towards this activation energy would be
equal and in this case if you see this so, this arm and this arm both are equal. That
suggests that contribution of the total over voltage or total energy change, which is this
one would be this fraction and this fraction and now you need to be need to know that
what is that free energy change due to over voltage? This is the amount of free energy
change for over voltage, which is equal to nF neta and interestingly if you see this, this
was the initial free energy when both ia and ic were equal.
Now, after this distribution when ia is higher than ic in this particular situation you could
see that del d Gc would be equal to delta G star which is this one this is delta G star plus
and if we consider this to be alpha F neta. So, this becomes alpha n F neta and delta G
because this height plus this one is basically constituting delta Gc and whereas, delta Ga
would be equal to delta G star. So this amount plus this amount minus this amount. So,
delta G star minus n F neta plus alpha nF neta. So, then it becomes delta G star minus 1
minus alpha nF neta. Now you could see that these value is greater than delta Ga, hence
it would lead to ia greater than ic. We are taking mod because we have assumed that this
is a negative current means the flow is opposite to anodic current. Now this is the
situation when alpha is equal to 0.5.
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So; that means, the contribution of this over voltage and finally, the contribution of free
energy change towards activation energy of cathodic side, anodic side both are equal.
Now there could be a situation where alpha is less than 0.5. The situation can be
predicted in this fashion, this is also let us say distance. This is OHP and this is IHP.
Now I can initially I have a situation like this. This is on the same plane and then if we
have a situation, same situation that ia is increasing, now you could see that alpha is less
than 0.5. Since this part is alpha nF neta and interestingly if we see the expression for
alpha, expression for alpha is this one.
So, let me write down again which is RT by F d dE ln 1 by kc equal to alpha which is

reductive symmetry factor.
Now we can have a situation when we have alpha greater than 0.5 that case the plot
would look like in this case one more thing see now this is my total free energy change
and out of that a small fraction because alpha is less, the small fraction is contributing to
the activation energy for delta Gc whereas, similar way we can have activation energy
change for anodic side. But if we see this arm, these two arms and this arm from this
point these arm is smaller than this and this is equal to this total value, because they
parallel planes. This is parallel to this.
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So, that is what the contribution would be this much towards delta G c and the equation
would be similar like this and the contribution of this one would give us the same
formula which is delta Gc minus 1 minus alpha into nF neta this is the situation on alpha
is less than 0.5. Now we can have greater than 0.5 this is IHP, OHP distance.
So, the slope of this line would be steeper since alpha is greater than 0.5 and then if we
have the similar variation in anodic current density and cathodic current density; that
means, the activation energy for the anodic side would decrease then you can see that
this becomes my alpha nF neta and this becomes my alpha 1 minus alpha nF neta. And
you could see that these two arms this arm and this arm the ratio is greater than 0.5
which is alpha.
So, we could see that how alpha changes the slope of this two free energy lines, one is
from the R to the activation energy another one is ox to the activation energy peak. So,
these two lines are changing because of this variation in symmetry factor, but in our
discussion we would consider alpha to be 0.5.
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.
Now as we have seen before, let us get back to this particular plot, this particular plot.
So, if we see that we have seen how the broad pattern changes if we would like to get
preferably anodic reaction and preferably cathodic reactions. Let us consider that
particular situation. Now here we are considering alpha to be 0.5 and now we are seeing
the change in free energy plot. Now here initially the free energy plot was like this which
was on the same line and it was G is same for these two points.
Now, we are having preferably anodic reactions. So, I am having a change in my free
energy plots and this is M, this is Mn plus this is distance and this part is IHP and this is
OHP and you could see that the total change in free energy is after this preferable ia and
preferable ic depending on whether in this case in this particular plot we are getting
preferably i the anodic reactions. That means, the rate of anodic reaction is increasing as
compared to the backward reaction which is rate of cathodic reaction and this is the total
over voltage and now the free energy change would be nF neta and out of that if we
consider this to be alpha n F neta and this part would be then 1 minus alpha nF neta.
So, then accordingly we can calculate now initially this was my free energy where when
delta G equal to delta G star that activation energy that time ia equal to ic equal to i0. Now
interestingly before we analyze this part we need to understand one more issue, the issue
is if we try to see same equation, which is r1 rc equal to kc concentration of ox and ra
equal to ka concentration of R.
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Now, this r can be converted to current density by doing the simple formula which is ic
by nF equal to kc CO and here it will be i a nF equal to ka CR and when ic equal to ia then
we have i0 but if ic is equal to not equal to ia then there would be a net current flow which
I can write in terms of i applied which is ic minus ia equal to to kc CO minus ka CR this is
the net with multiplication factor nF, because I have to consider ic equal to nF k CO as
well as ia equal to nF ka CR.
Now, I can also go back to this alpha now I know that RT by nF d dE ln 1 by kc equal to
alpha and here I have put n because we are considering this reaction. So, the number of
electrons is basically n. Now if I integrate this so d ln 1 by kc equal to alpha since these
are all constants, this entire part is constants we are taking it out from integration sign.
So, this becomes and now we have to see the limit. Now when we have polarization,
because of that net current flow either it can go to positive side or negative side.
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So, now if E0 is basically my initial equilibrium potential and E is basically the initial
equilibrium potential and this is the final potential after polarization. So, then this should
be E0 E and when E equal to E0 my kc should be equal to kc0 and similarly I can put
this is k c0 and this is kc.
So, these are two limits then I would get ln kc0 by kc equal to nF alpha divided by RT E
minus E0. Similarly, I can have this relation for the oxidative symmetry factor, we can
also find out the limits we can write it in this fashion d ln k equal to nF 1 minus alpha by
RT d here also the limit would be same. So, this is this and here it would be ka0 and ka
when E equal to E0 kc equal to kc0.
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So, I would get ln kc1 minus alpha RT E minus E0 this is oxidative and another case ln
k0 sorry here it would be if we see this should be ka. So, this would be ka ka0 and this is
kc0 by kc equal to nF alpha by RT E minus E0. Now I can write it as ln ka or ka equal to
exponential n F 0 minus alpha E minus E0 divided by RT and here in this side kc0 or kc
would be equal to kc0 exponential minus nF alpha E0.
Now, interestingly if we consider that i applied equal to kc C of oxidant minus ka

concentration of reductant and if we put those equations. So, I get kc0 exponential minus
nF alpha E minus E0 by RT minus ka0 exponential of course, there would be
concentration part also this is CR minus nF 1 minus it should be plus E minus E0 by RT I
am just putting these formulas here I am replacing this kc and k0.
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Now, if we assume that CO and CR are equal, these concentrations are equal; that means,
whatever number of ions are forming on the outermost layer is equal to the number of
atoms that are coming out. So, if we have this situation then of course, when E equal to
E0 kc equal to ka0 this is the condition. So, then I can replace this C part in both the
sides it will be simply k0 this is the new formula I am getting.
Now, this is nothing, but Butler-Volmer equation, this equation is called Butler-Volmer
equation and this is coming from the rate of flow of charges those metal ions to the inner
surface or the metal from the inner to outer surface or outer Helmholtz layer and we are
considering the activation jump of those ions as well as atoms. So, the Butler-Volmer
equation actually relates important parameters of electro chemistry one is faradic current
which is i applied then it relates to the electrode potential, then it relates to concentration
of reactants and product.
So, you can consider either M or Mn plus depending on the reaction you are considering
whether oxidation or reduction. So, all four are connected, now this condition is
subjected to a situation when i equal to i0 equal to ia and i applied is equal to 0, the net
current flow is 0. So, when we have two current density this is ic this is ia there are the
same magnitude, but flowing opposite then there will be no net current flow in the
circuit.
So, in that situation the concentration of this reactant as well as product or concentration
of oxidant and reductant both are same and that time we have got in this particular
relation. Now when it actually polarized that time this concentration may change
depending on whether it is activation polarization or concentration polarization. So, we
would look into that part little later, but for the time being now we see that this Butler-
Volmer equation has the correlation has a relation between faraday current electrode
potential and concentration of reactant and product and from this reaction we can
actually derive Nernst equation too.
Now, before I conclude I would like to say that when we have this particular relation I
can equate it k0 and then I can write k0 here also. So, in lecture 33 we need to have a
modification since i applied is equal to ic minus ia then with this we need to multiply nF
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and here also nF is to be multiplied since, ic by nF equal to rc and ia by nF equal to ra.
So, the only small change there should be nF term added to this and that becomes my
Butler-Volmer equation.
Thank you.
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Prof. Kallol Mondal
Lecture – 34
Derivation of Tafel Equation
So, let us start lecture 34. We will continue our discussion on kinetics of corrosion. And
now, actually we are looking into the electrochemistry part and then we will try to relate
this electrochemistry to corrosion. Now, we have derived this Butler Volmer equation
which is nFCOko exponential minus alpha nF by RT E minus E0 minus nFCRk0
exponential minus 1 plus 1 minus alpha nF E minus E0 by RT, this is Butler Volmer
equation.
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And if, we see the previous analysis, we see this is my iapplied and then I am replacing
this kc and ka with these two formulas. And later we have understood that why kc0 equal
to ka0 and that one we are considering k0, we are replacing that and we hence, we are
getting this Butler Volmer equation. It has relation between faradaic current, electrode
potential and concentration of reactant as well as product which are basically, oxidant
and reductant.
Now, then we started saying that this particular equation can yield us Nernst equation.
Now, we can do little bit of redistribution of this entire formula; iapplied equal to nFk0
exponential minus alpha nF E minus E0 divided by RT minus this is CO CR exponential
nFE minus E0 divided by RT into exponential minus alpha nFE minus E0 divided by
RT. Then, we can write equal to nFk0 exponential minus alpha nFE minus E0 divided by
RT CO minus CR exponential nFE minus E0 by RT equal to it turns out to be then CO
minus CR exponential nFE minus E0 by RT equal to iapplied divided by nFk0
exponential minus alpha nFE minus E0 by RT, so this we are getting.
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Now, we see that when, E equal to E0, ic equal to ia equal to i0 and i applied equal to ia
minus ic equal to 0. So that means, when it is non corroding situation or reversible
situation then, this right hand side become 0, so the CO minus CR exponential would be
equal to exponential nFE minus E0 by RT equal to nFE minus E0 equal to ln CO CR or E
equal to E0 plus RT by nF ln CO by CR.
So, this is nothing but Nernst equation. So, we are also getting Nernst equation. So, this
particular condition or the equation what we are seeing in this they have two components
one is CO and CR. Now, if we assume that CO and CR are the same values; that means, the
physically it means that the concentration at the interface for oxidant and reductant they
are not changing and they are having the same value. So, that time, it would turn out to
be in this case and then CO if we consider CR equal to C then, I could see that, i0 could
have a proportionality with the C, the concentration.
Now, since the concentration and this particular equation in a simplified mode can be
found out if we look at this situation this diagram.
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So, this diagram would enable us to get the i applied as a function of over voltage. And
that time, this concentration part is already inherited, already included in this particular
formula which is i0 equal to nFNf nu exponential minus delta G star by RT. So, this
concentration of R as well as CO they are included here and that time we are saying that
there equal and it becomes C. And let us see whether, we can get similar sort of
equations by analyzing this particular plot.
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This particular plot let me redraw again. This is the over voltage related change in free
energy. So, this is become nF eta and the contribution towards the anodic side is alpha
nF eta and this part if I consider or (Refer Time: 09:28) alpha prime, alpha prime or
simply we put it alpha 1 minus alpha nF eta. This is IHP, this is OHP, this is M or R
reductant, this is Mn plus or oxidant.
In the beginning, the free energy difference, the activation energy barrier was delta G
star and then after redistribution when we are assuming that ia greater than i c, so, this is
my ia and this opposite direction flow is ic with a negative sign, this becomes my delta G
a.
Change in activation energy for the cathodic side would be this much, this is delta Gc
and this knows a delta Gc equal to delta G star plus 1 minus alpha nF eta; so, this plus
this much. Whereas, delta Ga equal to this delta G star minus this much. So, delta G star
minus alpha nF eta. And we are assuming that alpha is equal to 0.5; that means, the
distribution of this total change in free energy towards the activation energy is same
quantity; so, these 2 are equal since, if alpha equal to 0.5.
Now, I know that the rate of forward reaction. So, the rate of forward reaction or it is
better to say that ia; so that means, M minus equal to Mn plus ne, so this is the forward
direction ia and this is my ic. We can relate in this form n F N, frequency factor and nu,
this fraction of atoms that are going towards the OHP and the fraction of this is the
fraction of atom of that goes to the other end and then, exponential minus delta Ga by
RT. Similarly, ic can be related as n F N f nu exponential minus delta Gc by RT. And this
particular general equation for i is equal to nothing but n F N, which is the surface
density of moles into f, which is the fraction of atoms or ions that are going from one
plane to the other plane and this is the frequency vibrational frequency exponential
minus activation energy divided by RT; since, this is considered in terms of moles per
unit area.
So, now, ia equal to n F N f nu exponential minus delta Ga, I am just replacing this
values minus alpha nF eta divided by RT, so this becomes nF N f nu exponential minus
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delta Ga by RT into exponential alpha n F eta divided by RT. This part is nothing but i0,
since, i0 equal to nF Nf nu exponential minus sorry here we have to put delta G star.
Since, delta G is delta G star minus alpha F n N f eta delta G star by RT. So, this is i 0, so
it becomes i a equal to i 0 exponential alpha n F eta by RT.
And similar way i can see ic equal to n F N f nu exponential minus delta Gc by RT, so I
replace this Gc with delta G star plus 1 minus alpha nF eta by RT. Again nF N f nu
exponential minus delta G star by RT into exponential minus 1 minus alpha nF eta by
RT.
So, this is again i0, so ic equal to i0 exponential minus 1 minus alpha nF eta by RT. So, i
applied equal to ia minus ic equal to i0 exponential alpha nF eta by RT minus exponential
1 minus alpha nF eta by RT. So, here we are considering this quantity, when we are
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consider this quantity to be this part and the rest part would be 1 minus alpha. So, you
can also reverse instead of taking alpha this, you can take 1 minus alpha that time it will
be reducive alpha or the reducive symmetry factor. And in this case, we are considering
oxidative symmetry factor.
Now, once we have this, now if I compare with this particular Butler Volmer equation
here, here we are seeing that there are two concentration parts. Now, when we have these
concentrations to be same then, we can get the same equations what we are having here
ok, so, where in this i0 that concentration is included. So we are not going into that part,
the only we are seeing that this is also a Butler Volmer equation.
Now, these equation has got huge importance on the corrosion of a particular method.
We will look into that part, but before that, see this eta is nothing but E minus E0 and if
eta is very large whether, it is positive or negative, when it is positive it is anodic, when
it is negative it is called cathodic. Interestingly, if you see that here there is a negative
sign and it is there is a negative sign here; so that means, it is actually potential actually
goes down from the reversible non corroding potential.
And in the case of anodic case, if I say the anodic case where we have a positive sign in
front of it. So that means, it indicates that the potential should not go up from the
reversible potential. But, if I try to look at this equation, let us say if it is positive, let us
say eta is positive and large positive, let us say eta is large positive value, so that time if
we consider this particular part, this part we can omit, we can ignore because, there is a
negative sign and this particular value is very high. So, your where I simply say i applied
equal to i0 exponential alpha nF eta by RT.
And since, this i applied would be also equal to ia or the anodic current density because,
this part can be ignored because of this is a positive value. Now, in case and that time we
can term it as eta a. So, this we can term it as anodic over voltage. Similarly, if has got
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large negative value, so that time, it will be considered as eta c and this equation will go
to i applied equal to i 0 exponential minus 1 minus alpha nF eta by RT. And
interestingly, you see this equation is exactly similar to this, so that time we can write it
as ic and this would become eta c.
So, now we have two equations, one is ia equal to i0 exponential minus exponential alpha
nF eta by RT, which is a another way ic equal to i0 exponential minus 1 minus alpha nF
eta c by RT. This is valid when there is a large over voltage either, cathodic or anodic.
But when it is not large, then we have to consider this i applied. And that time i applied
is not ic or is not ia, small over voltage. So, this is valid, these two equations are valid for
large over voltage, but for a small over voltage and that time i applied equal to ia or i
applied equal to ic. When a small over voltage, that time I should write combination of
this i0 exponential alpha nF eta by RT minus exponential minus 1 minus alpha nF eta by
RT. This is for a small over voltage.
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So, let us simplify this particular equation. This equation becomes ia i0 equal to alpha nF
eta a divided by RT with exponential equal to. So, then I can write na equal to RT by
alpha nF ln ia by i0 or na equal to RT 2.303 by alpha nF log ia by i0. Now, this particular
factor which is RT into 2.303 by alpha nF is called as beta a or the slope between over
voltage and ia or rather sorry this should be log ia. The plot between beta this basically
nothing but a slope between over voltage and log ia and this we can relate in a linear
equation, a equal to beta a log ia plus minus beta a log i0.
Now, this is a constant since, RT alpha is 0.5, nF is constant, RT is constant, eta reaction
happens at a constant temperature, so this becomes a constant, so this is equivalent to na
beta a log ia plus some constant.
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Similarly, if I take ic equal to exponential minus 1 minus alpha nF eta c by RT, so then, it
will also give us eta c equal to if we do the way we have done, you would get
exponential ic by ia and RT by 1 minus alpha nF eta into 2 point sorry here it should be
log into 2.303 by this and with a minus sign.
Now, this RT into 2.303 by 1 minus alpha nF, sorry this should not be here, this is called
beta c and we consider this negative sign inside this and that is what it is it has a negative
slope. So, this is also over voltage slope between over voltage and log ic.
So, this is called Tafel equation. This is also called so we can write this one as eta c equal
to beta c log ic plus constant, this is also a Tafel equation. So, we would continue our
discussion from this Tafel equation, let us stop here.
Thank you.
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Prof. Kallol Mondal
Lecture – 35
Tafel Plot and Activation Polarization
So, let us start lecture 35.
And we will continue our discussion on Kinetics of Corrosion. In fact, we have already
reached to the state of state where we can find the relation between current density and
over voltage. And that relation we have found in the last lecture which is ia equal to beta
a log of i eta a which is anodic over voltage rather high over voltage value positive
quantity ia plus constant. This is we termed it as a Tafel equation.
Similarly, for cathodic over voltage it was beta c log ic plus constant and they were you
can this constant value also and if we try to write it the complete one which is eta a equal
to beta a log ia by i0 and here it is eta c equal to minus beta c log ic by i0.
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So, this we can put it plus because I can take this negative sign minus sign into beta c
and where beta a equal to RT into 2.303 divided by alpha n F and beta c equal to RT into
2.303 divided by 1 minus alpha nF. And these two equation these are same as Tafel’s for
anodic and this is for cathodic Tafel equation and this beta c this main as minuses minus
sign is incorporated here.
So, that is what beta c is basically the negative slope between over voltage and i plot and
this is definitely a positive slope between over voltage and i plot, which is the current
density plot, rather I would say log i plot.
Now, these two equations we have derived from a basic Butler Volmer equation. We
have two forms of Butler Volmer equation; one we have found out from consideration of
atomic jump from one side to another which is inner Helmholtz plane to the outer
Helmholtz plane. And that time we have this particular energy distribution initially it was
like this and then we have considered that the anodic current density is higher than the
cathodic current density.
So, that is what we have this kind of energy distribution plot which this one is alpha nF
eta and this part is 1 minus alpha nF eta and this is M side this is Mn plus side. So, this is
ia and this side is ic with a negative sign because its flowing negative opposite to ia.
When they were equal when ic equal to ia they are experiencing same activation barrier,
but when ia is higher than the ic then the activation barrier for the forward reaction is
reducing; this is my activation barrier for the forward reaction and the backward reaction
we are getting higher activation barrier.
So, that is what the rate of backward reaction is reducing. So, that time we are getting a
equation of this short which is i0 exponential alpha nF eta by RT minus exponential
minus 1 minus alpha nF eta by RT. So, this with this consideration we would get to this
particular equation what we have proven in the last lecture. Now, there is one more form
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which is i equal to n F k 0 concentration of oxidant exponential minus alpha nF, if we
consider the way we have considered here I can write the similar fashion which this one
should be CR then; then it would be alpha n F eta by RT minus CO exponential minus 1
minus alpha n F eta by RT, where this eta was taken as E minus E0.
And remember in this case, the previous case what we have seen earlier if we go back to
that particular expression go back to that particular expression. If you see this that time
we have considered the reducive symmetry factor that alpha was reducive.
But in this current case we are considering oxidative reducing factor that is what this CR
part is coming before than CO. Now, that time if we consider condition ia equal to ic
equal to i0 and that time E equal to E0 and that case r a equal to ka C of R concentration
of R and since it is E equal to E0 that time we have considered it to be k0.
And then I can convert into ia equal to n F k0 CR and similarly I can convert rc equal to
kc CO which I can write in this form CO. And in that case we have considered one more
consideration which is CR equal to CO equal to C if we consider and then in that situation
ka 0 equal to kc 0 if you go back in the last lecture you can find it.
So, this I can consider as k0. So, I can replace this C with the CR, CR with C as well as C,
because I am considering that the concentration for reductant as well as oxidant, both are
same. So, then from this equation I can get i0 equal to ia equal to ic equal to n F k0 C. Is
not it?
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So, then I am if I take this C out then I am getting the same expression here because this
part is nothing but i0. Is not it?
So, we are getting the same equation considering the both the roots; one was considering
the rate equation and then another one is the jumped system jump theory that classical
rate theory and where we are considering the jump of atom due to their vibration of the
atoms from one plane to the another. Now, coming back to these two equations; these
two equations are very important when we try to look at the corrosion part.
Now, before we try to relate this corrosion theory corrosion of metal with these Tafel
equations, first see how they can be plotted. In fact, when I consider this over voltage let
us say eta a equal to beta a log ia plus constant that it means that this is potential and this
is that means, thermodynamic quantity. And this part is nothing but current density, this
part also involves current density because this part this constant is nothing but beta a of
log i with a minus sign log i0, this is exchange current density.
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So, this is current density, this is a kinetic parameter. So, this equation relates
thermodynamic quantity with the kinetic parameter that means, whenever we have a
current flow; that means, the net current flow we are going to get polarization which
shifts the potential due to kinetic influence. And during corrosion you would see that yes
we would try to shift the potential of a particular metal from one potential to the another
and during that process we can either get higher corrosion, or we can control corrosion.
So, that would be more scientific ways of considering the corrosion control and that is
what we have considered. We will see that there are two routes of protection mechanism
of metals and alloys from corrosion; one is cathodic protection, another one is anodic
protection until unless we know and we until unless we understand this Tafel equation or
the relation between current density and polarize potential, till then we will not be able to
understand those protection mechanisms properly.
Now, let us look at so it is basically relating these two kinetics and thermodynamics of
electrode processes electrode reactions or electrode or the corrosion I would say because
we have to considering in terms of corrosion, we are not looking at the deposition part.
Here we have to look at the anodic current density all the time. So, let us try to see how it
can be plotted in a particular diagram.
So, let us try to see the plot between eta a and log ia as well as eta c and log ic. Let us say
this side is log i and this direction is this particular axis is eta.
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Now, we before we when we when the system reaches equilibrium for example, this
particular system we have considered M, when it reaches equilibrium; that means, i equal
to i0 equal to ia equal to ic and E equal to E0, if it is in standard condition that time this is
equal to 0. So, this is 0 value equal to 0 and let us say this is that point we are
considering, where this is i0.
Now, at this I know that over voltage is 0. Now, if I try to plot eta a beta a log ia plus
constant, s, that plot would be this and if we extend this it will go through this point.
Because at this point eta a goes to 0 also because this term is nothing but beta a log ia and
i0 log i0 and at this point I do not get any net current rather I would remain at i0.
And the slope is beta a. I can also have a plot between eta c and beta ic. So, that plot
would be this one and if we extend, this would also follow through this particular i0 point
and this slope is beta c which is of negative slope and the relation is eta c equal to beta c
log ic plus constant and here the constant is beta c log i0. Of course, here also it is a
minus term and this minus this beta c is the negative slope has a negative slope. Now that
means, when I am doing cathodic polarization eta is going down. So, this is eta c and this
is anodic polarization eta a.
Now let us see that if we send a preferential current; that means, this is ic, this is ia, and
when I send extra negative current then I would get i applied equal to ic minus ia that is
the difference. Now, if I go to a very high over voltage let us say this is my over voltage
1, eta 1 that time the current density is log of that current densities let us say that current
density part is this is minus 1 and this is minus 5.
So, it corresponds to the current of 10 to the power minus 5 ampere per centimeter
square and this corresponds to the current of 10 to the power minus 1 ampere per
centimeter square. So, that occasion my i applied would be 10 to the power minus 1
minus 10 to the power minus 5 which is equal to 0.09999. And then if I try to take a log
of this it would be close to minus 1 rather minus 1.0004 which is close to minus 1.
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(Refer Slide Time: 18:19).
Similarly, log ic equal to log of 10 to the power minus 1 equal to minus 1. So that means,
if I try to plot log i applied this would also lie on the same point of ic and remember this
corresponds to ia and this corresponds to ic because this particular point which is
corresponding to current of 10 to the power minus 5 ampere per centimeter square that
time we this particular point is lying on the anodic line, anodic Tafel plot and this
particular point is lying on the cathodic Tafel plot.
So, this particular point should indicate ic and this one should indicate ia and here I am
putting minus 5 and minus 1 because we are taking log axis. So, we could see that log i
applied is also it is falling on the same point of ic.
Now, if we go for a different level of over voltage which is let us say eta 2 that time this
value is 10 to the power minus 4 and this is 10 to the power minus 2 that time also I
could see that they are coming close approximation. So, i applied would be equal to
0.0999 and then also I could see that log i applied equal to log of ic.
So that means, that time also if I try to plot log i applied which is the excess current that
the current that is flowing through the circuit would be falling on the same point. But if I
go much lower over voltage let us say this is n eta 2, eta 3 that time this value is let us
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say 10 to the power minus 3 and 10 to the power this is this is let us say this point is
0.005. Then I will not be able to see that log I applied is equal to log ic.
Because in this case i applied equal to ic minus ia equal to 0.005 minus 0.00 rather 0.001,
so then it becomes 0.004. So, log i applied equal to 2 point minus 2.39, whereas, log ic
equal to log 0.005 equal to minus 2.30. So, then it is not equal, we cannot say that they
are equal. So, that time we see that log i applied this particular point at eta 3 should be
lined left to this.
Now, as we go let us delete this part. So, that we will be able to understand carefully as
we go closer to this particular point I could see that that point also would shift to the left.
Because the difference is log of that particular ic minus ia is not falling on the same ic line
rather it is switching to the left side.
And now once this as we go much lower over voltage it is falling on this particular point.
Now finally, when the over voltage reaches to 0, so; that means, it becomes undefined.
So, that point would be meeting somewhere and then if I try to connect those locus of
those points i applied point I get a plot like this. Where this portion is a straight line
portion which is falling exactly on the beta c line on the eta c versus log ic line.
Similar situation we can think of on the positive side, there also it will be similar way we
can construct this particular experimental plot where, this portion which is a straight line
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portion is falling exactly on the eta a versus log ia plot. And in fact, this green line is
basically the polarization plot or the Tafel plot we call it Tafel plot.
So, this Tafel plot actually can be experimentally determined by sending extra current
through the system through this particular system. And then try to we just measure the
potential as a function of log i applied. And then we get this plot and interestingly you
see as the over voltage is very high then we are reaching towards that linearity of that
particular Tafel plot for the anodic as well as cathodic sides and that linearity will be
enable will enable us to find out beta a or beta c.
So, this beta a which are called Tafel slope, this Tafel slope is important factor to
determine the corrosion rate or the corrosion current density, we will see later on. So that
means, this is the experimental diagram which is the green line and that green
experimental line has been drawn from the concept of polarization which is related to
this relation or this relation.
Now coming back to this particular general equation eta c is beta log i plus constant.
If we see it carefully, here we are considering that the concentration on IHP or OHP they
are same, they are not changing during the polarization and when it does not change
during its not changing because if I see the actual system, we have a bulk system where
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this is IHP and this is OHP. And then we have a bulk system where Mn plus ions are also
present.
Now, if I try to see the concentration if I plot this is concentration, this is concentration
axis. So, in this case CR as well as CO they are similar. At the same time CO is also the
bulk concentration of Mn plus ions so. In fact, we do not get any concentration
difference from the bulk to the interface of that electrode and that time this particular
situation is arriving.
Now in fact, if I try to see anodic this particular reaction which is cathodic reaction.
Now, in that case if we have this continuous cathodic reaction there could be a
possibility that metal ion is consumed heavily. So, that there could be a depletion of
metal ion at the interface. And so, that depletion is with regard to the bulk concentration
of metal ion in the in that particular medium of the aqueous solution.
So, that time we have a concentration difference that concentration difference might lead
to some polarization again that polarization is called concentration polarization; we will
talk about that part. But if there is enough supply of these ions to the interface that
means, OHP, then we would not experience any concentration related polarization.
Now, if we have this condition that the rate of diffusion of ions from the bulk solution is
greater than the rate of jump of ions over the activation barrier that time we can say that
the slowest step for the overall reaction is this one. And the slowest step actually controls
the overall reaction and overall rate of that particular process.
So, then because this is guided this polarization is guided by the rate of the jump of ions
over the activation barrier, we call it activation polarization. And this activation
polarization it has got two terms na as well as nc which is activation activated activation
polarization for anodic polarization and this is cathodic polarization. So that means, we
are getting this Tafel equation is basically indicating activation polarization or the rate of
the jump of ions or atom from one plane to another. And we will consider concentration
polarization in our next lecture. Let us stop here.
Thank you.
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Prof. Kallol Mondal
Lecture – 36
Activation polarization, concentration polarization and total polarization
So, let us begin lecture 36.
We will continue our discussion on polarization, which is part of Kinetics of Corrosion.

Now, there we have seen that, this particular equation is a Tafel equation.
Beta is Tafel slope and there also we have seen that how this experimental log I applied
varies with over voltage. This is the point with i0 and it varies like this, fine. And at this
point I see Mn plus plus ne equal to M and on this side I have preferential anodic
reaction and this side we have preferential cathodic reaction, fine.
So, these were our concept that we have seen in the last lecture. And this eta C is nothing
but, eta C or eta a either it could be cathodic over voltage or anodic over voltage, which
is due to cathodic as well as anodic polarization; respectively is due to activation
polarization. Since, we could see that if I have a bulk medium, this is IHP, this is OHP
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and the concentration of CR and CO and then bulk concentration C let us say prime, they
are on the same plane and this is distance.
And we are saying that reaction or this particular process is taking place, because of the
interface jump of ions or atoms over the energy barrier. This energy barrier could be
depending on whether it is a anodic current density or cathodic current density, which
one is more compared to as compared to the other, then this particular plot will rearrange
itself. So, then this would be in this case this is the situation where we have ic to be more
than ia.
So, when there is enough supply of cations to this particular plane. So, that concentration
is flat in the solution side, this is solution side. Then the rate at which these interface
jump is taking place that will control the overall potential drop or potential increase, or
cathodic polarization or anodic polarization. And that would lead to over voltage; either
it could be cathodic or anodic polarization anodic over voltage. Now, let us say this at
certain point the supply of ions from bulk to the interface to the OHP and if I say that
rate of supply is less than the rate of atomic or ionic jump across the activation barrier,
then there would definitely be a lag of metal ion supply to the bulk to the interface.
So, there would be a lag from this section to this section. And that lag could be generated
because since this rate is increasing. So, that suggest that the current density which is
nothing but a rate is very high, at a very high current density, there could be a situation
there is a lag of ion supply to the interface OHP for the ionic jump from OHP to the IHP;
because when we have this kind of modification in the energy distribution, then we have
more of ic, in this case ic is greater than ia, so there would be a lag.
So now, there could be concentration profile with decreasing concentration as we come

from the bulk concentration to the interface. So, this concentration would have a
distribution like this. So, here it would become then C O prime. So, this is the interface
concentration due to this very high activation, this very high rate of current flow because
of this higher rate of ionic jump across the activation barrier.
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So, that situation we would come across the another type of polarization which is called
concentration polarization. This is due to variation in concentration at the reaction front.
And that happens at a very high activation current density, at a very high current density
because, if it is a low current density, the rate of atomic jump is little low. So, it can be
possible that the rate of ions supply from the bulk would be equal to the rate of ionic
jump.
So, there should not be any a lag of concentration from bulk to the interface. Now, in this
situation, let us look at this concentration polarization in a little depth.
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So, let us talk about concentration polarization. So, as we have saying that, there could
be so this is IHP, this is OHP and this is the initial concentration, this is the concentration
in the bulk, which is similar to C O let us say. Because, the bulk concentration is similar
to the interface concentration, in the beginning when there was no current supply or the
over voltage is 0. And after supply after the current flow and let us say it is a little bit
higher current density, so then there could be a concentration profile, this is the
concentration profile and this axis is concentration. This is C R this is similar to C O;
because the bulk concentration I am considering C O.
And let us say this concentration is C, which is the interface concentration; now when eta
equal to 0, or i equal to i0 I would get C equal to C 0. The concentration or C 0 equal to I
would say equal to 0 or interface concentration; concentration of metal ion n plus. Now,
when eta equal to eta and i equal to i max let us say; that means, the if as the current
density is increasing, I am getting over voltage, as well as the over voltage is increasing,
I am seeing that this particular concentration is going down gradually.
So, this concentration profile will keep changing as we increase the current density. And
finally, it will reach to 0 value, this is 0 0 axis let us say so, it will reach to 0 value. So
that means, when i equal to i max, I should get concentration should be 0 at the interface
ok so, these 2 are boundary conditions. Now, I know that when i equal to i, so then
concentration would be C at the interface and that time I would get some over voltage.
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Now, when this concentration is changing from this point to this point, I can apply
equilibrium condition and find out potential developed at the electrode; because of this
concentration change via by applying Nernst equation.
So, then E equal to E0 plus RT nF ln concentration of O divided by concentration of R.

Now, if I consider the concentration of R is or in terms of activity, if it is concentration is
considered to be 1, so then I can write it is only dependent on the concentration of ln C0
and that time that potential I consider to be E1 and E2 would be E0 plus RT by nF, when
concentration is C.
So, this I am getting these two equations. So, the over voltage would be is equal to E2
minus E1. And this over voltage is due to this concentration change of this metal line, so
I can put it as concentration or in short I can mention it as concentration. And this is
concentration polarization or over voltage.
Now, whenever I have this diffusion or concentration profile, I have a boundary layer
thickness which let us say I consider to be dell which is the boundary layer thickness.
This is the dell which is the boundary layer thickness.
Now, I can use Fick's first law here. J which is the flux I can write in these form moles
per unit area per unit time equal to minus D dc dx, I am considering steady state situation
here.
And this can be when the situation is; situation is this and this is C, then the flow of
metal ion from this bulk to the interface or bulk to the interface that rate would be
decided by this particular equation, which is the Fick's first law and we are considering
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steady state flow. This can be approximated as minus D dc can be written as del C and x
can be written as del; which is minus D C 0 minus C divided by delta.
Now, I know i by nF equal to moles per unit area per unit time if you go back if you
check you will see that this is the rate of flow of metal ions per unit area per unit time,
which should be equal to J. Then I can write i equal to nF J so, I put this particular
situation minus nF D C0 by minus C delta. Now, I use these two conditions; when i
equal to i, so that time the concentration difference is C 0 minus C.
And when i equal to i max, so that means, that maximum current density where the
whatever metaline is coming from the bulk to the interface that meta line is immediately
getting reduced and going to the IHP the or inner Helmholtz plane, at that situation the
concentration at OHP should be 0. So, then C equal to 0 or del C would be then equal to
C 0.
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So, in those situation, I let us continue from here, now then I can write i max equal to
minus nF D C 0 by delta. Therefore, Nita equal to or concentration E 2 minus E 1 equal
to E 0 E 0 they both will get cancelled.
So, that means, we are left with nF ln C by C 0. And remember whenever we try to
understand over voltage, we have to always differentiate between initial final to initial.
So, the over voltage should be E final minus E initial. Here this one is initial potential
when the concentration of metal ion at the interface is C 0 and this particular is the final.
So, that is what the over voltage is E2 minus E1. So, this I can write in terms of nF into
2.303 log I can have C minus C 0 plus 1. And if I take R to be 8.314 t equal to 25 degree
Celsius; that means, 298 Kelvin. And F equal to 9 6 5 0 0 coulomb, then I can get 0.059
by n log 1 minus C 0 minus C by C 0. Here I have sorry; this should be minus I have just
made some modification here. Here it is I am just adding 1 and then also subtracting 1
from that.
So, that is what I am getting this equation. And then this I can write 0.059 eta log 1
minus I will put this expression. So, in this case C0 minus C equal to minus delta by nF
D i and here I can put C0 equal to minus delta i max divided by nF D. So, if we put them,
so delta delta as well as this nF D part would get cancelled, so we would be left with this
equation.
So, this is concentration. So, this is the expression for concentration polarized over
voltage. And as we have said that what is i max? I max is basically the current; current
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density we have explained also, at which whatever metal ions are coming from bulk to
the interface are getting reduced are reduced.
So, that means, my interface concentration should be 0 when i reaches i max so, this is
another equation. Now, if I try to connect this both this concentration, so this means this
is concentration polarization. So, overall polarization should be equal to activation
polarization plus concentration polarization. So, I can write total equal to n activation
plus n concentration.
So, then I can put it as plus, so there should be 1 n log 1 minus I by i max.
Because, when we have overall polarization if we try to reach to the concentration

polarization end, we should go first to activation part and then the concentration part will
come up. Because, when we have activation part, when we have activation control
polarization, then I have enough supply of metal ions from the bulk to the interface. So,
there is no compentation concentration depletion in that interface.
But, as we go higher and higher activation polarization; that means, we as we are going
for higher and higher current density, we could see that there will be depletion of metal
ions, at this OHP as we have seen in the present case. And then we will get to the
concentration polarization regime. So, there if we have concentration polarization, then
there should be it should start with the activation polarization, then we will reach to the
concentration polarization.
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So now, if I try to plot concentration polarization which is n is equal to 0.0591 n log of i

minus i by i max; where i max equal to minus D nF C 0 by delta.
So, this plot would look like this so, this is log i again, this is polarization. Now, when
we have 0 over voltage, this is my i equal to 0 i0, this is fairly basically i0 value, where
the polarization is nil or over voltage is 0. Then first concentration polarization will start.
And then immediately once we reach to the i max, because I am seeing that the current
density is gradually increasing, I would get immediate because when I reach i max, so
this becomes 1, this becomes 1.
So, this eta concentration would be infinite, the over voltage have been infinite. So, it
would be a flat parallel line, parallel to the over voltage axis. Until this particular current
i max if I try to plot this particular equation, I would see a plot like this ok. So, this is
activation polarization and this part is concentration polarization. And this particular
current density for that particular reaction is i max. This is also termed as i L which is L
is nothing but limiting so, this is i L is equal to limiting current density.
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Now, here couple of interesting facts is this term, this term as well as this term. Now, if
C0 increases, let us say I increase the C0 and I am not changing other things are
remaining same. So, that situation I would get i max should increase. If we do not change
D which is function of temperature, n and F for this particular redox reaction (Refer
Time: 25:30) reaction should be same, delta if we do not change the boundary layer
thickness, so I should have this particular consequence.
Now, if I change delta let us say delta increases; that means, delta increase means if we
have the concentration profile like this. So, then this is my delta; delta, if it increases let
us say if it becomes like this so; that means, it increases to this much. So, then as per this
equation if you concentration is not changing, D is not changing the consequence should
be i max should decrease.
And how can we change this delta? Delta can be changed if we incorporate agitation.
Agitation means, if we churn the solution we would lead to have this kind of situation.
Now, if D increases; that means, diffusivity increases as per this formula, this minus sign
remember this minus sign is indicating of indicative of flow of ions against the
concentration profile. Concentration this minus sign is basically indicative of cative of
flow of ions from higher to lower concentration and this D increases i max also
increases.
So, these are some factors which affects this affect concentration polarization, fine. So,
let us stop here, we will continue our discussion in the next lecture onward. We would
try to connect this activation as well as concentration polarization and get to a concept
called mixed potential theory; which will enable as to understand corrosion mechanism
in a much better way, rather than going through a very analytical path ok. So, let us stop
it stop here and we will continue our discussion in the next lecture.
Thank you.
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Prof. Kallol Mondal
Lecture – 37
Summary of concentration polarization (CP) and introduction to mixed potential
theory-I
Hello everyone, today we will have lecture 37. Since now, we have been talking on
several aspects of thermodynamics and kinetics of electrochemistry. In thermodynamics,
we have looked at Pourbaix diagram and in the kinetics part, we actually looked at
polarization, which is the manifestation of current flow during electrochemical reactions
on a metal surface. And, when we have looked at the polarization part, we saw that it
actually relates kinetics of rate of transformation of metal into ions or ions into metal
with the voltage.
So, the voltage part is talking about thermodynamics and the current is actually looking
at the kinetics. So, it is a basically relation between kinetics and thermodynamics and
then now today, actually will step into the aspect, which is called mixed potential theory.
In the mixed potential theory, which is basically a very modern theory to understand
corrosion and here you would be able to see that, yes it can allow us to understand why
that different kinetic factors like exchange current density, like one is exchange current
density of course, if it increases as a function of galvanic coupling between active metal
with the noble metal.
And the exchange current density of hydrogen evolution reaction, if it increases on those
active components, we would see that the metal dissolution increases to a great extent
that active component dissolves quickly. Even in case of zinc, we have seen 3 examples
that, if we have pure HCl without any oxygen in it then we have some rate. If we have
oxygen in it we see that the rate increases and if we have one more that impurity in the
form of ferric ion, we see that the corrosion rate of zinc increases enormously.
So, we this particular theory can explain it better that why those changes in corrosion
rate of zinc happens due to those kinetic factors as well as the environmental factors
coming into the picture coming into consideration, while considering the corrosion of a
particular metal.
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So today, we have lecture 37, and we will still continue on kinetics of corrosion and
eventually, we will get to the modern theory of mixed potential theory. Now as we have
seen that the polarization has two components activation plus concentration.
And the activation part is can be related with beta log i i0 and this one can be related as
0591 n log 1 minus i by i max and this i max in different books, it is sometimes it is
written as i max or sometime it is written as i l which is nothing, but i limiting current
density.
Now apart from that there is one more polarization, because of that the potential can shift
from equilibrium potential to other potential or the stable potentials to other potential that
particular polarization, we call it resistance polarization which is a eta, over voltage
resistance is basically nothing, but IR drop that resistance of the circuit, which will lead
to some drop in voltage in the form of IR, I is the current and that polarization is called
resistance polarization.
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But in case of corrosive environment, when we see that the metal is put up put in or
immersed in a in an electrolyte, which is sufficiently very high conductivity. And that is
what that IR drop in kind of conducting electrolyte is very small and that is what we will
not be able to consider, this IR drop in our common corrosion processes, but definitely,
we will talk about over voltage due to activation and over voltage due to concentration
affect on the corrosion of a particular metal.
And now if I try to plot these two particular polarization remember this, beta i by i0, I
can write either a which is activation or c which is a is anodic c is cathodic and here also
accordingly, we can write a or c i0 is nothing, but the exchange current density and here
n is the number of electrons participating in that redox reaction. Now if I try to plot, the
plot nature as we have seen before would be like this, if I try to plot this one, this is over
voltage, this is log i. And, if this is the point, where over voltage is 0 and corresponding
to i0 of that particular metal and if I try to plot this plot will look like this is the plot
pattern.
Now, if I try to plot this one same eta here is equal to 0 eta over voltage is 0
corresponding to i0 and this plot would look like this corresponding to beta c since, we
are considering cathodic over voltage, now if I try to see the total over voltage. So, we
have to just combine these 2. So, the combination of these 2 would be so, this is the point
eta equal to 0, i0 equal to this is the point, which corresponding to log i0 and this axis is
log i, this axis is also log i.
Now, once we combine the combination curve will look like. So, if I combination curve
will look like this. So, this part is activation and this part is concentration polarization
and we have also seen that this concentration polarization actually depends on several
factors of course, the metal type of metal, metal surface, agitation, temperature, all those
will have affect on this i max, this particular current is i max.
Since once, i max is reached you see that this over voltage becomes infinitely large. So,
that is what the act when it reaches i max it actually, drops vertically with reference to
the log i axis; that means, this point is also i max ok. Now, if I try to see one factor let us
say, agitation let us say I increase the velocity. If I increase the velocity because of the
churning it could lead to temperature increase and once temperature increases diffusivity
increases.
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Now, and once I increase the velocity, if I try to look at the boundary layer as well as the
way concentration is changing so, this is the IHP OHP and we have seen the
concentration is changing like this is the bulk concentration and if this is the C. So, then
this is my diffusion distance delta or boundary layer thickness and then if I increase
velocity of course, I am seeing temperature increases and if temperature increases
diffusivity increases. Now if agitation increases then or the velocity increases delta
decreases and interestingly concentration polarization, the cathodic current side 0.0591
by n log 1 minus i by i max, you could see that this i also related to minus D n F C0
minus C divided by delta and i max is equal to minus D n F C0 by delta.
Now for a particular process reduction process n and f are constant now because of this
velocity increases I am increasing this I am increasing temperature and due to this D is
increasing delta is decreasing. So, i max also. So, if I try to write here. So, i max
increases now interestingly, if i max increases then I would have also corresponding
change in the polarization response. Now you could see that combination of those 2
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situations, one is activation and another one is concentration and this is the combination
of these 2.
Now, here if I try to see the combination first it will go like this, which is activation part
and then concentration part would increase this particular polarization, which is cathodic
side this is i0 and corresponding to (Refer Time: 11:40) equal to 0, now as the i max is
increasing that suggests that this i max would go to the right direction. So now, i max
would appear at new position. So now, if this is my i max. So, then this activation
polarization would still extend till i max is reached in the second case.
So, now this case it is velocity 1 and this case it is velocity 2 and V 2 greater than
velocity one. So, i max increases and that is what this curve is switching to the new
position which is this one. Now if your velocity increases farther. So, i max will again
switch to the right. So, then we will have another new position of i max let us say, this is
my i max when V 3 and V 3 greater than V 1 as well as V 2. So, this activation
polarization part would still increase further.
Now interestingly, you could see that as we are increasing velocity, because of these
factors, we are increasing i max and that is what that polarization curve is switching to
shifting towards right; that means, the i max appearance of i max is shifting towards
right, this situation will be explained will have strong effect on corrosion of metal. We
will see later that actually after certain time, after certain velocity in some metal
corrosion, we see that the corrosion of metal initially increases and then it becomes
stable or constant corrosion rate.
So, that will be explained with the help of mixed potential theory. So, this is one factor,
the second factor sometimes, we have combination more than 1 cathodic reactions. For
example, if a system has got dissolved oxygen then and if that system is acidic.
So, we can have this reaction, this cathodic reaction as well as since it is acidic. So, we
can have this reaction also. Now here, the standard reduction potential is E0 equal to 0
and here E0 equal to 1.227 volt, if I try to see the response of cathodic polarization as
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well as what happens in the concentration as well as activation polarization regime, we
can have a response like this.
This is log i this is over voltage. Now, if this is eta for oxygen reaction is equal to 0 at
this point and corresponding to the potential, which is E 0 equal to 1.227 volt, remember
this is the equilibrium voltage and at equilibrium voltage, we have over voltage to be 0
for that oxygen reduction and if I try to see if E is equal to 0 here then it corresponds to
eta H2 evolution to be 0 at this point and let us say, this is the i shift switch, this
particular plot little down. So, then only we will be able to see the variation, this is log I,
this is i0 for hydrogen reaction, this is i0 for oxygen reaction.
Now, for oxygen it will have it is own activation polarization. Let us say this is my
activation polarization of oxygen reduction, now let us say, this is my i max for oxygen
reduction so; that means, it cannot go, it can come to this point up to this point and then
it will take this particular path. So, this part is out as per our understanding. Now for
once, it is going towards cathodic polarization regime and it is polarized over voltage is
increasing gradually.
Now, this hydrogen reaction also has got it is own activation polarization, if that one
moves like this. So, then if it comes like this, because once I max is reached for option
reduction, it will fall rapidly almost perpendicular to the log i axis and then it will
experience the activation polarization of hydrogen reduction and hydrogen ion, if I
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consider H plus ion diffusivity D H plus let us say and if i consider D O 2. So, D O 2 is
actually less than D H plus then correspondingly i max O 2 O 2 should be should be less
than i max H plus i.
Considering that fact that delta and C0 are fixed of course, temperature is also fixed, I
am just saying the size of those particular molecules. Since, it is a very small size that is
why it is diffusivity would be very fast. So, that case i max should be high for H plus ion
so; that means, if I try to without considering this oxygen polarization part, if I try to
look at only the hydrogen polarization part, it will have it is own polarization and then
finally, it will reach it is i max H plus.
So, the curve pattern would be since, it is polarization is starting from higher potential
from oxygen reduction. So, it will fall like this, if I try to draw it in a different color. So,
this particular fall would be like this, it will follow this pattern and then it will switch to
this pattern and then follow like this. So, this red color lines would be the actual
polarization line for both the reactions, if I can go up to a very very high over voltage or
very very great bit of polarization occurs in the cathodic side.
So, this also has got relation with the non the diffusivity part and finally, it is basically,
this equation which is governing, this kind of i max variation, which is minus D n F C0
by delta.
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So, this is about concentration polarization as well as activation polarization and how in
combination, how do you look? Now, let us get to the fundamental of mixed potential
theory, whatever understanding we have on kinetics of corrosion that part will be now
used for understanding corrosion events. And, then you will see that yes whatever
understanding, we have we have whatever fundamentals, we are going through they will
be really useful in corrosion events.
This mixed potential theory is as we have mentioned that it is a very modern theory and
it starts it actually, it was known way back in 1990 in 1900 and, but it was proposed and
formalized by two scientists, C Wagner and W Traud in 1938. This was formally
formulated, I would say and they had a famous paper in journal of electrochem (Refer
Time: 20:58) it is 1938 publication. This is on the interpretation of corrosion process
through, the superposition of electrochemical partial processes and on the potential of
mix electrons.
So, if I try to see the paper name it is says on the interpretation of corrosion process
processes through the superposition of electrochemical partial processes. And, on the
potential of mixed electrode. Interestingly, if you see this corrosion processes through
superposition of electrochemical partial processes, this is very important partial and also
on the potential of mix electrode.
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Now, if I could get back to the corrosion of zinc in pure deaerated dilute HCl solution.
So, this is a beaker and where I have put HCl, which is pure deaerated and dilute
solution. In that case, I have put a zinc piece and immediately I could see that hydrogen
bubble will form on the metal surface. Now if I analyze this, I will see that the actual
processes, this is the actual reaction that takes place interestingly, this is a full redox
reaction and here.
So, this full redox reaction in case of instead of processes, I could see that this is a single
process, this redox reaction can be broken into 1 oxidation and 1 reduction process. So,
the oxidation is this is the oxidation or anodic process or I could say corrosion process
and the second part is H plus plus 2 e equal to H2. So, this is cathodic process so; that
means, the first statement, which says the corrosion process through the superposition of
electrochemical partial processes.
Now, you see that this one full redox reaction has been broken into 2 redox reaction 2 2
of reactions partial reactions, one is oxidation and other one is reduction. Now instead of
that if we have ferric ions then of course, there could be one more red or a reduction
process, which is plus 3 plus 1 electron, it go to plus 2. So, this is another cathodic
process so; that means, whenever an actually the anodic processes this one, which is the
corrosion event, the corrosion event is single corrosion event, but you have that entire
process has been divided into 3 partial reactions 1 anodic and 2 cathodic.
So, from there the first hypothesis has been drawn. So, this says that any electrochemical
reaction can be divided into two or more partial oxidation and reduction reaction. Now
the second, this is the first hypothesis by from C Wagner and W Traud in 1938, this is
the hypothesis of mixed potential theory and the second hypothesis they are saying that
the, what they are saying in the title is potential of mixed electrode. In fact, that potential
of mixed electrode or the mixed potential of electrode will be achieved due to these
reactions due to these partial reactions.
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And when this mixed potential of electrode is attained, due to these reactions partial
reactions, it says that the there will be no accumulation of charge or in other words it
says that laws of conservation of charges. So now, we see that there is 1 cathode, there
are 2 for example, if I consider these particular reactions I could see that there are 1
cathodic and 1 anodic reaction.
So, if there is no accumulation of charge net accumulation rather, I would say this net
part net accumulation. So; that means, that all the charges are balanced that case I must
say this for example, for this reaction there could be a current called ia, because this is the
anodic current density for anodic process and this for this reaction there should be i c,
which is the cathodic current or current density I would say. So, that case ic should be
equal to ia at mixed potential. So, this is the second hypothesis. So, on these two
hypothesis, we will start looking at the understanding of corrosion events in our next
lecture, let us stop here.
368
Corrosion - Part I
Prof. Kallol Mondal
Lecture – 38
Mixed potential theory–II
So, in the last lecture we just started discussing on Mixed potential theory. And this
lecture is lecture number 38.
And here we will continue Kinetics of Corrosion. And now we are our discussion mode
would be mixed potential theory.
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In fact, in the last lecture if we see that we have put forward two hypothesis and those
two hypotheses are basically any electrochemical reactions this is first hypothesis can be
divided into two or more partial oxidation or reduction reactions.
And the second hypothesis says that because of this process, that means more partial
oxidation and 1 or 2 or more partial oxidation and reduction reactions, the electrode will
achieve a mixed potential which is attain due to this partial reaction definitely and there
should be no net accumulation of charges. And this no net accumulation of charge would
basically indicate the laws of conservation of charge and that time ia should be equal to
ic. And that ia equal to ic means, there is for example a metal, when it is electrically
isolated and then there should be no current flow. In fact, if I try to look at this particular
example where, zinc is immersed in HCl.
So, actually there is no net current flow in the zinc rather, when this mix potential is
achieved ia equal to ic. And that also indicates i corrosion because, at this rate the
corrosion will take place. And that also corresponds to a mixed potential which is also
called Ecorr. Since zinc is acting as that electrode. And on top, you have cathodic as well
as anodic reaction, zinc minus 2e equal to zinc plus plus and H plus plus 2e equal to H2.
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So, this leads to 1 redox reaction which is zinc plus 2H plus zinc equal to zinc plus plus
plus H2. So, and this electrode would achieve, unique mixed potential which is not same
as the potential for zinc zinc plus plus, that is single redox reaction this half cell reaction
they would also have their reversible potential to begin with. And this potential is not the
same as that particular begin with the potential where from it has began to shift from that
potential to this Ecorr due to these combined reactions.
So, now we see that the concept of icorr and Ecorr. Now let us try to understand this
mixed potential theory and kinetic reaction, kinetic equations rather in the form of and i
max these two equations. If we combine them we would see that it leads to modern
electrode kinetics theory kinetics effects rather, electrode kinetics theory or effect.
So, it would lead to modern electrode kinetics theory, so this combination of these 2.
Now to begin with when we have this situation let us say that for zinc, it would have a
potential E0, which is minus 0.76 volt and in that time I have zinc plus plus plus 2e equal
to zinc for this reduction reaction is actually happening in the standard state. Let us
assume that in the beginning it has zinc ions and then we have this potential to achieve
which is the equilibrium potential.
So, at that potential I have i0, which is exchange current density of course, it is on zinc
surface zinc plus plus zinc has got some value it is let us say, it is values around 10 to the
power minus 7 ampere per centimeter square to begin with.
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Now, similarly if I consider hydrogen electrode, which is forming on zinc surface, so

hydrogen electrode the standard hydrogen electrode what we have seen before it is
basically platinum electrode or platonized platina electrode is used. But on zinc surface,
we can also constitute a hydrogen electrode and that time I have E0 to be 0 volt and i0 of
hydrogen exchange current density which is actually on the zinc surface would be let us
say some value around 10 to the power minus 11 ampere per centimeter square.
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If I try to plot them on Log i versus potential axis let us say this is my zinc potential
which is 0.76 minus volt which is equivalent to E0. And this is my E0 for volt for
hydrogen. Now exchange current density of hydrogen on zinc surface i0 zinc, H2 and
exchange current density on zinc surface for zinc reaction so this is i0 zinc, I simply put
zinc without putting that zinc plus plus plus zinc because, it is taking little bit of space.
This is the situation in the beginning to begin with. So, here it indicates H2. This is non
corroding reversible situation at this point. Here also this is zinc plus plus plus 2e equal
to zinc. This is non corroding and reversible condition and this was the potential in the
beginning for both these half cell reactions because we have to consider these two half
cell reactions. This is oxidation and this is reduction these are basically two half cell
reactions and to begin with we have assumed that they are starting from the standard
potential.
Now, for both the cases for hydrogen and zinc let us say you let us draw that, this is for
hydrogen this is for zinc; if I try to see over voltage as a function of log i, this is let us
say 0 over voltage is equal to 0, which is actually indicating E0 to be 0 volt and here eta
equal to 0, this is indicating 0, which is actually indicating E0 for E0 equal to minus 0.76
volt for zinc. They would have their own cathodic and anodic polarization plot. And let
us say that we are in the activation polarization region, that means, in the low current
region because, concentration polarization starts at a very high current density.
So, if I consider the activation polarization for hydrogen reactions, it has also has its own
cathodic and anodic reactions. So, this is cathodic part, anodic part for hydrogen. So, this
is 2 hydrogen equal to 2H plus plus 2e and this is cathodic part H2 and in case of zinc,
this is anodic part which is zinc minus 2 equal to zinc and this is cathodic part zinc plus
plus plus 2 equal to zinc.
So, they have their own cathodic as well as anodic tafel plots. I would say that this
equation eta equal to beta log i by i0. According to these equations they have their own
plots. But since they are potential as far off are far off, 1 is at 0 and another 1 is 0. minus
0.76. As per this mixed potential theory, if I look at that mixed potential theory it says
that the mixed potential of electrode will be achieved due to partial reactions.
Now, there are two different potentials, so they must achieve some potential which is in
between these two potential and that is unique for this particular situation. How can they
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achieve? That can only be achieved for example, if it goes anodic side and if it goes
cathodic side, they cannot achieve a single unique potential because, their potentials are
basically moving away from each other. So, the only way they can achieve a mixed
potential by moving this one on the anodic side and this one on the cathodic.
Then only they can reach unique potential. And when they would like to do that so; that
means, they would follow their own anodic polarization plot and cathodic polarization
plot as per these equations. So, in this case, in case of zinc case this polarization would
follow according to this line and here the polarization of hydrogen reaction would follow
this line. So, now, they will meet somewhere here.
Once they meet somewhere here, you see that the potential is Ecorr which is in between
this and this. And for that you could see that polarization for zinc is on the positive side
and the polarization for hydrogen is on the negative side. So, hydrogen is cathodically
polarized and zinc is anodically polarized, in order to achieve this mixed potential.
Now, interesting thing the second postulate or the second hypothesis is also met here. If
you see this it says that, when it reaches that mixed potential there is no net accumulation
of charges. So, that means the current density for cathodic reaction which actually
accepts electron and then current density for anodic reaction which actually leaves
electron, these two equation these two rates are same. So, that means, the rate at which
electrons are consumed due to cathodic reaction which is hydrogen evolution reaction is
same as the rate at which electrons are generated by this zinc dissolution which is anodic
or corrosion reaction and they are meeting at this Ecorr point.
And corresponding current density should be icorr which is nothing, but ia equal to ic.
And whenever we have this situation there is whatever electrons are generated are
basically consumed. So, there is no net accumulation of charges for this electrically
isolated zinc piece in HCl medium. So, if I try to plot here. So, it would be, so this is
Ecorr and this is icorr, this is the crux of mixed potential theory.
So, this potential is called mixed potential. And the system would like to stay here and
the corrosion of zinc would take place as per the rate decided by this icorr. Now how do I
get this icorr and Ecorr experimentally? Now whenever this zinc plate is zinc block is put
up put immersed in HCl medium after some time it will try to achieve this because, this
rates are going at a different this icorr and this ia as well as ic, they are actually taking
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time because finally, it has to reach to this constant rate and then there will be no net
current flow in the system.
So, the system this zinc would remain at this potential. So, if I try to measure this
potential of zinc without sending any current through that particular zinc plate by a
standard hydrogen electrode. So; that means, if we have this zinc HCl medium and then I
connect it to hydrogen standard hydrogen electrode and I connect a wire with this zinc
and then if I try to measure the potential, it gives me potential, after achieving this
potential these potential we call it without sending current remember without sending
current we are not connecting that circuit. So, that time we see that the potential is
termed as OCP Open Circuit Potential.
Remember once we try to measure this same potential with a standard hydrogen
electrode then initially that potential is actually switching from one potential to another
until unless it reaches to this potential. So, once we allow little bit of time we see that the
potential is actually potential has achieved this particular Ecorr or OCP and it is
maintaining at that potential with time.
So, this open circuit potential is the new point from where we have to consider the
polarization during experimentation. And that is what in the lab we do polarization
experiment and that time we give we try to achieve this open circuit potential which is
rather stable open circuit potential and then that one would be considered as a 0 over
voltage, the new 0 over voltage and then we try to go positive or negative side and then
try to see that what is my what is my net current flow or i applied. In case of single
electrode system, we see we have seen that the actually in case of single electrode
system, what we have done?
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So, this is eta equal to 0, this is i0, these are the 2 sides and then we saw that if I send
applied current; that means, when the rate of cathodic anodic reactions are different then
the plot would look like this So, this is my i0 and when i0 is achieved there is no net
current flow in the.
Similar way here it is Mn plus equal plus ne equal to M as well as this forward as well as
backward reactions; this is a non corroding situation or single electrode case. But, here
we have 2 different reactions, it is not single electrode reaction, one reaction is zinc
dissolution, another one is hydrogen evolution. And this point would be the new set point
the way we have considered eta equal to 0 for single electrode case.
Or then if I try to do the same experiment, we will get a curve like this. And then the
linear portion we have to consider, this linear portion and the linear portion we have a
extend and then finally, we will achieve to this point. And this linear portion is achieved
the way we have done for this case, it is the same way in this case we have to consider ic
minus ia and this is for hydrogen and this is for zinc. And in this case also we have to
consider the difference between ia minus ic and this is for zinc and this is for hydrogen.
So, that is what we get this Tafel plots and accordingly we can extend this linear portion
and these 2 linear portion backward and we can achieve this particular point and that is
basically nothing, but icorr and Ecorr. This is one important information what we
achieve what we what we get by doing Tafel experimentation. So, these particular part
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will come in the corrosion part 2, but still when we have considered this we are just
explaining little bit.
So, if I try to look at the mixed potential theory in nutshell we could see that the new
potential is achieved and that new potential is when it is achieved due to the polarization
of those partial reactions; one definitely would be cathodic, another one is definitely
anodic polarization in this simple situation where this entire reaction is divided into two
parts. One is one single cathodic reaction, another one is one single anodic reaction.
Then once we reach to that mixed potential that mixed potential at that mix potential, I
could see that if it is isolated metal block in that particular solution there is no net current
flow and that can achieve if I could see that ia equal to ic at this point. That is what we
have understood in the in these particular diagrams. In addition to this remember this is
an open system. If it is an open system, so since this is open system the hydrogen
bubbles are forming and they are actually going out.
Now, if we have it is habit in a closed system, definitely this reaction would arrive at
equilibrium. This reaction will arrive at equilibrium. That time also it will be Ecorr and i
0, which is equal i0 is basically icorr the same point will be achieved. But if it is an open
system, if we do not change the temperature, then hydrogen will keep on going out and
then this reaction will go forward. So, the zinc will keep on corroding.
So, that time it will not be equilibrium situation, it will be non equilibrium spontaneous
situation; since hydrogen is going out. So, now, let us consider some of those effects of
mixed potential theory; some of those consideration of kinetic factors.
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So, one such kinetic factors is definitely i0. Now i0 for let us say hydrogen evolution
reaction on different metal surface surfaces are different. For example on platinum
surface as we have seen its value is around 10 to the power minus 2 to 10 to the power
minus 3 ampere per centimeter square. For gold it is around 10 to the power minus 4 to
10 to power minus 5 ampere per centimeter square and for zinc for this hydrogen
evolution reactions remember this i0 value I am just putting this i 0 value it is around 10
to the minus 11 ampere per centimeter square.
All these values would have definite effect on the zinc corrosion rate. Now how we are
considering? For example, if we have a particular beaker, let us say 2 beakers, 1 beaker
we have a zinc plate, zinc block and the concentration of both the electrolytes that is acid
medium HCl is same and another case I have a zinc in connection with a platinum plate,
this is let us say platinum plate and this is zinc.
Now, we would see that in this case we would have very very high rate of corrosion of
zinc, why? This can be explained by using mixed potential theory. So, when we try to
see these 2 situations, we have to first look at the diagram. Which the diagram, the
diagram what we have shown here these diagrams are called Evans diagram. So, this
Evans diagram are basically not considering the practical diagram which is i applied
versus potential or potential versus i applied, this is basically potential versus log i as per
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this polarization or the Tafel equation. We will not consider there this what happens if
we go on positive side or negative side and what would be the variation of i applied.
So, that case we have to again consider this for zinc this is E0 zinc and this is i0 zinc, on
zinc surface and then we have E0 for hydrogen which is 0, this is minus 0.76 volt and
then we could see that this is my i0 of hydrogen reaction on zinc surface. And
accordingly we are achieving the mixed potential theory, as per the theory this is the
potential what we would achieve, this is the mixed potential which is Ecorr and this is
icorr, isn’t it? So, that is what we have seen.
Of course, it will have its own anodic over voltage also, but since as per the discussion
what we have seen that it will go to negative side and this will go to positive side, isn’t
it? Now if we have another reaction this in this case, this is the situation this diagram this
Evan’s diagram is indicating this situation. Now in this situation it will be little
complicated and if I have understood this mixed potential theory it can be analyzed very
easily, but we will take it up in our next lecture and let us stop here.
Thank you very much and wait for the next lecture where we will talk about this effect of
increase in exchange current density for a particular cathodic reaction by changing the
metal surface and then its effect on corrosion of metal. Let us stop it.
Thank you.
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Corrosion- Part I
Prof. Kallol Mondal
Lecture – 39
Understanding of mixed potential theory through the case studies and events of
corrosion-I
Let us start the Lecture 39.
So, we are left with two more lectures and in these two lectures remaining lectures we
will consider some of the case studies or where corrosion happens in case of metallic
object and we will try to understand those corrosion events with the help of mixed
potential theory.
And in fact, in the last lecture we saw how this mixed potential theory can explain the
corrosion event of in case of zinc in HCl. And then we try to draw Evans diagram which
is basically plot between potential and log of current density.
And then we try to consider the activation polarization part only in the beginning and
later on we will also see some more examples considering the concentration polarization.
In this particular so that means, we will look at some of the case studies or events of
corrosion considering mixed potential theory. We will try to understand through this
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theory; as I have mentioned that we will be concentrating on the activation polarization
part initially, and try to draw evans diagram, but later on also will look at concentration
polarization part also.
So, we have two situations one is eta equal to beta log i by i0, another one is eta equal to
0.0591 n log 1 minus i by i max. So, these are this is basically concentration, polarization
this is activation, and in the concentration polarization we would consider cathodic
polarization.
Now in this particular junction we would like to mention that we would consider
cathodic polarization not the anodic polarization. Because the anodic polarization event
is very uncommon there are two possible reasons one is of course, when you consider
anodic polarization there should be depletion of metal ions in the interface around that
interface due to corrosion event.
But since it is anodic polarization, so metal is going into ion form. So, there would be
enough supply of metal for the formation of metal ion. So, the depletion of metal ion is
unlikely so; that means, depletion is unlikely and second part is when it is during of
course, during anodic polarization. Since during anodic polarization is actually going to
metal ion. In the second part during anodic polarization there could be a possibility of
passivation. This passivation can be explained on the basis of Pourbaix diagram.
So, if you let us say some metal E versus log i if I consider the Pourbaix diagram let us
say it looks like this. And this is metal oxide part, this is metal ion part and this is metal
part. Let us say if I am operating at this pH sorry this is not log i axis this is pH axis. So,
if I operate at this pH axis as I go upward; that means, if I go on the anodic side, or the
positive side eta is positive. So, then initially it is in the metal part and then kindly
finally, it goes to metal oxide part. So, then you have actually metal oxide forming on the
metal surface and which can lead to passivation.
So, at a large over voltage or positive over voltage there could be possibility of
passivation also. But the main reason is this depletion of metal line is unlikely in case of
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anodic polarization. And this concentration polarization happens due to depletion of
concentration of ions, but in this case it is unlikely that is at anodic polarization we
would not be able to consider we will see some of the examples considering cathodic
polarization.
And of course, in the beginning we will consider an activation polarization. In the last
lecture at the end we started talking on the effect of galvanic coupling of a metal object
which is active with a noble component. And that is what we started looking at if I see
the last part we started looking at combination of zinc and platinum in acid media.
So, now, you have two beakers and in one beaker you have a block of zinc, another
beaker you have as block of zinc which is connected to block of platinum. And they have
the same area, which are exposed to the acid medium, this is acid medium, same
condition, temperature, pressure both the cases.
In that case we have to draw Evans diagram. And let us draw the Evans diagram, log i
this is E, and we start with zinc and there because the anodic reaction is zinc dissolution
and here platinum is noble, and zinc is active component. The zinc dissolution is anodic
reaction, and hydrogen evolution is the cathodic reaction when we have mixed potential
theory to be active.
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Now, it is this is basically i0 for H2 gas evolution. Let us say this is on zinc surface in this
case this is the case what we are considering now. This is 0 equal to and this E is equal to
minus 0.76 volt. And this is for zinc plus plus zinc and this is for hydrogen H2. And it is
lying here for zinc this is i0 for zinc on zinc surface, i0 for zinc on zinc surface.
And then we see mix potential this is my Ecorr and this particular current this particular
current is icorr of zinc. When there is no galvanic coupling between zinc and noble
component which is platinum. Now once we have hydrogen evolution on platinum
surface as we know that i0 of hydrogen on zinc is less than equal to less than less than
equal to i0 of hydrogen evolution on platinum.
Since this value is close to 10 to the power minus 2, 10 to the power minus 3 ampere per
centimeter square. And here it is 10 to the power minus 10, to 10 to the power minus 11
ampere per centimeter square, so this is the difference in their values. When we have this
particular let us say this particular situation now. Now hydrogen evolution would also
take place on zinc surface as well as platinum surface and since platinum is noble.
So, platinum will act as cathode and zinc will act as anode, but hydrogen evolution can
take place on both the surfaces. Now if I consider hydrogen evolution on platinum
surface it is exchange current density is pretty high at this point. So, this is i0 hydrogen
on platinum surface and E0 of course, it would be same 0. Because we are considering
hydrogen evolution and then it would also have it is own cathodic polarization and it is
cutting here.
Now, question is would this be my new over new mix potential no because as per the
mixed potential theory we see that there will be a possibility of existence of a mixed
potential where there should not be no net current flow in this in the system. Now in
order to have this second criteria to be criterion to be fulfilled. We must have summation
of ic should be equal to summation of ia.
So; that means, in the system we must have to see that total cathodic current density is
equal to total anodic current density. Now here we have two sets of cathodic reactions;
one is on zinc surface, another is on platinum surface. And one set of anodic reaction.
So, this is two sets of cathodic and one sets of anodic. Here I am considering two sets
means this is happening on platinum surface, this is happening on zinc surface. But zinc
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is dissolving from the zinc surface only platinum would not dissolve because it is a
cathodic component.
Now that case since there are two cathodic reactions in order to fulfill this criteria that
total cathodic current density should be equal to total anodic current density. I should add
up these two polarizations. Now in order to add up since it is a log scale. So, it will go at
this point because I have to add at every potential every potential I should add this one
and this one. These two current densities and get to the new current density which is this
one.
Similarly, here we have to add this point as well as this point to get to the new current
density, which is this point which is new ic which is ic. Let us say this is ic prime equal to
ic hydrogen on zinc plus ic hydrogen on platinum and at this point it is basically ic
hydrogen on zinc plus ic hydrogen on platinum. So, like that we have to add up all the
cathodic reactions. Now if we add up then if we connect them then we will see that the
added part would follow the red line.
And now if I look at this point this point here I have ia which is this one and if I try to see
the total ic. So, this is these are the two points where I could see that at this point the
circle point I see ic equal to ia and this ic has two parts, one is this ic another one is this ic.
So, ic on hydrogen evolution on zinc surface plus ic hydrogen evolution on platinum
surface. Then I could see that at this point at this point, I have two hypothesis of mixed
potential theory are met first one is it is reaching to a mixed potential.
And then at that potential I could see that this condition is fulfilled; that means, when this
condition is fulfilled. So, since ic and ia they are flowing opposite directions and of equal
magnitude there will not be no net current density. So, now this particular potential
would be new Ecorr and corresponding current density which is ia is basically icorr new.
Now when there were no platinum connection between zinc there. There was no
connection between zinc and platinum only this case I had current density for the
corrosion is this one this particular current density was the corrosion current density.
But as we have connected to platinum which is a noble component I could see that the
current density for the corrosion has gone up enormously. Because you remember this is
a log scale and also one more thing since it is a log scale value. So, when you add this
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particular polarization with this particular polarization that the current densities for the
cathodic reactions it will not shift log wider distance.
Because the scale has to be maintained that is what if there is a small increase on the
right side of this point. So, that small increase is coming because of this log scale nature
of this x axis.
Now you could see that this case one when we have connection of an active component
with a noble component. The corrosion rate of the active component goes up enormously
this is the explanation why it goes up with the help of Evans diagram. Now let us look at
a second case this is case one I would say this is case one. Case one is effect of galvanic
coupling and with active plus noble this is the galvanic coupling considering.
But remember when we have seen this galvanic coupling we have said that that they
have the similar same area which is exposed to the acid medium. The area is not
changing, the galvanic that active component has got the some area let us say one
centimeter square then platinum would also have the same area.
Now, interestingly if we have another metal let us say if it is connected to another

component in let us say instead of platinum we add platinized platinum that case the
corrosion rate would further increase. In that time what happens? This particular current
density would shift to switch to some other current density let us say at this point.
Because current density exchange current density for hydrogen evolution on platinized
platina is higher than that on say plane platinum surface. So, again further if I follow the
same way what we have done in case of platinum this one would be the new mix
potential and we could see that the corrosion current density has gone up where this line
indicates the addition of this current density.
The current density following this particular polarization of hydrogen evolution on zinc
surface and hydrogen evolution on platinized platina following this particular arrowhead.
If I see the green arrow head this particular polarization so that this particular line this
blue line is nothing, but the addition of this one and this one. So, then only at this point I
could see ic summation equal to ia is equal to icorr. So, that way we have discussion or
the explanation of increase in corrosion rate when we combine an active component with
a noble component.
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Now, let us consider the second case study case two where we consider the effect of
presence of oxidant or we call it oxidizer. And that should be strong oxidizer for example
Fe 3 plus presence on the corrosion rate of active metal. Now again let us draw Evans
diagram.
Now whenever we have let us say this is an acid medium. So, if it is an acid medium we
have hydrogen evolution reaction E equal to E0 equal to 0 here. And let us say this is my
E0 of this some value. Let the some this value is in the minus direction now they will
have their own mix potential, this is my mix potential. Now Fe plus 3 plus e equal to Fe
plus 2 this has got a very large E 0 this is almost about close to 0.77 volt if I remember
correctly.
Now, if I try to see this is positive 0.77 equal to E0 Fe plus 3 Fe. So, let us say it is
position is here this is i0 Fe plus 3, F e plus plus on metal surface. Because this is in the
ionic form in the solution, so you have a system like this, this is a acid this is the metal.
And on top of it I have hydrogen cathodic reaction as well as this reduction reaction.
So, and dissolution reaction is 2 plus, this is my anodic reaction and these two are
cathodic reaction. So, now you could see that this entire corrosion process is divided into
a one anodic reaction and two cathodic reactions. And both these cathodic reactions are
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taking place on metal surface. So, that is what we are considering i0 for Fe plus 3 to Fe
plus 2 on the metal surface. So, it would have it is own activation polarization cathodic
as well as anodic.
Now, since this particular point which is i0 M 2 plus M on metal surface and hydrogen
this is i0 hydrogen on metal surface. Since these two potentials are lying below this
potential, so then everything will be coming between these two extreme.
But mixed potential would come in between these two extreme, depending on the
situation where I have the (Refer Time: 22:38) cathodic current density is equal to the net
anodic current density. So, that particular point we have to find out. So, now without this
Fe plus 3 presence; I would have gotten this particular point to be my new mixed
potential and corresponding corrosion current density. This is icorr, this is Ecorr 1, let us
say this is 1.
Now once we have this presence of Fe plus 3 it is a strong oxidant, that means, it will
have a very large very high tendency to get reduced and there would be strong cathodic
polarization. Because it is in very strong cathodic reaction and remember all this
individual redox reactions, or half cell reactions would have their own anodic as well as
cathodic polarization.
So, this is anodic polarization for hydrogen evolution, this is cathodic polarization for
metal and this is the cathodic as well as anodic polarization for Fe plus 3 to Fe plus 2. So,
now it would come like this and once it reaches to this particular plane immediately it is
seeing that there is another cathodic reactions which is hydrogen evolution reactions.
So, now as per our concept in the previous example we have add up the total cathodic
current densities. So, now we have to add up that total current densities, so had it gone
through the actual path it should have been like this.
But since there is one more cathodic reaction which is hydrogen evolution it would add
up. Since this is in log scale, so this adding will not go very far. So, it will be small
increment as per the value at different potentials. So, then we add up and we get to this
and then if we extend it we could see that at this point which is new Ecorr let us say
condition 2 where this is my icorr case 2. And then if we extend this particular line I
have 2 current densities cathodic current densities these two.
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So, now let us say this is i H2 on metal surface, or rather I say i H2 cap ic of H2 and this is
ic Fe plus 3 Fe plus 2 and at this point I could see that ia equal to icorr equal to ic, and this
ic is basically addition of ic H2 plus ic Fe plus 3 Fe plus 2 at E equal to Ecorr to the
condition 2.
So, then we could see that again the corrosion rate of the metal is going up and since it is
a log scale. So, this corrosion rate increment of that metal is very very high. And
interestingly one more thing if you look at this carefully had there been no Fe plus 3, the
corrosion rate would have been here. And this should have been my the rate of hydrogen
evolution on metal surface.
But once we have Fe plus 3 the corrosion rate is increasing, but the rate of hydrogen
evolution on zinc surface is decreasing as compared to the rate what it should have been
there without Fe plus 3 presences in the solution. So, then you could see that the metal
ion on the metal hydrogen bubbling rate bubble formation is reduced somewhat.
And this reduction is coming because of depolarization effect what is depolarization?

Depolarization means what should have been the polarization. Now that polarization
amount or the over voltage has reduced had it been only M and hydrogen reductions
metal dissolution and hydrogen evolution reactions my over voltage would have been
this much.
Now with the presence of Fe plus 3 the over voltage for hydrogen evolution is this much.
So, this is when Fe plus 3 is presents and this is without Fe plus 3. So, we could see that
the over voltage for hydrogen evolution reaction has gone down or decrease due to the
presence of Fe plus 3, that particular effect we call it depolarization effect on hydrogen
evolution because of presence of Fe plus 3.
So that is what Fe plus 3 is called depolarizer. And in fact, the same effect was seen in
this case also you could see that when platinum when the platinum is connected
hydrogen evolution rate on the zinc surface is reducing.
So, platinum is also acting as a depolarization for hydrogen evolution on zinc surface.
So, now we have seen two examples case 1 when we connect active component with a
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noble component. And the second case when we have a presence of strong oxidizer and
both the cases I could see that the corrosion rate of no active metal is increasing to a
great extent. So, let us stop here we will continue our discussion considering few more
case studies.
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Corrosion - Part 1
Prof. Kallol Mondal
Lecture - 40
corrosion-II
So, let us start lecture 40.
And we will continue our discussion on case studies on corrosion event and try to
explain with the help of mixed potential theory. In fact, in the last two cases we have
looked at 2 instances: one is when we have a galvanic coupling of an active metal with a
noble metal where, the areas of both the components were same. And the second case we
looked at the effect of an oxidant or oxidizer on the corrosion rate of a metal, of a metal
active metal.
So, in both the cases we could see that concept of mixed potential theories are made; that
means, it achieves a mixed potential and then at that potential, the total the net corrosion
current densities is equal to the net cathodic current density. So, we could see that first
instance mixed potential is achieved and second part ic equal to ia and here ia since, there
were in both the cases we considered only one corrosion event which is ia, so is equal to
icorr.
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And we could see in that case the total reactions are broken into in first case first
example, it is broken into hydrogen evolution and second case metal dissolution case I
and case II hydrogen evolution, 2 ferric ion reduction and third metal dissolution case II.
And case I, we had only 1 cathodic reactions, but this cathodic reaction was taking place
on 2 surfaces, one was on zinc surface another one was platinum surface. And in the case
of second case, we had 2 cathodic reactions one is hydrogen evolution other one is ferric
ion reduction. And, one oxidation reaction in both the cases metal dissolution which is
the main oxidation reaction or corrosion reaction happening in both the cases.
Now, if I try to look at case 1 carefully, we had the situation with the area of cathode
equal to area of anode. Now we had already explained the situation when we have a
situation like let us say copper and in between you have an iron rivet, this is copper, this
is copper. And, if this particular component with the iron rivet joint is placed in an
electrolyte, we did see that the rate of iron rivet corrosion has gone up enormously.
Because, there the cathodic component has got a higher area as compared to the anodic
component area and that increase in area ratio which is nothing, but area of cathode
divided by area of anode.
So, this area if it goes up, I could see the rate of corrosion of active component goes up
enormously. And there we could see that of course, the current density the effective
current density on active component has gone up because of larger number of cathodic
reactions on the larger area of cathode. So, this particular situation the effect of area ratio
this is our case III, the case studies III. So, let us explain this particular situation, in order
to do that we have to first look at for the peculiarity in this particular situation.
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As we have seen that the Evans diagrams in first two cases, we explained on the basis of
E versus log i. This i is the current density. And we saw that this is my mixed potential,
this is E0 of metal dissolution, this is i0 metal dissolution on metal surface and this was
my hydrogen evolution of i0 on metal surface and this is E0 of hydrogen. So, that was the
pattern. This particular potential was Ecorr and this particular current density was icorr
and here I could see ic equal to ia. This is no problem.
But interestingly that time this was on 1 centimeter square area, this was on 1 centimeter
square area. For the time being we consider 1 centimeter square, it can also consider 1
meter square does not matter so; that means, they have the same area. But, when we have
let us say this hydrogen evolution reaction is taking place on 1 centimeter square area
and it is taking on let us say 10 centimeter square area. Since, it is i0 and of hydrogen
evolution and it is on the same metal surface and if temperature, pressure, the surface
condition of that metal if these are not changing, the only thing that is changing is the
area.
Then these two would be, have would have same values because, they cannot change this
is exchange current density which is basically the number of reaction cathodic or anodic
reaction per unit area when the system is equilibrium, in equilibrium and reversible
condition and that too non corroding situation. So, if I consider in this particular diagram
if I need to consider these area effect we will not be able to do it because, if it is 1
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centimeter square or 10 centimeter square, it will lie on the same point. And if it is the
same metal it is not an issue because, both the cases it will lie on the same point. But, if
let us say the situation arises when 1 centimeter square metal is connected to 10
centimeter square platinum or noble component, so then i0 hydrogen on metal and i0
hydrogen on platinum surface, they would be a different.
If it is so, this value would be greater than greater than this. Now whether it is on 1
centimeter square platinum surface or 10 centimeter square platinum surface both the
cases this value would remain same. So, then if I have this point to be my i0 of hydrogen
evolution on platinum surface. So then whether it is 1 centimeter square or 10 centimeter
square, it will lie on the same point and accordingly I have the new mix potential and
accordingly new corrosion current density. So, actually it should be here this point.
But as we have understood from this example that if we have a higher area of that noble
component then the corrosion rate of the active component increases enormously. But,
on this Evans diagram if we consider current density, I could see that whether it is 1
centimeter square or 10 centimeter square it does not matter the corrosion rate remains
same. So that means, it is missing something, this Evans diagram is missing something.
Now in order to tackle this if we consider current instead of current density, we would
see that this can be explained in the same by the same Evans diagram.
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Only change would be instead of current density, we will consider we will shift to
current. Now current density is I by A and current is I. Now, if it is 1 centimeter square,
1 centimeter square, so the i would be same as I by I magnitude wise. But, once it goes to
10 centimeter square, then i will not be equal to I magnitude wise because, i would be
always I by A, but i the small i would be I by A capital I by A, which is current by area.
But, when we have 10 centimeter then I would be equal to capital I would be equal to i
into 10.
So, then I could see that current value is changing. Now if I look at the Tafel equation,
this is beta general Tafel equation log i by i0. Now this i could be ia or ic, this is ia, ic, i0
would remain like this and that time this was a or c anodic or cathodic polarization. Now
this I can write it as beta log I by A I by I0 by A. I can write this. So, this can be
converted to log I by I0, capital I by I0, which is current. Now if I try to plot the current
instead of current density in the Evans diagram, we could see a difference.
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Now, let us say this is log I which is ampere or this is ampere instead of ampere per
centimeter square this is E in volt. This point let us say E0 M 2 plus, let us say 2 plus M
is this value this is i0 M on metal surface, it would have its own cathodic and anodic
polarization plot and let us say this is my E0 hydrogen evolution let us say this is 0 volt.
And now this point is i0 hydrogen on metal surface and here I am writing area, area as
centimeter square or 1 centimeter square area and this is also 1 centimeter square area.
Now, instead of i0 I right now capital I0 here also it should be capital I0.
Now, accordingly because the equation for the cathodic as well as anodic polarization
would be same as before only thing is I am converting small i with capital I. So, this will
also follow the same track this. So, this is my Icorr, this is my Ecorr. Now if we have
platinum of 1 centimeter square area; this would be I0 H2 on platinum surface and then
accordingly I have. So, now this is my new Ecorr, let us say 2 this is 1, this is 1 and
accordingly we have Icorr 1 sorry 2. Now interestingly if I try to see the relation between
these 2, since I am not changing the area of the metal they it would be magnitude wise, it
would be equal to i corr1 equal to this is i corr1 magnitude wise. This would be equal to i
corr2, since I am not changing the magnitude.
But now if I change the area of the platinum, this is let us say platinum of 10 centimeter
square area now i0 equal to capital I1 centimeter square 0 by A or I would say I0 by A0,
now if A0 equal to 1 centimeter square then I0 equal to capital I0 equal to 1 centimeter
square. So, this is equal to i0, but A 0 equal to 10 centimeter square then I 0 10
centimeter square on 10 centimeters here value would be i0 into 10 centimeter square and
this i0 is on 1 centimeter square area.
So, now, I could see that the I0 of hydrogen evolution on 10 centimeter square is
increasing, that means, the exchange current on 10 centimeter square area on platinum is
increasing. So, now this point would be I0 hydrogen on platinum of 10 centimeter
square. So it would have its own polarization and then you have to add this current
density because, this particular part is for 1 centimeter square. Now I have replaced this 1
centimeter square platinum area with the 10 centimeter square per platinum area. So, the
hydrogen evolution is taking place on 1 centimeter square area of metal and 10
centimeter square area of platinum.
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So, this current density and these current densities are to be added for getting the total
cathodic current densities. So, I just add them. So, only thing is it will be little bit closer
than what we had here because it is in the log scale. So, this is the part. So, now if I
extend it this is the new Ecorr case 3 and this current density is the Icorr or capital Icorr
case 3. And since the area of metal is not changing which is still remaining same 1
centimeter square is equal to icorr since equal to current density magnitude wise.
Remember this is magnitude wise, when I am writing this is magnitude. They are, their
units are different, in this case it is ampere and in this case it is ampere per centimeter
square.
Since, its area is not changing for metals, so that is what this value would be equal to
this. Now you see that: what is the change in the current density for anodic reaction.
Now in the beginning when there was no connection between active and noble metal my
ia was at this point and at this point I have ic equal to ia case 1. This particular region, this
particular part here again ic equal to ia situation 2 and here also I could see ic equal to ia
equal to icorr and in this case ic is basically, this current and these current densities
another current. Now here we have to add current because, now we are changing the
area.
Now once we could see this ia, this ia has gone up enormously, if I see the log scale
value. So, the corrosion rate why the corrosion rate of the active component increases, if
we increase the area of the noble component that can be explained with the help of Evans
diagram. Rather it is modified Evans diagram modified because, Evans diagram is
basically E versus log i, but here it is E versus log capital I.
Now, we could understand why the corrosion rate of that active component increases
when it is joined to a metal which is noble and of larger area. And, that explains the
effect of iron rivet dissolution, when the copper area is very large and the rivet area is
very small. And this particular situation is explained better by this Evans modified Evans
diagram. So, this is about case 3. Let us consider another case which is case IV.
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The case IV is about effect of presence of oxygen. Let us say in acid medium let us say
HCl, we have zinc piece and if it is aerated, so that means we have oxygen, that case we
see that the corrosion rate of zinc increases to a large extent as per our previous
understanding. It can be also explained with the help of Evans diagram. This is log i
ampere per centimeter square, I just missed 1 point here, the unit is ampere, but if we see
here the unit is ampere per centimeter square.
Now, coming to this, this is E, let us say this is zinc plus plus zinc E0 equal to 0.76 of
course, minus sign and this is H let us say this point is E0 H plus H2 equal to 0 volt is
involved. And oxygen in case of acid medium oxygen evolution reaction, oxygen
reduction is like this, this is oxygen reduction and the potential E0 equal to 1.227 volt, so
I put it as 1.227 volt equal to E0 oxygen. So, this is the Ecorr and this is the icorr when
there is no dissolve oxygen.
Now, once we have dissolved oxygen that this is i0 of dissolve oxygen on zinc and this is
i0 hydrogen evolution on zinc and this particular one is i0 zinc on zinc surface. So, it
would also have its own polarization, so this is my own polarization. It is cathodic
polarization and it has to move downwards and this has to move upwards because, the
mix potential should lie between these 2 extreme potentials. So, now, once it reaches to
this potential it is coming across another cathodic reaction. So, the total cathodic reaction
should be added up.
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So, we add up and then we extend this, this is my new corrosion rate. So, this is icorr
case 2 when we have oxygen presence and this particular potential is Ecorr 2 case 2
when we have oxygen. And remember when we have this, the hydrogen evolution
reaction on zinc surface is decreasing to a great extent because of depolarization effect.
So, this is the similar situation when we what we had in case of presence of Fe plus 3 in
the acid medium. So, let us stop here, we will continue our discussion.
There will be one more lecture which will be concluding lecture and there we will
consider one more major 2 case studies and then we will conclude for the corrosion 1.
And then we will see what the more understanding on corrosion in the phase 2, which is
the corrosion 2. Let us stop here, we will continue our discussion in the next lecture.
Thank you.
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Prof. Kallol Mondal
Lecture - 41
corrosion-III
So, we have come to the concluding lecture of this particular course which is Corrosion
I; today we have a lecture 41.
And till now what we have done in a last couple of lectures, we have try to understand
corrosion events of metals from consideration of by the by considering mixed potential
theory. And we have taken three examples, today we are have two three more examples
and then we will conclude our session and the rest of this there will be more on this
corrosion which will be covered in corrosion II later on.
Now, coming to this lecture 41, we will continue our discussion on case studies and
understanding the corrosion event with the use of mixed potential theory. So, what we
have done before? We have one of the case studies that a noble metal is galvanically
coupled to an active metal. And we saw that the because of the noble nature of that
galvanic coupled material the corrosion rate of active component increases. And then if
the area of the noble metal increases without increasing the area of the active component,
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the corrosion rate further increases because of this enhancement in the cathodic area as
compared to the anodic area.
So, now in this case studies, the case studies I case study I today’s case study rather I
would say a case study IV, here we will try to see the corrosion event when two active
components are coupled. And when they are coupled one of the components will become
cathode and another component will become anode and then the anodic component will
corrode and the cathodic component after joining these two active metals, the cathodic
part will get protected because of this enhance corrosion of the anodic part.
Now, let us say what I am pointing is, let us say iron and zinc they are both are both
corrode in HCl solution or rather they corrode heavily when they are not joined together.
Now in case of separate situation for example, in one beaker you have HCl where you
have a Fe and other beaker you have HCl and you have zinc rod zinc block. Both the
metals will corrode as per the explanation given with reference to mix potential theory. If
I try to draw Evans diagram for both the metals in HCl, will have the nature of the plot
will be like this.
I am just drawing one after another and this is one below another. So, log i this is also
log i this is E this is E volt, volt let say this is E0, hydrogen equal to 0 and let say this is
E0 zinc plus plus zinc which is equal to 0.76 volt.
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This is in case of zinc and let say this is for E0 H plus H2 equal to 0 in case of iron and
here it is E 0 Fe plus plus Fe equal to minus minus 0.44 volt; i0 of H simply I am writing
H plus because H 2 simply writing H 2 because this is I do exchange current density of
hydrogen reaction on zinc surface is a here. And then i0 zinc on zinc surface at this point,
now they will have their mix potential this is E corr and this is i corr of zinc and at this
point ic equal to ia.
Similarly in case of iron generally the exchange current density of hydrogen evolution
reaction is higher. So, this is i0 of hydrogen reaction on iron surface and it is almost on
the similar level this is i0 iron on iron surface they will have their own mix potential
when they are kept separately this case and this case. So, this is in case of this at this
point this is the point up icorr this is Ecorr and here we have ic equal to ia or i equal to ic.
So, at this point we have no net current, but the iron corrodes at a rate of ia which is equal
to icorr.
Now, interestingly if you see generally if you are plotting it on the same marking or the
same values I see that this corrosion rate of iron in HCl is little more than the zinc, but
zinc E0 is lower than E0 of iron now we have to join them. So, now, this is iron, this is
zinc, now we had putting it in HCl for the same concentration, now what happens? That
case you see in separately this is also active, this is also active and the cathodic reactions
here is H2 and similar reaction cathode reaction is happening here.
So, both the cathodic reactions are here and here the anodic reaction is and here it is zinc
plus plus. But when they are connected galvanically, then what happens to this Evans
diagram? That will tell us which one would corrode more and which one would corrode
less. Now, if I combine them.
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This is E0 zinc minus 0.76 volt this is E volt let say this is E0 plus plus Fe equal to my
0.44 which is minus volt and this where point is E0 H plus H2 equal to 0. Now this point
lies here, this point lies here. So, now, if I i0 H2 on zinc this is i0 zinc on zinc, I will shift
this point little bit so that this is the point. Now, if this is my point for iron which is
basically the E0 point, let us say it is this is i0 H2 on iron surface, this is i0 Fe on Fe
surface. So, they met at this point so I put it in a different colour, this is the point which
is i0 for hydrogen reaction on iron surface.
Now I am just marking those potential points or the E0 points, for individual half cells
reaction. As we have known from mixed potential theory that during polarization
whenever a reaction whether its a cathodic or anodic polarization experiences another
reduction reaction or oxidation reaction, they should be clubbed or they should be joined
or they should be added. In order to reach to the mixed potential where the net current
density should be 0 or total cathodic current density is equal to the total anodic current
density.
Now, this is one, this is hydrogen evolution reaction and polarization, cathodic
polarization for hydrogen reaction on zinc surface and this is the second hydrogen
evolution reaction on iron surface. So, these are two cathodic polarization lines and then
at each potential we have to add up those two current densities corresponding to this two
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polarization plots. And then we have to get a new polarization line so, this is let us say
this color I am putting green color.
So, this becomes my line which corresponds to ic equal to ic 1 plus ic c 2 so; that means,
this is for this one and this is for this one at each potential. For example, if I consider this
potential then this point indicates current density ic at this point and ic at this point. So,
this i c is equal to let us say this is A this is B. So, ic A plus ic B that is what this line has
been drawn; Similarly when this polarization line is extending, once it reaches to this
potential then again it is experiencing one more anodic reaction which is let us say this
one I am putting as 3, so and this was 4.
So, 4 and 3 they are two anodic reactions and when this four is reaching to the polarized
value of this potential, then it is experiencing iron oxidation reaction which is also
polarizing. So, from there, if we continue this line then here we have to add that part
also. So, if I add it again with a green color or let us say blue color so this is the added
part, this line this black line is the polarization line for zinc and this blue line is the
polarization line for iron polarization or anodic iron polarization plus zinc polarization
and here both are anodic.
And at any point let us say if I consider this potential, at that potential let us say if I
consider this potential and this value let us say ia k and this particular current density let
us say ia P. So, here this is ia total and this one is ic total also, this one also ic total equal
to ia ia k plus ia p this is for iron this is for zinc. So, now, now we could see that this line,
this one and this one these two wherever they are meeting that point indicates the new
mixed potential where ic total is equal to ia total. So, this is the point where they are
meeting.
Now, at this point ic total equal to ia total when they are combined. So, this plot is
basically when they are clubbed, they are joined iron and zinc are forming galvanic
couple. So, at this particular point let us see what are the current densities of iron
corrosion; iron current density for the anodic reaction of iron and the current density
corresponding to anodic reaction for zinc that can be easily found out. Since this is my
new Ecorr and this point is also icorr.
Now, if I draw a line, this becomes my Ecorr and then this point is basically ic for
hydrogen evolution on iron surface and this point is equal to ic of hydrogen on zinc
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surface. Similarly, since this particular two points this particular point is, cutting this
particular line and here it is cutting the black line corresponding to this line. So, that is
what they are our two current densities for cathodic polarization and similarly this point
is cuttings on the zinc anodic polarization lines. So, this is ia zinc and here also it is
cutting the iron polarization line. So, this becomes ia of iron. So, now if we combine
them so this combination of this and combination of this that would lead to the condition
which is ic total equal to ia total.
Now interestingly in the beginning when they were not connected, they were separately
immersed in HCl solution, we could see that the iron corrosion rate was this one. So, this
point is Ecorr for iron and this point is also icorr for iron before joining. So now, after
joining the corrosion rate of iron has gone to has reduced from this value to this value.
So that means the corrosion rate of iron has reduced when they are joined together.
And what happens to the corrosion rate of zinc? The corrosion rate of zinc has actually
increased when they are combined, the corrosion rate of zinc was at this point this is
icorr zinc when they were uncoupled and this was the value Ecorr when they were
uncoupled, but after coupling I could see that the corrosion rate of zinc has gone to. So,
the corrosion rate and this value at this point the ia is much higher than the ia what used
to be here before coupling. So, the corrosion rate of zinc has increased.
So, now interestingly one more information before coupling the corrosion rate that ic of
hydrogen evolution reaction on zinc surface was at this point and after coupling I could
see that hydrogen evolution reaction rate or ic on zinc surface has gone to this at this
point. So, I could see that corrosion rate of the sorry, not corrosion rate the cathodic
current density for the hydrogen evolution reaction has moved from this point to this
point.
So, the rate of hydrogen evolution has gone down, has decrease rather on zinc surface
whereas, if I could see the, what happens to the corrosion, what happens to the rate of
hydrogen evolution on iron surface. The iron surface it is here the hydrogen evolution
rate or ic on iron surface is at this point and before coupling hydrogen evolution rate or ic
on iron surface was at this point. So, I could see that the rate of hydrogen evolution has
increased on iron surface.
404
This is important observation; that means, the hydrogen evolution or hydrogen reaction
on zinc surface has gone down or has decrease has decreased whereas; hydrogen
evolution on the iron surface has increased. Or in other ways since hydrogen evolution is
the cathodic reaction that is taking place on both the surfaces I could see that the
hydrogen evolution of the cathode reaction is preferably taking place on iron surface
rather than zinc surface. And from the zinc surface I could see that the corrosion rate of
zinc has increased whereas, the corrosion rate of iron has decrease because of this
coupling.
So, as we have understood before that if we have preferable cathodic reaction on a

surface that surface becomes cathode and if we have preferably anodic reaction on some
surface that surface becomes cathode. So, here iron turns out to be cathode area since
preferably hydrogen evolution takes place on that an iron dissolution or iron dissolution
or the anodic reaction for iron has decreased to a great extent.
Remember this is in log scale log i scale; that means, that that decreases quite a lot
because it could be a of the order of 10 to the power 2 to 3 order scale so the cathode
area. So, iron becomes cathode and since zinc surface rate of hydrogen evolution has
decreased; that means the cathodic reaction is less on zinc surface so and zinc dissolution
has increased on the zinc surface. So, this becomes zinc becomes anodic area or it will
act as anode.
405
Exactly this similar situation happens when we have iron phase, this is iron and on top of
it if I put a zinc layer zinc layer, this is the red color is the zinc layer. So, until and unless
zinc is covering iron surface we have one single reaction which is zinc dissolution. But
the effect of zinc on the iron corrosion will take place whenever there is a opening. Let
us say this is the opening part, now this opening region is basically iron this is iron and
rest of this case is zinc.
Now zinc would act as anode and iron would act as cathode and in the environment this
reaction would take place since the environment is nearly neutral and this reaction would
take place on cathode since iron act as cathode and the anodic reaction would take place
on zinc so where zinc.
So, zinc dissolves and iron is protected because of this mechanism and that mechanism
can be easily understood from this diagram which is the Evans diagram for the combined
situation. This particular method of protecting iron surface we call it sacrificial anode in
the zinc becomes sacrificial anode and this is called sacrificial cathodic protection. So, as
by using sacrificial anode we are creating that iron surfaces cathode and then it is
basically that zinc is sacrificing itself in order to protect iron; we call this particular
method as galvanization. Galvanization is nothing, but the putting zinc plating or zinc
coating on iron surface, this since we have talked about sacrificial protection method. So,
there are cathodic protection, we call it cathodic protection.
And this cathodic protection works on the basis of sending negative current to the
cathode let us say if we have this E verses log i and if this is i0 for cathodic reaction. Let
us say this is the cathodic polarization this is anodic polarization, this is iron and this is
the potential which is the new potential or new mix potential and this is the icorr and
these are corresponding E0 values of 1 and 2.
Now, how can I decrease decrease in corrosion rate if I need to decrease I need to
decrease ia and this particular line is ia and this is ic. Now in order to do that if I go
downwards, now this is my new starting point corresponding to over voltage is 0. Now
as we go down; that means, if I put eta to be negative then I will go down, let us see if I
reach to this potential I could see and let me draw the corresponding two other lines.
406
For this case it is cathodic polarization, this case it is anodic depolarization, but since
these potentials are extreme. So, this new potential will arrive in between two potentials.
So, now, this particular point is let us say ic prime and this particular point is ia prime and
I if I keep this potential at this potential with this over negative overvoltage or the
cathodic overvoltage I could see that the corrosion rate, which was initially here before
polarization I can reach to the new current density of that iron dissolution at this point
ok.
So, it is decreasing corrosion rate of iron and interestingly during that I am sending this
extra negative current and then i applied is nothing, but ic minus ia and here ic is greater
than ia. So, that is the philosophy of cathodic protection and you can do it by using
sacrificial anode by zinc or you can have it by sending negative current to the iron
structure, which is to be protected cathodically from a DC power source, it is DC
because we have to keep this iron surface to be cathode all the time now in case of this in
case of sacrificial anode case.
So, if we have this is a soil this is a soil below the soil we have iron piece and zinc piece
they need to be connected, I can connect them I can connect them and then leave it like
this. So, in that case in this becomes my electrolyte this becomes my anode this becomes
my cathode as discussed before and the current ic will go from this to this, because if it
becomes cathode in case of galvanic corrosion this becomes positive terminal this
407
becomes negative terminal so the current which is i flows negative to the electron flow.
So, ic is going this way it means electron is coming from this end to this end electron
flow and once electron comes here. So, these electrons will be consumed for cathodic
reaction.
So, CR is cathodic reaction and the electron would be supplied by dissolution of zinc and
the current this current will flow from this direction. So, it will flow through this to this
and then coming back like this. So, whenever the current enters into electrolyte from a
metal that zone is the corrosion prone zone and whenever current enters into a metal
object that part is protected. So, that is what this part is protected like that way current
will flow like this all the time and then the entire surface of the metal is protected and by
that time during that time zinc surface is actually corroding.
So, this is sacrificial anode. So, another situation I could have where I have an iron piece
and this is an auxiliary anode, this is auxiliary anode which does not take part in any
reaction rather the anodic reactions take place on this auxiliary anode. So, now, if I
connected to external this is in below the soil and if I connect this end with a DC power
source. So, and this is the negative terminal this is positive terminal. So, electron is going
to iron and current is flowing to this auxiliary anode.
Now, since electron is coming here so; that means, I am sending preferably ic to the iron
surface. So, if I send ic to the preferably ic to the iron surface; that means, I am going
towards this; that means, I am going towards the anodic cathodic polarization on the iron
surface. So, this becomes cathode. So, cathodic reaction happens on those surface and
iron is protected.
So, this particular process is called impressed current cathodic protection. So, now, it
would see there are two ways to protect the method one by using sacrificial anode and
other by using auxiliary anode by using a DC power source, and why DC power source?
All the time with this iron should be maintained as cathode. So, that is what it is DC
power source.
In case of AC power source this terminal polarization changes. So, one time it becomes
negative another time it becomes positive. So, that time iron also become vulnerable to
dissolution. Now finally, I would just explain one more example and then will rap it off
for this particular session.
408
Now as we have informed that this is case 5 let us say, previously we could see that if we
have concentration polarization let us say. So, these are basically i max value i max 1, i
max 2, i max 3 and we have seen that with increase in velocity. So, this is if I increase
velocity, I could see that the i max increases, velocity increases i max increases. Now, if
we have two metals in one metal we have the polarization behavior is like this another
case the polarization behavior is like this. So; that means, in two cases I would have
different corrosion rate situation corrosion rate variation with velocity.
Now, we could see in this case of metal 1, this is this is metal 1 and this is metal 2 and
this is the polarization this is the corrosion potential and corrosion rate for metal 1. So,
this is icorr M1 and this is Ecorr metal1 and whereas, in case of metal 2 I am just
drawing the other lines, cathodic as well as anodic polarization line. In this case I could
see when the velocity is this much V1 let us say corresponding to V1, this is V2 this is
V3 when it is V1 I could see that it is cutting at this point.
Since that time this is the point where ia equal to ic; now if we increase the velocity the
new mixed potential is at this point where again ia equal to ic. Now, if you increase
velocity further at this particular V3, but I could see that it is not cutting in that
concentration polarization region, I am cutting the potential this cathodic potential
cathodic polarization line at this point where again ic equal to ia and ia is nothing, but the
corrosion rate.
409
So, if I plot in case of two metal this is corrosion rate, let us say I plot corrosion rate in
case of metal 1 whether its V1, V2 or V3 does not matter because its cutting all the time
on the activation polarization part of that cathodic polarization line. So, its corrosion rate
with velocity will be constant one, whether it is a V1, V2 or V3 now let say this is V1
this is V2 and this is V3 that all the time it is the same point same corrosion rate or icorr.
Now in case of metal 2 this is metal 1; in case metal 2 situation is little different now
when the velocity was V1 the corrosion rate was at this point when the velocity is V2 the
corrosion rate was at this point. And when the velocity has become V3 the corrosion rate
has gone to this point and beyond that if I increase velocity further it will all the time cut
the cathodic polarization line at this particular point. So, it will become constant. So,
now, in V1 the corrosion rate is the lowest.
And then or as per this diagram I could say that the corrosion rate is at this point now V2
to the corrosion rate has increased and then V3 still increased and then if we increase the
velocity it will be constant. So, now, the corrosion rate plot is like this, now in this case
even if you go for V4. So, it was like this. So, this is V1, V2, V3, V4, but in case of M2
the corrosion rate variation is like this since, they are cutting at different points
depending on the velocity increment as well as change in imax.
So, this is another behavior that can be explained with the help of mixed potential theory
finally, we have come to the end and as we have seen that we could understand corrosion
or the fundamentals of corrosion has got two parts, one is definitely Pourbaix diagram
another one is the kinetics part one is thermodynamic another kinematics.
And in case of thermodynamics we could see that we could select a areas in the potential
pH access where we could get passivity and where we could get corrosion or immune
zone. We have given some examples for example in case of iron and aluminium, if we
have a pH of around 9 in case of aluminium it dissolves even if aluminium is considered
to be highly passivating metal.
But in case of iron if we go beyond around 13 pH again there could be a possibility of

dissolution that is what in case of concrete the rebar the pH is maintain around 12.5 to 13
around that level. So, that is what the iron always remains in passivated condition, but if
we have aluminium there and if we increase that pH to 13 then aluminium definitely
would corrode.
410
So, that was one part, another part is this mixed potential theory as well as its associated
complications as well as the not complication I would say. The associated equations and
then finally, how we could analyze some of the corrosion event from the basis of Evans
diagram those are defected in this particular corrosion one.
So, that is it for corrosion I part and in corrosion II which will be taken up in future near
future I would say where we will take a passivation, you know the passivation happens
when we go for anodic polarization or either high anodic polarization. And we will try to
understand corrosion events on the basis of passivation and mixed potential theory, we
will also consider some of the practical events of corrosion like cavitation damage of
blades (Refer Time: 47:00), then we would also consider a high temperature corrosion
mainly oxidation part; so that is it.
Thank you.
411
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INDEX

Now, as I have mentioned in my introduction that corrosion is a very very important

(Refer Slide Time: 04:09)

For example, if some sections some in if for example, in Kanpur specially, in it is

(Refer Slide Time: 16:18)

(Refer Slide Time: 17:28)

Now, direct cost is basically US data infrastructure. Infrastructure when I am talking

(Refer Slide Time: 22:49)

Mechanisms of material degradation and the characteristics of the economically

Now, we would concentrate on electrochemical reactions not chemical reactions of

(Refer Slide Time: 00:46)

(Refer Slide Time: 02:48)

Now, if I consider materials this is coming under this. Alloying compositions it is

Now, corrosion part.

(Refer Slide Time: 11:26)

(Refer Slide Time: 25:32)

(Refer Slide Time: 30:03)

(Refer Slide Time: 30:56)

(Refer Slide Time: 31:25)

(Refer Slide Time: 31:53)

So, next topic is forms of corrosion.

(Refer Slide Time: 16:58)

Now, dealloying interestingly, if we have a brass 70-30; 70 percent copper and 30

Finally, fifth it is a time. Of course, if something is exposed for longer duration of

(Refer Slide Time: 00:23)

Now, when you talk about uniform corrosion, uniform corrosion

(Refer Slide Time: 11:33)

Now, let us analyze it.

(Refer Slide Time: 17:38)

Similarly, I have M 2, M 3. Let us say this becomes my M 3 component and M 3 can

Now, question is sometimes in order to design a component, we have to choose different

(Refer Slide Time: 00:32)

(Refer Slide Time: 14:40)

(Refer Slide Time: 18:24)

(Refer Slide Time: 20:51)

Here, I am talking about electrochemical activity, so that regions if we place that

(Refer Slide Time: 25:20)

(Refer Slide Time: 01:11)

(Refer Slide Time: 07:46)

(Refer Slide Time: 24:39)

In case of stress corrosion, if an object is component is under tensile stress and if it is

(Refer Slide Time: 00:33)

Now, when this particular thing is H plus plus 2 equal to H2;

(Refer Slide Time: 19:27)

Let us start 8th lecture.

(Refer Slide Time: 00:20)

(Refer Slide Time: 09:37)

(Refer Slide Time: 19:02)

(Refer Slide Time: 29:03)

Hello everyone, today we have our 9th lecture.

(Refer Slide Time: 00:20)

And here we would continue our discussion on Thermodynamics Aspects of Corrosion

So, this much is basically my free energy change.

Because then our heat of reaction would be H of c plus H of D minus H of A minus H of

(Refer Slide Time: 00:17)

(Refer Slide Time: 19:13)

Now, for example, if we have a P, V, T P, V, T system for example, if it is here, now we

(Refer Slide Time: 25:06)

So, if we try to see G as a function of P, T and number of components compositions, so

(Refer Slide Time: 00:19)

(Refer Slide Time: 10:08)

So, now whenever we have the P equal to 1 atmosphere we take it as a superscript 0 is

For example, in case of enthalpy we let us say aluminium in case of aluminium if we