Corrosion of platinum (Pt) in HCl What happens if we connect Zn and Pt in HCl solution?

Now if we place a piece of Pt in HCl, what will happen? 1. If Zn and Pt are not connected

There will be no reaction on Pt

Dissolution of Zn
Zn → Zn+2 +2e- Current flows

Pt does not corrode – does not
H2 evolution on Zn

take part in the electrochemical 2H+ + 2e- → H2
reaction

Pt is a noble metal
2. If Zn and Pt are connected • Zn Pt

Pt acts as a reference to calculate emf • • •
• • H2↑ • •
value for other metals
Current flows •• • •• • H2↑

Dissolution of Zn • • • •

Evolution of H2 on Pt

Thermodynamics of aqueous Corrosion:
The magnitude of the change in free energy (∆G) is a measure of the
tendency of the reaction.

Free energy changes provide the driving force and control the
spontaneous direction for a chemical reaction.
The more negative the value of ∆G the greater is the tendency for the
reaction to proceed.

Corrosion reactions being electrochemical in nature, by calculating
calculating the
free energy change it is possible to indicate whether or not the
corrosion occurs.
occurs.
Mg + H 2 O + 1
2 O2 = Mg (OH ) 2 , ∆G = −596 KJmol −1

Thermodynamics. However, cannot predict the rate of the corrosion
reaction (corrosion rate)
Cu + H 2 O + 1
2 O2 = Cu (OH ) 2 , ∆G = −119 KJmol −1

Au + 3
2 H 2 O + 3 4 O 2 = Au (OH ) 3 , ∆G = +66 KJmol −1

The free energy change accompanying a corrosion reaction can be Electrochemical Force or EMF series:
calculated as follows:

The emf series is an arrangement of
the standard (unit(unit activity or 1M
∆G = -nFE conditions) half-
half-cell potentials.

The standard emf series is very useful

E is known as the “electrochemical cell potential”
potential” in volts. to rank general resistance of metals to
corrosion, but more practical rankings

Since an electrochemical reaction has 2 electrodes (anode and must be developed for each electrolyte
cathode), each of this electrode has its own potential developed at the of interest.
electrode – electrolyte interface, called “half-
half-cell potential”
potential”.

Since it is impossible to measure the
absolute value of any half- half-cell
electrode potential, the values of half-
half-
E = Ea + Ec cell potentials found in the emf series
have been measured against a
reference electrode (H2).

Anodic reaction: Electrochemical cell

1.10 V
Zn → Zn+2 +2e-
e- e- e-

Cathodic reaction: e- e-

Cu+2 + 2e- → Cu

Overall reaction:

Zn + Cu+2 → Zn+2 + Cu

E = Ea + Ec = -(-0.76) + 0.34
= 1.10 V
This is also called Galvanic Cell
The direction of the reaction is reversed than the reduction reactions
shown in emf table. So the negative sign must included.
 example
Dependence of cell potential on concentration:
• One-half of an electrochemical cell consists of a pure nickel
electrode in a solution of Ni2+ ions; the other half is a

What happens to the cell potential when the concentration is not
cadmium electrode immersed in a Cd2+ solution.
standard (not 1M)?
Compute the cell potential at 25oC if the Cd2+ and Ni2+

We use the Nernst equation:
equation: concentrations are 0.5 and 10-3 M respectively.

0.0592
E = Eo + log Cion
n

Standard potential
E = new emf of half-cell
Eo = standard electrode potential, emf of half cell
n = number of electrons transferred (e.g. M → Mn+ + ne-)
Cion = molar concentration of ions

solution
First, assume the dilutions from 1M solutions will not affect the Kinetics of Corrosion:
order of the potentials of Ni and Cd in the standard electrode
potential series. Thus, Cd with more negative potential, -0.403 V
Thermodynamics tell whether the metal will corrode under the given
given
will be the anode of the Ni-Cd electrochemical cell and Ni will be conditions or not
cathode.

Kinetics of corrosion tell the rate at which corrosion will occur
occur
Next use Nernst equation

Understanding of the fundamental laws of electrochemical reaction
reaction
0.0592 kinetics is essential to develop more corrosion-
corrosion-resistant materials and
o
E=E + log Cion improve the methods of protection against corrosion.
n
Faraday’
Faraday’s Law:
EA = - {-0.403 V + (0.0592/2) log 0.5} = 0.4119 V

Electrochemical reactions either produce electrons (oxidation) or or
EC = -0.250 + (0.0592/2) log 10-3 } = - 0.3388 V
consume electrons (reduction).
Ecell = EA + EC = 0.4119 + (-0.3388) = 0.0731 V
The rate of electron flow to or from a reaction interface is a measure
measure of
***The cadmium is oxidized and nickel is reduced. reaction rate.

Electron flow is measured as current, I, in amperes.
The corrosion rate ,r, can also be obtained by dividing the above
above
equation by the surface area (dm2 – (decimeter)2) of the metal, A,
Ita
m = m ia
nF r = = (mdd: mg/dm2/day)
tA nF
Q: charge (C ),
F: Faraday’
Faraday’s number = 96,500 C/mol
n: number of electrons transferred,
The corrosion rate in mpy (mils per year or millimeters per year
m: mass of metal oxidised (corroded) (weight loss), mm/year ) is given by:
a or M:
M: atomic weight of metal (g/mol) (***some ref sign as M for atomic weight)
ia
I: current (A), r = 0.129
t: time (s) nD (mpy: mills per year)

Where D: density of the metal (g/cm3)

Ita
m nF
r = =
The corrosion rate depends on the following:
tA tA
Sometimes the uniform aqueous corrosion of a metal is
expressed in terms of a current density, i which is often
expressed in amperes per square centimeter. Now replacing I 1. Electrode potential of anode
by iA 2. Electrode potential of cathode
3. Presence of intermediary resistive material (passive
iAta layer) – (protective surface layer). Corrosion
m ia resistance like Ni, stainless steel, Ni alloy etc.
r = = nF =
tA tA nF 4. Areas of electrode surfaces
5. Temperature
 POLARISATION:

If equilibrium electrode is disturbed, a net current flows across

across its
surface displacing the potential in a direction and to an extent
High Temperature Corrosion depending on the direction and magnitude of the current.

• The products of high temperature corrosion can potentially
This shift in potential is called polarisation and its value, η, is called
be turned to the advantage of the engineer. overpotential.
overpotential.

• The formation of oxides on stainless steels, for example,
Polarization is the displacement of an electrode potential from its
can provide a protective layer preventing further atmospheric equilibrium value as a result of current flow.
attack, allowing for a material to be used for sustained
periods at both room and high temperature in hostile
If electrons are made available (excess of electrons) to the cathode,
cathode,
conditions. the potential becomes more negative,
negative, meaning the reaction is not fast
enough to accommodate all the available electrons. This is called
called
cathodic polarisation.
polarisation.

If there is a deficiency of electrons liberated by the anode, a positive

potential is produced and is called anodic polarisation (represents a
driving force for corrosion)

PASSIVITY OF METALS

Anodic polarisation
Passivity refers to the phenomenon of loss of chemical reactivity of a

With polarisation, metal in an environment where thermodynamically the reaction ought
ought to
the corrosion rate have occurred.
will increase (will
(+) follow this line)
A passive metal is one that is active in the emf series but which
which
corrodes a very low rate.
E

Passivity results from the formation of a thin, oxidised and protective

protective film
P
O If NO polarisation, on the metal surface
T the corrosion rate
E ηa (Overpotential) will increase faster
N
Important engineering alloys such as Al, Ti, Ni, Cr can be passivated
passivated by
horizontally. direct exposure to oxidising media or by anodic polarisation.
T polarisation.
I
A Ecorr
L
When a passive film is formed, the current density drops markedly
markedly due
to the resistance of the film and its effect as a barrier to corrosion.
corrosion.
(-)
Corrosion rate Passive metals and alloys– means very
corrosion resistant
 Polarization curve of a passive metal

Active – Passive Corrosion Behaviour

When the potential of a metal is anodically polarised, the currentcurrent Passive region:
required for the shift has the polarisation curve as shown in the
the Figure stable passive Active - Passive
film is formed transition: i decreases as
below. The metal is in the active – passive state.
the passive film starts to
form

Active
corrosion

source:

Transpassive
Passive region:
stable passive Active - Passive
Two types of Passivation exist:
film is formed transition: i decreases as
the passive film starts to
form 1. Spontaneous Passivation:
Passive

Some metals passivate in water if the pH is within ranges
corresponding to potential – independent domains of stability for
oxides or hydroxides (these domains appear in the Pourbaix
Active diagrams).
corrosion M→M2++2e-
Active

This passivation is due to the formation of thin protective oxide
oxide film.

This oxide film must be coherent and adherent to the metal surface
surface
source: and must not be impaired by impurities (in the metal or environment).
environment).

-At relatively low potential values, within the active region, the behavior is linear as it is for normal metals.
- With increasing potential, the current density suddenly decreases to a very low values that remains
independent of potential; this is termed the “passive” region.
- Finally even at higher potentials values, the current density again increases with potential in the
“transpassive” region.
 2. Anodic Passivation: Pourbaix Diagram (E – pH diagram)

For some metals and their alloys, passivation is both pH and potential
potential
a Pourbaix diagram, also known as a potential/pH diagram, maps
dependent. out possible stable (equilibrium) phases of an aqueous
electrochemical system.

In this case, the metal may corrode at low potentials but can passivate
passivate
by increasing its potential to a more positive value.
Pourbaix diagrams are charts based on thermodynamic calculations
which can be used to distinguish a corroding condition from a non
non-
corroding condition.

Pourbaix diagrams do not predict the kinetics of corrosion (rate of

corrosion)

The Pourbaix diagram of Fe in water is shown in the Figure below.

The dashed lines represent the practical region of stability of water to

oxidation or reduction.

2.0
1.6 Corrosion is
possible
Corrosion

1.2
Passivity
Potential, V

0.8
0.4 Corrosion
Corrosion is
0.0 possible, but likely
-0.4 to be stopped by
solid corrosion
-0.8 product
-1.2
Immunity
-1.6
-A Pourbaix diagram indicates regions of "Immunity", "Corrosion" and "Passivity”. 0 7 14 Corrosion is
-This diagram give a guide to the stability of a particular metal in a specific environment. impossible
-Immunity means that the metal is not attacked. pH
-corrosion shows that general attack will occur.
-Passivation occurs when the metal forms a stable coating of an oxide or other salt on its E – pH diagram for Zn in water
surface, the best example being the relative stability of Al because of the alumina layer formed
on its surface when exposed to air.

The possible regions of a Pourbaix diagram are:

1. Immunity: if the metal is thermodynamically stable

2. Passivity: if the soluble ion is thermodynamically most stable
3. Corrosion: if an insoluble corrosion product is most stable

Applications of Pourbaix diagrams

Formulation of corrosion control techniques ((cathodic protection

protection
(CP), anodic protection (AP), Inhibitors (chemical compound to slow
slow
down the corrosion rate)

Identify the possible corroding states of metal – media system

Limitations of Pourbaix diagrams

Is for pure metals not alloys

No kinetic information (rate of reaction) is given

Effect of velocity on the stability of passivity is not taken into
into account