Electrochemistry and Corrosion

Objective:
To introduce the basic principles of Electrochemistry and Corrosion

Dr. Baby Viswambharan

Dept. of Chemistry
 Learning outcome
➢ To introduce the basics principles of electrochemistry
❖ Cell emf
❖ Types of cell
❖ Application of emf measurements

➢ Understanding “Corrosion” through principles of electrochemistry

❖ Types of corrosion
❖ 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.
 Introduction

Blue-Green Patina of copper

Tarnish on silver

Rust on iron

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
➢ Waste is produced
➢ Polymers react with oxygen and degrade
➢ Machineries get damaged
➢ Structures get damaged

An engineer must understand corrosion !

➢ Corrosion occurs only at the surface of the metal
➢ Due to corrosion,
➢ Lost is more than the metal cost
➢ 2-3 billion dollars all over the world

Understand and deal with!

Control and prevent corrosion!
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 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: 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, Pt
2. Unstable or Reversible oxide formation (Non-Corrosive), Metal Metal oxide, Ag, Au, Pt
3. Formation of Volatile oxide Leads to extensive corrosion Mo ==> MoO3
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

➢ Tin (Sn) forms porous SnCl4 (highly volatile),→

corrode the metal

➢ H2S gas leads steel to form porous FeS scale→ affect petroleum industry
Corrosion affects
• Suction pumps
• Drinking water pipes
• Sewage pipes
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

https://materials.nuc.berkeley.edu/sunshot
 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 or alloys are either
immersed or dipped partially in a solution Where a conducting liquid is in contact with the
metal

Basic principles of Electrochemistry

Mechanism of corrosion
Wet Corrosion Type of corrosion
Prevention of corrosion
Basic principles of Electrochemistry
➢ 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 occurs

➢ Double layer formation leads to a 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 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.
Thus, w = nF. Eel ❖ n is the number of electrons transferred;
❖ 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 = nF Eel for a reversible electrode.
𝑷𝒓𝒐𝒅𝒖𝒄𝒕
𝑷𝒓𝒐𝒅𝒖𝒄𝒕
−∆𝑮 = −∆𝑮° − 𝑹𝑻𝒍𝒏 ---(1) 𝑹𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝑸𝒖𝒐𝒕𝒊𝒆𝒏𝒕, 𝑸 =
𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕

𝑴 We know that,
𝒏𝑭𝑬𝒆𝒍 = 𝒏𝑭𝑬𝟎𝒆𝒍 − 𝑹𝑻𝒍𝒏 ---(2) −∆𝑮 = 𝒏𝑭𝑬𝒆𝒍, 𝒂𝒏𝒅
𝑴𝒏+ 𝒂𝒒
−∆𝑮𝟎 = 𝒏𝑭𝑬𝟎𝒆𝒍
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 −
𝟐.𝟑𝟎𝟑 𝑹𝑻
𝒍𝒐𝒈 𝒏+
𝟏
---(3) “Standard electrode potential E0
𝒏𝑭 𝑴 𝒂𝒒 [M] = 1
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 +
𝟐.𝟑𝟎𝟑 𝑹𝑻
𝒍𝒐𝒈[𝑴𝒏+
𝒂𝒒 ] ---(4)
The Nernst’s Equation
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 ➢ The magnitude of the potential difference is a measure of the
Anode tendency of the electrode to undergo oxidation or reduction
➢ EMF of a cell is the algebraic sum of the single electrode
potential provided the proper sign has to be taken care

Ecell = Ecathode - Eanode

Ecell = Eright – Eleft

E0 cell = 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)
➢ SHE is an eg of Gas electrode
➢ Consists of a gas (e.g. Cl2, O2) in contact with a solution containing the ions derivable from
the gas +(con.)
➢ e.g. H , Cl , OH .
+ - - Pt, H 2 (pressure) H
➢ The potential of the gas electrode depends upon the concentration of its ions in the solution and
the pressure of a gas
Hydrogen gas (1 atm. pressure) is in contact with the H+ ions (1 Molar) Pt, H2(1 atm) H+(1 M)
E0 for SHE is assigned as zero at 295K
Electrochemical series
(activity series)

➢ E0 of an electrode can
be measured with
reference to SHE

➢ 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 in contact with saturated solution of Hg+ ion (usually Hg2Cl2-calomel).
(Hg is liquid and Hg2Cl2-is a solid)
➢ Also contain a known concentration of KCl Hg (l) Hg2Cl2 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 in KCl that is [Cl-]
➢ 0.1M, E = 0.335V;
➢ 3.5M, E = 0.25V,
➢ Saturated:- E = 0.244 V (Saturated Calomel Electrode is widely used Vycor plug

If the electrode undergoes reduction, If the electrode undergoes oxidation,

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

𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑆𝐶𝐸 , 𝐻𝑔2 𝐶𝑙2 𝑠 ⇌ 𝐻𝑔2 2+ 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. Ag/AgCl Electrode

➢ [Cl-] in KCl; 3.5M:- E = 0.205,

saturated:- E = 0.194 V
𝑵𝒆𝒓𝒏𝒔𝒕 𝒆𝒒𝒏,
𝑬 = 𝑬𝟎𝑨𝒈𝑪𝒍/𝑨𝒈 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 𝒂𝑪𝒍− = +𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 𝒂𝑪𝒍−

Vycor plug

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−
𝑬 = 𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 𝒂𝑪𝒍−
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 using SHE:
E0 is relative with respect to Standard Hydrogen electrode (for SHE, E0 = 0)
0.26 V (SHE)
Sign of Standard electrode potential E0
SHE act as Anode SHE act as Cathode
Pt, H2 (1 atm)  H+(1 M)   Mn+(xM)  M M  Mn+(xM)   H+(1 M)  Pt, H2 (1 atm)
❖For reduction at an electrode “+” ve sign. ❖For oxidation at the electrode “-” sign.
Pt, H2 (1 atm) H+(1 M)   Cu Cu2+ (1M) Zn Zn2+(1M)   H+(1 M) H2 (1 atm) Pt
E0 for Cu is +0.34 V E0 for Zn is -0.76 V

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

SCE Ag+ (aq.) Ag(s) T h e h a lf c e ll r e a c tio n

+
A g A g
Ecell = EInd – ERef
1
𝐸𝑐𝑒𝑙𝑙 = 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 − 0.242 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 −∆𝑮° = 𝑹𝑻 𝒍𝒏 𝑲 = 𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍
𝒏𝑭𝑬𝟎 𝒄𝒆𝒍𝒍
𝑻𝒉𝒆𝒓𝒆𝒇𝒐𝒓𝒆, 𝒍𝒏 K =
𝑹𝑻

Standard cell potential vs. K

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
+ 2+ 𝟎 𝑪×𝑽×𝒎𝒐𝒍−𝟏 𝑲−𝟏 ×𝑲
Ni + 2Ag Ni + 2Ag 𝒏𝑭𝑬 𝒄𝒆𝒍𝒍
𝒍𝒏 K = K = 1.479x1035 𝒎𝒐𝒍
𝑹𝑻
 2. Determining solubility product constant
➢ The solubility product of a sparingly soluble salt is like an equilibrium constant.
➢ Consider the dissolution of any sparingly soluble salt MX (AgCl, Hg2Cl2) MX (s) ⇋ M+ (aq.) + X- (aq.)

The solubility product of the salt is given by Ksp = [M+ ][X-], for very dilute solution

For the above reaction the Cell can be represented by

L.H. E,
M  M +X-
(sat. soln.)  MX (S) M R.H.E.
M ⇋ M+ (aq.) + e- MX (S) + e- ⇋ M + X-

Overall reaction is given by MX (s) ⇋ M+ (aq.) + X- (aq.) 𝒂𝒏𝒅 𝑬𝟎 𝒄𝒆𝒍𝒍 = E R-EL

Reduction potential can get from electrochemical series

𝒏𝑭𝑬𝟎 𝒄𝒆𝒍𝒍
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 solubility
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 𝑬𝟎 𝑨𝒈𝑩𝒓/𝑨𝒈 = 0.07V and 𝑬𝟎 𝑨𝒈 /𝑨𝒈 = 0.80V

AgBr(S) ⇋ Ag+( aq.)+ Br- (aq.)

𝒏𝑭𝑬𝟎 𝒄𝒆𝒍𝒍
R.H. E, Ag Br(S) + 2e- ⇋ Br- (aq.) + Ag(S) 𝒍og Ksp =
𝟐. 𝟑𝟎𝟑𝑹𝑻
L.H. E, Ag(s) ⇋ Ag+(aq.) + e-

𝑬 = 𝑬𝑹 − 𝑬𝑳 = 0.07 - 0.80 = -0.73V

𝑬𝟎 −𝟎.𝟕𝟑
𝒍og Ksp = =
𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏

Ksp = 4.81 x 10-11

3. Determining pH
The potential of a hydrogen electrode in contact with the a 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 ]
𝟎.𝟎𝟓𝟗𝟏 𝟏
𝑬𝒆𝒍 = − 𝒍𝒐𝒈 + = − 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯
𝟏 [𝑯 ]
➢ 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. 𝟐𝟒𝟐𝟐 − (−𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯)

= 𝟎. 𝟐𝟒𝟐𝟐 + 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯)
𝑬−𝟎.𝟐𝟒𝟐𝟐
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−𝟎.𝟐𝟒𝟐𝟐 𝟎.𝟕𝟏𝟓−𝟎.𝟐𝟒𝟐𝟐 𝟎.𝟒𝟕𝟐𝟖
pH = = = =𝟖
𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏