Electrochemistry and Corrosion

Objective:
To understand and deal with corrosion through the basic principles of Electrochemistry

Dr. Baby Viswambharan

Dept. of Chemistry, NITT
 Introduction

Blue-Green Patina of copper (CuCO3+Cu(OH)2)

(Ag2S)Tarnish on silver

Rust on iron (Fe3O4 )

Good side :
Bio degradable materials
Computer chips can be replaced by
https://doi.org/10.1038/ncomms8170 cellulose nanofibril (CNF)
What is Corrosion?
Corrosion is the process of gradual and irreversible damage or deterioration of a material due to the
unwanted chemical or electro chemical interaction with its environment.
➢ Metals get oxidized
➢ Ceramic refractories get dissolved in molten materials
➢ Materials may undergo irradiation damage
➢ Polymers react with oxygen and degrade
An engineer must understand corrosion !
➢ Corrosion occurs only at the surface of the metal ➢ Waste is produced
➢ Machineries get damaged
➢ Due to corrosion, ➢ Structures get damaged
➢ Loss of useful properties of the metal and efficiency
➢ Decrease in production rate and high maintenance cost
➢ Product contamination
➢ Lost is more than the metal cost
➢ 2-3 billion dollars all over the world

Understand and deal with! Control and prevent corrosion!

 Learning outcome

➢ Understanding “Corrosion” through principles of electrochemistry

❖ Types of corrosion
➢ To introduce the basics principles of electrochemistry
❖ Cell emf
❖ Types of cell
❖ Prevention of corrosion

Referance: 1. Shashi Chawla, A Text book of Engineering Chemistry.

2. P.C. Jain, M. Jain, Engineering Chemistry.
3. P. Atkins, J.D. Paula, Physical Chemistry.
Why is Corrosion?

Ores: Metal in combined state Input Metal Natural tendency

Ores Ores Compounds
Ores
(Oxides, sulfides, carbonates) energy Excited state to loose energy

Metallurgy Corrosion when exposed

To environment

Ore of iron :
Oxides, sufides Rusting of iron :
Fe2O3 formation

Corrosion is a Spontaneous process of “Reverse of extraction of metals”

 Corrosion
Chemical or Dry corrosion Electrochemical or
Direct Chemical attack Wet corrosion
(By environment) Electro chemical attack

Direct chemical action on metal Formation of galvanic cell and

➢Absence of water electron flow
➢Environment/atmospheric gases
➢Anhydrous inorganic liquids.
A. Galvanic or bimetallic
B. Differential aeration or
A. Oxidation Corrosion
Concentration cell corrosion
B. Corrosion by other gases
C. Liquid metal corrosion
 Chemical or Dry corrosion
A. Oxidation Corrosion
➢ Direct action of Oxygen & In the absence of water
➢ At low temperature alkali and alkaline earth metals get oxidized
➢ Other metals except Ag, Au & Pt gets oxidized at high temperature

➢ Oxidation occurs at the surface (Metal oxide scale )

➢ Scale prevents further corrosion : Act as barrier

➢ Scale allow further corrosion:

▪ Both oxygen and metal can migrate
▪ Smaller metal atoms migrates rapidly to the surface than inward migration of larger oxide ion
Nature of the metal oxide (scale) decides further corrosion
Pilling – Bedworth’s rule: An oxide is protective if the volume of the oxide is at-least as great as the volume of the
metal from which the metal formed
Smaller the specific volume ratio (RPB) of metal
oxide to metal, greater is the oxidation corrosion.

➢ RPB < 1, Tensile stresses in oxide film, thin film can crack (Non Protective)
➢ RPB > 1, (1~2), Compressive stresses in oxide film → uniformly cover metal surface and is protective
➢ RPB >> 1, Too much compressive stresses in oxide film → oxide cracks

Pilling-Bedworth ratio for some oxides

K2O Na2O MgO Al2O3 NiO Cu2O Cr2O3 Fe2O3
0.41 0.58 0.79 1.38 1.60 1.71 2.03 2.16

1. Some metals form Stable oxides (Protective), Al, Sn, Pb, Cu

2. Unstable or Reversible oxide formation (Non-Corrosive), Metal Metal oxide, Ag, Au, Pt
3. Formation of Volatile oxide Leads to extensive corrosion Mo ==> MoO 3
4. Porous oxide formation leads to rapid corrosion, Fe2O, Fe2O3
Oxygen diffuse through the porous metal oxide bringing further corrosion.
B .Corrosion by other gases (SO2, CO2, Cl2, H2S, F2)
➢ Extend of corrosion depends on the affinity of the metal towards gas
➢ Degree of attach depends on protective or non protective layer formed

➢ Ag forms non-porous protective AgCl layer

Corrosion affects
➢ Tin (Sn) forms porous SnCl4 (highly volatile),→ corrode the metal
• Suction pumps
• Drinking water pipes
• Sewage pipes

➢ H2S gas leads steel to form porous FeS scale→ affect petroleum industry
C. Liquid metal corrosion
➢ Chemical action of flowing liquid metal on solid metal or alloy at high temperature
➢ Corrosion cause weakening solid metal (Components of the Machinery)

❖ Dissolution of solid metal by liquid metal

❖ Internal penetration of the liquid metal to solid

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 Corrosion
Direct Chemical attack Electro chemical attack
(By environment) Electrochemical or
Chemical or Dry corrosion Wet corrosion

Direct chemical action on metal Formation of galvanic cell and

➢Environment/atmospheric gases electron flow
(O2, Halogen, N2, H2S, SO2)
➢Anhydrous inorganic liquids.
A. Galvanic or bimetallic
B. Differential aeration or
A. Oxidation Corrosion
Concentration cell corrosion
B. Corrosion by other gases
C. Liquid metal corrosion
➢ Most common than
dry corrosion
 Wet corrosion or Electrochemical Corrosion
➢ Mostly takes place under wet or moist condition.
➢ Formation of a short circuit cell (Cathodic and Anodic part)

Two type of corrosion

A. Galvanic or bimetallic: B. Differential aeration or Concentration cell
corrosion:
Two dissimilar metals/alloys are either
A conducting liquid is in contact with the metal
immersed or dipped partially in a solution

Basic principles of Electrochemistry

Mechanism of corrosion
Wet Corrosion Type of corrosion
Prevention of corrosion
 Electrochemistry

➢ Investigation of the properties of ionic conductors and the electric circuit involving ionic conductors
➢ Investigation of the phenomena occurring during the passage of an electric current through a conducting medium

➢ Single electrodes (metallic/liquid/gas/Alloy)

➢ Reduction potential
➢ Cell and Different Type of Cell
➢ Cell EMF- its measurement and applications
 Single electrode or half cell and its Potential (Eel) ❖ Specified for the reduction reaction
➢ The metal dipped in its ion solution represent a single electrode
➢ The electrode is represented as M Mn+(Concentration)

Zinc metal

Zn Zn2+(Concentration)

E(Zn2+  Zn) = -0.76 V

➢ At the interface, Oxidation or Reduction can occurs

➢ Double layer formation leads to Potential at the interface of the metal and the solution (Electrode potential -Eel )

Electrode potential (Eel) is the tendency to lose or gain electrons

❖ Eel depends on the concentration of the ion in solution (specify the concentration )
• Metal-metal ion electrode
• Gas electrode
Types of electrode • Metal – Metal insoluble salt electrode, (Ag-AgCl , Hg-Hg2Cl2)
• Membrane electrode
Thermodynamics of Electrode potential : Eel and Change in Free energy (G )
𝑪𝒐𝒏𝒔𝒊𝒅𝒆𝒓 𝒕𝒉𝒆 𝒓𝒆𝒗𝒆𝒓𝒔𝒊𝒃𝒍𝒆 electrode 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝑴𝒏+ 𝒂𝒒 + 𝒏𝒆 ⇋ 𝑴(𝒔)
Where,
Electrical work done by the electrode, W = q. Eel ❖ q = nF is the charge moved through the potential difference E.
❖ n is the number of electrons transferred
Thus, w = n F Eel ❖ F is the Faraday = 96500C
𝑬𝒍𝒆𝒄𝒕𝒓𝒊𝒄𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚 (Eel) 𝒊𝒔 𝒑𝒓𝒐𝒅𝒖𝒄𝒆𝒅 𝒂𝒕 𝒕𝒉𝒆 𝒆𝒙𝒑𝒆𝒏𝒄𝒆 𝒐𝒇 𝒅𝒆𝒄𝒓𝒆𝒂𝒔𝒆 𝒊𝒏 F𝒓𝒆𝒆 𝒆𝒏𝒆𝒓𝒈𝒚 (-G ) 𝒅𝒖𝒓𝒊𝒏𝒈
𝒕𝒉𝒆 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏:- By Helmholtz’s
-G = n F Eel for a reversible electrode.
𝑷𝒓𝒐𝒅𝒖𝒄𝒕
𝑷𝒓𝒐𝒅𝒖𝒄𝒕 𝑹𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝑸𝒖𝒐𝒕𝒊𝒆𝒏𝒕, 𝑸=
−∆𝑮 = −∆𝑮° − 𝑹𝑻𝒍𝒏 𝑸 = −∆𝑮° − 𝑹𝑻𝒍𝒏 ---(1) 𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕
𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕
𝑴 −∆𝑮𝟎 = 𝒏𝑭𝑬𝟎𝒆𝒍
𝒏𝑭𝑬𝒆𝒍 = 𝒏𝑭𝑬𝟎𝒆𝒍 − 𝑹𝑻𝒍𝒏 ---(2) “Standard electrode potential E0
𝑴𝒏+ 𝒂𝒒

𝟐.𝟑𝟎𝟑 𝑹𝑻 𝟏
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 − 𝒍𝒐𝒈 𝒏+ ---(3) [M] = 1
𝒏𝑭 𝑴 𝒂𝒒
The Nernst’s Equation
𝟐.𝟑𝟎𝟑 𝑹𝑻
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 + 𝒍𝒐𝒈[𝑴𝒏+ 𝒂𝒒 ] ---(4)
𝒏𝑭

𝟎.𝟎𝟓𝟗𝟏
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 + 𝒍𝒐𝒈[𝑴𝒏+ 𝒂𝒒 ] ---(5) at 298K
𝒏
The cell, its Representation and its emf

Zn  Zn2+(Conc.) Cu Cu2+(Conc.)

Zn → Zn2+ + 2e- Cu2+ + 2e- → Cu

Overall (Redox) reaction
Zn + Cu2+→ Cu + Zn2+
Potential Difference or EMF (emf) of a cell
Cathode ➢ EMF of a cell is the algebraic sum of the single electrode
Anode
potentials provided the proper sign has to be taken care
➢ The magnitude of the potential difference is a measure of the
tendency of the electrode to undergo oxidation or reduction

Ecell = Ecathode - Eanode

Ecell = Eright – Eleft

E0cell = 0.34 – (-0.76)

= 1.1 V
“Standard electrode potential E0 of a metal at 298K is the potential developed at an electrode when
the metal is dipped in one molar solution of its own ion”

Determining E0 for a half cell or single electrode:

By constructing a galvanic cell with a reference electrode

Reference electrode
Characteristics of a reference electrode
➢ An electrode half cell with a known half cell potential Eref
➢ The value of Eref will not change with the concentration of
the analyte solution (Eref is constant throughout)
➢ Always function at left hand side of the potentiometric cell

Some Reference electrode are

1. Standard Hydrogen electrode , (for SHE, E0 = 0)
2. Standard Silver-Silver chloride electrode (Ag-AgCl), ( E0 =0.197V)
3. Saturated Calomel Electrode (Hg-Hg2Cl2) (for SCE, E0 = 0.244V)
https://www.sciencedirect.com/topics/chemistry/reference-electrode
1. Standard Hydrogen electrode (SHE) ➢ Gas electrode: Consists of a gas in contact with a solution containing the
ions derivable from the gas (e.g. Cl2/Cl-, O2 /OH-, H+/ H2 etc.)
➢ SHE is an example of Gas electrode ➢ The potential of the gas electrode depends upon the concentration of its
ions in the solution and the pressure of a gas
Pt, H2(1 atm) H+(1 M)

Hydrogen gas (1 atm. pressure) is in contact with the H+ ions (1 Molar)

Non-consumable (inert) platinum electrode is used

for electrical contact
E0 for SHE is assigned as zero at 295K

SHE act as anode, the electrode reaction is oxidation

H2(g)→ 2H+ + 2e-

SHE act as cathode, the electrode reaction is

reduction(Hydrogen gas evolution)

2H+ + 2e-→H2(g)
Electrochemical series
(activity series)

➢ E0 of any electrode can

be measured using
SHE as reference
electrode

➢ These electrodes can

be arranged in the
increasing/decreasing
order of reduction
potentials
Importance of electrochemical series
1. Predicting the reducing and oxidizing power of a metal
2. In metallurgy
3. Constructing a cell and Calculating Standard emf of the cell
4. Predicting whether a metal can liberate Hydrogen from acid solution
5. Predicting the feasibility of a reaction

Practical difficulty in using Standard Hydrogen electrode (SHE)

2. Calomel Electrode (CE)
➢ Hg(l) in contact with saturated solution of Hg+ ion (usually Hg2Cl2(s)-calomel).
Electrolyte is KCl with a known concentration Hg Hg Cl
(l) 2 2 (s) (sat’d), KCl(xM) 
Electrode junction is through a Vycor plug.
Electrode potential depends on
➢ Temperature (cut off is 60 ℃), Nernst equation
➢ The chloride ion concentration [Cl-] in KCl
➢ 0.1M, E = 0.335V; Vycor plug
➢ 3.5M, E = 0.25V,
➢ Saturated, E = 0.244 V (Saturated Calomel Electrode is widely used
If the electrode undergoes reduction, If the electrode undergoes oxidation,
𝐻𝑔22+ 𝑎𝑞 + 2𝑒 − ⇌ 2𝐻𝑔 𝑙 2𝐻𝑔 𝑙 ⇌ 𝐻𝑔22+ 𝑎𝑞 + 2𝑒 −

𝐻𝑔2 𝐶𝑙2 𝑠 ⇌ 𝐻𝑔22+ 𝑎𝑞 + 2𝐶𝑙 − [Cl-] increases in solution 𝐻𝑔22+ 𝑎𝑞 + 2𝐶𝑙 − ⇌ 𝐻𝑔2 𝐶𝑙2 𝑠 [Cl-] decreases in solution

+
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑆𝐶𝐸 , 𝐻𝑔2 𝐶𝑙2 𝑠 ⇌ 𝐻𝑔22 𝑎𝑞 + 2𝐶𝑙 − Electrode is reversible with respect to Cl- ions

0 0.0591
𝑁𝑒𝑟𝑛𝑠𝑡 𝑒𝑞𝑛 𝐸 = 𝐸𝐻𝑔2𝐶𝑙2/𝐻𝑔 − 𝑙𝑜𝑔 𝑎𝐶𝑙− 2
2
0.0591
= +0.268 𝑉 − 𝑙𝑜𝑔 𝑎𝐶𝑙− 2
2
3. Silver-Silver chloride (Ag/AgCl) Electrode
➢ Ag wire coated with AgCl paste in contact with saturated KCl solution.
➢ Most widely used electrode system Ag AgCl
(s) , KCl
(sat’d) (Saturated) 
➢ [Cl-] in KCl; 3.5M:- E = 0.205,
saturated:- E = 0.194 V
The electrode reaction is AgCl(sat’d), + 𝑒− ⇌ 𝐴𝑔(𝑠) + 𝐶𝑙−
𝑵𝒆𝒓𝒏𝒔𝒕 𝒆𝒒𝒏,
𝑬 = 𝑬𝟎𝑨𝒈𝑪𝒍/𝑨𝒈 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈(𝒂𝑪𝒍− ) = +𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈(𝒂𝑪𝒍− )
Calculate the potential of silver electrode in contact with a 0.01 M sodium chloride solution

𝑵𝒆𝒓𝒏𝒔𝒕 𝒆𝒒𝒏, 𝑬 = 𝑬𝟎𝑨𝒈𝑪𝒍/𝑨𝒈 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈(𝒂𝑪𝒍− )

Vycor plug
𝑬 = 𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 𝟎. 𝟎𝟏
𝑬 = 𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 ∗ −𝟐 = 0.199 + 0.1182 = 0.3172 V
Determining E0 for a half cell or single electrode:
By constructing a galvanic cell with a reference electrode

Reference electrode Indicator electrode

E0 With various reference electrode

➢ The potential relative to a standard hydrogen electrode is shown in blue,

➢ The potential relative to a saturated silver/silver chloride electrode is shown in red,
➢ And the potential relative to a saturated calomel electrode is shown in green.
Problem 1
Calculate the potential of the cell consisting of a silver electrode dipping in a silver nitrate solution with [Ag+] of
0.0100 M and a SCE reference electrode. E° (Ag+ /Ag) = 0.80V

Reference electrode SCE Ag+ (aq.) Ag(s) Indicator electrode

Ecell = EInd – Eref T h e h a lf c e ll r e a c tio n

+
Ecell = EInd – SCE A g A g
1
𝐸𝐼𝑛𝑑𝑖 = E° (Ag+ /Ag) − 0.0591 log
[Ag+]

1
𝐸𝑐𝑒𝑙𝑙 = E° (Ag+ /Ag) − 0.0591 log − 𝐸𝑆𝐶𝐸
[Ag+]

1
𝐸𝑐𝑒𝑙𝑙 = 0.80 𝑉 − 0.0591 log − 0.244 𝑉
[0.01 M]

Ecell = 0.4398 V
Applications of measuring Cell emf
1. Determining equilibrium constant of a reaction
The Van’t Hoff reaction isotherm equates decreasing free energy with equilibrium constant

−∆𝑮° = 𝑹𝑻 𝒍𝒏 𝑲 = 𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍

𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍
𝑻𝒉𝒆𝒓𝒆𝒇𝒐𝒓𝒆, 𝒍𝒏 K =
𝑹𝑻
If 𝑬𝟎𝒄𝒆𝒍𝒍 > 0, Then K >1 and equilibrium favors products
If 𝑬𝟎𝒄𝒆𝒍𝒍 < 0, Then K < 1 and equilibrium favors reactant

Problem 2
For a cell reaction: Ni(s)Ni2+ (aq)Ag+ (aq) Ag(s)
Write the cell reactions and calculate the equilibrium constant at 25 ℃, E° (Ni2+ /Ni) = -0.25V; E° (Ag+ /Ag) = 0.80V

At anode, At cathode E0cell = E0Right – E0Left

Ag+ + e 𝟐 × 𝟗𝟔𝟓𝟎𝟎 𝑪 × 𝟏. 𝟎𝟓 𝑽
Ni Ni2+ + 2e Ag E0cell = 0.80 – (-0.25) 𝒍𝒏 K =
8.314 J𝒎𝒐𝒍−𝟏 𝑲−𝟏 × 𝟐𝟗𝟖 𝑲
The cell reaction = 1.05V
𝑪×𝑽
= 𝟖𝟏 = 81 moles
𝑪×𝑽×𝒎𝒐𝒍−𝟏 𝑲−𝟏 ×𝑲
Ni + 2Ag +
Ni 2+
+ 2Ag 𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍
𝒍𝒏 K = K = 1.479x1035 𝒎𝒐𝒍
𝑹𝑻
2. Determining solubility product constant MX (s) ⇋ M+ (aq.) + X- (aq.)
The solubility product of the salt is given by Ksp = [M+ ][X-], for very dilute solution
The solubility product of a sparingly soluble salt is the equilibrium constant.
➢ Consider the dissolution of any sparingly soluble salt MX (AgCl, Hg2Cl2)

For the above reaction, the Cell can be represented by

M  M+X-(sat. soln.)MX (S) M
L.H. E, R.H.E.
M ⇋ M+ (aq.) + e- MX (S) + e- ⇋ M + X-
Overall reaction is given by MX (s) ⇋ M+ (aq.) + X- (aq.)
𝒂𝒏𝒅 𝑬𝟎𝒄𝒆𝒍𝒍 = E R- EL
Reduction potential can get from electrochemical series
𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍
𝒍og Ksp =
𝟐. 𝟑𝟎𝟑𝑹𝑻

➢ Voltages are relatively easy to measure accurately using a voltmeter,

➢ Electrochemical methods provide a convenient way to determine the concentrations of very dilute solutions and the solubil
ity products (Ksp) of sparingly soluble substances
Problem 3: Calculate the solubility product of a sparingly soluble salt AgBr in water at 25 oC from the cell.
Ag  Ag+Br-(sat. soln.)  AgBr (S) Ag.

Provided the standard potentials 𝑬𝟎𝑨𝒈𝑩𝒓/𝑨𝒈 = 0.07V and 𝑬𝟎𝑨𝒈+/𝑨𝒈 = 0.80V

AgBr(S) ⇋ Ag+( aq.)+ Br- (aq.)

R.H. E, Ag Br(S) + 2e- ⇋ Br- (aq.) + Ag(S) 𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍

𝒍og Ksp =
L.H. E, Ag(s) ⇋ Ag+(aq.) + e- 𝟐. 𝟑𝟎𝟑𝑹𝑻
𝑬 = 𝑬𝑹 − 𝑬𝑳 = 0.80 - 0.07 = 0.73V

𝑬𝟎𝒄𝒆𝒍𝒍 𝟎.𝟕𝟑
𝒍og Ksp = =
𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏

Ksp = ?????
3. Determining pH
The potential of a hydrogen electrode (working electrode) in contact with the solution of hydrogen ion

PtH2(1 atm)  H+(unknown concentration)

The reaction involved is H+ + e- ⇋ ½ H2 (1 atm)
𝟎.𝟎𝟓𝟗𝟏 𝟏
Nernst equation corresponding to the equation is 𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 − 𝒍𝒐𝒈 + at 298 K 𝑬𝟎𝒆𝒍 = 0
𝒏 [𝑯 ]
+
𝑬𝒆𝒍 = 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈[𝑯 ] = − 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯

➢ The potential of a hydrogen electrode depends on the hydrogen ion concentration (pH)

Combine hydrogen electrode with a reference electrode, Eg SCE PtH2(1 atm)  H+(unknown conc.)   SCE
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑹 − 𝑬𝑳 = 𝟎. 𝟐𝟒𝟒 − (−𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯)

= 𝟎. 𝟐𝟒𝟒 + 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯)
𝑬𝒄𝒆𝒍𝒍−𝟎.𝟐𝟒𝟒
pH =
𝟎.𝟎𝟓𝟗𝟏
Calculate the potential of a hydrogen electrode when connected with a standard calomel electrode is measured to be +0.715 V.
Calculate the pH of the solution used in hydrogen electrode
𝑬−𝟎.𝟐𝟒𝟒 𝟎.𝟕𝟏𝟓−𝟎.𝟐𝟒𝟒 𝟎.𝟒𝟕𝟐𝟖
pH = = = =𝟖
𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏
 Types of Cell

Electrochemical cell Electrolytic cell

(Potential is drawn from the cell) (Potential is applied externally)

Concentration cell
Chemical cell Electrical energy through mass transfer of ions
Electrical energy (emf) through chemical reaction
Two different electrodes and a common ion in electrolyte

With Transference (Transport) Without Transference (Transport)

The electrode is reversible with one of the ion in electrolyte ➢ When electrolytes in two half cell are not in
➢ Half cells are in direct contact (no liquid junction) direct contact (connected indirectly using salt
➢ Ionic transport between half cells bridge)
Zn H2SO4 (aq.) Cu
➢ No direct ionic transport from one half cell to
❖ When electrolytes of the two half cells are different,
mechanical mixing is prevented using membrane another
❖ An Ag-AgCl electrode is immersed in a hydrogen electrode PtH2(g)HCl(aq.)  AgCl(s) Ag
Zn ZnSO4(aq.) CuSO4 (aq.)  Cu
Pt, H2 (1 atm)  HCl (M)  KCl (M)  AgCl (s)  Ag
H+ X
H+ Cl-
Cl- X
 Concentration cell

➢ Electrodes/Electrolytes of similar material with a deference in concentration

➢ Emf is drawn from concentration difference in two half cell (from mass transfer between one half-cell to
another)

Electrolyte Conc. cell

Electrode conc. cell
Two half cell with same electrolyte but with
Electrodes are made up of two different composition of
different concentration
same material
1. With two different hydrogen electrodes are connected
2. Alloy electrodes 1.Without Transport(Transference)
2. With Transport(Transferance)
Electrode concentration cell: Two electrodes of different concentration are dipped in a same solution
Gas concentration cell: Connecting two hydrogen electrodes with different partial pressures (P) of hydrogen gas
dipped in solution containing H+ ions
➢ Emf depends on the pressure of hydrogen gas pass through

L.H. E, PtH2(P1)  HCl H2(P2)  Pt R.H.E.

H2(P1) ⇋ 2H+ + 2e- 2H+ + 2e- ⇋ H2(P2)
Overall process H2(P1) ⇋ H2(P2)
➢ Emf is independent of concentration electrolyte
Electrode potential for LHS and RHS at 298K
𝟎. 𝟎𝟓𝟗𝟏 𝑷𝟏 𝟎.𝟎𝟓𝟗𝟏 𝑷𝟐
𝟎
𝑬𝑳 = 𝑬 𝒆𝒍 − 𝒍𝒐𝒈 𝑬𝑹 = 𝑬𝟎𝒆𝒍 − 𝒍𝒐𝒈 +
+ 𝒏 𝑯
𝒏 𝑯
Always reduction potential and subtract
𝑷𝟐
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑹 − 𝑬𝑳 = −𝟎. 𝟎𝟐𝟗𝟓𝟓 𝒍𝒐𝒈 ---at 298K
𝑷𝟏

𝑷𝟏 ➢ P2 < P1, Ecell is positive and spontaneous

= 𝟎. 𝟎𝟐𝟗𝟓𝟓 𝒍𝒐𝒈 at 298K
𝑷𝟐 ➢ Equivalent to expansion of H2 gas
➢ EMF is independent of hydrogen ion concentration
Electrode concentration cell conti…
➢ Two electrodes of different concentration are dipped in a same solution
Alloy Electrode
Hg-Pb (C1)  PbSO4(Sol.) Hg-Pb (C2)

𝑪𝟐 𝑪𝟏
𝑬𝒄𝒆𝒍𝒍 = −𝟎. 𝟎𝟐𝟗𝟓𝟓 𝒍𝒐𝒈 = 𝟎. 𝟎𝟐𝟗𝟓𝟓 𝒍𝒐𝒈
𝑪𝟏 𝑪𝟐

➢ C2 < C1, Ecell is positive,

➢ lead will spontaneously flow from higher amalgam concentration to to lower concentration
Electrolyte concentration cell: Two electrolytes of different concentration are connected
Classified in to two
1. Concentration cell without transport (Transference-w.o.t) 2. Concentration cell with transference(Transport)
1. Concentration cell without transference (Transport)-w.o.t. :
➢ Electrolytes in two half cell are not in direct contact (Connected through a salt bridge or porous membrane)
➢ Ion transport from one half cell to another will not take place directly
H+(C1) X H+(C2)
Zn2+(C1) X Zn2+(C2)
PtH H +(C ) H+(C ) H
2(1atm)  Pt
ZnZn2+ (C1) Zn2+ (C2) Zn
2(1atm) 1 2
L.H. E, R.H.E,
Zn ⇋ Zn (C1) + 2e-
2+
Zn2+(C2) + 2e- ⇋ Zn
Overall process for 1 faraday of electricity
Zn2+ (C2) ⇋ Zn2+ (C1),
Transfer of one mole of Zn2+ (C2) to Zn2+ (C1)
𝟐.𝟑𝟎𝟑 𝑹𝑻 𝟏
𝑬𝑳 = 𝑬𝟎𝒆𝒍 − 𝒍𝒐𝒈 𝑬𝑹 = 𝑬𝟎𝒆𝒍 −
𝟐.𝟑𝟎𝟑 𝑹𝑻
𝒍𝒐𝒈
𝟏
𝒏𝑭 𝒁𝒏𝟐+
𝑪𝟏 𝒏𝑭 𝒁𝒏𝟐+
𝑪𝟐
𝟐. 𝟑𝟎𝟑 𝑹𝑻 𝟐.𝟑𝟎𝟑 𝑹𝑻
= 𝑬𝟎𝒆𝒍 + 𝒍𝒐𝒈 𝒁𝒏𝟐+ = 𝑬𝟎𝒆𝒍 + 𝒍𝒐𝒈 𝒁𝒏𝟐+
𝒏𝑭 𝑪𝟏
𝒏𝑭 𝑪𝟐
Overall process
𝟐. 𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 ➢ C2 > C1, Ecell is positive
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑹 − 𝑬𝑳 = 𝒍𝒐𝒈
𝒏𝑭 𝑪𝟏
Question 3 : Calculate the EMF of the concentration cell consisting of zinc electrodes, one immersed in a solution of 0.01
molality and other in a solution of 0.1 at 25 oC.
Question 4: Write the half cell reaction, overall cell reaction, Nernst equation for R.H.S, L.H.S
and for the given cell
PtH2(1atm) H+(C1) H+(C2) H2(1atm)  Pt

Question 5: Write the half cell reaction, overall cell reaction, Nernst equation for R.H.S, L.H.S
and for the given cell

Pt H2(1atm)  H+(C1) AgCl(s) Ag Ag AgCl(s) H+(C2) H2(1atm)  Pt

H+ X
X Cl-

𝑪𝟐
𝑬 𝒘. 𝒐. 𝒕 𝟎. 𝟎𝟓𝟗𝟏𝒍𝒐𝒈
= 𝑪𝟏
2. Concentration Cell with Transference Pt  H2 (1 atm)  HCl(C1 M)  HCl C2 M) H2 (1 atm)  Pt

➢ The electrolytes in two half cell are in direct contact

➢ Mechanical mixing can be avoided by membrane
➢ Ion transport from one half cell to another will take place

➢ The electrical circuit is completed by movement of ions

through the solutions

▪ At junctions:
▪ H + ions moves faster than Cl- ions
▪ This mobility difference creates an additional potential
called Liquid Junction Potential (LJP), ELj in mV

➢ LJP depends on the relative mobilities of ions present in the solution

2. Concentration Cell with Transference cont.. Pt  H2 (1 atm)  HCl(C1 M)  HCl C2 M) H2 (1 atm)  Pt

LJP depends on the relative mobilities of ions present in the solution

Faradays 1st Law: Amount of electricity passed through a solution is

proportional to the number of ion discharged at an electrode
➢The number of ion discharged at the electrode depends on
the mobility (speed) of that ion.

The quantity of electricity that passes through the solution  Sum of the mobilities of the ion
The quantity of electricity that carried by a particular ion  Mobility of a particular ion
Fraction of total current carried by each ion is called transport number (t) of that ion
If u+ is the speed of cation and u- is the speed of an anion .
𝐂𝐮𝐫𝐫𝐞𝐧𝐭 𝐜𝐚𝐫𝐫𝐢𝐞𝐝 𝐛𝐲 𝐂𝐚𝐭𝐢𝐨𝐧 u+
transport number of cation (t+) = =
𝐓𝐨𝐭𝐚𝐥 𝐂𝐮𝐫𝐫𝐞𝐧𝐭 u++ u−
u−
transport number of anion (t-) =
u++ u−
t+ + t- = 𝟏 ➢ If transport number of one ion is known other can be calculated
Transport number and Cell potential of Con. Cell with Transference
L.H. E, R.H. E,
Pt  H2 (1 atm)  HCl(C1 M)  HCl C2 M) H2 (1 atm)  Pt
½ H2(g) ⇋ H+(C1) + e- H+(C1) + e- ⇋ ½ H2(g)
If t+ transport number of H + and t- is for Cl- , where t++ t-= 𝟏
For one faraday of electricity to pass through the cell,
➢ t+ faraday will be carried by cation H + ➢ t- faraday will be carried by anion Cl-
t+ equivalent of H + will be transferred from a t- equivalent of Cl- will be transferred from a
solution of concentration C1 to a solution of solution of concentration C2 to a solution of
concentration C2 concentration C1

t+ H + (C1) ⇋ t+ H + (C2) ------1 t- Cl- (C1) ⇋ t- Cl- (C2) --------2

L.H. E, R.H. E,
Gain of 1 gm eq. of H+ ion by oxidation Loss of 1 gm eq. of H+ ion by reduction
Loss of t+ gm eq. of H+ ion by process 1 Gain of t+ gm eq. of H+ ion by process 2
Net gain of H+ ion = (1- t+ ) gm. eq.
= t- gm. eq. Net transfer of t- equivalent of H + and Net loss of H+ ion = (1- t+ ) gm. eq.
Net gain of Cl- ion = t- gm. eq. t- equivalent of Cl – = t- gm. eq.
t- H + (C1) ⇋ t- H +(C2) ------3 Net loss of Cl- ion = t- gm. eq.
t- Cl- (C1) ⇋ t- Cl- (C2) --------2
Transport number and Cell potential of Con. Cell with Transference
L.H. E, R.H. E,
Pt  H2 (1 atm)  HCl(C1 M)  HCl C2 M) H2 (1 atm)  Pt
½ H2(g) ⇋ H+(C1) + e- H+(C1) + e- ⇋ ½ H2(g)
t+ transport number of H + and t- is for Cl- , where t++ t-= 1

Net transfer of t- equivalent of H + and

t- equivalent of Cl –

t- H + (C1) ⇋ t- H +(C2) ------3

t- Cl- (C1) ⇋ t- Cl- (C2) --------2

𝟐. 𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 𝑯 + 𝟐. 𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 𝑪𝒍 −
𝑬 𝒘 . 𝒕 = t− 𝒍𝒐𝒈 + t− 𝒍𝒐𝒈
𝑭 𝑪𝟏 𝑯 + 𝑭 𝑪𝟏 𝑪𝒍 −
𝟐
𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐
𝑬 𝒘. 𝒕 = t− 𝒍𝒐𝒈 𝟐
𝑯𝑪𝒍
= 2 t− 𝒍𝒐𝒈
𝑭 𝑪𝟏 𝑯𝑪𝒍 𝑭 𝑪𝟏

𝑬 𝒘. 𝒕 includs junction potential

Liquid Junction Potential (LJP), Ej
• Cell potential of Con. Cell with Transference includes junction potential because of the mobility difference
𝟐. 𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 𝟐. 𝟑𝟎𝟑𝑹𝑻 𝑪𝟐
𝑬 𝒘. 𝒕 = 2 t− 𝒍𝒐𝒈 𝑬 𝒘. 𝒐. 𝒕 𝒍𝒐𝒈
𝑭 𝑪𝟏 = 𝑭 𝑪𝟏

𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐
Ej = 𝑬 𝒘. 𝒕 − 𝑬 𝒘. 𝒐 . 𝒕 2 t− 𝑭 𝒍𝒐𝒈 − 𝑭 𝒍𝒐𝒈 𝑪𝟏
= 𝑪𝟏

𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐
Ej = (2 t− − 𝟏) 𝑭
𝒍𝒐𝒈 𝑪𝟏
= (t− + t− − 𝟏) 𝑭
𝒍𝒐𝒈 𝑪𝟏
𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐
E j = t− + 1− t+ − 𝟏) 𝑭 𝒍𝒐𝒈 𝑪𝟏

𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐
Ej = (t− − t+ ) 𝒍𝒐𝒈
𝑭 𝑪𝟏

➢ Sign and Magnitude of L.J.P. depends on transference numbers of cation and anion
𝐈𝐟 t− = t+ , then no L.J.P 𝑲𝑪𝒍 𝒂𝒏𝒅 𝑨𝒎𝒎𝒐𝒏𝒊𝒖𝒎
(t− > t+ ), then L.J.P will be positive 𝒏𝒊𝒕𝒓𝒂𝒕𝒆 𝒘𝒊𝒍𝒍 𝒉𝒂𝒗𝒆 𝒔𝒂𝒎𝒆
(t− < t+ ), then L.J.P will be negative 𝒔𝒊𝒛𝒆 𝒂𝒏𝒅 𝒎𝒐𝒃𝒊𝒍𝒊𝒕𝒚
 Salt bridge
To avoid liquid junction potential due to concentration difference

▪ U – shaped glass tube filled with an electrolyte, typically in the

form of a gel
▪ KCl, NaCl, KNO3, K2SO4 etc in agar - agar or gelatin

Functions:
▪ It provides a low electrical connections between the two half-cells and allows the flow of
ions from one half cell to the other half cells
▪ Keeps the two half cells electrically neutral
▪ Zn2+ ions accumulated @ anode and the charge will be neutralized
▪ -ve charge on the cathode will be neutralized by the K+ ions
▪ The solutions of two half cells will be electrically neutral
Personnel copy
 Electro chemical or wet corrosion
❖ When two dissimilar metals are in contact with each other
❖ Metal is in contact with a conducting medium
❖ Chemically non uniform surface of metal behave like electrochemical cell in
presence of water containing O2 & CO2
❖ Anodic and cathodic areas are formed
❖ Corrosion occurs at anodic areas and Metal gets destroyed at anodic areas

Mechanism of Electro chemical corrosion

❖ Corrosion involves Oxidation (anode) – Reduction (cathode) process
❖ At anodic areas, metal get oxidized/consumed (Liberation of electron)

Dissolved metal Metal oxide

❖ Electrons flows through the metal to cathode area

Cathode: Depending on the environment, two process occurs

❖ Evolution of Hydrogen (absence of oxygen)
❖ Absorption of Oxygen
❖ Non-metallic ions can form (OH-, O2-)
 Mechanism of corrosion by evolution of Hydrogen gas (absence of Oxygen)
In acidic medium

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In Neutral or Alkaline medium

2H2O + 2e- H2 + 2OH-
 Mechanism of corrosion by absorption of Oxygen gas (Presence of Oxygen)

❖ Fe2+ irons originates at anode

❖ OH- ions originate at cathode

❖ Fe2+ ions diffuses more rapidly as the size is

small
❖ So corrosion occurs at anode but rust deposited
at cathode

In Acidic medium

4H+ + O2 + 4e- 2H2O

Comparison
Passivation(Powerlessness ):-
The phenomenon by which the a metal or alloy shows high corrosion resistance due to the
formation of a highly protective very thin (usually 0-0004 mm), and quite invisible surface film
Takes place only in certain environment which tend to maintain the protective film
• Eg: The stainless steel alloy of Fe (Ti, Cr, Al, and Cr) exhibit outstanding corrosion resistance
in the presence of Oxygen
❖ An Oxide (Chromium oxide) film formed in oxidizing environment automatically repairs
• But corrode easily in reductive environment

❖ Conc. HNO3 have no effect on Al but it does have on Fe.

• Presence of Cr maintain a protective oxide and shows high corrosion resistance in
HNO3 solution.

Passivity of metals follows in the order

Ti → Al → Cr → Be → Mo → Mg → Ni → Co → Fe →Mn → Zn → Cd
→ Sn → Pb → Cu
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 Type of wet corrosion
A. Concentration cell corrosion B. Galvanic or bimetallic:
When a metal is in contact with Two dissimilar metals or alloys are either
▪ Two different air concentration immersed or dipped partially in a solution
▪ A conducting liquid of different
concentration (Differential aeration)

1. Pitting corrosion
2. Crevice corrosion 1. Galvanic corrosion
3. Waterline corrosion
4. Intergranular corrosion
A. Concentration cell corrosion: Electrochemical attack on metal
Due to
➢ Where a metal is in contact (partially immersed) with the a ➢ Temperature difference
conducting medium (varying concentration or aeration) results in ➢ Inadequate agitation
local difference in metal ion concentration ➢ Slow diffusion of metal -ion
Differential aeration corrosion (DAC): Metal is exposed to different air concentration
➢ The part where low oxygen concentration act as anode and gets corroded
Water line corrosion
▪ Eg: Zinc metal partially immersed in neutral solution gets corroded
▪ Iron corrode under drop of water ( part above water is aerated : cathode)

➢ Corrosion is accelerated in apparently inaccessible • Neutral water, little corrosion

place (Oxygen deficient area gets corrode) • Marine plants cause waterline corrosion to
➢ eg: pit, scale or sand accumulated area ocean going ships
➢ Corrosion gets intensified by time • Bottom of the ships are red in color why
1. Pitting corrosion
• Localized corrosion of a metal surface confined to a point or small area, that takes the form
of cavities
• Usually found on passive metals and alloys of aluminum, copper, cobalt, stainless steels, etc
• Breakdown or cracking of protective films by chemical or mechanical damaged and does not immediately re-
passivate.
• Due to scratches, non uniform finish, local staining of other metal stress etc.
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Passive film

• Forms small anodic and large cathodic areas

• Non-uniform (specific points)
• Results in the formation of pits, pin holes or cavities
• Resulting from a localized accelerated attack
• Once a small pit is formed, the rate of corrosion is high.
2. Crevice (contact) corrosion
▪ Occurs when stagnant solution got trapped within localized volumes of pockets, corners, crevices or beneath a
shield

➢ Cleanliness and proper usage of sealants (gasket, fastener, etc) avoid corrosion
➢ Proper welding to avoid sharp ends
3. Intergranular (Inter-crystalline or interdendritic) corrosion

➢ Localized type of attack that occurs along microstructure grain boundaries in the
presence of corrosive liquids (Grain Boundary Depletion)
➢ Grains center material shows more anodic electrode potential than that of grain
boundaries
➢ Corrosive liquid attack the grain boundaries than grain interiors
➢ Because of tensile stress, cracking may occur along grain boundaries and the crack
propagate through the grain boundaries than the grain centers,
➢ This also affects adjacent areas without the external sign of intensive attack

Eg : Intergranular corrosion in stainless steel may result from

➢ Precipitation of carbides, nitrides or intermetallic phases during welding process
➢ Occurs in steel alloys with chromium (Cr C), niobium or titanium
➢ Solid solution forms due to precipitation of some material at the boundaries during welding, annealing, etc
➢ Aluminum alloys with copper or magnesium

➢ Usage of low carbon content (0.03%) avoids this problem or

➢ Usage of trace of Ti in 0.08% steel avoid steel corrosion
➢ Heating to 1000 0C and suddenly immersed in water resulting the dissolution of Chromium carbide
 B. Galvanic corrosion or differential metal corrosion(DMC)

• Galvanic corrosion can occur when dissimilar metals are in contact in

the presence of an electrolyte (any non-metal substance that will
conduct an electric current).
• Metal which is higher up in the electrochemical series can act as anode (High
electrode potential) and undergo corrosion
• Eg, Zn (corroded) & Cu (protected), Zn & Ag, Fe & Cu

• Steel screw in a brass marine hardware,

• Pb-Sb solder around copper wire,
• A steel propeller shaft in bronze bearing,
• Steel pipe connected to copper plumbing
It can be minimized by,
➢ Providing insulating material like gaskets
➢ Avoiding galvanic couple
Galvanic series:-
• Galvanic corrosion occurs when two different metals immersed in an electrolyte are joined together.
• The galvanic series determines the electrochemical potential and nobility of metals & metal alloys
• The galvanic series plays a vital role in determining and preventing corrosion.
• Also known as the "electropotential series," this series identifies semi-metal and metal nobility.

• Passivation makes effective electrode potentials of some metals more positive so they act as Cathodic and
exhibit noble behavior
 Difference between Electro chemical series and Galvanic series

Electrochemical series Galvanic series

Predicts the relative displacement tendencies of Predicts the corrosion tendencies of both metals
metals and nonmetals and non metals in actual environment
Depends on concentration of salt in the It does not
electrolyte (Particularly the same metal)
Reference electrode is SHE Reference electrode is calomel electrode
Position of the alloy is not listed Position of the metal alloy is deferent from metal

Effect of environment is not predicted Predicted

 Factors influencing corrosion:
Nature of Environment

➢ Temperature: Diffusion rate will increase and there by corrosion too

➢ Humidity: Protective oxide layer can washed away; Critical Humidity : above which the corrosion rate is high.
It depends on nature of metal and corrosion product.
➢ Presence of impurities in atmosphere: Industrial gases like CO2, SO2, H2S and fumes of HCl and H2SO4
increases corrosion. Marine chemicals can corrode vassals.
➢ Presence of suspended particle in atmosphere: Chemically inactive suspended particle like charcoal dust can
adsorb corrosive gases
➢ Effect of pH: Acidic (pH<7) media are more corrosive than alkali or neutral. But some metal (Zn, Al, Pb etc)
can dissolve in alkaline media
➢ Conductance of corroding medium: For submerged structures, conductance of dry soil is less than mineralized
soil. Stray current will be there in clay or mineralized soil
➢ Formation of Oxygen concentration cell: varying concentration of oxygen cause corrosion
➢ Flow velocity of process stream: for non-passivate or slow passivate metal, flow velocity of the stream can
increase rate of corrosion
Nature of metal Factors influencing corrosion:
➢ Position in the galvanic series: more active metal undergo corrosion and rate of corrosion depends on
difference in their position

➢ Relative area of anode and cathode: corrosion of anode is directly proportional to the ratio of surface area of
cathode to anode

➢ Purity of metal: heterogeneity in metal causes the formation of electrochemical cell (Fe or Pb in Zinc metal)

➢ Physical state of metal: Smaller the grain size of the metal or alloy, greater will be the solubility and greater
will be the corrosion. Stressed areas get corroded

➢ Nature of oxide film: Specific volume ratio decides the corrosion rate

➢ Passive character of metal: Metals like Ti, Al, Cr, Ni, Co are passive

➢ Solubilities of product of corrosion: If corrosion products are highly soluble in the medium, the rate of
corrosion will be maximum

➢ Volatility of corrosion product: Volatile corrosion product leads to excessive corrosion

➢ Overvoltage due to polarization of electrode: high overvoltage lower the corrosion

 Polarization: Variation of potential from the equilibrium value
➢ Polarization leads to accumulation of charge at the electrode and alters the potential
➢ cathode to less cathodic (higher anodic or more negative)
➢ anode to less anodic (more cathodic or more positive)
➢ The polarized galvanic cell develop a lower potential and decreased current than
predicted theoretically ❖ Presence of surface film
❖ Concentration change
❖ Overvoltage

1. Polarization due to Concentration difference

➢ The electrode potential is given by the Nernst’s equation
𝟎.𝟎𝟓𝟗𝟏 𝑽 +
E = Eo + 𝒍𝒐𝒈 [𝑴𝒏 ]
𝒏
+
➢ When electric current is passed, the [𝐌𝐧 ] in the vicinity of the electrode surface decreases due to the
electrode process, Consequently there is a change the electrode potential
➢ The equilibrium will be re-established as the metal ion from the bulk of the solution diffuses (concentration
gradient) towards the electrode
➢ If the diffusion rate is low then there will be variation in electrode potential
Concentration polarization : Process by which there is a variation in electrode potential owing to the
inadequate diffusion of species from the bulk of the electrolyte solution to the vicinity of electrode
Extend of polarization depends on the following factors
➢ Size of the electrode: Larger the surface area lower will be the polarization
➢ Nature of Electrode surface: Smoother the electrode surface higher the polarization
➢ Nature of ion deposited on the electrode: Extend of polarization increases when liberated/discharged ion
adhere to the surface to form a porous film
➢ Concentration of electrolyte: low concentration of electrolyte decreases the polarization effect
➢ Temperature: higher temperature decreases the polarization effect
➢ Stirring electrolyte : decreases the polarization effect
➢ Conductivity of electrolyte solution: Lower Conductivity causes lower polarization

Polarization and corrosion

Cell potential is the driving force for corrosion
Corrosion rate is controlled by the current flow
➢ Polarization of electrode alters the potential of cathode to less cathodic (More anodic)and anode to less
anodic (More cathodic)
➢ So potential difference will decrease there by the current and the corrosion rate too
 Polarization and corrosion
➢ Initially the corrosion rate is low but increase as the potential difference between cathodic and anodic areas
increases, ultimately reached a steady state called corrosion potential (Ecorr)
➢ At the steady state, the sum of all anodic reaction will be equal to cathodic reaction and the corresponding value of
current is called Corrosion Current (Icorr)
Corrosion Current (Icorr) = Anodic current density (Ia) - Cathodic current density (Ic)
The value of Corrosion Current (Icorr) depends on
➢ Current densities at anode and cathode ➢ Relative area of anode and cathode
➢ Polarization characteristic of anode and cathode If the surface area of cathode is larger than anode,
➢ Potential difference between anode and cathode ▪ Ia > Ic
➢ Low Temperature→ low diffusion→: Low ▪ Icorr will be larger
corrosion ▪ anode material will undergo accelerated corrosion)

Evans Diagram (Polarization curves) : A plot of potentials of polarized electrodes against current density
Steeper slope represents a greater polarization
➢ The point of intersection of the two curve is the Ecorr and the current at this point is Ic

Anodic
Both Anode
polarization
and Cathode
Cathode are undergoing
polarization polarization
 Overvoltage (Bubble voltage)
Polarization means the deviation of the electrode potential from the value predicted
by Nernst equation on the passage of current.
Extent of polarization or Overvoltage,  = ETheo - Ereal
➢ Overvoltage  is the difference between the theoretical cell potential and the
corrected Nernst equation
➢ High overvoltage reduces rate of corrosion
The additional voltage needed to maintain the ETheo Ereal
predicted current, ETheo - Ereal = IR I= − Ereal
𝑹 𝑹
Overvoltage is high when the activation energy for the half cell reaction is high
➢ It occurs when there is a gas (H2, O2, Cl2) evolution at either electrode
➢ Over voltage for H2 or O2 evolution is much higher than Cl2
1.Corrosion rate of Zn is accelerated by the presence of CuSO 4 in 1N H2SO4 zn = 0.77V, Cu =0.33V
2.Dissolution of Pb (E0 = -0.13V) in HCl doesn't occur as Pb = -0.52 V

But in oxidizing atmosphere metals with high overpotential will corrode easily

Fe-Pb couple corrode in Oxygen atmosphere etc

Overvoltage at various electrode
67
 Protective measures against Corrosion
• Modification of the environment:- either by removal of corrosion stimulant or by the use
of corrosion inhibitors
• Modification of the properties of metal:- like alloying, Refining, Annealing etc
• Use of protective coating (metallic, organic or inorganic)

• Cathodic protection
• Electroplating etc
• Cathodic protection

In acidic environment,
Metal undergo oxidation(act as anode)
Accompanied by a reduction reaction

Cathodic protection prevents corrosion by:-

converting all of the anodic (active) sites on the metal
surface to cathodic (passive) sites
Two types:-
1. Sacrificial anodic protection
2. Impressed current cathodic protection
 1. Sacrificial anodic protection
• Metal is connected with a wire to a more active metal called sacrificial anode
• The corrosion is concentrated at the more active metal eg, Zn, Al, Mg and their alloys
• Zn is used when there is good electrolyte like sea water
• Mg is used in case of high resistivity electrolytes such as soil

Application

(a) Protection of underground cable and pipelines from soil

corrosion

(b) Protection ships and boats hull from marine corrosion, Zn and Mg
sheets are hung around the ship which act as an anode

(c) In domestic water boilers or tanks, Mg is used to prevent the formation of

rusty water
 2. Impressed current cathodic protection
• Current from an external source is applied in opposite direction to nullify the corrosion current
• This convert the corroding anode to cathode and prevent corrosion
• The anode may be an inert material such as graphite, carbon, stainless steel, scarp iron

cathode

anode
 Electro plating
• The process of plating one metal onto a base metal by passing
current through an electrolyte containing soluble salt of the
coating metal to prevent corrosion of a metal.
• There are also specific types of electroplating such as copper
plating, silver plating, and chromium plating.
• Electroplating enhances the resistance propertiesto corrosion,
physical appearance, hardness and surface
• Clean metal is acting as a cathode and inert material such as
carbon or graphite act as anode
• The electrolyte is a solution of soluble salt of the metal to be
deposited