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
 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

Good side: Bio degradable materials

Computer chips can be replaced by
cellulose nanofibril (CNF)
https://doi.org/10.1038/ncomms8170
 Why is Corrosion?

Ores: Metal in combined state Input Metal Natural tendency

Ores carbonates)
(Oxides, sulfides, Ores Compounds
Ores
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”

 An engineer must understand corrosion !
 Corrosion occurs only at the surface of the metal
Impact of corrosion,
Waste is produced
Machineries get damaged
Structures get damaged

Lost is more than the metal cost

 2-3 billion dollars all over the world

Understand and deal with!

Control and prevent corrosion!
 Corrosion
Chemical or Dry corrosion Electrochemical or
Direct Chemical attack Wet corrosion
(By environment) Electro chemical attack

Direct chemical action on metal

 Absence of water Formation of galvanic cell
 Environment/atmospheric gases and
 Anhydrous inorganic liquids. electron flow

A. Oxidation Corrosion
B. Corrosion by other gases A. Galvanic or bimetallic
C. Liquid metal corrosion B. Differential aeration or
Concentration cell 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
https://www.ntt-review.jp/archive/ntttechnical.php?contents=ntr201207fa4.html

 Both oxygen and metal can migrate

 Smaller metal atoms migrates rapidly to the surface than inward migration of larger oxygen molecule
 Faster scale formation may prevent the metal migration

https://www.nature.com/articles/s41467-020-20876-9.pdf
Mechanism
 Oxidation occurs at the surface (Metal oxide scale )
Nature of the metal oxide (scale) decides further corrosion!!
 Scale prevents further corrosion : Act as barrier
 Scale allow 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’s 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

 Nature of the metal oxide (scale) decides further corrosion
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, Fe2O4,

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

Corrosion affects
• Petroleum industry
• 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
SEM image of liquid metal corrosion

https://www.sciencedirect.com/topics/engineering/concentrated-solar-power
 Corrosion
Direct Chemical attack Electro chemical attack
(By environment) Electrochemical or Wet corrosion
Chemical or Dry corrosion

Direct chemical action on metal Formation of galvanic cell and electron flow
Environment/atmospheric gases
Anhydrous inorganic liquids.

A. Galvanic or bimetallic
A. Oxidation Corrosion B. Differential aeration or 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:

Two dissimilar metals or alloys are either Where a conducting liquid is in contact with the
immersed or dipped partially in a solution metal

Basic principles of Electrochemistry Mechanism of corrosion

Wet Corrosion Different types of cell
Type of corrosion
Prevention of corrosion
Basic principles of Electrochemistry
 Single electrodes
 Types of electrodes
 Electrode potential
 Cell EMF- its measurement and applications
 Cell and Type of Cell
Single electrode or half cell and its Potential (Eel)
 The metal dipped in its ion solution represent a single electrode
 The electrode is represented as M Mn+(Concentration)

Zinc metal

Zn Zn2+(xM)

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 )
 Specified for the reduction reaction

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

 Eel depends on the concentration of the ion in solution (specify the concentration )
Types of electrode
• Metal-metal ion electrode
• Gas electrode
• Metal – Metal insoluble salt electrode, (Ag-AgCl , Hg-Hg2Cl2)
• Membrane electrode
• Quinhydrone electrode, etc
Gas electrode
 Consists of a gas (e.g. Cl2, O2) in contact with a solution containing the ions derivable from
the gas e.g. H+, Cl-, OH-.
Eg: Hydrogen electrode (HE)
Hydrogen gas is in contact with the H+ ions
Electrical contact through inert metal

Pt, H2(pressure) H+(con.)

“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)  Standard hydrogen electrode

 Thermodynamics of Electrode potential (Eel) and Change in Free energy (G)
𝑪𝒐𝒏𝒔𝒊𝒅𝒆𝒓 𝒕𝒉𝒆 𝒓𝒆𝒗𝒆𝒓𝒔𝒊𝒃𝒍𝒆 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏, 𝑴𝒏 𝒂𝒒
+ 𝒏𝒆 ⇋ 𝑴(𝒔)
n is the number of electrons transferred;
Electrical work done by the electrode w = nF.Eelectrode 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 Eelectrode for a reversible electrode.
𝑷𝒓𝒐𝒅𝒖𝒄𝒕
𝑻𝒉𝒆𝒓𝒎𝒐𝒅𝒚𝒏𝒂𝒎𝒊𝒄𝒂𝒍𝒍𝒚, −∆𝑮 = −∆𝑮° − 𝑹𝑻𝒍𝒏 𝑸---(1) 𝑹𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝑸𝒖𝒐𝒕𝒊𝒆𝒏𝒕, 𝑸 =
𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕
𝑴
𝒏𝑭𝑬𝒆𝒍 = 𝒏𝑭𝑬𝟎𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 − 𝑹𝑻𝒍𝒏 𝑴𝒏 𝒂𝒒
---(2)

𝟐.𝟑𝟎𝟑 𝑹𝑻 𝟏
𝑬𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 = 𝑬𝟎𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 − 𝒏𝑭
𝒍𝒐𝒈 𝑴𝒏 𝒂𝒒
---(3) [M] = 1, for solids
𝟐.𝟑𝟎𝟑 𝑹𝑻 [𝑹𝒆𝒅𝒖𝒄𝒆𝒅 𝒔𝒕𝒂𝒕𝒆]
𝑬𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 = 𝑬𝟎𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 − 𝒏𝑭
𝒍𝒐𝒈 𝑶𝒙𝒊𝒅𝒊𝒔𝒆𝒅 𝒔𝒕𝒂𝒕𝒆
---(4) The Nernst’s Equation

𝟎.𝟎𝟓𝟗𝟏
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 + 𝒏
𝒍𝒐𝒈[𝑴𝒏 𝒂𝒒 ] ---(5) at 298K
Representation of a cell and its emf
EMF (emf) of a cell
Zn  Zn2+(Conc.) Cu Cu2+(Conc.) Ecell = Ecathode - Eanode

Ecell = Eright – Eleft

 The magnitude of the potential difference is a
measure of the tendency of the electrode to
Zn  Zn2+ + 2e- Cu2+ + 2e-  Cu
undergo oxidation or reduction
Anode Cathode
𝟐. 𝟑𝟎𝟑 𝑹𝑻 [Cu] [Zn2+]
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈
𝒏𝑭 [Cu2+][Zn]
Overall (Redox) reaction Zn + Cu2+ Cu + Zn2+ 𝟐. 𝟑𝟎𝟑 𝑹𝑻 [Zn2+]
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈
𝒏𝑭 [Cu2+]

Reactant Product

𝟐. 𝟑𝟎𝟑 𝑹𝑻 𝑷𝒓𝒐𝒅𝒖𝒄𝒕
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈
𝒏𝑭 𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕

Thermodynamically, Ecell
Predicting the feasibility of a reaction
Determining E0 for a half cell or single electrode:

“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”

By constructing a galvanic cell by connecting with a reference electrode

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)

Some Reference electrode are

Reference electrode Indicator electrode

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
https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Supplemental_Modules_(Analytical_Chemistry)/Analytical_Sciences_Digital_Library/JASDL/Course
ware/Analytical_Electrochemistry%3A_Potentiometry/03_Potentiometric_Theory/04_Reference_Electrodes
 Standard Hydrogen electrode (SHE) E0 for SHE is assigned as zero at 298K
Hydrogen gas (1 atm. pressure) is in contact with the H+ ions (1 Molar) Pt, H2(1 atm.) H+(1 M)

When SHE act as Anode, When SHE act as Cathode,

Oxidation of H2 oxidizes to H2 will be liberated
H2 H+ + 2e- 2H+ + 2e-  H2
Pt, H2 (1 atm)  H+(1 M)   Mn+(xM)  M M  Mn+(xM)   H+(1 M)  Pt, H2 (1 atm)

Determining E0 for a half cell SHE: Sign of Standard electrode potential E0

When coupled with SHE,
 For reduction at an electrode “+” ve sign.
Pt, H2 (1 atm) H+(1 M)   Cu Cu2+(1M)

E0 for Cu is +0.34 V

For oxidation occurs at the electrode “-” sign.

Zn Zn2+(1M)   H+(1 M) H2 (1 atm) Pt
E0 for Zn is -0.76 V

Ni  Ni2+(1M)   H+(1 M)  Pt, H2 (1 atm)

Electrochemical series (activity series)

 E0 of an electrode are
measured w. reff. to SHE

 Electrodes are arranged in

the increasing/decreasing
order of reduction
potentials
2. Calomel Electrode (SCE)
 Hg(liq.) in contact with saturated solution of Hg+ (Hg22+) ion usually Hg2Cl2 (solid calomel)
with a known concentration of KCl as electrolyte

Hg (l) Hg2Cl2 (s), KCl(xM)   Electrode junction is through a Vycor plug.

 Electrode potential depends on the [Cl-] in KCl and Temperature (cut off is 60 ℃)
 0.1M KCl, E = 0.335V;
 3.5M KCl, E = 0.25V,
 Saturated KCl, E = 0.244 V (widely used)
If the electrode undergoes reduction (cathode), If the electrode undergoes oxidation (Anode),
Hg22+ 𝑎𝑞 + 2𝑒 ⇌ 2𝐻𝑔 𝑙 2𝐻𝑔 𝑙 ⇌ Hg22+ 𝑎𝑞 + 2𝑒
𝐻𝑔 𝐶𝑙 𝑠 ⇌ Hg22+ 𝑎𝑞 + 2𝐶𝑙 Hg22+ 𝑎𝑞 + 2𝐶𝑙 ⇌ 𝐻𝑔 𝐶𝑙 𝑠
Concentration of chloride ions increases in solution Concentration of chloride ions decreases in solution

𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑆𝐶𝐸, 𝐻𝑔 𝐶𝑙 𝑠 ⇌ Hg22+ 𝑎𝑞 + 2𝐶𝑙

Electrode is reversible with respect to [Cl-] ions

0.0591 0.0591
𝑵𝒆𝒓𝒏𝒔𝒕 𝒆𝒒𝒏, 𝐸=𝐸 / − 𝑙𝑜𝑔 𝑎 = +0.268 𝑉 − 𝑙𝑜𝑔 𝑎
2 2
Personnel copy
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

Problem: Calculate the potential of silver electrode in contact with a 0.01 M NaCl solution
𝑬 = 𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 𝟎. 𝟎𝟏 Vycor plug
𝑬 = 𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒙 (−𝟐) = 0.199 + 0.1182 = 0.3172 V
 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) The half cell reaction

Ag+ Ag
Ecell = EInd – ERef
1
𝐸 = E° (Ag+ /Ag) − 0.0591 log
[Ag+]

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

1
𝐸 = 0.80 𝑉 − 0.0591 log − 0.242 𝑉
[0.01 M]

Ecell = 0.4398 V
Importance of electrochemical series (Assignment)

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
6. Determining equilibrium constant of a reaction
Determining equilibrium constant of a reaction
The Van’t hoff reaction isotherm, 𝟎
𝒄𝒆𝒍𝒍
𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍
𝑻𝒉𝒆𝒓𝒆𝒇𝒐𝒓𝒆, 𝒍𝒏 K =
𝑹𝑻
 If Ecell is positive then equilibrium constant is positive (more product formation)
 If Ecell is negative then equilibrium constant is negative

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
Ni Ni2+ + 2e Ag+ + e Ag
E0cell = 0.80 – (-0.25) = 1.05V
The cell reaction
Ni + 2Ag+ Ni2+ + 2Ag 𝟐 × 𝟗𝟔𝟓𝟎𝟎 𝑪 × 𝟏. 𝟎𝟓 𝑽
𝒍𝒏 K =
8.314 J𝒎𝒐𝒍 𝟏 𝑲 𝟏 × 𝟐𝟗𝟖 𝑲
𝑪×𝑽
= 𝟖𝟏 𝑪×𝑽×𝒎𝒐𝒍 𝟏 𝑲 𝟏 ×𝑲 = 81 moles
K = 1.479x1035 mol
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 = E0R-E0L

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.
𝟎 𝟎 +
soln.)  AgBr (S) Ag. Provided the standard potentials 𝑬 𝑨𝒈𝑩𝒓/𝑨𝒈 = 0.07V and 𝑬 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

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)
Nernst equation corresponding to the equation is
𝟎.𝟎𝟓𝟗𝟏 𝟏
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 − 𝒍𝒐𝒈 at 298 K 𝒘𝒉𝒆𝒓𝒆 𝑬𝟎𝒆𝒍 = 0
𝒏 [𝑯 ]
𝟎.𝟎𝟓𝟗𝟏 𝟏
𝑬𝒆𝒍 = − 𝟏
𝒍𝒐𝒈 [𝑯 ]
= − 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯

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

Combine hydrogen electrode with a reference electrode, PtH2(1 atm)  H+(unknown conc.)  SCE
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑹 − 𝑬𝑳 = 𝟎. 𝟐𝟒𝟐𝟐 − (−𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯) 𝑬 𝟎.𝟐𝟒𝟐𝟐
pH =
= 𝟎. 𝟐𝟒𝟐𝟐 + 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯) 𝟎.𝟎𝟓𝟗𝟏

Problem: 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 =
𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏
 Types of Cell

Electrochemical cell Electrolytic cell

(Cell emf is from spontaneous reaction) (Potential is applied externally to
perform the cell reaction )

Chemical cell Concentration cell

➢ Emf drawn from chemical reaction

➢ Two different electrodes and a common ion in electrolyte
𝟐.𝟑𝟎𝟑 𝑹𝑻
➢ 𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈𝑸
𝒏𝑭

➢Electrolytes in two half cell are in direct contact
➢The electrode should be reversible with one of the ion in
electrolyte, Zn H2SO4 (aq.) Cu
➢ When electrolytes in two half cell are not in direct contact
➢ The two solutions are connected indirectly through slat bridge
➢ Ion transport from one half cell to another will not take place
directly
➢ Junction potential
PtH2(g)HCl(aq.)  AgCl(s) Ag
Zn ZnSO4(aq.) CuSO4 (aq.)  Cu
 LJP in Chemical cell
▪ In a galvanic cell when working, another potential (in mVolts) will be created due to
▪ the accumulation of positive ions in anodic compartment and
▪ Excess consumption of positive ions in cathodic compartment

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 compartment and the charge will be neutralized
▪ -ve charge at the cathode compartment will be neutralized by the K+ ions
▪ The solutions of two half cells will be electrically neutral
Personnel copy
Liquid Junction Potential (LJP), Ej

▪ If two solutions of different concentrations are in contact with each other, potential (in mVolts) will be created
at the interface due to the differential mobilities of cation and anion

▪ At junctions:
▪ H + ions moves to lower concentrations
▪ Cl- ions follows
 Concentration cell
➢ Electrodes/Electrolytes of similar material with a deference in concentration
➢ Emf is drawn from concentration difference in two half cell
➢ Emf drawn from mass transfer between one half-cell to another
𝟐.𝟑𝟎𝟑 𝑹𝑻
➢ 𝑬𝒄𝒆𝒍𝒍 = − 𝒍𝒐𝒈𝑸,
𝒏𝑭

Cu Cu2+(C1)   Cu2+(C2) Cu

1. Electrode conc. Cell 2. Electrolyte Conc. cell

Two half cells with different electrode composition Two half cells with different electrolyte concentration
Do not have liquid junction potential Usually have liquid junction potential
1. Gas electrode concentration cell Ionic mobilities will be taken in to account
2. Alloy electrodes concentration cell
1. With Transport
2. Without Transport (Junction potential is
nullified)
1. Electrode Concentration cell: Two electrodes of different concentration are dipped in a same solution
Gas concentration cell:
➢ Connecting two hydrogen electrodes with hydrogen gas different partial pressures (P)
➢ Emf depends on the pressure of hydrogen gas pass through

L.H. E, PtH R.H.E.

2(P1)  HCl H2(P2)  Pt
H2(P1) ⇋ 2H+ + 2e- 2H+ + 2e- ⇋ H2(P2)
Overall process H2(P1) ⇋ H2(P2)
EMF is Independent of hydrogen ion concentration
𝑷 𝑷
Potential at 298K is 𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑹 − 𝑬𝑳 = −𝟎. 𝟎𝟐𝟗𝟓𝟓 𝒍𝒐𝒈 𝑷𝟐 = 𝟎. 𝟎𝟐𝟗𝟓𝟓 𝒍𝒐𝒈 𝑷𝟏
𝟏 𝟐
➢ P2 < P1, Ecell is positive and spontaneous
➢ Equivalent to expansion of H2 gas
Alloy Electrode
Hg-Pb (C1)  PbSO4(Sol.) Hg-Pb (C2)
𝑪 𝑪
𝑬𝒄𝒆𝒍𝒍 = −𝟎. 𝟎𝟐𝟗𝟓𝟓 𝒍𝒐𝒈 𝑪𝟐 = 𝟎. 𝟎𝟐𝟗𝟓𝟓 𝒍𝒐𝒈 𝑪𝟏
𝟏 𝟐

➢ C2 < C1, Ecell is positive,

➢ lead will spontaneously flow from higher amalgam concentration to to lower concentration
 2. Electrolyte Concentration Cell: Two electrolytes of different concentration are connected
Classified in to two 1. Concentration cell without transport or transference (w.o.t)
2. Concentration cell with Transport
1. Concentration cell without transference (w.o.t.) :
➢ When electrolytes in two half cell are not in direct contact
➢ Ion transport from one half cell to another will not take place directly
➢ To nullify the junction potential, connected through a salt bridge
H+ X
X Cl-
ZnZn2+ (C1) Zn2+ (C2) Zn PtH2(1atm) H+(C1) H+(C2) H2(1atm)  Pt
Potential of electrolyte conc. Cell:
L.H. E, Zn ⇋ Zn2+(C1) + 2e- R.H.E, Zn2+(C2) + 2e- ⇋ Zn

Zn2+ (C2) ⇋ Zn2+ (C1),

Overall process for 1 faraday of electricity is the transfer of one mole of Zn2+ (C2) to Zn2+ (C1)
𝟐. 𝟑𝟎𝟑𝑹𝑻 𝑪𝟐
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑹 − 𝑬𝑳 = 𝒍𝒐𝒈 ➢ C2 > C1, Ecell is positive
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.
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 and
➢ 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
▪ There will be a mobility difference and
▪ creates a Liquid Junction Potential (LJP), Ej
➢ The 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.
Fraction of total current carried by each ion is called transport number (t) 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
If u+ is the speed of cation and u- is the speed of an anion .
𝐂𝐮𝐫𝐫𝐞𝐧𝐭 𝐜𝐚𝐫𝐫𝐢𝐞𝐝 𝐛𝐲 𝐂𝐚𝐭𝐢𝐨𝐧 u+ u−
transport number of cation (t+) = = transport number of anion (t-) =
𝐓𝐨𝐭𝐚𝐥 𝐂𝐮𝐫𝐫𝐞𝐧𝐭 u++ u− 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, Pt  H2 (1 atm)  HCl(C1 M)  HCl C2 M) H2 (1 atm)  Pt R.H. E,
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 solution t- equivalent of Cl- will be transferred from a solution
of concentration C1 to a solution of concentration C2 of concentration C2 to a solution of concentration C1
t+ H + (C1) ⇋ t+ H + (C2) ------1 t- Cl- (C2) ⇋ t- Cl- (C1) --------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 Net transfer of t- equivalent of H + and Gain of t+ gm eq. of H+ ion by process 2
Net gain of H+ ion = (1- t+ ) gm. eq. t- equivalent of Cl – Net loss of H+ ion = (1- t+ ) gm. eq.
= t- gm. eq. t- H + (C2) ⇋ t- H + (C1) ------3 = t- gm. eq.
Net gain of Cl- ion = t- gm. eq. t- Cl- (C2) ⇋ t- Cl- (C1) --------2 Net loss of Cl- ion = t- gm. eq.

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− 𝑭 𝒍𝒐𝒈 𝑪𝟏 𝟐
𝑯𝑪𝒍
= 2 t− 𝑭
𝒍𝒐𝒈 𝑪𝟏
Including junction potential
𝑯𝑪𝒍
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− 𝒍𝒐𝒈 − 𝒍𝒐𝒈
= 𝑭 𝑪𝟏 𝑭 𝑪𝟏
𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 2 t− − 𝟏 = t− + t− − 𝟏
Ej = (2 t− − 𝟏) 𝒍𝒐𝒈
𝑭 𝑪𝟏 = 1-t+ + t− − 𝟏
𝟐.𝟑𝟎𝟑𝑹𝑻 𝑪𝟐 = - t+ + t−
Ej = (t− − t+ ) 𝒍𝒐𝒈 = t− − t+
𝑭 𝑪𝟏

➢ Sign and Magnitude of L.J.P. depends of transference numbers of cation and anion
𝐈𝐟 t− = t+ , then no L.J.P
(t− > t+ ), then L.J.P will be positive
(t− < t+ ), then L.J.P will be negative

𝑲𝑪𝒍 𝒂𝒏𝒅 𝑨𝒎𝒎𝒐𝒏𝒊𝒖𝒎 𝒏𝒊𝒕𝒓𝒂𝒕𝒆 are used in salt bridges 𝒘𝒊𝒍𝒍 𝒉𝒂𝒗𝒆 𝒔𝒂𝒎𝒆 𝒔𝒊𝒛𝒆 𝒂𝒏𝒅 𝒎𝒐𝒃𝒊𝒍𝒊𝒕𝒚
 Five important and interrelated Concepts electrochemistry

➢ In addition to oxidation–reduction reaction, the analyte may participate in other reactions

➢ Current is a measure of the rate of the analyte’s oxidation or reduction

➢ Cannot simultaneously control current and potential

➢ The electrode’s potential determines the analytes form at the electrode’s surface

𝟐. 𝟑𝟎𝟑 𝑹𝑻 [𝑹𝒆𝒅𝒖𝒄𝒆𝒅 𝒔𝒕𝒂𝒕𝒆]

𝑬𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 = 𝑬𝟎𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 − 𝒍𝒐𝒈
𝒏𝑭 𝑶𝒙𝒊𝒅𝒊𝒔𝒆𝒅 𝒔𝒕𝒂𝒕𝒆

➢ The concentration of analyte at the electrode’s surface may not be the same as its concentration in bulk
solution
Polarization: Variation of Electrode potential
➢ The deviation of the electrode potential from the value predicted by Nernst equation
➢ The polarized galvanic cell develop a lower potential and decreased current than predicted
theoretically
➢ Polarization leads to accumulation of charge at the electrode and alters the potential of
➢ cathode to less cathodic (more anodic) and anode to less anodic (more cathodic)
❖ Concentration change
Polarization due to Concentration difference ❖ Presence of surface film

➢ The electrode potential is given by the Nernst’s equation

𝟎.𝟎𝟓𝟗𝟏 +
E = Eo + 𝒍𝒐𝒈 [𝑴𝒏 ]
𝒏

➢ Arises from the inadequate diffusion of species from the bulk of the electrolyte solution to the
vicinity of electrode
+
➢ 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 the variation in electrode potential will also vary
Polarization:
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

 Overvoltage (): is the difference between the theoretical cell
potential and the corrected Nernst equation
➢ Extent of polarization is given by Overvoltage ()
➢ The additional voltage needed to maintain the predicted current

Ecell - Ereal =  = IR Ecell Ereal

I= −
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 Ereal

Overvoltage for Oxygen and hydrogen formation at various electrode

➢ High overvoltage
reduces rate of
corrosion
Electro chemical Or wet corrosion
❖ When the metal is in contact with a conducting liquid
❖ When two metals or alloys are are partially immersed in a solution

❖ Chemically non-uniform surface of metal behave like electrochemical cell (presence of water
containing O2 & CO2)
❖ Anodic (Oxidation) and cathodic (Reduction) areas are formed
❖ Corrosion occurs at anodic areas and metal get oxidized/consumed (Liberation of electron)

Dissolved metal Metal oxide ❖ Electrons flows through the metal to cathode area

Cathode: Mostly not affected (cannot be further redused)

❖ Reduction of H+ or O2 occurs and non-metallic ions can be formed (OH-, O2-)
❖ Depending on the environment, two process occurs
1. Evolution of Hydrogen (absence of oxygen)
2. Absorption of Oxygen
❖ Corrosion product accumulate between anode and cathode
1. Mechanism of corrosion by evolution of Hydrogen gas
In acidic medium (absence of Oxygen)

https://www.sciencedirect.com/science/article/pii/S0013468616305576

In Neutral or Alkaline medium

2H2O + 2e- H2 + 2OH-
2. Mechanism of corrosion by absorption of Oxygen gas

❖ 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:-
• The phenomenon by which the a metal or alloy shows high corrosion resistance than expected from its
position of galvanic series
• 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: Ti, Cr, Al and a wide verity of stainless steel alloys contain Cr metals exhibit
corrosion resistance in oxidative condition

• 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
• shows high corrosion resistance in HNO3 solution.
Ti → Al → Cr → Be → Mo → Mg → Ni → Co → Fe → Mn → Zn → Cd → Sn → Pb →Cu

Passivation is not a permanent state.

Presence of Oxygen automatically repairs the damage
https://www.walter.com/surfox/passivation?setLocale=true
 Type of wet corrosion
A.Concentration cell corrosion: Where a B. Galvanic or bimetallic: Two dissimilar
conducting liquid is in contact with the metal metals or alloys are either immersed or
dipped partially in a solution
Differential aeration
 A. Concentration cell corrosion: Electrochemical attack on metal
➢ Where a metal is in contact (partially immersed) with the a conducting medium of varying concentration or aeration
results in local difference in metal ion concentration
➢ Due to Temperature difference
➢ Inadequate agitation
➢ 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
➢ 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 place(Oxygen deficient area gets corrode)

eg: pit, scale or sand accumulated area
➢ Corrosion gets intensified by time 1. Pitting corrosion
2. Crevice corrosion
3. Concentration cell corrosion
4. Waterline corrosion
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 (formation of pin holes or cavities) by chemical or

mechanical damaged and does not immediately re-passivate.

https://www.ddcoatings.co.uk/2276/what-is-pitting-corrosion
More reading

Passive film

• Due to scratches, non uniform finish, local staining of

other metal stress etc.

• 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 metal is in contact with metal or non metal when oxygen cannot diffuse to
➢ Occurs when stagnant solution got trapped within localized volumes of pockets, corners or
beneath a shield
➢ Corrosion occurring under metal washers

• Crevice area has lack of oxygen (become anodic)

• Exposed area become cathode

➢ Cleanliness and proper usage of sealants (gasket, fastener, etc) avoid corrosion
3. Water-line corrosion
• When metallic surface is partially immersed in an electrolyte and partially exposed to air
• Eg: water is stored in a metallic tank, the metal below the waterline gets corroded.
• Because the water below the waterline is poorly oxygenated and acts as an anode.
• The metal above the waterline is highly oxygenated and acts as a cathode.
• Hence corrosion of metal below the waterline takes place.

• Neutral water, little corrosion

• Marine plants cause waterline corrosion to ocean going ships
• Bottom of the ships are red in color why
4. Intergranular (Inter-crystalline or interdendritic) corrosion
➢ When a corrosive liquid attack the grain boundaries than grain interiors in the presence of
tensile stress, cracking may occur along grain boundaries
➢ The crack forms through the grain boundaries and does not propagate through the grains
interiors
➢ Localized type of attack that occurs along microstructure grain boundaries and might
also affects adjacent areas without the external sign of intensive attack

➢ During corrosive liquid attack, solid solution forms due to precipitation of some material at the boundaries
➢ When grains contain material, which shows electrode potential more anodic than that of grain center material at boundaries
Eg: Occurs in steel alloys with chromium, niobium or titanium, and in aluminum alloys with copper or magnesium

➢ Intergranular corrosion in stainless steel may result from precipitation of carbides, nitrides or intermetallic phases during
welding process

➢ Usage of low carbon content (0.03%) avoids this problem or usage of trace of Ti in 0.08% steel avoid steel corrosion
 5. Stress corrosion (static stress cracking) or Stress corrosion cracking (SCC)
A combined effect of static tensile stress and corrosive environment such as
I. Chlorides affects steels and aluminum
II. Caustic alkalis and strong nitrates on mild steel,
III. Trace of ammonia on Zn & Ni brass,
➢ Stress (even small bending) produce strains and cracking , which results in localized zone of higher
potential
➢ SCC localized electrochemical attack, then narrow stressed paths act as anode all other part act as
cathode

Eg: Materials (ceramics, glasses, polymers etc.) which SCC generally occurs, pipework, highly stressed components and
pressure vessels
Metals that undergo stress corrosion are stainless steel, copper and aluminum alloys
➢ Stress corrosion occur in three steps (1) crack initiation, (2) crack propagates or stays,
(3) crack propagate until final failure
Types of Stress corrosion
1. Season cracking (residual stress in copper alloys due to cold working)
2. Caustic embrittlement (corrosion of mild steel caused by strong alkali ) Prevention
1. Giving suitable treatment to relieve the stress
2. Adjusting the composition and eliminating inmpurites
3. Removing corrosive environment
 B. Galvanic corrosion or differential metal corrosion(DMC)
• Galvanic corrosion can occur when dissimilar metals are in contact in the presence of an
electrolyte.
• An electrolyte is 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 soldar 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:-
• Essentially, galvanic corrosion occurs when two different metals immersed in an electrolyte are joined
together.
• 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 electrolyte It does not
(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 metal
➢ Position in the galvanic series: more active metal under go corrosion, rate of corrosion depends on difference in their
position
➢ Overvoltage: high overvoltage lower the corrosion
1. Zinc rode with Cu impurity dipped in in H2SO4, accelerate corrosion
2. Fe-Pb alloy get corroded 3. Fe-Sn couple corrode in Oxygen atmosphere etc
➢ 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
 Nature of Environment
➢ Temperature: Diffusion rate will increase and there by corrosion too
➢ Humidity: deciding factor of corrosion. Critical Humidity : above which the corrosion rate is high. It depends on nature of
metal and corrosion product. (Protective oxide layer can washed away)
➢ Presence of impurities in atmosphere: Industrial gases like CO2, SO2, H2S and fumes of HCl and H2SO4 increases
corrosion. Marine chemicals can corrode vessals.
➢ 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 clayey 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
➢ Polarization electrode: Corrosion rate is controlled by the current flow
Polarization electrode: Potential difference between the cathode and anode is the driving force for corrosion
➢ Polarization of electrode alters the potential of
➢ cathode to less cathodic (More anodic)and
➢ anode to less anodic (More cathodic)
➢ potential difference will decrease there by the current and the corrosion rate too

➢ Rate of corrosion can be minimized by adding some inhibiters that will bring irreversible change in the electrode and tend to
oppose the direction of current flow.

➢ Initially the corrosion rate is low but increase as the potential difference between cathodic and anodic areas increases,
ultimately reach 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)
Value of Corrosion Current (Icorr) = Anodic current density (Ia) - Cathodic current density (Ic)

➢ The value of Corrosion Current (Icorr) depends on

➢ Relative area of anode and cathode
➢ Current densities at anode and cathode
➢ Potential difference between anode and cathode
➢ Polarization characteristic of anode and cathode
➢ Temperature: corrosion rate will be lower as diffusion will be lower
 Corrosion Current (Icorr) = Anodic current density (Ia) - Cathodic current density (Ic)
➢ If the anode surface area is larger than cathode surface area then Ia > Ic then Icorr will be larger and anode material will
undergo accelerated corrosion
➢ Greater the extent of polarization of electrode then the corrosion will be smaller

A plot of potentials of Polarized electrodes against current density is called Evans diagram Or polarization curves and
Steeper slope represents a greater polarization
➢ The point of intersection of the two cure is the Ecorr and the current at this point is Ic

Anode is undergoing Cathode is undergoing Anode and Cathode are

polarization polarization undergoing polarization

➢ Inhibitors are added to enhance the polarization to control corrosion

66
 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 to corrosion, physical
appearance, hardness and surface properties
• 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
 Electrochemistry

Study of relationship between chemical and electrical energy

Galvanic Cell Electrolytic Cell

A spontaneous chemical Electric current drives a
reaction generates an non-spontaneous reaction
electric current

Recollect the basics: Conductor, insulator, metallic conductors,

electrolytic conductors, electrolytes (Strong, Weak, non-electrolyte)
Electrode Potential (E) (Oxidation Potential & Reduction Potential)
Standard Electrode Potential (E)
Daniel Cell
Cell Potential / Cell EMF Determination of Electrode Potential

(Nernst Equation)
Electrochemical Series Poggendorff’s Compensation Method
For Determination of Cell EMF

𝐸𝑥 𝐴𝐷
=
𝐸𝑠 𝐴𝐷 ′
Applications of EMF measurement Electrolytic Cell
Electrorefining of Cu
1. Determination of G and K
2. Determination of feasibility
Concentration Cells
Electrode Concentration Cell Electrolyte Concentration Cell
(Without transference)
Zn-Hg (C1) / ZnSO4 / Zn-Hg (C2)
Pt, H2 (P1) / H+ (C1) / Pt, H2 (P2) Pt, H2 (1 atm) / H+ (C1) // H+ (C2) / Pt, H2 (1 atm)

0.0591 𝑐2
𝐸= log
0.0591 𝑐1 𝑛 𝑐1
𝐸= log
𝑛 𝑐2 Electrolyte Concentration Cell
(With transference)

Pt, H2 (1 atm) / H+ (C1) // H+ (C2) / Pt, H2 (1 atm)

0.0591 𝑐2
𝐸 = t− log
𝑛 𝑐1
Applications of Concentration Cells

1. Determination of solubility of sparingly soluble salt

2. Determination of valency of an ion in doubtful cases
3. Determination of pH
Corrosion
Wet Corrosion / Electrochemical Corrosion
 DMC DAC

Intergranular Corrosion
Pitting Corrosion
Polarization of Electrodes
Concentration change in the electrode region
Formation of film

Chemical Conversion Coatings

Phosphate coatings
Chromate coatings
Chemical oxide coatings
Anodized coatings

Organic Coatings (Paints, Varnish, Enamels, etc.)

Paints – Dispersion of dyes in vehicles

Vehicle = drying oil + thinner
Drying oil – Glyceryl esters of fatty acids
Thinners – Turpentine, kerosene, benzene, etc.
 ARTICLE
https://doi.org/10.1038/s41467-020-20876-9 OPEN

Defect-driven selective metal oxidation at atomic

scale
Qi Zhu 1,6, Zhiliang Pan2,6, Zhiyu Zhao1,6, Guang Cao1, Langli Luo 3, Chaolun Ni1, Hua Wei4, Ze Zhang1 ✉,
Frederic Sansoz 5 ✉ & Jiangwei Wang 1 ✉
1234567890():,;

Nanoscale materials modified by crystal defects exhibit significantly different behaviours

upon chemical reactions such as oxidation, catalysis, lithiation and epitaxial growth. However,
unveiling the exact defect-controlled reaction dynamics (e.g. oxidation) at atomic scale
remains a challenge for applications. Here, using in situ high-resolution transmission electron
microscopy and first-principles calculations, we reveal the dynamics of a general site-
selective oxidation behaviour in nanotwinned silver and palladium driven by individual
stacking-faults and twin boundaries. The coherent planar defects crossing the surface exhibit
the highest oxygen binding energies, leading to preferential nucleation of oxides at these
intersections. Planar-fault mediated diffusion of oxygen atoms is shown to catalyse sub-
sequent layer-by-layer inward oxide growth via atomic steps migrating on the oxide-metal
interface. These findings provide an atomistic visualization of the complex reaction dynamics
controlled by planar defects in metallic nanostructures, which could enable the modification
of physiochemical performances in nanomaterials through defect engineering.

1 Center of Electron Microscopy and State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou
310027, China. 2 School of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, Guilin 541004, China. 3 Institute of Molecular
Plus, Tianjin University, Tianjin 300072, China. 4 Center for Hypergravity Experimental and Interdisciplinary Research, Zhejiang University, Hangzhou 310027,
China. 5 Department of Mechanical Engineering and Materials Science Program, The University of Vermont, Burlington, VT 05405, USA. 6These authors
contributed equally: Qi Zhu, Zhiliang Pan, Zhiyu Zhao. ✉email: zezhang@zju.edu.cn; frederic.sansoz@uvm.edu; jiangwei_wang@zju.edu.cn

NATURE COMMUNICATIONS | (2021)12:558 | https://doi.org/10.1038/s41467-020-20876-9 | www.nature.com/naturecommunications 1

ARTICLE
N
anotwinned materials possess a wide range of unprece-
dented mechanical and physical properties such as ideal
maximum strength1–3, excellent ductility4, good fatigue
resistance5, high electrical conductivity6, and exceptional thermal
stability7 due to the existence of coherent twin boundaries (TBs).
With the advent of nanotechnology, TBs have also been revealed
to critically influence the catalytic reactivity8, electrochemical
efficiency9, growth dynamics10, and oxidation rate11,12 of metallic
nanomaterials, which can be ascribed to the change of both
surface properties (e.g., coordination number, stress state, and
charge density) and internal lattice dynamics (e.g., diffusion) by
TBs. Since the reaction dynamics at TBs play an important role in
subsequent structural evolution and functionality of metallic
nanomaterials10,12,13, an atomic-scale understanding of this
coherent defect contribution to chemical/electrochemical reac-
tivity in nanomaterials is of general significance. However, in
stark contrast to the well-established understanding of strength-
ening and softening mechanisms in nanotwinned materials3,14,15,
the atomistic origins of TB-assisted reactivity in nanotwinned
materials have been largely elusive.
Recent studies of nanotwinned metallic nanoparticles attrib-
uted their superior catalytic performance to low-coordinated
atomic steps, large tension, and high density of negative charges
on the surface, which are critically affected by the presence of
TBs16–20. These studies suggest that coherent TBs act as pre-
ferential sites for selective chemical/electrochemical reactions and
as channels for fast atom transport19,21. Likewise, experimental
studies have found that TBs significantly reduce the energy bar-
riers for growth13, mass transport9, and solid-state reaction22. On
the contrary, the twin-modified surface structures were reported
to enhance the resistance to corrosion and oxidation in nanot-
winned metals, compared to their twin-free nanocrystalline
counterparts12,23. Therefore, the critical influence of TBs on the
chemical response of metallic nanomaterials under different
environments is still under debate. To date, however, systematic
investigations of the defect-assisted oxidation dynamics at the
atomic scale remain challenging in practice.
Here, we study the oxidation dynamics of nanotwinned
metallic nanocrystals in atomistic detail by conducting integrated
in situ transmission electron microscopy (TEM) characterizations
and density-functional-theory (DFT)-based ab initio calculations.
The results expose a unique site-selective oxidation behaviour in
nanotwinned silver (Ag) and palladium (Pd), where the inherent
planar defects including coherent TBs and stacking faults (SFs)
strongly favour surface oxygen binding and accelerate oxide
nucleation. Subsequent inward growth of the oxide is governed by
the promoted oxygen diffusion along the planar defects that
intersect with the oxide–metal interface, leading to layer-by-layer
oxidation. Furthermore, we qualitatively validate this defect-
assisted oxidation dynamics in air over largely different time
scales spanning from few seconds to several days. These findings
provide atomistic visualization and mechanistic understanding of
defect-assisted reaction dynamics in nanoscale metals, which has
direct ramifications for the development of advanced nanoma-
terials through defect engineering.
Results
Selective oxidation of nanotwinned Ag along isolated TBs and
SFs. In contrast to the widely reported oxidation of nanosized
face-centred cubic (FCC) metals (e.g., Cu and Pd) from the {111}
and {100} facets24–26, our in situ experiments unambiguously
demonstrate preferential oxide nucleation at the TB-surface
junction, even in the presence of numerous low-energy (111)
facets on the nearby surface. As shown in Fig. 1a, the as-
2 NATURE COMMUNICATIONS | (2021)12:558 | https://doi.org/10.1038/s41467-020-20876-9 | www.nature.com/naturecommunications
NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-20876-9
fabricated Ag nanocrystal consists of a coherent TB along the
axial direction, which is confirmed by the fast Fourier transform
(FFT) pattern in Fig. 1f. Upon oxidation, sequential images
clearly show that an oxide embryo preferentially nucleates at the
twinned tip (Fig. 1b), although the lattice structure of this as-
formed oxide embryo cannot be quantitatively identified. After
88 s, recognizable lattices appear as the oxide grows continuously
inward along the TB (Fig. 1c). Meanwhile, the oxide expands
laterally to form an asymmetrical conical cap sitting on top of the
nanocrystal (Fig. 1d). No oxidation was detected on {111} facets
away from the TB, suggesting a strong site-selective behaviour
upon oxidation of this nanotwinned Ag. A close-up high-reso-
lution TEM image is presented in Fig. 1e to show the atomistic
structure of the oxidation product (Ag2O) above the Ag matrix at
the tip. The interface is atomically sharp with a one-atom-layer
(111) step. The corresponding FFT patterns (Fig. 1g) further
confirm the as-formed oxide of Ag2O with a lattice constant of a
= 4.718 Å (space group: Pn3m), which bears a specific orientation
relation with the Ag matrix as ð110ÞAg //ð100ÞAg2 O and (111)Ag//
ð010ÞAg2 O . It is further observed that oxidation along the TB
always precedes that of the neighbouring lattices, as shown in
Fig. 1e, which reflects an evident TB-assisted oxidation. Such
selective oxidation mechanism is more conspicuous during the
subsequent growth of this oxide layer, because the thickness of
oxide (along axial direction) decreases gradually from ~ 3.4 nm at
the tip down to almost zero at free surfaces on both sides (Fig.
1d). No other defect activity is observed throughout the oxidation
process of this Ag nanocrystal.
Atomic-level snapshots in Fig. 1h–k further emphasize the
preferential oxide nucleation at the TB-surface junction. A
zoomed-in image shows the atomic structure of the Ag
nanocrystal with a clean surface, which exposes two conjugate
(111) facets with multiple atomic kink steps very close to the TB-
surface junction, while a high density of alternate (111) and (111)
atomic facets dominate on both sides of the surface away from the
TB (Fig. 1h). The oxygen atoms are preferentially adsorbed to the
surface layer of Ag near the TB (shown by the blurred profile of
the top surface in Fig. 1i), which induces an evident lattice
distortion in the sub-surface layers. In contrast, the faceted
morphology of the surface away from the TB is generally retained,
indicating less oxygen adsorption on these low-energy facets.
Eventually, the adsorbed oxygen accumulating at the TB-surface
junction incubates an oxide nucleus with an average height of 4.8
Å (Fig. 1j). With prolonged oxidation, the Ag2O layer
simultaneously grows inward along the TB and expands laterally
along conjugate oxide–metal interfaces (Fig. 1k).
The above experiment demonstrates a TB-assisted site-specific
oxidation behaviour in Ag nanocrystal, which dominates over
those widely reported low-energy surface facets for the nucleation
and growth of oxides24–26. This unique behaviour is further
validated in additional examples of Ag nanocrystals with an axial
coherent TB (see Supplementary Fig. 1), where the TB-surface
junction serves as a universally preferential nucleation site for
oxide embryos, followed by oxide growth along the TB. Similar
oxidation behaviours are also observed in other FCC metallic
nanocrystals, e.g. Pd, with significantly higher stacking fault
energy (Supplementary Figs. 2–4). This common site-selective
nucleation and TB-assisted growth of oxide clearly indicate that
an isolated TB can effectively promote the oxidation of FCC
metals, which markedly differs from the suppressed chemical
reactivity of nanotwinned Cu nanowires reported previously27.
Furthermore, this phenomenon was found to occur with an
individual TB positioned away from the Ag tip (i.e., with different
surface curvatures, see Supplementary Fig. 5), which suggests that
the TB effect is mainly intrinsic. DFT-based atomistic simulations
NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-20876-9 ARTICLE

a 0s b 80 s c 88 s d 96 s e f (111)M (111)T
(002)M
(002)T

UHV 2.5 nm 3.4 nm

Ag2O
(111)
(111)TT (111)M
Ag2O
BD=[110] Ag
TB
g (020)

TB (011) (011)
(111)

Ag
Ag BD=[100] Ag2O

h (111) facet
Kink step
i O absorption j Nucleus k Ag2O
(111)

TB

Fig. 1 Twin boundary-favoured oxidation of Ag nanocrystal. a Pristine Ag nanocrystal with a pre-existing twin boundary (TB) along the axial direction,
which was placed in the ultrahigh vacuum (UHV) column of the transmission electron microscope (TEM). The nanocrystal has a clean surface with
dominant (111) facets. b–d Dynamic snapshots showing the oxidation process of the Ag nanocrystal. The oxide embryo preferentially nucleated at the TB-
surface junction (b), which grew continuously along the TB and expanded laterally on the nanocrystal surface (c, d). The red dotted loop delineates the
oxidized region. e Zoomed-in image showing the atomistic structure of the as-formed Ag2O (top) and the Ag matrix (bottom). f, g Fast Fourier transform
(FFT) patterns of the Ag nanocrystal with an axial TB and the oxidation product of Ag2O, respectively. h–k Atomistic nucleation and growth of oxide at the
surface–TB junction. h Clean surface of the nanocrystal with alternate (111) atomic facets and kink steps, where a higher density of kink steps pre-exist near
the TB. i Preferential surface adsorption of oxygen at the TB tip, as indicated by the red dotted curve. j A tiny oxide nucleus formed at the TB-surface
junction. k Continuous growth of Ag2O along the TB, as shown by the red arrow. Scale bars in a 5 nm; e, h 2 nm.

were performed to quantitatively confirm our hypothesis by
calculating the Ag–O surface binding energy (Eb), which further
decoupled the intrinsic influence of TB from other atomic surface
steps. We first constructed a twinned Ag tip (consistent with our
experiments) with a junction between a vertically aligned
coherent TB and two perfectly smooth (111) conjugate surfaces.
These calculations reveal that the O interstitial sites closest to the
TB possess the highest mean oxygen binding energy Eb = 3.907
eV, compared with Eb = 3.855 eV at the neighbouring interstitial
sites on the (111) surface farther away from TBs of the
nanocrystal (Fig. 2a, b). Therefore, oxide nucleation should
preferentially occur at the TB-surface junctions, which matches
perfectly with our experimental observations. Furthermore, we
find that the mean Ag–O binding energy at a kink step on the
(111) surface (Eb = 3.870 eV, see Fig. 2c and Supplementary
Fig. 6) is slightly higher than that at the smooth (111) surface,
which may also serve as preferential oxygen absorption sites.
These theoretical results are significant in three aspects. First, the
DFT calculations quantitatively prove that both isolated TBs and
kink steps give rise to stronger surface binding of O atoms.
Second, it has been reported that twinning creates low-
coordinated sites at the TB-surface junctions of nanotwinned
metals, to which dioxygen preferentially bonds28, suggesting that
the reactivity of surface atoms maybe directly relate to their
coordination number (CN). Here, our DFT-based calculations
confirm that the higher oxgen binding energy is closely related to
the lowest CN at a convex TB-surface (CN = 8), compared with
its neighbouring sites (CN = 9). Third, we noted that the
difference of mean oxygen binding energy between a twinned
tip and a kink step without TB is comparatively small (Fig. 2b, c).
However, it is important to emphasize that these two types of
binding site structures are not directly comparable because it is
only justifiable to study the two equivalent sites for the twinned
tip and smooth (111) facets, as opposed to surveying multiple
sites with severely fluctuant binding environments at the kink
step (Supplementary Fig. 6). Occasionally, Eb of certain binding
sites at the kink step can even exceeds that at the TB tip.
Nevertheless, the mean binding energy at an individual TB
surpasses that at a kink step, despite the naturally lower CN =7 of
the kink step. Therefore, we can conclude that the lowest CN is a
good indicator for local maximum of Eb when comparing the
binding sites near or away from the TB in the same model, but
this is not the case when comparing sites across completely
different surface configurations.
Oxidation efficiency as a function of defect configuration and
spacing. Analogous to the strong twin-size dependence of
mechanical behaviours in nanotwinned metals1–3, it is significant
to study how the chemical reactivity and oxidation behaviour
could vary with TB spacing, because smaller twins are frequently
observed to reduce the reactivity via surface modification12. To
this end, DFT calculations are used to quantify the mean oxygen
binding energy averaged over multiple O interstitial sites of dif-
ferent defect-modified surface configurations (as shown in Fig. 2d
and Supplementary Fig. 7), which overcome the technical diffi-
culties in controlling TB spacing experimentally. Specifically, we
calculated the mean binding energies of different nanotwins
(NTs) with a constant TB spacing varied from 4.8 Å to 28.8 Å, in
comparison to that of two single-crystal configurations contain-
ing either an isolated SF or no imperfection (SGL), as shown in
Supplementary Figs. 8 and 9. The surface intersecting either TB
or SF is composed of zig-zag low-energy (111) and (001) facets
(insets of Fig. 2d). For consistency, the perfect single crystal
configuration was constructed with the same type of zig-zag facets
on the surface. Figure 2d shows that the mean Eb of NTs is
noticeably higher than that of SGL, which agrees with our
experimental observations (Fig. 1). However, the binding energy
tends to decrease as the TB spacing is reduced, which is in good
agreement with the uniform and slower oxide growth observed in
regions of copper nanowires containing dense and evenly spaced
TBs12,27. The lower binding energy with decreased TB spacing
could be attributed to the local change in the bonding environ-
ment of the oxidation site at the surface. Specifically, we have
found that the oxidation sites with neighbouring atoms of lower
CN tend to possess higher binding energies. Atoms at the convex
tip and on the neighbouring (111) surfaces have a CN of 8 and 9,
respectively, while those at the concave V-edge TB site have a
larger CN of 10. Increasing the twin density decreases the dis-
tance between the V-edge site and the tip site. When the distance
between the two types of sites is small (i.e., low TB spacing), the

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ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-20876-9

Fig. 2 Density functional theory based calculations of the mean Ag–O binding energy at different surface sites of single crystal (SGL), nanotwinned
(NT) and stacking fault (SF) contained Ag. a, b Mean oxygen binding energy (Eb) at the atomically smooth (111) facets and the twinned tip, respectively.
The oxygen atom is shown in red colour. Atoms at the planar faults are highlighted in green and other atoms in Ag are coloured using the coordination
number analysis (CNA), as defined by the colour scale bar (black for lowest CN = 7 and yellow for highest CN = 12). c Mean Eb for a (111) kink step in SGL
Ag. d Mean Eb at different surface sites of SGL, NT and SF contained Ag nanocrystals, where the twin-boundary spacing (TBS) varies from 4.8 Å to 28.8 Å.
The highest mean Eb is predicted to occur near isolated TBs (TBS = 14.4 Å and 28.8 Å) and near the SF. The different surface configurations are shown in
the insets, where the (001) and (111) surface facets are delineated with solid and dotted lines, respectively. Error bars represent the standard deviations
from statistical analyses, where the two highest energies (n = 2) are chosen for each nanocrystal configuration.

increased average CN among the neighbouring atoms at the tip
will reduce the binding energy. Such effects on the average CN
and bonding environment become substantial when the V-edge
site is close enough to the tip, which explains the negligible
change of Eb from TBS = 28.8 Å to 14.4 Å followed by con-
siderable drop with decreasing TBS thereafter. Even more
remarkably, the mean Eb at an isolated SF reaches 3.981 eV
(Supplementary Fig. 9), which surpasses those of NTs with any
size, indicating a preferential oxidation at the SF as compared
with NTs. It is worth mentioning that the V-edge at the TB-
surface junction (concave configuration) could act as a pinning
site for diffusing Cu adatoms and promotes the dynamic for-
mation of a Cu atom row (termed as W-chain) with lower CN
and high chemical reactivity28. Therefore, while the CN principle
is generally consistent with the results of our theoretical calcu-
lations, certain local differences may exist experimentally at the
concave and convex configurations due to dynamic surface atom
reconstruction.
Additional experiments in samples with different planar
defects further confirm the strong site-selective and defect-
assisted surface oxidation in Ag and Pd nanocrystals, as shown in
Fig. 3 and Supplementary Figs. 4 and 5. Specifically, Fig. 3a–d
gives clear evidence for the SF-assisted oxidation in Ag
nanocrystals with an isolated horizontal SF and multiple inclined
TBs. The pre-existing SF laid almost perpendicular to the [111]
axial direction of the Ag nanocrystal (Fig. 3a), intersecting the
nanocrystal surfaces on both sides. A close-up image in the inset
shows that the surface is oriented almost perfectly parallel to the
(112) plane, albeit some (111) kink steps exist near the surface-SF
junction. Upon initial oxidation, two oxide embryos nucleate
simultaneously at the SF-surface junctions on both sides (Fig. 3b).
This observation agrees well with the highest O binding energy at
SF predicted by DFT. Moreover, the oxide embryo is followed by
inward growth along the SF (Fig. 3c, d) similarly to our previous
observations at individual TBs, where the average oxidation rate
(along the SF) is calculated to be ~0.06 nm s−1 (Supplementary
Fig. 10). In contrast, the nucleation and growth of the oxide
embryo at the TB occurred far later than that at the SF,
confirming the preferential oxygen adsorption at the SF-surface
junction predicted in our DFT calculations.
To further compare the oxygen binding energy at the SF and
TB under the same orientation, in situ oxidation experiments
were conducted on an Ag nanocrystal containing SF and multiple
parallel TBs with uneven spacing, as shown in Fig. 3e–h. The

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NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-20876-9 ARTICLE

a 0s b 11 s c 22 s d 50 s

SF
(111)

(112) Embryo
(L)

Ag2O
Embryo
(R)
Ag2O

e 0s f 16 s g 24 s h 38 s

SF

Ag SF SF Ag2O

UHV Ag2O
Embryo

Fig. 3 Selective oxidation of Ag nanocrystals with different planar defect configurations. a–d Preferential oxidation of an Ag nanocrystal with an isolated
SF. a, b Two oxide embryos formed preferentially at the SF-surface junctions on both sides (indicated by the light blue arrows), while the TB-surface
 plane and several (111)
junctions remained intact. Inset in a shows the atomistic structure of the surface near the SF, which consists of atomically flat (112)
kink steps. c, d Subsequent SF-assisted fast inward and lateral growth of Ag2O island. Meanwhile, oxide nucleation and growth was initiated at the TB3-
surface junction away from the SF. e–h Preferential oxidation in an Ag nanocrystal with unevenly spaced planar defects. e Multiple parallel TBs (#1–6) and a
SF (indicted by the white arrow) pre-existed in the as-fabricated Ag nanocrystal with a clean surface. f Oxide embryo nucleated preferentially at the SF-
surface junction. g Inward growth of the Ag2O island along the SF plane. h Integrated inward and lateral growth of the Ag2O oxide with the annihilation of
the SF. No evident oxidation was observed at the TB-surface intersection sites nearby. Insets in e, f are zoomed-in snapshots presenting the atomistic
nucleation processes of the oxide embryo at the SF-(111) surface facet junction. Scale bars in a and e: 5 nm.

surface configuration is almost identical near the intersection sites
with either SF or TB (Fig. 3e), which decouples the influence of
different surface facets on the defect-assisted oxidation. An oxide
embryo preferentially nucleates at the SF-surface junction located
between two TBs (TB3 and TB4 with a spacing of 1.88 nm),
connecting a large twin to one of the smallest twins (Fig. 3f). It is
worth noting, however, that no observable oxidation occurs at the
nearby surface intersected by TBs. Subsequent inward growth of
this oxide island preferentially proceeds along the SF (Fig. 3g, h),
suggesting that SF is a faster pathway for oxygen diffusion.
Associated with the inward oxide growth is the lateral expansion
of the oxide along the surface facets (consistent with that at the
surface–TB junction), which generates a spindle-shaped oxide. In
summary, strong site-selection dictates the defect-assisted surface
oxidation in metallic nanocrystals containing multiple TBs and
SFs, and the general significance of coherent planar defects as fast
pathways for oxygen diffusion is unambiguously demonstrated
(see an additional example in Supplementary Fig. 11).
Defect-assisted oxidation mechanism and kinetics. Figure 4a–d
presents a series of TEM snapshots showing the atom-level
dynamics of TB-assisted oxide growth during the twinned tip
experiment in Fig. 1. Upon nucleation, the interface between Ag
nanocrystal and as-formed Ag2O contains six single-atom-layer
steps (Fig. 4a). For the next second, the pre-existing steps migrate
laterally along the Ag/Ag2O interface away from the TB, while the
atoms at the TB tip react into Ag2O, inducing a pair of new steps
(7 and 8) in the sub-layer (Fig. 4b). This specific event suggests
that interstitial O atoms are more rapidly diffused along the TB to
bind with freshly exposed Ag atom columns, during which short-
cut diffusions along the TB plane is likely to occur29. In the
following seconds, each newly formed step moves away on the
Ag/Ag2O interface (Fig. 4c) and gives space for the formation of
new Ag2O lattices into sub-layers initiated from the TB (Fig. 4d).
This layer-by-layer oxide growth is similar to the growth of CuO
nanowires assisted by (002) TBs13, and eventually generates a
conical oxide cap on the Ag nanocrystal (Fig. 1d).
The layer-by-layer growth mechanism is schematically illu-
strated in Fig. 4e, where the TB atoms in the top Ag layer and
atomic steps on the Ag/Ag2O interface naturally possess a lower
CN than those in the perfect FCC lattice (CN = 12). In fact, our
DFT calculations have indicated that the CN of FCC Ag atoms
decreases to CN = 10 at the Ag/Ag2O interface (Supplementary
Fig. 12). Therefore, these low-coordinated Ag atoms at the oxide
interface favour oxygen binding and induce a ledge flow
mechanism at the reaction front30, which is supported by
experimental evidence (Fig. 4a–d). Furthermore, the surface
oxide sitting on the nanotwinned tip is observed to grow
continuously, suggesting that the coupled axial and lateral
propagation of the Ag/Ag2O interface arises from fast diffusion
of O atoms along the TB31. Similar TB-assisted diffusion has been
reported in SnO2 nanowire for Li ions (during lithiation)9 and in α-
Ti for O interstitials32. Also, the same evidence of TB-assisted layer-
by-layer oxidation dynamics was found in our additional experi-
ments of nanotwinned Pd, as exemplified in Supplementary Fig. 3.
The time-dependent oxidation kinetics along the TB is
quantified in Fig. 4f. The TB-assisted oxidation of Ag nanocrystal
(shown in Fig. 1) can be divided into three stages, i.e., fast
nucleation, steady growth, and self-limiting equilibrium. During
the fast nucleation (t ≤ 80 s), an oxide embryo nucleates by

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ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-20876-9

a Ag2O 84 s e O2 f
5 Fast nucleation Steady growth Self-limiting
4 6
1 2 3 (0-80 s) (80-200 s) (200-240 s)
10
Ag

B (nLm(nm)
TB
L=0.0085t+0.0678

)
b 85 s
TB 1.5
i
8

long TTB,
4 6 1.0
7 8 5

L (nm)
1 2 3

ngth aalong
6 0.5
L=−12.169+4.5ln(t-64.56)
c

Oxide ledepth
86 s 0.0
0 40 80 ii
t (s) 10
7 6 4

L (nm)
4

Oxidation
3 5+8
5

Ag2O 2
d 87 s 0
100 150 200 250
t (s)
7 9 10 5 0
3 4 8 0 50 100 150 200 250
Oxidization time(s)
Oxidation time (s)

Fig. 4 Dynamics of TB-assisted oxidation in Ag nanocrystal. a The sharp reaction interface between the Ag matrix and the as-formed Ag2O containing
atomic steps (#1–6). b Inward oxidation along the TB, as shown by the dissolution of atoms at the TB tip (pointed out by the aqua arrow) into the oxide
(Ag2O), which induces two new atomic steps (#7 and 8). c, d Consecutive nucleation of interface steps from the TB junction, which migrate laterally along
the conjugate (111) facets, leading to layer-by-layer oxidation of the Ag nanocrystal. e Schematic showing the layer-by-layer kinetics of TB-assisted
oxidation in Ag nanocrystal. The atom columns at the TB tip, interface steps, and interface terraces are coloured aqua, dark blue and red, respectively. f The
time-dependent inward oxide growth (characterized by oxidation depth, L) along TB in the Ag nanocrystal presented in Fig. 1. The oxidation depth-time plot
was obtained by measuring the distance between the original surface–TB junction and the advancing interface–TB junction. Insets are the mathematical
fitting of time-dependent oxide growth during different stages. Scale bar in a: 1 nm.

adsorption of rarefied oxygen atoms from the ultrahigh vacuum
chamber of TEM. Our DFT calculations have predicted intrinsic
TB and SF effects that yield a substantial increase in the surface
binding energy of oxygen in Ag nanocrystals. Quantitative
analysis in inset 1 of Fig. 4f confirms this theory by revealing
that the axial oxidation depth L (along TB) during the nucleation
period is a linear function of time. A linear-type reaction is
commonly associated with initial fast oxidation observed on a
number of metals at low temperatures33. Subsequently, TB-
assisted inward growth of the oxide proceeds layer-by-layer
(Fig. 4e), which is referred to as the steady-growth stage (80 s <
t ≤ 200 s). We have also plotted the cumulative step migration at
the reaction front with time during the initial stage of inward
oxide growth (Supplementary Fig. 13), which is consistent with
the trend of L−t plot, indicating the dominant role of layer-by-
layer oxide growth via the TB-promoted nucleation and
migration of interface steps. Our quantitative study in inset 2 of
Fig. 4f further shows that the overall oxide growth kinetics follows
a logarithmic law during steady growth, which is typically due to
the electron tunnelling and ionic O flow in very thin oxide
films33. However, the observation of spindle-shaped oxide islands
(see Fig. 3 and Supplementary Fig. 2) indicates that oxygen
diffusivity along TBs in the thin oxide layer is generally enhanced
in comparison to the diffusivity on close-packed {111} planes in
FCC metals, which agrees well with recent DFT calculations32.
Meanwhile, the high oxygen concentration radiates from the TB
to propel the lateral flow of newly formed steps along the Ag/
Ag2O reaction front with low CN. As the oxide thickness grows to
~10 nm, however, few O ions are pumped towards the oxidation
front (i.e., short of oxygen supply), leading to a gradually
decreased oxide growth rate. This process is self-limiting under
our experimental condition, because oxygen is rare in the TEM
chamber. A similar oxidation trend is observed along an SF as
well (see Supplementary Fig. 10).
Discussion
It is established that by tunning the defect density and config-
urations, the surface morphology, strain gradient, or charge
density can be changed markedly16–19,27, enhancing the chemical
reactivities in metallic nanoparticles. In essence, the TB-mediated
oxidations have already been reported11; however, the kinetic
origin of the defect-facilitated oxidation at the atomic scale has
been largely elusive. Here, our integrated in situ TEM observa-
trions and DFT calculations unambiguously elucidated a CN-
governed site-selective oxidation at both the TB and SF in FCC
metallic nanocrystals. The highest Eb at the TB/SF–surface
junctions favours the preferential oxygen adsorption and thus
oxide nucleation; meanwhile, the enhanced oxygen diffusion
along the planar defects greatly facilitates the continuous for-
mation of steps at the reaction front and their lateral migration
along the oxide–metal interface, leading to layer-by-layer growth
of the oxide. Namely, the site-selective oxidation of Ag and Pd
nanocrystals with pre-existing planar defects is not only con-
trolled by the nucleation dynamics, but also facilitated by the
diffusive growth kinetics, resulting in a nucleation-growth cou-
pling of oxidation. This coordinated oxidation mechanism of
metallic nanocrystals advances our mechanistic understanding of
the defect-assisted reactivities.
From the thermodynamic perspective, the formation of oxide
on the Ag surface is governed by the change of free energy, which
can be derived according to Eq. (1):


ΔG ¼ ΣAs γs þ ΣAi γi þ ΔG Ag2 O ΣAAg γAg ð1Þ
where γs, γi, and γAg represent the surface energies of the oxide,
oxide–metal interface, and the Ag matrix; As, Ai, and AAg denote
the corresponding surface or interface area; ΔG (Ag2O) is the
volume energy of Ag2O34. It is widely acknowledged that the
chemisorbed layer on the fresh metallic surface reduces the cor-
responding surface energy, resulting in a decreased value of
ΣAAgγAg. Therefore, the surface adsorption of oxygen atoms
impairs the intrinsic dynamics for further oxidation. However,
the higher oxygen binding energy at the TB/SF results in a site-
selective oxygen adsorption, where only localized oxide embryo
and oxide–metal interface forms, in stark contrast to the large
area interface over the entire metal substrate. Therefore, the
energy rise associated with the formation of oxide surface and
oxide–metal interface can be significantly reduced, leading to a
lower oxide nucleation barrier ΔG. This qualitative thermo-
dynamic analysis indicates that further oxidation process at room
temperature should be essentially accelerated at the TB/SF, as

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NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-20876-9
TBs
SF
SF Ag
SF SF
Ag2O
48 hours in air
Fig. 5 Natural oxidation of an Ag nanocrystal with multiple planar
defects. The Ag nanocrystal was exposed in ambient environment at room
temperature for 2 days. The naturally oxidized Ag also exhibits similar site-
selective oxidation behaviours along the pre-existing SFs. Scale bar: 10 nm.
verified with our experimental observations in Figs. 1 and 3. In
contrast, homogeneous oxidation initiates from multiple sites
simultaneously in defect-free nanocrystals, and the migration of
the oxide–metal interface is mainly dominated by conventional
bulk diffusion rather than the defect-assisted diffusion, leading to
significantly slower inward growth (as shown in Supplementary
Fig. 14 and schematically illustrated in Supplementary Fig. 15).
Similar TB-assisted growth dynamics have also been reported in
other systems such as CuO and Ge13,35, providing general
implications for the universality of the site-selective chemical
reaction in a broad class of nanomaterials.
Despite the exceptional chemical inertness of bulk Ag and Pd,
nanosized noble metals are inherently vulnerable to oxidation, which
probably originates from the increased specific surface area. Under
electron beam irradiation, the binding of oxygen with metallic atoms
could be significantly facilitated at room temperature36,37, even under
low oxygen partial pressure in the ultrahigh vacuum TEM column
(~2.5 × 10−7 Torr). Owing to the high thermal conductivity of Ag
(429 W mK−1) and Pd (72 W mK−1), temperature rise induced by
the electron beam should be negligible in Ag and Pd nanocrystals38.
However, the electron beam could also alter chemical bonds in the
samples and induce ionization of gas molecules39, thereby catalysing
the oxidation. To exclude the possible beam effects on oxidation,
nanotwinned Ag with multiple pre-existing TBs and SFs (fabricated
with the same method) was exposed in air at room temperature for
48 h. The TEM image captured after natural oxidation (Fig. 5) shows
that the naturally oxidized nanotwinned Ag underwent conspicuous
site-selective oxidation along pre-existing isolated SFs, where negli-
gible oxide was formed at defect-free areas nearby (Fig. 5), consistent
with our in situ observation inside the TEM chamber. It needs to be
clarified that although the size of the oxide appeared to be larger than
those inside TEM, the oxide growth still appeared to proceed through
a layer-by-layer mechanism, where the size of the oxide keeps
increasing as long as the oxygen is stably supplied. Therefore, the
extensive oxide growth in air (Fig. 5) should be reasonable, given the
apparently higher oxygen pressure compared with that inside the
TEM chamber. This natural oxidation experiment provides qualita-
tive evidence for the generally retained site-selective oxidation
mechanism under different oxygen concentrations and oxidation
conditions, as well as to the time scale for oxidation.
In conclusion, the in situ atomic-scale observations and DFT
calculations in this work have revealed a site-selective preferential
oxidation behaviour in nanotwinned metals at planar defects
including TBs and SFs. Such site-selective dynamics originates
from the synergistic high binding energy at the TB/SF-surface
NATURE COMMUNICATIONS | (2021)12:558 | https://doi.org/10.1038/s41467-020-20876-9 | www.nature.com/naturecommunications
ARTICLE
junctions and enhanced diffusion along TBs or SFs in metals,
which is critically influenced by the planar defect density.
Moreover, this defect-assisted surface oxidation mechanism
underscores the general significance of the coupling between
nucleation and subsequent growth dynamics upon chemical
reactions in metallic nanocrystals, unravelling the relations
between lattice defects and physicochemical phenomena at the
atomic scale. Given that nanoscale twins and SFs are common in
metallic nanocrystals with low stacking fault energies, this site-
selective mechanism should play important roles during the
nanowire growth, catalytic/chemical/electrochemical reactions,
and solid-state phase transformation in a wide range of materi-
als16–19,40,41. Therefore, our findings of atomistic reaction
dynamics of defective nanocrystals hold fundamental and tech-
nological ramifications for the development of advanced nano-
materials through defect engineering.
Methods
In situ TEM oxidation. In situ oxidation experiments were performed in a FEI
Titan G2 60–300 transmission electron microscope equipped with a single-tilt
STM-TEM holder from Zeptools Co. Before in situ oxidation experiments, Ag and
Pd rods (0.25 mm in diameter, 99.99 wt% purity, ordered from Alfa Aesar Inc.)
were mechanically fractured using a ProsKit wire cutter to obtain a clean fracture
surface with numerous nanoscale tips. Due to the severe plastic deformation in the
fracture zone, numerous nanoscale twins were induced in the nanotips on the
fracture surface. Then, an Ag or Pd rod was loaded on to the TEM holder and
inserted instantly into the TEM chamber. To characterize the twin structure,
nanoscale tips in the <110> zone axis were selected for the in situ oxidation
experiments. Then, in situ oxidation experiments were conducted at room tem-
perature under ultrahigh vacuum (UHV) atmosphere ~2.5 × 10−7 Torr (corre-
sponding to an oxygen partial pressure of ~5 × 10−8 Torr) to characterize the
oxidation dynamics at the atomic scale. The extremely low oxygen pressure in the
TEM chamber is sufficient to induce evident oxidation of the nanoscale metal.
Besides, some oxygen may be pre-adsorbed on the fracture surface of Ag and Pd
rods. For natural oxidation experiments, the fractured Ag rods were exposed in air
at room temperature for 48 h before ex situ TEM characterization. In all experi-
ments, the TEM was operated at 300 kV with a low electron beam current density
of ~100 A s−1 to minimize the possible beam effects. To investigate the oxidation
dynamics, a Gatan 994 charge-coupled device (CCD) camera was used to record all
experiments in real time at a rate of ~0.3 s per frame.
First-principles calculations. Ab initio calculations were performed using the
Vienna ab initio simulation package (VASP) implemented based on the
Kohn–Sham density functional theory42. Plane-wave basis set was used to expand
the Kohn–Sham orbitals with an energy cutoff of 450 eV. The exchange-correlation
functional was in the form of generalized gradient approximation developed by
Perdew, Burke, and Ernzerhof (PBE)43. The projector augmented plane-wave
method (PAW) pseudopotential was used to reduce the number of plane waves
near the nucleus. Geometry optimization was performed to calculate the local
minimum potential energy of each atomic configuration, where the ion positions
were updated until the maximum force acting on the atoms was less than 1 × 10−4
eV Å−1. Since the simulation cell was large enough in X and Y direction, but only
~6 Å in Z direction, k-point calculation within a mesh of 1 × 1 × 3 was performed
for the wavefunction optimization with a convergence criterion of 1 × 10−6 eV. The
O binding energy, i.e., the energy required to remove one O atom from its bonded
matrix configuration was calculated according to Eq. (2):
Ag Ag; O
EbO ¼ EISO
O
þ EMatrix  EMatrix ð2Þ
Ag Ag;O
where O
EISO , EMatrix , EMatrix
are the potential energy of an isolated O atom, that of
the pure Ag configuration without O atom, and that of the same Ag configuration
bonded with a surface O atom, respectively. For each Ag model, we studied
between two and six different interstitial positions of surface O bond. For the single
crystal, nanotwinned and SF models, the mean Eb was determined by averaging the
two highest energies among neighbouring sites of a specific surface junction; for the
kink step model, the mean Eb was determined by surveying five interstitial sites
with fluctuant binding environments, see Supplementary Information.
Data availability
The data that support the findings of this study are available from the corresponding
author upon reasonable request.
Received: 29 June 2020; Accepted: 23 December 2020;
7
ARTICLE
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Acknowledgements
J.W., Z. Zhang, and H.W. acknowledge the support of Basic Science Center Program for
Multiphase Evolution in Hypergravity of the National Natural Science Foundation of
China (51988101). J.W. acknowledges the support of the National Natural Science
Foundation of China (52071284, 51771172, and 51701179) and the Innovation Fund of
the Zhejiang Kechuang New Materials Research Institute (ZKN-18-Z02). Z.P. and F.S.
are grateful for the support from the US Department of Energy (DOE) (grants no. DE-
SC0016270 and no. DE-SC0020054) and the supercomputer Cori of the National Energy
Research Scientific Computing Centre, supported by DOE contract no. DE-AC02-
05CH11231.
Author contributions
J.W. and F.S. conceived and guided the research. J.W., Q.Z., Z. Zhao, G.C., and N.C.
designed, conducted, and analysed the experiments. Z.P. and F.S. developed, performed
and analysed the DFT simulations. L.L., H.W., and Z. Zhang helped with data analysis.
Q.Z., J.W., Z.P., and F.S. prepared the manuscript. All authors contributed to the data
discussion and manuscript revision.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/s41467-
020-20876-9.
Correspondence and requests for materials should be addressed to Z.Z., F.S. or J.W.
Peer review information Nature Communications thanks Guangwen Zhou, Chien-Neng
Liao and the other, anonymous, reviewer(s) for their contribution to the peer review of
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Review Article
Si-alloy negative electrodes for Li-ion batteries
M.N. Obrovac∗
The use of Si-alloys as negative electrode materials in Li-ion
cells can increase their energy density by as much as 20%,
compared to conventional graphite electrodes. However,
several technical challenges related with the massive volume
expansion associated with Si-alloy lithiation have impeded their
implementation. A number of advances in recent years have
occurred in the understanding of these challenges and in
means of overcoming them through new materials, electrolyte
additives, binders and electrode formulations. Here, the current
understanding of these challenges and the latest advances in
the field are reviewed.
Address
Department of Chemistry, and Department of Physics and Atmospheric
Science, Dalhousie University, Halifax, Nova Scotia B3H 4R2, Canada
∗
Corresponding author: Obrovac, M.N. (mnobrovac@dal.ca)
Current Opinion in Electrochemistry 2018, 9:8–17
This review comes from a themed issue on Batteries and Superca-
pacitors
Edited by Daniel Belanger
For a complete overview see the Issue and the Editorial
Available online 05 March 2018
https://doi.org/10.1016/j.coelec.2018.02.002
2451-9103/© 2018 Published by Elsevier B.V.
Introduction
Conventional Li-ion cells use a layered lithium transi-
tion metal oxide positive electrode (e.g. LiCoO2 ) and a
graphite negative electrode. When a Li-ion cell is charged,
Li+ ions deintercalate from the cathode and simultane-
ously intercalate into the graphite electrode. Such inter-
calation reactions are highly reversible as the host lat-
tices remain unchanged and little volume expansion (10%
in the case of graphite) occurs during the Li+ ion inser-
tion/deinsertion process. Such properties are highly desir-
able in electrode materials for batteries intended to have
a long cycle life. However, significant increases in en-
ergy density are theoretically possible if non-intercalation
materials are used. For most applications (e.g. consumer
electronics and electric vehicles), volumetric energy den-
sity is more important than specific energy density. Since
these are the most important applications for Si-alloys,
volumetric quantities will be chiefly used here. A con-
ventional graphite negative electrode can intercalate up
Current Opinion in Electrochemistry 2018, 9:8–17
to one lithium per six carbon, to form LiC6 . This corre-
sponds to a volumetric capacity of 719 Ah/L. In contrast,
3.75Li can insert into Si to form Li15 Si4 [1] (22.5 times as
much Li per host atom compared to graphite!). This cor-
responds to a volumetric capacity of 2194 Ah/L. There-
fore, an Si negative electrode with the same capacity as
a graphite electrode would take up a third of the space
in a battery. This extra space allows the accommodation
of additional electrode area into the battery, theoretically
resulting in a cell energy increase of about 34% [2]. How-
ever, because of various restrictions (e.g. porosity to allow
electrolyte permeation) 15–20% improvements are more
achievable in practice.
A key challenge for the utilization of Si is its volume ex-
pansion during lithiation. Unlike intercalation electrodes,
Si expands by 280%. This causes the passivation layers
on the lithiated Si surface (the so-called solid electrolyte
interphase (SEI)) to become disrupted, leading to elec-
trolyte degradation on the highly reducing lithiated Si
surface. In addition, thick electrode coatings comprising
particulate active materials held together with polymer
binders are used to achieve high energy density. Mechan-
ical failure of such composite coatings can result from the
huge volume expansion of Si. Overcoming these chal-
lenges to enable practical utilization of Si in commer-
cial cells requires solutions at the atomic, particle, binder,
electrode, electrolyte and cell levels. These research ar-
eas define the Si-alloy field today. This article presents a
review of recent results in these individual research ar-
eas which seem important to the author. Some have been
highly cited, some are more obscure. Many excellent arti-
cles could not be mentioned because of size limitations.
Advanced binders for Si-alloy electrodes
In this author’s opinion, the current high performance
binders for Si-alloy materials can be generally classi-
fied in two groups: functionalized aliphatic binders and
aromatic binders (including conductive binders and sin-
tered/carbonized binders) and they are discussed here un-
der these classifications.
Functionalized aliphatic binders (FAB), including
poly(acrylic acid) (PAA) and carboxymethyl cellulose
(CMC), bond to native silicon oxide (Si−O−Si) and
silanol (Si−OH) groups on silicon surfaces with either
strong ester-like covalent bonds or weaker hydrogen
bonds, depending on the pH of the coating slurry [3–5].
The solution pH can also alter the configuration of
the polymer to enhance binding with the alloy surface
[6]. FABs have little electrochemical activity at low
www.sciencedirect.com

potentials [7• ], apart from the reduction of acidic hydro-
gens in un-neutralized poly(acids) [8]. They are believed
to modify the alloy surface, forming a protective "artifi-
cial" SEI layer and have self-healing properties, resulting
in good cycling performance [9–11•• ].
Recent systematic studies have confirmed the importance
of strong bonds being formed between FABs and Si-alloy
surfaces [11•• –14•• ] and additionally the Cu current col-
lector [14•• ,15]. Peptide-type bonding was newly found
to take part in this mechanism [16• ]. Bonding (and cycling
performance) was improved when binders were polymer-
ized in the slurry in situ [15] and cycling was shown to
improve if the polymer backbone was made flexible [17].
Of particular interest is the finding that high voltage cy-
cling disrupts the SEI layer, increasing cycling fade [16• ].
Therefore researchers are encouraged to stay within the
cycling limits of 0–0.9 V, which has been pointed out pre-
viously to be most relevant range for evaluating Si-alloy
materials for commercial cells [18].
An exciting development was the finding that a post-
cure humidification step ("maturation") can drastically im-
prove cycling performance [11]. The maturation step low-
ers Tg , and results in FAB aggregation at particle inter-
faces, where it is needed most. Most surprising is that mat-
uration can even heal broken bonds that occur during the
calendering process, resulting in substantially improved
cycling of calendered electrodes [19•• ]. This is the effect
shown in Figure 1. Also impressive is that maturation en-
abled cycling at high loadings (2.7 mAh/cm2 or higher).
This is important for practical application, since increas-
ing loading generally reduces the cycle life of electrodes
containing alloy materials [19•• ].
Si-alloys have been shown to cycle well when aro-
matic binders are used. Unlike FAB type binders, aro-
matic binders have significant electrochemical activity
[7• ,20•• ,21]. Wilkes et al. developed a method enabling
measurement of binder electrochemistry in the same en-
vironment as they exist in composite electrode coatings
[20•• ]. Unlike traditional spin-coated electrodes, com-
posite electrodes contain regions where binders are si-
multaneously exposed to electrolyte and electrons from
the conductive particles, considerably enhancing electro-
chemical activity [20•• ], as shown in Figure 2. PI and
phenolic resin binders have a large first lithiation capac-
ity and reversible capacity (∼2000 mAh/g and 900 mAh/g,
respectively for PI), consistent with full reduction to hy-
drogen containing carbon [7• ,20•• ,22,23]. Because of the
excellent cycling properties of Si-alloy electrodes with
AB binders, it was suggested that the reduction of ABs
formed a carbon coating around the alloy particles, im-
proving electronic contact and reducing electrolyte de-
composition [20•• ]. This carbon also contributes to the
reversible cell capacity [7• ,20•• ]. This result is consis-
tent with the recently found good cycling achieved with
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Si-alloy negative electrodes for Li-ion batteries Obrovac 9
thermally carbonized binders [21,24,25]. Since thermal
carbonization eliminates the need for electrochemical re-
duction, irreversible capacity is also reduced [21].
The result that aromatic binders reduce in situ to hydro-
gen containing carbons is important and needs further
confirmation. If true, then aromatic binders that also show
significant electrochemical activity, including conducting
binders such as PEDOT:PSS, polypyrrole, etc., may all be
reducing to carbon upon lithiation. Nevertheless, the type
of aromatic polymer binder used significantly affects alloy
cycling. For instance, the curing temperature and degree
of aromaticity significantly affect cycling performance and
the initial irreversible capacity of PI binder electrodes
[20•• ,26,27]. Similarly, the cycling performance of ther-
mally sintered binders is also highly dependent on the
polymer precursor used [21]. Presumably the nature of
the carbon formed either by electrochemical or thermal
reduction is highly dependent on the polymer binder pre-
cursor. Therefore, the selection of aromatic binders to en-
hance Si-alloy cycling performance is an important area of
research.
Alloy surface modification
Considering the important role alloy/binder/electrolyte
interphases have in influencing cycling performance, sur-
face modification is a method increasingly recognized
to be of high importance. Carbon coating has long
been recognized as a method to improve cycle life
[28,29• –32]. LiF has also been shown to be an effec-
tive coating material [33]. An excellent study by Wang
et al. shows direct evidence of how Si degradation dur-
ing cycling is suppressed by carbon coating, as shown in
Figure 3 [29• ]. Significant improvements to cycle life
have also been achieved by surface treatments that pro-
vide a direct chemical bond between the alloy and the
binder [34,35]. These studies demonstrate convincingly
the importance of establishing strong binder–alloy bonds
in order to achieve good cycle life. Lucht et al. showed
that the slurry out of which electrodes are cast can influ-
ence alloy/binder/electrolyte interphases [13]. Increasing
pH causes the formation of SiOx species on the surface of
Si, resulting in reduced cycle life.
Electrolyte additives
Electrolyte additives are crucial to Si-alloy cycling per-
formance. An excellent recent study shows that without
special additives, erosion of the Si surface occurs during
cycling, resulting in a significant increase in alloy surface
area [36• ], as shown in Figure 4, increasing its reactivity.
Fluoroethylene carbonate (FEC) is generally recognized
as the most effective electrolyte additive in forming a pas-
sivating SEI on Si-alloys. Recent studies have further con-
firmed its effectiveness in improving cycle life and fur-
ther confirmed the composition of the SEI formed when
FEC is present, which comprises polymeric species and
LiF [36• –40]. However, the passivation layer formed by
Current Opinion in Electrochemistry 2018, 9:8–17
10 Batteries and Supercapacitors

Figure 1

(a, b) Cycling performance of Si-based electrodes prepared by acoustic mixing: (a) calendered and not-calendered (both not-matured) (Si mass
loading = ∼2.7 mg/cm2 ) and (b) matured/not-calendered and matured before or after calendering (Si mass loading = ∼3.1 mg/cm2 ). Calendering was
performed at a pressure of 1 T/cm2 . (c) Schematic representation of the breaking-restoring of the particle/binder bonds during the
calendering-maturation procedure. Reprinted from Reference [19•• ], Copyright 2017, with permission from Elsevier.

FEC is not perfect, resulting in the continual consump-
tion of FEC during cell operation [36• ,41]. In full cells
with restricted electrolyte quantities, this results in the
eventual depletion of FEC and subsequent accelerated
cell fade/failure [36• ,41]. These studies highlight the in-
adequacy of half-cells as a means to study this slow deple-
tion.
A recent major discovery was the effectiveness of CO2 as
an additive for Si-alloys [42•• ]. CO2 was not only found
to be a superior additive than FEC for improving Si-alloy
cycle life, but also worked synergistically with FEC, such
that their use in combination improved cycle life further.
Interestingly, CO2 has also been found to be a product
of FEC reduction [41]. Like FEC, the passivation layer
formed by CO2 is not perfect, resulting in the continual
decomposition and depletion of CO2 in the electrolyte.
Therefore, additives that provide a source of CO2 may be
effective for good long term cycling.
Si-alloy materials
Important advancements have been made in the elec-
trochemistry of Si recently which could significantly
contribute to Si-alloy material design and ultimate per-
formance. These critically relate to the formation of the
Li15 Si4 phase, which forms when Si is delithiated below
about 50 mV [1,43]. The formation of this phase is gener-
ally considered detrimental to cycling [2,18,44•• ,45• ,46].

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Figure 2
(a)
(b)
Li+
Li+
e-
(a) Voltage curves of polyvinylidene fluoride (PVDF), aliphatic PI and aromatic PI binders. (b) Illustration of how electrochemical aro-PI reduction can
occur in a composite coating that provides percolating paths for electrons to reach the coating surface. Adapted from Reference [20•• ].
However, the Li15 Si4 phase’s role in cycling fade re-
mains controversial. For instance, Gao et al. found that
the Li15 Si4 phase was not only detrimental to cycling, but
also especially reactive to electrolyte [46]. In contrast, a
study by Schott et al. found that Li15 Si4 formation had
little detrimental effects in the cycling of n-Si powder
[47]. In the current author’s opinion, the phase bound-
ary stresses between Li15 Si4 and a-Lix Si during delithia-
tion likely leads to particle fracture, which generally leads
to fade. However, if electrical contact is maintained de-
spite the fracturing (e.g. by using large amounts of con-
ductive carbon (90 wt% high surface area graphite in the
case of Schott et al.)), then, in principle, good cycling may
be maintained regardless of particle fracture or Li15 Si4 for-
mation.
Suppression of Li15 Si4 formation was found to be highly
sensitive to cell polarization, whether induced by in-
creased rate or increased impedance from a thick SEI
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Si-alloy negative electrodes for Li-ion batteries Obrovac 11
Li+ Li+
e-
layer [18,46]. These studies show that if elemental Si is
held at low voltages, Li15 Si4 will form, even if the Si is
nano-sized. Therefore studies that show no Li15 Si4 for-
mation during the cycling of n-Si near zero volts likely
have polarization induced Li15 Si4 suppression. Slow con-
stant current cycling with a constant voltage hold at full
lithiation to simulate commercial cell cycling protocols
(i.e. constant current–constant voltage or CCCV cycling)
is therefore recommended for alloy evaluation [18].
A major development has been the recent finding that
stress from a substrate [44•• ] or an inactive phase
[45• ,48] can suppress Li15 Si4 formation via stress–voltage
coupling. Large induced stresses of up to 1.5 GPa can
shift the voltage curve of Si by as much as −200 mV dur-
ing lithiation [49]. Since the Li15 Si4 phase forms below
about 50 mV [1], a −200 mV shift is more than enough to
completely suppress Li15 Si4 phase formation. Therefore
the presence of Li15 Si4 is an indicator for unconstrained
Current Opinion in Electrochemistry 2018, 9:8–17
12 Batteries and Supercapacitors

Figure 3

(a) Coulombic efficiency and SEM images before and after cycling silicon nanocone (SNC) and carbon-coated silicon nanocone (SNC-C) electrodes.
(b) Schematic diagram of SEI formation on the SNC electrode and the SNC-C electrode. Adapted with permission from Reference [29• ], Copyright
2016, American Chemical Society.

Si [44•• ]. This is shown in Figure 5 for an a-Si thin film.
Initially the film is in complete contact with the sub-
strate. Li15 Si4 formation is exactly incident with lift-off
of the film and fade from the disconnection of Si flakes
[44•• ]. This has major implications for Si–M (M = transi-
tion metal) alloys. In such alloys inactive phases can cause
internal stress during Si expansion, resulting in Li15 Si4
suppression [45• ]. The same mechanism is likely respon-
sible for Li15 Si4 suppression in SiOx . Presumably, Li15 Si4
formation in such alloys is an indicator Si that has be-
come disconnected from the Si/inactive matrix particle,
which explains why fade often occurs when Li15 Si4 for-

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 Si-alloy negative electrodes for Li-ion batteries Obrovac 13

Figure 4

FESEM cross section images of negative electrodes from Gr:Si-alloy//LCO full pouch cells with 3EC:7EMC or 23EC:67EMC:10FEC in 1 M LiPF6. (a)
Without FEC after 30 cycles, (b) with FEC after 30 cycles, (c) without FEC after 75 cycles, and (d) with FEC after 75 cycles. (e) BET surface area of
negative electrodes from Gr:Si-alloy//LCO full pouch cells with 3EC:7EMC (red diamonds) or 23EC:67EMC:10FEC (blue circles) in 1 M LiPF6 , as a
function of cycle number. Adapted from Reference [36• ].

Figure 5

(a) (b)

(a) Relative Li15 Si4 differential capacity peak area, and delithiation capacity vs. cycle number of a 275 nm thick Si film sputtered onto Cu foil. The
differential capacity curve is shown in the inset. (b) Illustration of the processes that occur during the cycling of a Si thin film, resulting in Li15 Si4
formation, disconnection and fade. Adapted from Reference [44•• ].

mation is observed. In addition, voltage depression in
alloys from stress-voltage coupling can significantly re-
duce capacity [45• ]. This is a new concept for Si–M alloys,
as silicide formation was previously considered as only
the mechanism for capacity reduction [50]. In the case of
Si–Ni alloys the effect is extreme. All of the Si was found
to be active in such alloys and capacity reduction was
found to be caused solely by stress induced voltage de-
pression [45• ,51].
An interesting study also shows it is possible for Si to re-
crystallize after one full charge/discharge cycle, if a single
c-Si seed grain is present. This results in shape-memory
behavior (the Si returns to the same shape/size after ev-

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14 Batteries and Supercapacitors

Figure 6

Cross-sectional (a) schematic view and (b) SEM image of a Si-nanolayer-embedded graphite/carbon hybrid (SGC) particle. (c) Voltage curves of
pristine graphite (PG), Si-nanolayer-embedded graphite (SG), SGC, 9 wt%-SGC (SGC hybrid containing 9 wt% Si and < 3 wt% C), and physically
blended nano-Si/graphite (B–Si/G). (d) Cycling performance of LiCoO2 vs. SGC or graphite full cells. Adapted by permission from Macmillan
Publishers Limited, Reference [65•• ], Copyright 2016.

ery cycle) and good cycling performance [48]. Such mate-
rials might be good strategy to achieving high reversibility
when pure Si is used. A recent study has shown very nicely
that Li diffuses preferentially in the defects of micron-
sized Si particles [52• ]. Such uneven diffusion and volume
expansion represents another pathway for cell fade, which
should be taken into consideration in particle design. An-
other study showed that carbon coating thin film Si re-
duces interactions with electrolyte and moreover an inter-
nal carbon layer drastically reduces electrode degradation
and volume expansion induced porosity [53• ]. Although
focused on thin films, this study can also be seen as further
verification of the use of multicomponent Si-alloys for im-
proving cycling stability compared to the use of pure Si.
There were a great number of papers in the past year on
Si nanoparticles [28,31,46,47,54], nanowires [55], flakes
[56], microporous Si [57], SiOx [30,58], various Si-alloys
[59–62], engineered particles [32,63,64,65•• ,66,67], etc.
where references of some articles of particular importance
are listed. It is difficult to quantify differences among
these materials, since different electrode formulations,
electrolytes, binders, cell loadings, cell types, etc. are uti-
lized. Such quantification essentially become the domain
of commercial cell makers, as will be discussed further be-
low. A particularly interesting study is by Ko et al., in which
a scaleable low surface area Si–graphite composite parti-
cles are described [65•• ]. The particles, shown in Figure 6,
combine void structures to accommodate volume expan-
sion with carbon coating to reduce electrolyte reactions,
resulting in low volume expansion and good reported cy-
cling in full cells. Strategies such as this, which reduce al-
loy surface area, volume expansion and electrolyte reac-
tivity seem the most promising for implementation.
Summary and outlook
The past few years have seen a number of important ad-
vances in fundamental Si electrochemistry, binders, and

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electrolytes. These advances have been shown to make
real and significant improvements to the cycle life of Si-
alloy electrodes. It remains to be seen if these improve-
ments will translate into widespread commercial imple-
mentation in the short term. Considerations for Si-alloy
implementation are complex even for cell makers. De-
spite cell models showing clear improvements in energy
density of 15–25% for Si-alloy utilization [2], tradeoffs
from increased fade compared to conventional graphite
electrodes could limit this advantage to a few hundred
cycles [68]. Of further concern is that in all cell models
known to the author, an assumption is made that the sep-
arator and current collector used in cells with Si-alloys
will be the same as those used in cells with conventional
graphite electrodes. However, this may not be the case
[69].
Continuous improvements in conventional graphite cells
have allowed for the use of larger loadings, thinner cur-
rent collectors and thinner separators. It stands to reason
that these high energy/low tolerance cell designs may not
be compatible with electrodes that undergo significantly
higher volume expansion. If so, this would reduce the en-
ergy density improvement that is practically obtainable by
Si-alloys. Such questions inevitably need to be resolved
by cell makers. However, they clearly point to strategies
needed in alloy design to enable commercial implementa-
tion: for practical utilization, Si-alloys must be made com-
patible with the use of thin separators, thin current col-
lectors and cannot significantly increase fade. Therefore
minimization/elimination of alloy volume expansion and
electrolyte reactivity are of utmost importance.
Acknowledgments
The author would like to acknowledge financial support from NSERC and
3M Canada, Co. under the auspices of the Industrial Research Chair
program (grant no. IRCPJ 407487-09).
References and recommended reading
Papers of particular interest, published within the period of review, have
been highlighted as:
• Paper of special interest.
•• Paper of outstanding interest.
1. Obrovac MN, Krause LJ: Reversible cycling of crystalline silicon
powder. J Electrochem Soc 2007, 154:A103–A108.
2. Obrovac MN, Chevrier VL: Alloy negative electrodes for Li-ion
batteries. Chem Rev 2014, 114:11444–11502.
3. Bridel JS, Azaïs T, Morcrette M, Tarascon JM, Larcher D: Key
parameters governing the reversibility of Si/carbon/CMC
electrodes for Li-ion batteries. Chem Mater 2010, 22:1229–1241.
4. Hochgatterer NS, Schweiger MR, Koller S, Raimann PR, Woḧrle T,
Wurm C, Winter M: Silicon/graphite composite electrodes for
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stability. Electrochem Solid-State Lett 2008, 11:A76–A80.
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5. Bridel J-S, Azais̈ T, Morcrette M, Tarascon J-M, Larcher D: In situ
observation and long-term reactivity of Si/C/CMC composites
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7. Hatchard TD, Bissonnette P, Obrovac MN: Phenolic resin as an
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This paper demonstrates that inexpensive aromatic binders reduce to
carbon during lithiation, resulting in similar cycling performance as
previously reported conductive polymers. It raises the question if
conducting polymers also just reduce to carbon during the first lithiation
of the negative electrode.
8. Haregewoin AM, Terborg L, Zhang L, Jurng S, Lucht BL, Guo J,
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A very comprehensive study on coatings with FAB type binders
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A key study of the "maturation" process of CMC and PAA binders.
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An important study that demonstrates that binders with peptide-type
bonding can effectively bind to Si-alloys, resulting in good cycling, in
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In addition the deterioration of cycling with increasing upper cut-off
voltage is nicely demonstrated.
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An important paper demonstrating that aromatic binders reduce to
hydrogen containing carbon during lithiation. In addition, a new method
of evaluating the electrochemistry of binders in a composite coating
environment is introduced.
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A well elegant and thorough study that demonstrates the effectiveness
of carbon coating in improving alloy cycling performance.
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Yang J: Critical thickness of phenolic resin-based carbon
interfacial layer for improving long cycling stability of
silicon nanoparticle anodes. Nano Energy 2016, 27:255–264.
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performance improvement of inexpensive ball-milled Si
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Current Opinion in Electrochemistry 2018, 9:8–17
Phase Rule and Phase Equilibria
➢ To introduce the basic concept of Phase equilibrium and phase rule

Dr. Baby Viswambharan

Assistant professor
Dept. Chemistry
 Learning outcome

➢ To understand quantitatively a system in thermodynamic equilibrium

❖ Definition of terms like phase, components and degrees of freedom
❖ The Gibbs phase Rule
❖ Application to
➢ One component system
➢ Two component system
❖ Simple Eutectic system
❖ Systems that forms a stable Compound with
o Congruent melting point and
o Non-congruent melting point
➢ Three component system
Reference:
1. P.C. Jain, M. Jain, Engineering Chemistry.
2. P. Atkins, J.D. Paula, Physical Chemistry.
3. Puri, Sharma, Pathania, Principles of physical chemistry
 [Water System]
[CO2 System]
[Sulphur System]

[Pb-Ag System]

[Zn-Mg System] [Na2SO4-H2O System]

[Cu-Ni System]
 Phase rule: - Relationship governing all heterogeneous equilibria

➢ The phase Rule is an important generalization dealing with the behavior of heterogeneous systems
➢ With the help of a diagram, it is possible qualitatively to predict the effect of changing pressure,
temperature and concentration on a heterogeneous system in equilibrium

➢ It has found application in

Prof. Willard Gibbs
➢ Electronic industries- American physicist
Example: In Solder, it is an alloy and a homogeneous mixture having melting point lower than
the corresponding metal (Pb and Sn)
In safety plugs or safety fuses (Bi, Pb, Sn, Cd)
➢ Pharmaceutical science and Medical science
Freeze drying technique for tissues, fruits and vegetables

➢ The phase rule is based on hypothetical assumptions by knowing the nature and constitution of matter
 Gibb’s Phase rule: - Relationship governing all heterogeneous equilibria

“When a heterogeneous system is in equilibrium at a definite temperature and pressure, the number of degrees of
freedom (F) is related to the number of components (C) and the number of phases (P) that exist in equilibrium
provided the system is unaffected by any external factors such as electrical or magnetic forces, surface tension, etc’.

It may be stated mathematically as follows :

F=C–P+2
where
F is the number of degrees of freedom (variance),
C is the number of components and
P is the number of phases of the system.

➢ These terms have special significance and

➢ A clear understanding of these terms is essential
Definition of terms
Phases: any homogeneous part of a system having all physical and chemical properties the same throughout.

➢ A phase may or may not be continuous (One ice cube or few ice cubes)
A system may consist of one phase or more than one phases.

A system containing only liquid A system containing liquid water and A system containing liquid water,
water is one-phase (P = 1) ice is a 2-phase system (P = 2). water vapor and solid ice is a
3-phase system

➢ A system consisting of one phase only is called a homogeneous system.

➢ A system consisting of two or more phases is called a heterogeneous system.

Ordinarily three states of matter-gas, liquid, and solid are known as phases.
➢ However in phase rule, a uniform part of a system in equilibrium is termed a ‘phase’.
➢ Thus a liquid or a solid mixture could have two or more phases.
Few examples to understand the meaning of the term phase
➢ Pure substances (Solid, liquid, or gas) made of one chemical species only, is considered as one phase. Eg (O2), benzene
(C6H6), and ice (H2O) are all 1-phase systems.
➢ Mixtures of gases: All gases mix freely to form homogeneous mixtures. Therefore any mixture of gases, say O2 and N2, is a 1-
phase system.
➢ Two completely Miscible liquids yield a uniform solution. Thus a solution of ethanol and water is a 1-phase system.

➢ A mixture of two Non-miscible liquids on standing forms two separate layers. Hence a mixture of chloroform (CHCl3) and
water constitutes a 2-phase system.
➢ Aqueous solutions of a solid substance such as sodium chloride (or sugar) is uniform throughout and is a 1-phase system.
However, a saturated solution of sodium chloride in contact with excess solid sodium chloride is a 2-phase system.

➢ Mixtures of solids. By definition, a phase must have throughout the same physical and chemical properties.
Eg: Ordinary solid Sulphur is a mixture of monoclinic and rhombic form. (same chemical species but differ in physical
properties). Thus mixture of two allotropes is a 2-phase system.
➢ A mixture of two or more chemical substances contains as many phases. Each of these substances having different physical
and chemical properties makes a separate phase.
Eg: Thus a mixture of calcium carbonate (CaCO3) and calcium oxide (CaO) constitutes two phases.
But when calcium carbonate is heated in a closed vessel, it decomposes.
we have the equilibrium system
CaCO3 CaO + CO2
(solid) (solid) (gas)
There are two solid phases and one gas phase. Hence it is a 3-phase system.
Components: the least number of independent chemical constituents in terms of which the composition of
every phase can be expressed by means of a chemical equation.

▪ Water systems is 1-component systems. • Sulphur systems is 1-component systems.

▪ Three phases : ice water water vapour. • Four phases : rhombic, monoclinic, liquid Sulphur and
▪ The composition of all the three phases are expressed in Sulphur vapour.
terms of one chemical individual H2O. • The composition of all these phases can be expressed by one
▪ Thus water system has one component only. chemical individual Sulphur (S).

➢ Mixture of gases. A mixture of gases, say O2 and N2, constitutes one phase only. Its composition can be expressed by two
chemical substances O2 and N2.
Phase(1) Components(2)
Gaseous Mixture = x O2 + y N2
➢ Hence a mixture of O2 and N2 has two components.
➢ In general the number of components of a gaseous mixture is given by the number of individual gases present
➢ Sodium chloride solution (2-component system).
A solution of sodium chloride in water is a 1-phase system. Its composition (xNaCl.yH2O) can be expressed in terms
of two chemical individuals, sodium chloride and water.
Phase Components
Aq. solution of sodium chloride = x NaCl + y H2O

➢ A saturated solution of sodium chloride

Where the solution in contact with excess solid sodium chloride has two phase.
The composition of both phase can be expressed in terms of two chemical individuals NaCl and H2O.
Phase Components
Aq. solution of Sodium chloride = x NaCl + y H2O
Solid sodium chloride = NaCl + 0 H2O
➢ Hence a saturated solution of sodium chloride or any other solute in contact with solid solute, is 2-component system.
Decomposition of Calcium carbonate.
When calcium carbonate is heated in a closed vessel, the following equilibrium system results a 3-phase system.
CaCO3 CaO + CO2
(solid) (solid) (gas)
The composition of all the phase can be expressed in terms of any two of the three chemical substances in equilibrium.
Let us select calcium oxide (CaO) and carbon dioxide (CO2) as the components. Then we can write,
Phase Components
CaCO3 = CaO + CO2
CaO = CaCO3 – CO2
CO2 = CaCO3 – CaO
Again, selecting calcium carbonate (CaCO3) and calcium oxide (CaO) as the components, we have
Phase Components
CaCO3 = CaCO3 + 0 CaO
CaO = 0 CaCO3 + CaO
CO2 = CaCO3 – CaO
Thus decomposition of calcium carbonate is a 2-components system.

Furthermore, as is clear from the above examples, by the components of a system is meant the number of chemical
individuals and not any particular chemical substances by name.
 Dissociation of Ammonium chloride.
Ammonium chloride when heated in a closed vessel exists in equilibrium with the products of dissociation, ammonia
(NH3) and hydrogen chloride gas (HCl).
NH4Cl NH3 + HCl
(solid) (gas) (gas)
The system consists of two phase, namely, solid NH4Cl and the gaseous mixture containing NH3 and HCl.
The constituents of the mixture are present in the same proportion in which they are combined in solid NH4Cl.
The composition of both the phase can, therefore, be expressed in terms of the same chemical individual NH4Cl.
Phase Components
Solid = NH4Cl
Gaseous = x NH3 + x HCl or x NH4Cl
Thus dissociation of ammonium chloride is a one-component system.
➢ Points to remember when writing the equation for components
➢ The chemical formula representing the composition of a phase is written on LHS.
➢ The rest of the chemical constituents existing independently in the system as represented by chemical
formulas are placed on RHS.
➢ The quantities of constituents on RHS can be made minus (–) or zero (0) to get at the composition of the
phase on LHS.
Q. Find the number of components for the dissociation reaction
CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g)
The system consists of three phase, namely, two solid phases namely CuSO4.5H2O and CuSO4.3H2O(s) and
the gaseous phase containing H2O .
The composition of the phases can, therefore, be expressed in terms of the same chemical individual CuSO4 and H2O .
Phase Components
Solid => CuSO4.5 H2O = CuSO4 + 5 H2O And
CuSO4.3 H2O = CuSO4 + 3 H2O
Gaseous => H2O = 0 CuSO4 + H2O
Q. Find the number of phases and components for the below reaction
Fe + H2O (g) FeO(s) + H2(g)
The system consists of three phase, namely, two solid phases namely Fe and FeO(s) and
the gaseous mixture containing H2O and H2.
The composition of the phases can be expressed in terms of the three chemical individual Fe, FeO and H2.
Phase Components
Solid => Fe = FeO - H2O + H2 And [FeO][H2] [H2]
Keq. = = −−−−−−−2
` FeO = Fe + H2O - H2 [Fe][H2O] [H2O]
The system consists of four constituents
Gaseous => H2O + H2 = FeO –Fe + H2
C = No of constituents – no equations relating to constituents
= 4-1 = 3
In an equilibrium state, Number of components can alternatively defined as
The number of chemical constituents of the system (N) minus the number of equations relating the constituents(E)
C = N-E

Q. Find the number of phases and components for the below reaction?
2KClO3 (s) 2KCl(s) + 3O2(g) Total three constituents

[KCl][O2]3
Keq. = = [O2]3 Active masses of solids is taken as unity
[KClO3]2

Number of components (C) = No of constituents (N)– no equations relating to constituents (E)

➔ 3-1 = 2

Q. Find the number of phases and components for the dissociation of ammonium chloride in a closed vessel?
NH4Cl NH3 + HCl
(solid) (gas) (gas)
[NH3 ] = [HCl]--------------1 [NH3 ][HCl]
Keq. = = [NH3 ][HCl]−−−−−−−−−−−−2
[NH4Cl]

C = N-E → 3-2 = 1
Degrees of freedom: the least number of variable factors (concentration, pressure and temperature)
which must be arbitrarily specified in order to represent perfectly the conditions of the system so that the
remaining variables are fixed automatically

A system with F = 0 is known as nonvariant or having no degree of freedom.

A system with F = 1 is known as univariant or having one degree of freedom.
A system with F = 2 is known as bivariant or having two degrees of freedom.

A system is defined completely when it retains the same state of equilibrium

(or can be reproduced exactly) with the specified variables
The phase rule, F = C – P + 2
❖ For a pure gas, C = 1 and P = 1, So F = 1-1+2 = 2
➢ For a given sample of any pure gas PV = RT.
➢ If the values of pressure (P) and temperature (T) be specified, volume (V) can have only one definite value, or that the
volume (the third variable) is fixed automatically.

➢ Any other sample of the gas under the same pressure and temperature as specified above, will be identical with the first one.
Hence a system containing a pure gas has two degrees of freedom (F = 2, Bivarient).
❖ For a mixture of gases: C = 2 and P = 1, So F = 2-1+2 = 3, F = 3.
➢ A system containing a mixture of two or more gases is completely defined when its composition,
temperature and pressure are specified.
➢ If pressure and temperature only are specified, the third variable i.e., composition could be varied.
➢ Since it is necessary to specify three variables to define the system completely, a mixture of gases has three
degrees of freedom (F = 3, tri-varient).

❖ For H2O liq. H2O vapour, C = 1 and P = 2, So F = 1-2+2 = 1 (F = 1, uni-varient).

➢ The system water in equilibrium with water vapor, has one variables temperature or pressure.

➢ At a definite temperature the vapour pressure of water can have only one fixed value.
➢ Thus if one variable (temperature or pressure) is specified, the other is fixed automatically.
 ❖ For saturated NaCl solution, C = 2 and P = 3, So F = 2-3+2 = 2 = 1.
The saturated solution of sodium chloride in equilibrium with solid sodium chloride and water vapour.
NaCl NaCl-solution water vapour
(solid) (liquid) (vapour)
➢ The other two variables i.e,. the composition of NaCl-solution (solubility) and vapor pressure have a definite
value at a fixed temperature.
➢ Thus the system is completely defined if we specify temperature only.
➢ Hence the system has one degree of freedom.

❖ For ice - water - vapour system, C = 1 and P = 3, So F = 1-3+2 = 0, nonvarient

➢ In the system ice water vapour,
➢ The three phases coexist at the freezing point of water.
➢ Since the freezing temperature of water has a fixed value, the vapor pressure of water has also a definite value.
➢ The two variables (temperature and pressure) are already fixed.
➢ Thus the system is completely defined automatically, there being no need to specify any variable.
➢ Hence it has no degree of freedom (F = 0).
Merits of the Phase rule:

➢ It is applicable to both physical and chemical equilibria.

➢ It requires no information regarding molecular/micro-structure, since it is applicable to macroscopic
systems.
➢ It is a convenient method of classifying equilibrium states in terms of phases, components and degrees
of freedom.
➢ It helps us to predict the behavior of a system, under different sets of variables.
➢ It indicates that different systems with same degree of freedom behave similarly.
➢ It helps in deciding whether under a given set of conditions :
➢ Various substances would exist together in equilibrium
➢ Some of the substances present would be interconverted or
➢ Some of the substances present would be eliminated.
Limitations of Phase rule:

➢ It can be applied only for system in equilibrium. Consequently, it is of little value in case of very slow
equilibrium state attaining system.
➢ It applies only to a single equilibrium system and provide no information regarding any other possible
equilibria in the system.
➢ It requires at most care in deciding the number of phases existing in an equilibrium state, since it considers
only the number of phases rather than their amounts. Thus even if a trace of phase is present, it accounts
towards the total number of phases.
➢ It conditions that all phases of the system must be present simultaneously under the identical conditions of
temperature and pressure.
➢ It conditions that solid and liquid phases must not be in finely-divided state otherwise deviations occurs.
Conditions for different equilibria :

➢ The following conditions must be satisfied for the existence of equilibrium between various phases .
1. Thermal Equilibrium:
All phases must be in same temperature otherwise there will be a flow of heat from one phase from another phase
T = T
2. Mechanical Equilibrium:
All the phases must be having same pressure otherwise volume of one phase will increase at the expense of other
P = P
3. Chemical equilibrium:
The chemical potential () of a component should be same in all phases
 = 

The chemical potential tells how the Gibbs (Gibbs free energy) function will change as the composition of the mixture changes
Phase Diagrams
A phase diagram is a plot showing
❖ The conditions of Pressure and Temperature under which two or more physical states can exist together in a state of
dynamic equilibrium (P-T diagram, generally for C = 1).
❖ The conditions of Temperature and Composition under which two or more physical states can exist together in a state of
dynamic equilibrium (T-C diagram for C = 2).
The phase diagram consists of Regions (Areas), Lines (Bounderies), and Points (Junction between lines)
(a) The Regions or Areas; (Bivariant F = 2)
A single phase is represented by an area

(b) The Lines or Curves; (Univariant F = 1)

A two-phase system is depicted by a line
Represent conditions of equilibrium between any two phases
solid ⇄ liquid ; Melting curve or Fusion curve.
liquid ⇄ vapour: Vapour Pressure or Vaporisation curve
solid ⇄ vapour: Sublimation curve

(c) The Triple point; (Invariant F = 0)

A three-phase system is depicted by a point,
All the three phases (solid, liquid, vapour) can coexist in equilibrium.
How to construct a Phase diagram?
➢ For liquid–vapour and solid-vapour equilibrium, variation in vapour pressure can be measured by varying
temperature
➢ But for solid-solid and solid-liquid system, Cooling curves are recorded.
Thermal analysis or Constructing cooling curves
➢ Cooling curves(T of material vs time) are used to determine phase transition temperature
➢ Record T of material as it cools from its molten state through solidification and finally to RT (at a
constant pressure w.r.to time

➢ When cooled from its molten state temperature decreases

➢ But at freezing point temperature remines steady for a while or
until the freezing (exothermic) process is complete

➢ Get the cooling curve for various pressures

➢ Plot transition temperature as a function of pressure
Phase rule for One–Component (C = 1) System F=C–P+2
The phase rule equation will be : F = 1 – P + 2
F=3–P
Three cases may arise :
Case 1. When only one phase is present, (P = 1) F = 3 – 1 = 2, Bivarient
➢ The system can be completely defined by specifying the two variables, temperature and pressure.
➢ Or both the temperature and pressure can be varied independently
➢ Therefore a single phase is represented by an area on P, T-graph.
Case 2. When two phases are in equilibrium, (P = 2) F = 3 – 2 = 1, Monovarient H2O (l) ⇄ H2O (g)
➢ This means that the pressure cannot be changed independently if we change the temperature.
➢ A two-phase system is depicted by a line on a P, T-graph.

Case 3. When three phases are in equilibrium, (P = 3 ) F = 3 – 3 =0, F = 0, Invarient H2O (s) ⇄ H2O(l) ⇄ H2O(g)
➢ This special condition can be attained at a definite temperature and pressure.
➢ The system is, defined completely and no further statement of external conditions is necessary.
➢ A three-phase system is depicted by a point on the P, T-graph.
At this point the three phases (solid, liquid, vapour) are in equilibrium and, therefore, it is referred to as the Triple point.
Types of Phase diagram for One–Component (C = 1) System
Water System (ice, liquid and water vapour) P-T diagram
• Hence there will be three different equilibria Water Liquid

H2O (s) ⇄ H2O(l) H2O(l) ⇄ H2O(g) H2O (s) ⇄ H2O(g) Solid ice
• Each equilibria involve two phases.
The salient features of the phase diagram are
➢ The Curves OA, OB, OC
➢ The Triple Point O
➢ The Areas, AOC, AOB, BOC

Curve OA (Vapour pressure curve):monovariant with dynamic Water Vapour

equilibrium
• Represents the H2O(l) ⇄ H2O(g) at different Temperature
• For a given T only one value of vapour pressure

• At 100 0C, vapour pressure of water = 1 atm, the boiling point of water
• Point A is the critical temp. of water is 374 0C above which liquid water does not exist

Curve OA :-Variation of Vapour pressure with temperature is given by Clapeyron equation, like ideal gas
𝑑𝑃 Hvp
=
𝑑𝑇 𝑇 (Vg − Vl )
∆𝐻𝑣𝑝 = Heat of vaporisation
𝑃2 Hvp
⇒ 𝑙𝑛 = 𝑅 [𝑇𝑇2−𝑇 1
]
𝑃1 𝑇
2 1
Problem 1 :At 1000C, the specific volume of water and steam are, respectively, 1 c.c. and 1673 c.c. calculate the change in
vapour pressure of the system by 1 oC change in temperature. The molar heat of vaporization of water in this range may be
taken as 40584.8 J mol-1.

𝑑𝑃 HVp dT = 1 oC = 1+ 373K,
= ∆𝐻𝑣𝑝 = 40584.8 J mol-1
𝑑𝑇 𝑇 (Vg − Vl )
Vl = 18 cm3 mol-1 = 18x10-6 m3 mol-1
𝑑𝑇. HVp Vg = 18x1673 cm3 mol-1 = 302114x10-6 m3 mol-1
𝑑𝑃 =
𝑇 (Vg − Vl )

𝑑𝑃 = 0.003561x106 Nm-2 = 0.03561 atm

Problem 2 : The vapour pressure of water at 950C, is found to be 634 mm. what would be the vapour pressure at a temperature
of 100 0C. The molar heat of vaporization of water in this range may be taken as 40584.8 J mol-1.

= HVp
𝑃2 𝑇 −𝑇
𝑙𝑛 [ 2 1]
𝑃1 𝑅 𝑇𝑇 2 1

P2 = 759.8 mm
Water System
Water Liquid
Curve OC (Fusion curve): Ice and water co-exist; monovariant
• Represents the H2O(s) ⇄ H2O(l) at different Temperature Solid ice

• Slope of OC is negative
• Melting point of ice is lowered by increasing pressure

• Slope of OC is Steep
Water Vapour
• Enormous pressures are needed to bring about significant changes
Pressure Melting point of ice
1 atm 0 0C
128.3 atm -1 0C

Variation of Vapour pressure with temperature is given by Clapeyron equation

𝑑𝑃 Hf 𝑃2 ∆Hf 𝑇2−𝑇1
= 𝑇 (Vl −Vs)
⇒ 𝑙𝑛 = [𝑇𝑇 ]
𝑑𝑇 𝑃1 𝑅 2 1

∆𝐻𝑓 = Heat of fusion

Water System Water Liquid

Curve OB (sublimation curve): Monovariant Solid

• Represents the H2O(s) ⇄ H2O(g) at different Temperature ice
• Its lower end extends to absolute zero

Clapeyron equation: Variation of Vapour pressure with temperature

𝑑𝑃 Hsub 𝑃 Hsub 𝑇 −𝑇 Water Vapour

= ⇒ 𝑙𝑛 𝑃2 = [ 𝑇2 𝑇 1]
𝑑𝑇 𝑇 (Vg − Vl ) 1
𝑅 2 1

Hsub = Heat of sublimation

Triple point: Nonvariant

➢Curve OA, OC and OB meets at point O where three phase co-exist
➢Point O is at T = 0.0075 0C and 4.58 mm Hg

➢ If we supply heat at O more ice will melt keeping same T and

pressure, finally T will move in OA
➢ If apply pressure, vapor will condense to ice or liquid
Metastable Solid–Vapour equilibrium, Curve OA’ Water Liquid
➢ The vapour pressure curve AO of the liquid phase terminates at O, when the
liquid water freezes (or solidifies). Solid ice
➢ However by careful cooling of the liquid under conditions that crystals do not
form, the curve AO can be extended to A’.
➢ This means that the liquid can be cooled far below the freezing point or
‘supercooled (Unstable Excited state with shorter life)’ without separation of
the crystals. Water Vapour
➢ Thus the dashed curve OA' represents a metastable equilibrium, Supercooled
Liquid Vapour
➢ A slight disturbance or the introduction of a seed crystal, the entire liquid
solidifies rapidly.

➢ This system at once reverts to the true stable system Solid ⇄ Vapour under suitable
conditions.
➢ The dashed curve of the metastable liquid lies above the normal sublimation curve (BO).

➢ The vapour pressure of the metastable phase is always higher than that of the stable
phase at the same temperature.
Water System
x a
Areas Water Liquid
➢ Area AOC, BOC , AOB represents water, ice and c
vapour respectively. d
Solid ice
➢ C = 1 and P = 1 for areas, F = 1 – 1 +2 ; F = 2 b
➢ In order to define the system at any point in the areas,
it is essential to specify both temperature and pressure.

➢ The degree of freedom of the system is two. i.e.,

Bivariant.

➢ This is predicted by the phase rule

Water Vapour
Phase Diagram of CO2 System

Dry CO2 or dry ice?

➢ The triple point (217 K, 5.11 bar) lies well above atmospheric pressure.
➢ Liquid carbon dioxide does not exist under normal conditions.

➢ Slope of melting curve is +ve

➢ The melting temperature of solid carbon dioxide rises as the pressure is increased.

➢ The critical temperature 304.2 K (31.0°C) and pressure 72.9 atm are readily accessible
➢ Moreover carbon dioxide is cheap.
➢ Supercritical carbon dioxide, scCO2, is the center of attention for an increasing number of solvent-based processes.
Polymorphism: The occurrence of the same substance in more than one crystalline forms

➢ The individual crystalline forms of an element (Compounds) are referred to as polymorphs or allotropes.
➢ Rhombic and monoclinic sulphur are two allotropes of sulphur.
➢ The allotropic forms of an element have distinct physical properties and constitute separate phases.
Allotropy can be divided into three types :
(a) Enantiotropy, (b) Monotropy and (c) Dynamic allotropy.

a. Enantiotropy
➢ One polymorphic form (or allotrope) can reversibilily change into another at a definite temperature when the two forms
have a common vapour pressure.
➢ This temperature is known as the transition temperature.
➢ One form is stable above this temperature and the other form below it.
b. Monotropy
➢ It occurs when one form is stable and the other metastable.
➢ The metastable form changes to the stable form and the change is not reversible.
➢ There is no transition temperature as the vapour pressures are never equal.

Metastable stable Stable

c. Dynamic allotropy: Several forms which can coexist in equilibrium over a range of temperature.
➢ The amount of each is determined by the temperature.
➢ The separate forms usually have different molecular formulae but the same empirical formula.
➢ Dynamic allotropy is reversible but there is no fixed transition point.
➢ Liquid sulphur which consists of three allotropes Sµ (S8), S (S4) and S (unknown).
➢ The composition of the equilibrium mixture vary between 120ºC and 444.6ºC and there is no transition point
The Sulphur System: C=1 and maximum number of P = 4
Two solid polymorphic forms :
1. Rhombic Sulphur (SR) stable above 95.6ºC enantiotropy
2. Monoclinic Sulphur (SM) stable below 95.6ºC
3. Sulphur Liquid (SL) stable above 120 ºC
4. Sulphur Vapour (SV)

➢ At 120ºC, SM melts. Thus,

The salient features of the phase diagram are described below.

(i) The four areas :
ABG marked ‘solid Rhombic’
BEC marked ‘solid Monoclinic’
GECD marked ‘liquid Sulphur’
ABCD marked ‘Sulphur vapour’
(ii)The six curves AB, BC, CD, BE, CE, EG
(iii) The three Triple points B, C, E
(i) The Areas
➢ The phase diagram has four areas or regions.
➢ These are labelled as rhombic sulphur, monoclinic sulphur, liquid
sulphur and vapour.
➢ These represent single phase systems which have two degrees of
freedom,
F=C–P+2=1–1+2=2
➢ That is, each of the systems SR, SM, SL, and SV are bivariant.
(ii)The curves AB, BC, CD, BE, CE, EG: All are monovarient
These six curves divide the diagram into four areas.

Curve AB: Vapour Pressure curve of Rhombic SR at different temperatures.

➢ The two phases SR and sulphur vapour (SV) are in equilibrium.

Curve BC: Vapour Pressure curve of SM at different temperatures

➢ SM and SV coexist in equilibrium along this curve.
➢ The system SM/SV is monovariant.

Curve CD: Vapour Pressure curve of SL at different temperatures.

➢ SL and SV are in equilibrium along CD.
➢ One atmosphere line meets this curve at a temperature (444.6ºC) which is the boiling point of sulphur.
Curve BE (Transition curve ): The effect of pressure on the Transition Temperature for SR and SM.
➢ Transition temperature increases with increasing pressure (+ve slope)
➢ The transformation of SR and SM is accompanied by increase of volume (density of SR = 2.04; SM = 1.9) and absorption of heat.

Curve CE (Fusion curve of SM ): Represents the effect of pressure on the melting point of SM.
➢ The two phases in equilibrium along this curve are SM and SL.
➢ The melting of SM is accompanied by a slight increase of volume.
➢ The melting point will rise by increase of pressure (Le Chatelier’s principle).
➢ The curve ends at E because SM ceases to exist beyond this point.

Curve EG, the Fusion curve for SR.

➢ Here the two phases in equilibrium are SR and SL.
➢ At high pressure, rhombic sulphur directly melts without forming monoclinic
(iii) The Triple points B, C, E
Triple point B (The transition point 95.6ºC).
➢ This is the meeting point of the three curves AB, BC and BE.
➢ Three phases, solid SR, solid SM and SV are in equilibrium at the point B.
➢ There being three phases and one component, the system SR/SM/SL is nonvariant.
F=C–P+2=1–3+2=0
At B, SR is changed to SM and the process is reversible.

Triple point C (The melting point of SM at 120ºC)

➢ The curves BC, CD, CE meet at this point.
➢ The three phases in equilibrium are SM, SL and SV.
➢ There being three phases and one component, the system SM/SL/SV is nonvariant.

Triple point E.
➢ The two lines CE and BE, having different inclinations away from the pressure axis, meet at E where a third line EG also
joins.
➢ The three phases SR, SM and SL are in equilibrium
➢ This point gives the conditions of existence of the system SR/SM/SL at 155ºC and 1290 atmospheres pressure.
(4) Metastable Equilibria
➢ The change of SR to SM takes place very slowly.
➢ If Rhombic sulphur is heated rapidly, it is possible to pass well above the transition point
without getting SM.

The dashed curve BF, the Vapour Pressure curve of metastable SR.
➢ This is a continuation of the vapour pressure curve AB of stable SR.
➢ The metastable phases SR and SV are in equilibrium along this curve. It is a monovariant system.

The dashed curve CF, the Vapour Pressure curve of supercooled SL.
➢ Supercooling sulphur liquid can avoid the formation of SM until the point F where SR starts precipitating.
➢ The curve CF represents the metastable equilibrium between supercooled SL and SV.
➢ The curve CF represents the vapour pressure curve of supercooled SL. It meets the dashed curve BF at F.

The dashed curve FE, the Fusion curve of metastable SR.

➢ The two metastable phases SR and SL are in equilibrium along this curve and the system is monovariant.
➢ This shows that the melting point of metastable SR is increased with pressure. Beyond E, this curve depicts the conditions
for the stable equilibrium SR/SL as the metastable SR disappears.

The metastable Triple point F.

➢ At this point, three metastable phases SR, SL and SV are in equilibrium.
➢ The system is a metastable triple point with no degree of freedom.
➢ The corresponding temperature is the melting point of metastable SR (114ºC).
Phase diagram for pure substances Phase diagram for mixtures

[Water System]
[CO2 System]
[Sulphur System]

[Pb-Ag System]

[Zn-Mg System] [Na2SO4-H2O System]

[Cu-Ni System]
 Two–component Systems, C = 2
➢ The phase rule can be written as F = 2 – P + 2 = 4-P
➢ Minimum no of phase can be one,
➢ The maximum number of degrees of freedom would be F=2–1+2=3
➢ Three variables (Temperature, Pressure and Composition) must be specified in order to describe the condition of the phase
3D
diagram ➢ For condensed system, measurements of Temperature and composition (Mole fraction)is
done at atmospheric pressure (P is constant)

➢ For a solid/liquid equilibrium, the gas phase in usually

absent (condensed system)
➢ The effect of pressure on the equilibrium is very small

F’ = C-P + 1 ➔ Reduced Phase Rule

The reduced phase rule for two component system

F’ = 2-P + 1 In Binary systems,
F’ = 3-P ❖ Simple Eutectic (Isomorphous) system
❖ Systems that forms a stable Compound
Construction of Phase diagram by Thermal analysis (or) cooling curve
➢ A method involving the study of cooling curves of various compositions of a system during solidification.
➢ A molten liquid containing two components (A and B) is cooled slowly
➢ When the Temperature reaches the point ‘b’ one substance (either A or B) begins to
solidify (exothermic) out of the melt
➢ A break is indicated by change of the rate of cooling (different heat capacities)
➢ On further cooling at the break point ‘c’ the second compound also begins to solidify.
➢ The temperature remains constant until the liquid melt is completely solidified, which
forms the eutectic mixture

The temperature of horizontal line ‘cd’ gives the eutectic temperature.

Cooling curve of a mixture of varying composition

➢ As the mixtures differ in composition the freezing commence at different

temperatures

➢ The main phase diagram can be drawn by taking the compositions in X-

axis and temperature (point b) in Y-axis.
➢ Any point on line indicates the appearance of solid phase from the liquid.
➢ The area above this curve is only liquid phase.
Cooling curve of six alloys of different compositions

➢ Temperature is shown in the vertical axis as

function of time on the horizontal axis ➢ The fusion temperature and the liquidus and solidus
temperature are then plotted as a function of composition to
form the phase diagram

➢ The liquidus is the line above which the entire sample is liquid
➢ The solidus is the line below which the sample is entirely solid.
1. Simple Eutectic Isomorphous (easy melting) system-
➢ Two elements are completely miscible in each other in liquid and solid state
➢ Both pure materials have same crystal structure
➢ Atoms have similar radii
➢ Similar electronegativity (otherwise may form a compound instead)
➢ Solute should have higher valence Eg: Pb-Ag, Pb-Sn, Pb-Mg, Ag-Au, Zn -Cd etc.

The phase diagram of 2-component condensed system

Reduced phase rule F’ = 2-P + 1 = 3-P
The phase diagram consists of
➢ Regions (Areas), One phase
F’ = 3-P = 3-1 ➔ bivariant
➢ Lines (Bounderies), Two phases
F’ = 3-P = 3-2➔ univariant
➢ Point (Junction between lines), Three phases,
F’ = 3-3➔ nonevarient
The Ag–Pb System The phase diagram of Ag/Pb system.
➢ This system has two components and four phases.
➢ The phases are :
➢ Solid silver(M.P. 961 oC)
➢ Solid lead (M.P. 327 oC
➢ Solution of molten silver and lead
➢ Vapour. (The boiling points of silver and lead being
considerably high, the vapour phase is practically absent)
➢ Thus Ag/Pb is a condensed system with three phases.
➢ In such a case, pressure can have no effect on the system.
➢ Only the two remaining variables,
Temperature (T) and Concentration (C).
The salient features of the diagram are :
(a) Two curves, AC and BC
(b) Eutectic point, C ( At 303 0C with a composition 2.5% Ag in Pb)
(c) Three areas : (i) above ACB; (ii) below AC; (iii) below BC
The Ag–Pb System cont..
Curve AC; the Freezing point curve of Ag.
➢ The point A represents the freezing point of Ag (961 oC) .
➢ The freezing point of Ag falls by the addition of Pb.
➢ Thus along this line, the solid Ag is in equilibrium with the liquid
solution of Pb in Ag.
➢ F’ = 3-2= 1, Univariant

Curve BC; the Freezing point curve of Pb

➢ The point B shows the freezing point of Pb (327 oC).
➢ The curve BC exhibits the fall of freezing point by the addition of Ag to Pb.
➢ Along this curve, the solid Pb is in equilibrium with the liquid solution of Ag in Pb.
➢ The degree of freedom is one i.e., both equilibria are monovariant.
 Reduced phase rule F’ = C-P + 1
➢ The Eutectic point C (easy melting at 303 oC with 2.5Ag in 97.5 Pb).
➢ The two curves AC and BC meet at the point C.
➢ At C, solids Ag and Pb (of composition C, 2.5Ag in 97.5 Pb) must
be in equilibrium with the solution phase having same composition.
➢ The number of phases is 3.
➢ Applying the reduced phase rule equation,
F' = C – P + 1 = 2 – 3 + 1 = 0
➢ Thus the system represented by the point C is nonvariant.
➢ The temperature corresponding to C gives the lowest temperature
TE where the mixture of Ag and Pb melts (indicated on the graph)
➢ The point C is therefore, called the Eutectic point
➢ The corresponding composition (CE) and temperature (TE) are
known as the eutectic composition and the eutectic temperature
respectively of the system.

The eutectic mixture, although it has a definite melting point, is not to be regarded as a compound.
(i) The components are not in stoichiometric proportions;
(ii) Eutectic solid is a two-phase system, it crystallizes out in a nearly homogeneous mixture of microcrystals and
X-ray diffraction studies reveal the existence of separate crystals of the components.
The Areas Reduced phase rule F’ = C-P + 1

The Area above the curves AC and BC.

➢ The two components Ag and Pb are present as liquid solutions of varying
compositions.
➢ A homogeneous solution of Ag and Pb constitutes one phase only.
F = C – P + 1 = 2 – 1 + 1 = 2, Bivarient
➢ To define the system at any point in this area, both temperature and
composition have to be specified.

The Areas between AC and TE line

➢ Thus in the area below AC and above TE line, there exist two phases
viz., solid Ag and solution of varying composition of Ag and Pb and
is univariant

➢ Below TE line no liquid can exist, the entire area below this line would represent the system solid Ag and solid Pb (univariant)
Effect of Cooling
➢ When the solution of Ag and Pb at any (X) point in the area above ACB is cooled, the cooling dashed line meets the curve AC,
say at Y (composition x).

Z
➢ Here solid Pb separates and the equilibrium shifts down along the
curve YC.

➢ The change of composition and temperature continues (YC) till

the eutectic point C is reached when solid Ag also separates

➢ If the solution just above the eutectic point is

cooled (Z), a solid mixture (eutectic mixture) of
eutectic composition CE, will be obtained.

x
Pattinson’s Process for the Desilverisation of Argentiferous
Lead - This process of recovery of silver from argentiferous
lead (0.1% Ag in Pb)
Applications of Eutectic systems
Safety fuses, Safety plugs, Fire alarms, Pressure cooker
➢ Wood metals melts at 75 0C - Eutectic alloy of 50% bismuth, 26.7% lead, 13.3% tin, and 10% cadmium by mass.
➢ Rose's metal consists of 50% bismuth, 25–28% lead and 22–25% tin. (Melting point is between 94 and 98 °C). The
alloy does not appreciably contract or expand on solidification, this characteristic being a function of its bismuth
percentage. (https://www.chemistrylearner.com/rose-metal.html#google_vignette)
Solder
➢ Pb-Sn solder (37-67% of Pb, 31-60% of Sn and Sb in 0.12- 0.2% (used in soldering electrical connection)
➢ Brazing alloy Sn-92%, Sb-5.5% and Ca-2.5 % (used in tinning)
➢ Tin man’s solder Sn-66% and Pb- 34% (used in soldering electrical connection)
➢ Plumber solder Sn-50% and Pb- 50%

Examples of some other Eutectic systems

➢ NaCl (801 oC) and water (5 oC) form a eutectoid when
the mixture is 23.3% salt by mass with a eutectic point
at -21.2 oC.
➢ The system is used to melt ice and snow.
Assignment 2
1. Derivation of phase rule
2. The Cu–Ni System
The diagram with explanation on curve, region, use etc
Liquidus and solidus region
Effect of cooling
2. Two components system that form a solid compound

There are a number of systems known, in which two metals form

➢ An intermetallic compound, or
➢ Salt and water form a solid hydrate

❖ Systems that forms a stable compound are classified in to Two

A. System with Congruent melting point (A compound that melts sharply at a constant
temperature to a liquid of same composition as solid)
B. System with Non-congruent melting point (A compound melts with decomposition at a
constant temperature to a liquid of different composition as solid)
A. Compound formation with Congruent melting point (sharp melting point)
Phase diagram of Solid A and Solid B with a compound formation ABn, n = 1,2,3, etc

➢ There are three solid phases, A, B and AB and one liquid phase (or
solution) containing varying concentration of A, B and Compound AB.

The curves
➢ There are three freezing / melting point curves AC, CDE and EB.
➢ Two phases are in equilibrium, So, F = 2-2+1 = 1, Univariant

➢ Along AC, solid A is in equilibrium with solution of A and B

➢ Along BE, solid B is in equilibrium with solution of A and B
➢ Along CDE, Compound AB is in equilibrium with solution of A and B

Congruent Melting point D in the curve CDE:

➢ The compound melts sharply at a constant temperature to give a liquid of same composition as the solid.
➢ At D, Solid AB melts in to liquid AB (the system is having only one component-AB)
➢ So, F = 1-2+1 = 0 and D is a non-variant point
➢ The point D can be above, below or middle of the melting point of individual component A and B
➢ Sharper the maxima, stable is the compound formed, Flat maxima indicate appreciable dissociation
System with Congruent melting point
Phase diagram
Eutectic points C and E u
➢ At Point C, solid A is in equilibrium with compound AB and
melt(solution). x x’
t1
➢ Three phases. so, F = 2-3+1 = 0 and C is a non-variant point
v
➢ At Point E, solid B is in equilibrium with compound AB and liquid melt
and is non-variant point

At a given temperature “t1” w

➢ The liquid phase has two compositions, say x and x’ in equilibrium
with compound AB

➢ At x, solid AB is in equilibrium with a solution of A in compound AB

➢ At x’, solid AB is in equilibrium with a solution of B in compound AB Y
➢ Two 2 component system with a eutectic point is connected through
the line DX Eg,
➢ Zn-Mg System,
➢ Phenol-Aniline,
➢ FeCl3-H2O system
The Magnesium–Zinc System with the formation of MgZn2.

➢ It has four phases :

➢ solid magnesium (Mg),
➢ solid zinc (Zn),
➢ solid MgZn2 and
➢ the liquid solution of Mg, Zn and MgZn2 .

The curves AC, CDE and BE (Two phases: Mono variant).

380 oC ➢ AC (Mg/liquid equilibrium) is the freezing point curve of Mg
347 oC (FP decreases with Zn),
➢ BE (Zn/Liquid equilibrium) is the freezing point curve of Zn
(FP decreases with Mg);

➢ CDE (MgZn2 /liquid equilibrium)is for compound MgZn2

66.7:33.3 ➢ From the point C, the increase of concentration of Zn in the melt
Zn: Mg
causes the rise of melting temperature with the formation of MgZn2

➢ At the maximum point D, the composition of the melt and the solid compound becomes the same i.e.,MgZn2
➢ Curve DE shows the lowering of the melting point with the addition of Zn until the lowest point is attained. At E solid Zn
appears.
The Magnesium–Zinc System with the formation of MgZn2.

Eutectic points C and E.

➢ There are two eutectic points in the phase diagram, C and E.
➢ Two components and three phases in equilibrium.
Phases Present
➢ At C (347 oC) , Solid Mg, solid MgZn2 and the melt
➢ At E (380 oC), Solid Zn, solid MgZn2, and liquid the melt
➢ So, F = C – P + 1 = 2 – 3 + 1 = 0, These systems are nonvariant.
347 oC 380 oC

Congruent Melting Point (575 oC).

➢ At D, the composition of the solid and the melt is identical (MgZn2).
➢ Point D has two phases viz., the solid MgZn2 and the melt MgZn2.
➢ F = C – P + 1 = 1 – 2 + 1 = 0, Therefore the system at D is nonvariant
33.3:66.7
Mg:Zn
The Areas.
➢ The area above the curves AC, CDE and BE represents the solution of Mg and Zn (the melt).
➢ The single phase system at any point in this area is bivariant.

➢ The area below the curves AC, CDE and BE represent two phases and univarient.
➢ The phases present in the other regions of the phase diagram are as labelled.
Formation of Compounds with Incongruent Melting point
➢ In the system A-B-C, there is an intermediate stable phase, B,
A + C → B.
➢ Intermediate compound B melts incongruently (meritectic or peritectic reaction point) to a liquid of different composition.

➢ Point P (peritectic point )

❖ the temperature is the peritectic temperature Tp and
❖ the liquid composition is Lp.
➢ At P, the liquid of composition Lp reacts with the solid A to form solid B.

➢ To the right of the point P, the system can be considered as a simple eutectic
diagram (with components B and C)
➢ Cooling of compositions at Z results in the crystallization of C at T5 and the
system cools to yield B + C.

➢ For compositions between P and E, such as Y, the system also behaves as a simple eutectic
Na2SO4–H2O System
Solid Phase
➢ Anhydrous Sodium sulphate (Na2SO4) exhibit two enantiotropic crystalline phases
viz., rhombic and monoclinic.
➢ Sodium sulphate (Na2SO4) forms two hydrates
Na2SO4.10H2O (decahydrate) and Na2SO4.7H2O (heptahydrate).
➢ The remaining phases is Solid ice.

Liquid Phase
➢ One homogenous Solution Phase

Vapour Phase
➢ Since all determinations are made at atmospheric pressure, the vapour phase is ignored.

Thus Na2SO4-H2O system is a six phase condensed system

➢ The composition of all the six phases can be represented by two constituents
Na2SO4 and H2O (two components)
Na2SO4–H2O System

The Curve AB,

Melting point curve of ice. Ice/liquid equilibrium (Monovariant).
➢ The point A (0ºC) is the melting point of ice.
➢ The curve AB shows the lowering of melting point of ice on the addition of
anhydrous Na2SO4.

The Curve BF, Solubility curve of Na2SO410H2O(Monovariant).

➢ Along BF, saturated solution of Na2SO4 and Na2SO4.10H2O is in equilibrium.

➢ If the system at B is heated and more of anhydrous Na2SO4 added, curve BF
will be followed.
➢ Thus the curve BF shows that the solubility of Na2SO410H2O increases with
temperature until the point F is reached.
 Na2SO4–H2O System

The Eutectic point B (the lowest temperature attainable).

➢ At B (– 1.3ºC), a new solid phase Na2SO4.10H2O appears.
➢ This is the Eutectic Point where three phases (ice, solid Na2SO4.10H2O, Solution) can
coexist in equilibrium.
➢ Applying reduced phase rule equation, F = C – P + 1 = 2 – 3 + 1 = 0, nonvariant.

The Transition point F (32.2 ºC) .

➢ At F, Na2SO4.10H2O loses water and changes to the anhydrous rhombic Na2SO4.
➢ Thus, this point represents the transition temperature (32.2ºC).
Na2SO4. 10H2O ⇌ Na2SO4 + 10H2Ol
➢ This temperature may also be regarded as the incongruent melting point of Na2SO4.10H2O
➢ The composition of the liquid phase (solution) is different from that of the solid hydrate
➢ At F, there are two components and three phases viz., Na2SO4.10H2O, Na2SO4 and the solution.
Hence the system is nonvariant.
 Na2SO4–H2O System

The Curve FG, the solubility curve of rhombic Na2SO4.

➢ When the system at F is heated, ultimately all Na2SO4. 10H2O will disappear to form
anhydrous rhombic Na2SO4.
➢ The curve shows that the solubility decreases up to 125ºC with rise of temperature.
➢ The solubility increases till the point G.
➢ At G (234ºC), the rhombic Na2SO4 changes into the monoclinic form.
➢ Thus G represents a transition point where enantiotropic transformation occurs.
➢ With two components and three phases in equilibrium, the system at G is nonvariant.
➢ F=C–P+1=2–3+1=0

The Curve GH, the solubility curve of monoclinic Na2SO4.

➢ On continued heating the system at G, the rhombic Na2SO4 completely changes into the
monoclinic Na2SO4.
➢ Solubility falls gradually with rise in temperature up to 365ºC, the critical point of the
solution.
➢ The system along GH has two components and two phases, namely, Na2SO4 monoclinic and
solution. Thus, F = C – P + 1 = 2 – 2 + 1 = 1 the system is monovariant.
Metastable Equilibria of Na2SO4/H2O System (dashed lines )

➢ The Curve FF’: the solubility curve of metastable Na2SO4 10H2O.

If enough time is not allowed at F, Na2SO4 10H2O does not changed into anhydrous rhombic
Na2SO4.
➢ The Curve BC : the freezing point curve of metastable supercooled saturated solution of
Na2SO4 10H2O.
If by careful cooling, Na2SO4 10H2O does not separate at B, we pass along the dashed curve
BC.
➢ The Eutectic C (– 3.77º).
Metastable Na2SO4 7H2O appears. Therefore, the point C is the eutectic point where three
metastable phases viz., supercooled solution, ice, and Na2SO4 7H2O coexist in equilibrium.
➢ The Curve CD: represents the solubility curve of metastable Na2SO4 7H2O.
By slowly raising the temperature of the system at C.
➢ The Curve FD. When a saturated solution of rhombic Na2SO4 is cooled quickly Na2SO4
10H2O does not appear at F (32.2º) and we pass on to D.
➢ The Transition point D. The point D represents the transition point where the metastable
Na2SO4 7H2O is changed into metastable rhombic Na2SO4.
3. Three components system

General phase rule, F = C-P+2

For three component system, C = 3 and F = 3-P+2 = 5-P

For P = 1, and C= 3
F = 5-1 = 4 variables
Pressure
Constant
Temperature
Two compositions

Two compositions can be represented in

a triangular diagram (ternary graph)
Three components system
➢ Each of the apexes of the equilateral triangle represents the 100% of one component in terms of weight and 0% of the
remaining two components.

➢ The side opposite to corner/apex A have 0% A

➢ Horizontal lines, parallel to side BC across the triangle represents show increasing
percentage of A

➢ The three lines (AB, BC, CA) joining the vertex points represent the
combination of A, B and C, they represent the two component or binary
mixtures.

➢ Side AB: combination of A and B in weight percentage

➢ Towards apex B the weight % of A decreases
➢ The lines drawn parallel to side AB represents increasing
concentration of C from 0 to 100%

➢ A point inside the triangle have all the three components (ternary
system) and the total composition will be 100%
(x% A + y% B + z% C)
Ternary Eutectic Systems
Problem 1 :At 1000C, the specific volume of water and steam are, respectively, 1 c.c. and 1673 c.c. calculate the change in
vapour pressure of the system by 1 oC change in temperature. The molar heat of vaporization of water in this range may be
taken as 40584.8 J mol-1.

Problem 2 : The vapour pressure of water at 950C, is found to be 634 mm. what would be the vapour pressure at a temperature
of 100 0C. The molar heat of vaporization of water in this range may be taken as 40584.8 J mol-1.
 Spectroscopy
The study of the interaction of matter with the electromagnetic spectrum

❖ The best tool to study Matter

❖ What does light do to sample?
❖ Why there is a light absorption/emission

Thermal Infrared Imaging Spectrometer (TIS)

Ref:- Fundamentals of Molecular spectroscopy,
by C. N. Banwell and E.M.McCASH
What is light or Electromagnetic radiation ?
Light as a Wave
➢ Light as a simple harmonic wave of sinusoidal character
[y = A sine(2put)] A = maximum amplitude of the wave
u = frequency of the wave
t = time in sec
➢ Light has both electric and magnetic components, travelling in straight line except reflected or refracted
An EM radiation can be specified by
➢ Wavelength (l), has the unit of length ,
 α 1/l
➢ Frequency () in Hz (no of cycles per sec)  = c/l, c = 3 x 1010 cm/sec
➢ Wave number (ῡ = 1/l) in cm -1 & no of cycles/Wave per cm  = cῡ

Light as particle :- by Max Planck in 1900 and Quantization of Energy

➢ The particle component of light is called a photon (massless particle a small wave-packet of EM radiation/light).
The photon is the quantum of electromagnetic radiation.
➢ The energy (E) component of a photon is proportional to the frequency.
E = h
ie E = hc /l h = 6.626 X 10-34 Joules sec, Planks constant
How does light interact with sample?
Classically, light interacts with charges:
➢ Molecules/atoms are composed of charged particles and Light (electromagnetic field) exerts force on these charges.
➢ The force exerted on the molecules depends on the strength of the field, the magnitude of the charges

1. Absorption 2. Emission

DE = E2 – E1
DE = h joules
 = DE/h

A molecule can absorb or emit only in the multiples of Quanta

Jablonski diagram

EM radiation can interact with matter in two ways:

• Collision – particle-to-particle – energy is lost as heat and movement (scattering)

• Coupling – the wave property of the radiation matches the wave property of the particle
and “couple” to the next higher quantum mechanical energy level
The entire electromagnetic spectrum can be used
Frequency,  in Hz
~1019 ~1017 ~1015 ~1013 ~1010 ~105

Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m

Energy (J/mol)
> 109 > 107 105 103 ~10 ~10-1 to 10-3

g-rays X-rays UV IR Microwave Radio

Nuclear excitation Core electronic Outer electronic Molecular vibration Molecular rotation Nuclear/Electro
(PET) excitation excitation nic Magnetic
(X-ray diffraction) Electronic energy Vibrational Energy Rotational energy spin Resonance
Bond breaking NMR (MRI)

Visible
➢ A molecule absorb only selected frequencies
➢ Various energy levels in the molecule are quantized (discrete)
Transitions in molecules

Quantum mechanics demand discrete Energy levels in Molecule

Electronic Vibrational Rotational Translational
Energy Energy Energy energy
Instrumentation for spectroscopy
Monochromators

Select wave length

• Power Source: spectrochemical encoding system, For UV- Xe, H2 Or D2

and Tungsten Lamp. For IR- Nichrome wire, Globar, Laser source
• Monochromators: Prism, Gratings in combination with slits and mirrors
• Sample cell: Cuvette (Silica) for UV-VIS and for IR (glass or Plastic,
NaCl, NaBr)
• Wavelength Disperser: an information sorting system, spreads light out
spatially according to its wavelength
• Photodetector: radiation transducer changing optical info into electrical
information (Photomultiplier tube, Diode array)
• Readout: digital (ADC), meter, strip chart recorder
General Set Up for single bean instrument

General Set Up for double bean instrument

Representation of spectra
100% 0%

Transmittance (%)

Absorbance
0%
100%

UV and IR spectra of water

Practical spectroscopy: Factors affecting- (Molecular Spectroscopy- by Banwell..…)
1. Width of spectral lines 100% 0%

a. Collision broadening (more severe in liquids than gases)

Transmittance (%)
b. Doppler broadening (in gases this effect is more)

Absorbance
c. Heisenberg uncertainty principle (less effect )
ℎ
δE x δt   10-34Js;
2p 0%
100%
ℎ 1
h x δν x δt  ➔ δν  ➔ If δ t = 10−8 𝑠, δν = 108 Hz
2p 2p δ t
2. Intensity of spectral lines
a. Transition probability (TP) decided by selection rule
a. Allowed transition, TP  0 and
b. Forbidden transitions, TP = 0
b. Population of states (Boltzmann distribution)
N upper
= 𝑒 −∆𝐸/𝑘𝑇 , T = Temperature in K, k = 1.38 x 10−23 J𝐾 −1
N lower
Nupper = Nlower 𝑒 −∆𝐸/𝑘𝑇
Q. Calculate the ratio of molecules in the upper to those in the lower energy level when the separation between these energy
levels at 300 K is as follows
a) 11.9 J mol-1 b) 11.9 kJ mol-1 c) 119 kJ mol-1

N upper −23 −1
N lower = exp(-∆E/kT)], T = Temperature, k = 1.38 x 10 J𝐾

= exp(-11.9/ 1.38 x 10−23 J𝐾 −1 x 300K) =

= exp(-11.9 𝑥 103 / 1.38 x 10−23 J𝐾 −1 x 300K) =
= exp(-119 x 103 / 1.38 x 10−23 J𝐾 −1 x 300K) =
c. Intensity/Transition probability (Beer-Lambert Law)
“When light passes through a medium containing analyte solution, light gets absorbed by the medium (decrease in intensity)”

➢ The decrease in intensity of the light with thickness (l) is proportional to

intensity of the incident light (I0)
➢ The extend of absorption depend on
➢ Concentration of the sample (c in mol/L) and
➢ The length (l in cm) with which the light passes through the medium

𝑰
The intensity of the transmitted light, % 𝒐𝒇 𝑻𝒓𝒂𝒏𝒔𝒎𝒊𝒕𝒕𝒂𝒏𝒄𝒆 = % 𝑻 = 𝟏𝟎𝟎 𝑰𝟎 = 100T
I = I0 10 -  c l
𝟏 𝟏𝟎𝟎
𝑰
A = log = log
𝑻 %𝑻
T = Transmittance = = 10 - c l
𝑰𝟎
A = 2 log 10 - log %T
𝑰𝟎
𝒍𝒐𝒈 = 𝜺𝒄𝒍 = 𝑨 (Absorbance)
𝑰 = 2-log %T
A = -log T log %T = 2-A
➢ The Absorbance (A) is also called Optical density
➢ 𝜺 = Molar absorptivity / extinction coefficient in cm2 mol−1 (L mol−1 cm−1)
➢ (𝜺) represents the ability of the molecule to absorb light , ∣ 𝜺 ∣ is the transition probability
Molar absorptivity  (l) : Express the ability of a molecule to absorb =A/cl
❖ Classical mechanical approach consider molecule as oscillating dipole of strength “f ”
❖ “f ” is dimensionless, often normalized to “ 1”

Quantum mechanical approach

❖ A transient moment (instead of Oscillator strength ) is introduced for
characterizing transition between Ground and Excited State.
➢ Transient dipole resulting from the displacement of charges during the
transition (not strictly dipole moment)
➢ A molecule with zero permanent dipole moment can acquire a dipole
moment if it is placed in an electric field.
❖ The probability of excitation is proportional to the square of the scalar
product of the transition moment and the electric vector
 (l) values ranges from 0 to 106
❖ The molecule whose transition moments are parallel to the electronic
vector of incident light are preferentially excited (high Value of , ) ➢ High intensity absorption  = above 104
❖ The Value of , minimum when perpendicular. ➢ For p → p∗,   105 and f  1
➢ Low intensity absorption  = below 103
➢ Forbidden transitions   0-100 and f = 10−3
➢ For n → p* transition
Deviations from Beer lamberts law
Absorbance, A = 𝜺𝒄𝒍
A = -log T

Beer’s law suggests that

➢ a calibration curve is a straight line,
➢ a y-intercept of zero,
➢ a slope of εl .

Limitations of Beer lamberts law

The linearity of the Beer-Lambert law is limited by

Fundamental,
Chemical and
Instrumental factors.
Causes of nonlinearity include:

Fundamental (High Concentration):

➢ Molecules are in close proximity (electrostatic interaction)
➢ Cause deviation in absorptivity co-efficient at concentration higher than 0.01 M
➢ Changes in refractive index

Chemical interactions :
➢ Shift of equilibrium, association, dissociation, etc

Instrumental factors.
Requirement of Monochromatic radiations (usually a small band width)
➢Polychromatic radiation always gives a negative deviation
➢The effect is smaller if the value of ε is essentially constant over the
wavelength range
➢Always measure the absorbance maxima

Stray radiation
Arises from imperfections in the wavelength selector that allow light to enter the instrument and reach the detector without
passing through the sample, Like reflections, scattering etc
Q. The molar absorptivity for a complex formed between bismuth (III) and Thiourea is 9.32X10 3 L cm-1 mol -1 at
470 nm. Calculate the range of permissible concentrations of the complex if the absorbance is to be no less than
0.10 and not greater than 0.90 when the measurements are made in 1.00 cm cells.
Amin = 0.10; Amin = 0.90
A=cl
 = 9.32X10 3 L cm-1 mol -1
Cmax = A/  l
Cmin and Cmax = ?
l = 1.00 cm
Cmax = A/  l Cmin = A/  l
= (0.90/(9.32X10 3 L cm-1 mol -1 X 1.00 cm) = (0.1/(9.32X10 3 L cm-1 mol -1 X 1.00 cm)
= 9.6 X 10 -5 mol L-1 = 1.07 X 10 -5 mol L-1

Q. If the molar absorptivity of 1,10-phenanthroline is 12,000 litre mole-1 cm-1 and minimum detectable
absorbance is 0.004. Calculate the detectable minimum concentration for a 5.00 cm path length.

ε = 12,000 litre mole-1 cm-1; According to Beer – Lambert’s law A = εcl

A = 0.004; l = 5.00 cm; c = A/ εl
c=? 0.004
=
12,000litre mole−1 cm−1x 5cm

= 6.66 x 10-8 mole/Lit

 Infrared Spectroscopy
Vibrational spectroscopy

➢ The most common technique used is absorption spectroscopy.

➢ Used to identify chemical compounds based on how infrared radiations are absorbed by the compounds'
chemical bonds, and interacts with them.
➢ Infrared spectroscopy exploits the fact that molecules vibrate with specific frequencies corresponding to
discrete energy levels.
➢ Gives information about the functional groups present in molecules.

Ref:- 1. Fundamentals of Molecular spectroscopy,

by C. N. Banwell and E.M.McCASH, For theory
2. Spectroscopy,
by Lampman, Pavia, Kritz, Vyvyan: For application
IR Region of electromagnetic spectrum
X-Ray Ultraviolet Visible Infrared Microwave Radio

IR Spectra of limonene

Near IR Middle IR Far IR

 (µm) 0.8 2.5 25 250

ῡ (cm-1) 12500 4000 400 40
UV spectra of limonene

E = 1-10 kcal/mol,
Thermal energy

Stronger molecular Bond Vibrations

IR frequencies are usually expressed in wave number (cm-1) as this

is proportional to energy
 What happens when absorption of IR occurs?

➢ IR (thermal energy) absorption changes in the shape of molecules through Bond Vibration of covalent bonds
➢ Stretching of bonds
➢ Bending of bonds

Gross selction rule

NOT ALL bonds in a molecule are capable of

absorbing IR- energy.

➢ IR absorption only occurs when IR radiation interacts

with a molecule undergoing a change in dipole
moment as it vibrates.

➢ Infrared absorption only occurs when the incoming IR photon has sufficient energy for transition to the next
allowed vibrational state to take place (E = h).
 Vibrating diatomic molecule: Simple harmonic oscillator model (SHO)
Energy of diatomic molecule Hooke’s law :
1. Restoring force, f = -kx = - k (r-req)

k= force constant
x = displacement from equilibrium positions
(r = internuclear distance)
E2 Cl H’ H’’ ---1 2. The Energy,
Energy

𝟏
E = 𝟐 k(r-req)2

E1 Cl H’ H’’ ---- 2
➢ Every bond has an intrinsic vibrational frequency
➢ Frequency of bond vibration does not change with increase in the
energy of the system
Cl H
0 req ➢ The vibrational frequency depends on
Internuclear distance (r) ➢ the mass of the system
➢ the strength of the bond (force constant)
➢ is independent of degree of distortion
 Vibrating diatomic molecule: Simple harmonic oscillator model (SHO)

𝟏 𝒌
Frequency of stretching vibration of diatomic molecule osc = In Hz
𝟐 
𝟏 𝒌
ഥ 𝒐𝒔𝒄 = osc /c =
Converting the frequency to wave numbers, 𝝎 cm-1
𝟐𝒄 
➢ k is the force constant
➢ Is a measure of the bond strength
➢ Higher the force constant, stronger the bond
and higher the frequency of vibration

➢ μ is the reduced mass

➢ bonded atoms with higher masses (larger reduced mass) vibrate at lower frequencies than bonds between
lighter atoms.
 Energy levels for vibrating diatomic molecule, SHO
The allowed vibrational energies for vibrating diatomic molecule by solving Schrodinger equation,
𝑬𝝊 = 𝜐 + 𝟏𝟐 𝐡osc 𝐣𝐨𝐮𝐥𝐞𝐬 𝜐 (vibrational quantum number) = 0, 1, 2, 3--------
osc is the oscillating frequency of a bond vibrating in SHO

IR frequencies are usually expressed in wave number (cm-1) as this is proportional to energy
𝑬𝝊
Energy expressed in spectroscopic unit, (wave number in cm-1 = rad/m) 𝜺𝝊 = ഥ 𝒐𝒔𝒄 = osc /c
𝝎
𝒉𝒄
1
𝜺𝝊 = 𝜐 + ഥ𝑜𝑠𝑐 𝑐𝑚−1 --------- Eq 1
𝜔
2
To get energy in joules, multiply 𝜀𝜐 by speed of light (c) and Planck’s constant (h)
Zero point energy
𝟏 𝟏
When υ = 0, the minimum energy 𝑬𝟎 = 𝟎 + 𝒉𝝎𝒐𝒔𝒄 = 𝒉𝝎𝒐𝒔𝒄 joules
𝟐 𝟐
𝟏 ➢ A molecule can never have zero vibrational energy.
𝑶𝒓, 𝜺𝟎 = ഥ 𝒐𝒔𝒄 𝒄𝒎−𝟏 , Zero point energy
𝝎
𝟐 ➢ Atoms are never at rest relative to each other
First excited state energy, when υ = 1 ➢ Zero point energy depends only upon the strength of chemical bond
𝟏 𝟑 and atomic masses
𝑬𝟏 = 𝟏 + 𝒉𝝎𝒐𝒔𝒄 = 𝒉𝝎𝒐𝒔𝒄 joules
𝟐 𝟐
𝟓
𝑶𝒓, 𝜺𝟏 =
𝟑
ഥ 𝒐𝒔𝒄
𝝎 𝒄𝒎−𝟏 When υ = 2 , 𝜺𝟐 = ഥ 𝒐𝒔𝒄 𝒄𝒎−𝟏
𝝎
𝟐
𝟐
Energy levels for vibrating diatomic molecule, SHO
𝟏 1
𝑬= 𝜐+ 𝐡osc in Joules 𝜺𝝊 = 𝜐 + ഥ𝑜𝑠𝑐 𝑐𝑚−1
𝜔
𝟐 2
Allowed Transition for vibrating diatomic molecule, SHO
Specific Selection rule,  𝝊 = 1
a

The separation between adjacent energy levels 𝝊 and 𝝊 +1

𝜺𝝊 → 𝝊+𝟏 = 𝜺 𝝊+𝟏 − 𝜺𝝊
𝟏 𝟏
= 𝝊+𝟏+ 𝝎 ഥ 𝒐𝒔𝒄 − 𝝊 + 𝝎ഥ 𝒐𝒔𝒄 𝒄𝒎−𝟏
𝟐 𝟐
ഥ𝑜𝑠𝑐 𝑐𝑚−1
𝜺𝝊+𝟏 → 𝝊 = 𝜔
ഥ ഥ 𝒐𝒔𝒄 𝒄𝒎−𝟏
𝝂𝒔𝒑𝒆𝒄𝒕𝒓𝒐𝒔𝒄𝒐𝒑𝒊𝒄 = 𝜺 = 𝝎
a
The difference between energy levels expressed in cm-1 directly
gives the wavenumber of spectral line absorbed or emitted
a) The force constant of 79Br2 is 240 Nm-1. Calculate the fundamental vibrational frequency and the zero point
energy of 79Br2.

𝟕𝟗 𝟐𝒙 𝟏. 𝟔𝟔𝒙𝟏𝟎−𝟐𝟕 𝒌𝒈 𝟐
ഥ 𝒐𝒔𝒄
𝝎 cm-1 𝝁=
𝟐𝒙 𝟕𝟗 𝒙 𝟏. 𝟔𝟔 𝒙𝟏𝟎−𝟐𝟕

= 𝟔𝟓. 𝟓𝟕𝒙𝟏𝟎−𝟐𝟕 𝒌𝒈
(1/2 Mark) (1/2 Mark)

𝟏 𝟐𝟒𝟎 𝒌𝒈/𝒔𝟐
ഥ 𝒐𝒔𝒄 =
𝝎
𝟐𝒙𝟑.𝟏𝟒𝒙𝟑𝒙𝟏𝟎𝟏𝟎 𝒄𝒎/𝒔 𝟔𝟓.𝟓𝟕𝒙𝟏𝟎−𝟐𝟕 𝒌𝒈

= 320.63 cm-1 (1/2 Mark) Or osc= 9.612x1012 Hz

𝟏 𝟏
𝑬𝒗 = hosc J
𝜺𝝊 = 𝝎 ഥ 𝒐𝒔𝒄 𝒄𝒎−𝟏 𝟐
𝟐 = 3.18 x 10-21 J (or 1 Mark)
= 160.31 𝒄𝒎−𝟏 (1/2 Mark)
The force constant of a diatomic harmonic oscillator (AB) is 1550 Nm-1. Calculate the
vibrational frequency in cm-1. and the spacing between the energy levels in eV. (1 eV = 8066
cm-1, The atomic masses are A = 23.25x10-27 Kg, B = 26.6 x10-27 Kg

𝟐𝟑. 𝟐𝟓𝒙𝟐𝟔. 𝟔 𝟏𝟎−𝟐𝟕 𝟐

𝝁=
ഥ 𝒐𝒔𝒄
𝝎 cm-1 (𝟐𝟑. 𝟐𝟓 + 𝟐𝟔. 𝟔) 𝒙𝟏𝟎−𝟐𝟕

= 𝟏𝟐. 𝟒𝟎𝟔𝒙𝟏𝟎−𝟐𝟕 𝒌𝒈

𝟏 𝟏𝟓𝟓𝟎 𝒌𝒈/𝒔𝟐
ഥ 𝒐𝒔𝒄 =
𝝎
𝟐𝒙𝟑.𝟏𝟒𝒙𝟑𝒙𝟏𝟎𝟏𝟎 𝒄𝒎/𝒔 𝟏𝟐.𝟒𝟎𝟔𝒙𝟏𝟎−𝟐𝟕 𝒌𝒈

= 1876 cm-1 (1/2 Mark)

𝑬𝝊 1
Energy expressed in cm-1 𝜺𝝊 = = 𝜐+ ഥ𝑜𝑠𝑐 𝑐𝑚−1
𝜔
𝒉𝒄 2
𝟏
𝜺𝝊 = 𝟏𝟖𝟕𝟔 𝒄𝒎−𝟏
𝟐
= 938 𝒄𝒎−𝟏
= 938 / 8066 = 0.1162 eV
The anharmonic oscillator
Real molecules do not obey laws of simple harmonic oscillator for large amplitude vibrations

Allowed vibrational energies for AHO can be obtained by using

E = De [1- 𝒆{𝒂 𝒓𝒆−𝒓 } ]2 (Morse function)

a = constant for a particular molecule   2 1/ 2
De = dissociation energy a = 
 2hcDe 
The an-harmonic oscillator: the allowed vibrational levels
Allowed vibrational energies for a bond (AHO) can be obtained by solving
the Schrodinger equation using Morse function
𝟏 𝟏 𝟐 
𝜺𝝊 = 𝝊 + 𝝎 ഥ𝒆 − 𝝊 + 𝝎ഥ 𝒆 𝒙𝒆 𝒄𝒎−𝟏 ; (𝝊 =1,2,3………)
𝟐 𝟐

𝟏 𝟏
ഥ𝒆 𝝊 +
𝜺𝝊 = 𝝎 𝟏 − 𝒙𝒆 𝝊 + , 𝑐𝑚−1 ; (𝝊 =1,2,3………)
𝟐 𝟐
ഥ 𝒆 = vibrational frequency in cm-1
𝝎
𝒙𝒆 = anharmonicity constant
(for bond stretching vibrations 𝒙𝒆 = positive and small )
 Comparison of SHO and AHO :
An-harmonic oscillator: the allowed vibrational levels
𝟏 𝟏 ഥ 𝒆 = vibrational frequency in cm-1
𝝎
𝜺𝝊 = 𝝊 + ഥ 𝒆 𝟏 − 𝒙𝒆 𝝊 +
𝝎 , 𝑐𝑚−1 ; (𝝊 =1,2,3………) -----Eq 2
𝟐 𝟐 𝒙𝒆 = anharmonicity constant

Simple harmonic oscillator: the allowed vibrational levels

𝟏
𝜺𝝊 = 𝝊 + ഥ 𝒐𝒔𝒄 𝒄𝒎−𝟏 for SHO -------------------Eq 1
𝝎
𝟐

Comparing with the vibrational energies of SHO and AHO oscillators ie Eq 1 and Eq 2
1
ഥ 𝒐𝒔𝒄 = 𝝎𝒆 {1- 𝒙𝒆 𝜐 +
𝝎 } 𝑐𝑚−1
2

➢ An-harmonic oscillator behaves like SHO, but the oscillating frequency decreases
with increasing value of 𝝊

➢ The energy levels are crowded together at higher values of 𝝊.

➢ In an-harmonic oscillator the energy levels are not equally spaced,
➢ Molecule dissociates at largest separation
The an-harmonic oscillator: the allowed vibrational levels
𝟏 𝟏
ഥ 𝒆 𝟏 − 𝒙𝒆 𝝊 +
𝜺𝝊 = (𝝊 + )𝝎 𝑐𝑚−1
𝟐 𝟐
1
ഥ 𝒐𝒔𝒄 = 𝝎𝒆 {1- 𝒙𝒆 𝜐 +
𝝎 } 𝑐𝑚−1
2
Zero point energy, for 𝝊 = 0
𝟏 𝟏
𝟎=𝟐 𝝎
ഥ 𝒆 {1- 𝒙𝒆 } cm-1 Zero point energy
𝟐
𝟏
ഥ 𝒆 {1- 𝒙𝒆 } cm-1
ഥ 𝝊=𝟎 = 𝝎
𝝎
𝟐

F𝐢𝐫𝐬𝐭 𝐞𝐱𝐜𝐢𝐭𝐞𝐝 𝐬𝐭𝐚𝐭𝐞 𝝊 = 1

𝟑 𝟑
𝟎=𝟐 𝝎
ഥ 𝒆 {1- 𝒙𝒆 } cm-1
𝟐
𝟑 S𝐞𝐜𝐨𝐧𝐝 𝐞𝐱𝐜𝐢𝐭𝐞𝐝 𝐬𝐭𝐚𝐭𝐞 𝝊 = 2
ഥ 𝒆 {1- 𝒙𝒆 } cm-1
ഥ 𝝊=𝟏 = 𝝎
𝝎
𝟐
T𝐡𝐢𝐫𝐝 𝐞𝐱𝐜𝐢𝐭𝐞𝐝 𝐬𝐭𝐚𝐭𝐞 𝝊 = 3
The an-harmonic oscillator: the allowed transitions
The specific selection rules for an-harmonic oscillator

 𝝊 = 1, 2 etc

Probable transitions

𝝊 = 0 → 𝝊 = 1,  𝝊 = 1:
intense absorption (Fundamental absorption)
  =𝝎ഥ 𝒆 (1- 2 𝒙𝒆 ) cm-1

𝝊 = 0 → 𝝊 = 2,  𝝊 = 2:
with small intensity (First overtone)
  = 2𝝎
ഥ 𝒆 (1- 3𝒙𝒆 ) cm-1

𝝊 = 0 → 𝝊 = 3,  𝝊 = 3:
negligible intensity (Second overtone)
𝝊 = 1 → 𝝊 = 2,  𝝊 = 1:
  = 3𝝎
ഥ 𝒆 (1- 4 𝒙𝒆 ) cm-1 Week absorption (Hot band)
  =? cm-1
The equillibrium vibrational frequency of I2 is 215 cm-1, and the anharmonicity constant is 0.003. Compare the
intensity of the hotband (v=1 to v=2) to fundamental band. Justify your answer
𝟏 𝟏
ഥ 𝒆 𝟏 − 𝒙𝒆 𝝊 +
𝜺𝝊 = 𝝎 (𝝊 + ) , 𝑐𝑚−1 ; (𝝊 =1,2,3………)
𝟐 𝟐
𝟏 𝟏
ഥ 𝒆 𝟏 − 𝒙𝒆 𝟐 +
𝜺𝟐 = 𝝎 (𝟐 + ) , 𝑐𝑚−1 ഥ 𝒆 = 215 cm-1,
𝝎
𝟐 𝟐
𝟓 𝟓 𝒙𝒆 = 0.003.
𝜺𝟐 = ഥ 𝒆 𝟏 − 𝒙𝒆 , 𝑐𝑚−1 , similarly
𝝎
𝟐 𝟐
𝟑 𝟑
𝜺𝟏 = ഥ𝒆 𝟏 −
𝝎 𝒙 , 𝑐𝑚−1
𝟐 𝟐 𝒆

  fund =𝝎
ഥ 𝒆 (1- 2 𝒙𝒆 ) cm-1
So,   hot band =𝝎
ഥ 𝒆 (1- 4 𝒙𝒆 ) cm-1
  fund = 215 (1- 2x0.003) cm-1
So,   hot band = 𝟐𝟏𝟓 (1- 4x0.003) cm-1
= 213.71 cm-1
= 212.42 cm-1
 E hot= hc   hot band
 E hot= hc   hot band
= 4248.127x10-24 J
= 4222. 485x10-24 J

= 𝑒 −𝐸𝑓𝑢𝑛𝑑/𝑘𝑇
𝑁𝑢
𝑒 −𝐸ℎ𝑜𝑡/𝑘𝑇
𝑁𝑢
=
𝑁𝑙 𝑁𝑙
4222. 485x10−24 J
−
=𝑒
300Kx1.38x10−23 JK−1
= 0.3584 =0.36
= 0.3606 The population of N upper (v=1) is only 0.36 percent Nlower (v=0)
= 0.36 So the intensity of the hot band is lower
 IR Spectroscopy- Group Frequencies

Characteristic absorption for functional groups

2. Spectroscopy,
by Lampman, Pavia, Kritz, Vyvyan: For application
 IR Spectroscopy
The IR Spectroscopic Process
❖ Matter perceive this vibration as heat
❖ Bond length of a covalent bond between two atoms is an average because the bond is vibrating
❖ The quantum mechanical energy levels observed in IR spectroscopy are for molecular vibration

➢ Vibrating covalent bond is an oscillating (varying) dipole of the molecule –Generates a varying electromagnetic
field

➢ The greater the dipole moment change through the vibration, the more intense the EM field that is generated

➢ When a wave of infrared light encounters this oscillating EM field generated by the oscillating dipole of the
same frequency, the two waves couple, and IR light is absorbed
IR beam from spectrometer

“coupled” wave

EM oscillating wave ➢The coupled wave now vibrates

from bond vibration with twice the amplitude
For an IR Active molecule: there should be a change in dipole moment during vibration
The IR Spectroscopic Process
There are two types of bond vibration:
• Stretch – Vibration or oscillation along the line of the bond
Asymmetric
Symmetric
H H
C C
H H

• Bend – Vibration or oscillation not along the line of the bond

In plane Out of plane (Oops)
H H H
C C
scissor C
H H
H
twist wag

H
rock
C
H
 The vibrations of polyatomic molecules :-Normal modes
➢ For a molecule composed of N atoms, the total number of coordinates to specify the locations is 3N (e.g: x, y, z per
atom) and are said to have 3N degrees of freedom

➢ Translational-3,
➢ Rotational (3 for non-linear and 2 for linear molecules)
➢ The remaining coordinates are directly related to the vibrations between atoms.
➢ There are 3N-6 degrees of freedom (displacements) of the atoms relative to one another
for a non linear molecule
➢ These are the 3N-6 independent vibrational modes for non-linear molecules
➢ 3N-5 for linear molecules
Vibrational Modes for H2O (3)

Vibrational Modes for CO2 (4)

degenerate
INFRARED ACTIVE BONDS An IR Spectrum in TRANSMISSION mode

➢ All covalent bonds are not IR active. Only polar bonds are IR active
➢ The intensity of the bands depends on the magnitude of the change in
dipole moment associated with the bond in question:
➢ More polar bonds such as carbonyl groups (C=O) produce strong bands.
➢ Medium polarity bonds and asymmetric bonds produce medium bands.
➢ Weakly polar bond and symmetric bonds produce weak or non
observable bands. • Strong (s) – peak is tall
• Medium (m) – peak is mid-height
• Weak (w) – peak is short
Symmetric bond that has identical or nearly
➢ Narrow bands are thin and pointed, like a dagger.
identical groups on each end will not absorb in
the infrared ➢ Broad bands are wide and smoother.
Eg: O-H bonds, such as those found in alcohols
➢ Stronger bonds have a larger force constant K and vibrate at higher frequencies
than weaker bonds.

➢ Bonds between atoms of higher masses (larger reduced mass) vibrate at lower frequencies than bonds between
lighter atoms.

➢ Bending motions occur at lower energy (lower frequency) than the typical stretching motions because of
the lower value for the bending force constant K.

➢ Hybridization affects the force constant K, also sp>sp2>sp3

➢ Resonance also affects the strength and length of a bond and hence its force constant K.

➢ Thus, a normal ketone has its C=O stretching vibration at 1715 cm−1; a ketone that is conjugated with a C=C
double bond absorbs at a lower frequency, near 1675 to 1680 cm−1

➢ No two molecules will give exactly the same IR spectrum (except enantiomers)
Enantiomers are mirror images of each other that are non-superposable (not identical)
Entire IR region: 10-12800 cm-1 : Looking at a Spectrum in Mid IR 200-4000 cm-1
Divide the spectrum in to two regions:

4000 cm-1 → 1600 cm-1 “functional group” region. 1600 cm-1 → 400 cm-1 The “fingerprint” region.
➢ Most of the stretching bands, ➢ Most of the bending bands
➢ Specific functional groups (specific atom pairs). ➢ Many band of mixed origin (Combination bands).
➢ Some prominent bands are reliable.

Functional group region: Easy to interpret reliably. Fingerprint region: complex and difficult to interpret reliably.
HYDROCARBONS: ALKANES, ALKENES, AND ALKYNE

Absorptions due to C – H stretching vibrations

The characteristics of the hybridization of the carbon holding hydrogen
❖ Alkane sp3C-H : 2800-3000cm-1
❖ Alkene and aromatic (sp2) =C-H: 3000-3100 cm-1
❖ Terminal Alkyne (sp) R - CC-H : 3300cm-1
➢ Only alkenes and aromatics show a C -H stretch slightly higher than 3000 cm-1.
➢ Compounds do not have a C=C bond show C-H stretches only below 3000 cm-1

Absorptions due to C – C or C=C or CC stretching vibrations

❖ sp3- Alkane (sp3)C-C : 1250-1400cm-1
❖ sp2-Alkene and aromatic (sp2) C=C: 1680-1540 cm-1
❖ sp-terminal Alkyne (sp) R - CC : 2260-2100 cm-1
Alkanes:
The spectra of simple alkanes are characterized by absorptions due to C–H stretching and bending.
➢ C–H stretch from 3000–2850 cm-1
➢ C–H bend or scissoring from 1470-1450 cm-1

C–H rock, methyl from 1370-1350 cm-1

Only in long chain alkanes C–H rock of

methylene, seen from 725-720 cm-1

❖ sp3- Alkane (sp3)C-C : 1250-1400cm-1

Alkenes, –C=C–H
• The C=C bond stretching usually gives rise to a moderate band in the region 1680-1640 cm-1
• The –C=C–H bond Stretching are of higher frequency (higher wave number) than those of the –C–C–H bond
in alkanes above 3000 cm-1.
• Strong =C–H bending vibration: 1000-650 cm -1 (Strong)
➢ Alkyl substitution increases the
absorption frequencies

➢ Trans disubstituted alkenes absorb at

higher frequencies (less steric demands)
than cis alkene
➢ Conjugation lowers the absorption
frequencies (resonance)
➢ But increases its intensities (dipole
character increases)
➢ C=C stretching have lower intensity than
C=O (polarity of bonds)
IR Spectroscopy: Aromatics H

-C-H stretching
H H
• 3100-3000 cm-1
Skeletal Vibrations
• -C=C- Stretching with in the ring, H H

• 1600-1585 cm-1 and 1500-1400 cm-1 H

C-H bending
• Out-of-plane(“oop”) C-H bending 900-690 cm-1
• In-plane C-H bending, 1300-1000 cm-1

H
H H

H H
H
Alkynes:- -CC- , and C-H ,
-CC-H (terminal), -C  C- (Internal)
➢ -CC- stretching is week, (less polar bonds) 2260-2100 cm-1 for unsymmetrical alkynes
➢ Terminal alkynes (acetylenes) show strong band
➢ Conjugation increases the intensity of the band.
➢ -C-H stretching only for mono substituted alkynes 3333-3267 cm-1,
➢ strong narrow band -C-H bending vibrations 700-610 cm-1
IR Spectroscopy : Alcohols and Phenols Absorptions are sensitive to H- Bonding
➢ For “Free” alcohol, sharp peaks at 3700-
3584 cm-1
➢ Occur only in vapor or in very dilute
solutions or in non- polar solvents

➢ Intra-molecular H bonding shifts the OH

band to lower frequency
➢ “Does not depend on the concentration”
Effect of dilution on Hydrogen bonding- effect on O-H stretching
• Intermolecular Hydrogen bonding increases with concentration
• H- bonding decreases the absorption to lower values

Neat/ concentrated Diluted with CCl4 Very diluted, with CCl4

IR Spectroscopy : Amines (–NH2, -NRH, -NR2)
CARBONYL COMPOUNDS
Normal base values for the C=O stretching vibrations for carbonyl groups

Carboxylic acid
• Monomer acid – dilute – 1760 cm-1
• Dimer – concentrated - - 1710 cm-1
IR Spectroscopy : Ketones IR Spectroscopy : Aldehydes
➢ C=O Streach
➢ Aliphatic aldehyde 1740-1720 cm-1
➢ Conjugated aldehyde, 1710-1685 cm-1
➢ Two peak around 2830-2695 cm −1 for C-H;
➢ Appears as a shoulder-type peak just to the right of
the alkyl C–H stretches.

O=C stretch of the alpha, beta-unsaturated compound -- benzaldehyde -- is

at a lower wavenumber than that of the saturated butyraldehyde.
IR Spectroscopy : Carboxylic acids

➢ Carboxylic acids show a strong, wide band for the O–H stretch.
➢ Unlike the O–H stretch band observed in alcohols, the carboxylic acid O–H stretch appears as a very broad
band in the region 3300-2500 cm −1 , centered at about 3000 cm −1

The reason that the O–H stretch band of carboxylic acids is so broad
is because carboxylic acids usually exist as hydrogen-bonded dimers.

• Monomer acid – dilute – 1760 cm-1

• Dimer – concentrated - - 1710 cm-1

IR Spectroscopy : Esters
Look Again !!!!!!!!
 IR Spectroscopy : Carbonyl compounds
All carbonyl compounds absorb in the region 1760-1665 cm −1 due to the
stretching vibration of the C=O bond
 Electronic Spectroscopy or UV-Visible spectroscopy

References : 1. Fundamentals of Molecular spectroscopy by Colin N. Banwell, ElaineM.Mc cash

2. Spectroscopy by Lampman, Pavia, Kriz, Vyvyan
 UV-Vis regions: 10-780 nm
➢The vacuum UV region: below 190 nm.
➢The far UV region: 190-250 nm (Oxygen absorb).
➢The near UV region: 250-400 nm
➢Visible region: 400-780 nm

1. Molecular spectroscopy 2. Atomic spectroscopy

A. Absorption spectroscopy B. Emission spectroscopy

Changes in molecular structure upon excitation

➢ Large changes in molecular size as well as molecular shape
➢ Re –Emission, Fluorescence, Phosphorescence
➢ Bonds could break off upon electronic excitation
➢ Chemical reaction
Interaction of matter with UV and visible lights (125-650kJ/mole).
➢ All molecules give electronic (absorption or emission) spectra
➢ During absorption, electrons are promoted from ground state of a molecule to higher electronic states
(excited state).
➢ e.m.r. absorbed has energy exactly equal to E (The electronic energy gap)
➢ Change in electron distribution always results in a change in dipole moment

LUMO
LUMO

HOMO
HOMO

➢ Usually the transition is from HOMO(Highest Occupied Molecular Orbital → LUMO (Lowest Unoccupied Molecular Orbital).
Display of Electronic spectra
Spectral features
➢ Number of transition
➢ Energy of transition: Horizontal axis, Wavelength, λ, in nanometer (nm )
➢The λ max of an absorption band correspond to the excitation energy.
➢ Intensity of transition: Vertical axis: Absorbance, A, or Molar absorptivity, ε.
➢ εmax to the intensity of transition, a measure of the probability of
promoting an electron, given the excitation energy

Peaks are broad, why?

• Explained by Frank-Condon Principle

Frank Condon Principle: Intensities of vibrational electronic spectra:
The Born-Oppenheimer approximation, Total energy of a molecule
Etot = Eele + Evib + Erot +..,
Eele (10 5-6 cm-1) >>> Evib (10 3 cm-1) > Erot (1-10 cm-1)
➢Electrons move much faster than nucleus
➢The transition between different energy levels can occur independently
➢The electronic and nuclear motions can be treated separately

➢ Each electronic level can be represented by a

More’s curve for vibrational transition

➢ Each electronic level is associated with

vibrational levels

➢ Each Vibrational levels are associated with

rotational levels
 Vibrational coarse structure formed during electronic absorption: Vibronic progression

Excited state
E1 (v’)

Ground
state
E0 (v”)

The excited state might have different vibrational frequency, equilibrium internuclear distance
 Franck-Condon principle: Intensity of vibrational electronic spectra
The nuclear motion (10-13 s) is much slower as compared with electronic motion in transition (10-16 s).
Electronic transition take place so rapidly that a vibrating molecule does not change its internuclear distance
appreciably during the transition (little change in the geometry of the molecule).
The most probable component of a electronic transition involves only the vertical transitions

Other vertical transitions (0→2, 0 → 1,...,0 → 4, 0 → 5,...) are smaller in their probabilities of
transition as revealed in the composite fine structure of vibronic broad band.
Franck-Condon principle: Intensity of vibrational electronic spectra
The excited state might have different vibrational frequency, equilibrium internuclear distance
Possible electronic transitions for molecules
➢ The wavelength of an electronic transition depends on the energy difference between the
G.S. and the E.S.
➢ The order of energy for Molecular orbitals:
σ < π < n < π* < σ*

σ → σ* ; s → π* ; π → s*; π → π* ; n → π*; n → σ*
Selection rules for Allowed electronic transition
1. Spin allowed/ forbidden transitions
“Transition that involve a change in spin quantum number is not allowed”
Allowed transitions : S→S, and T→T
Spin multiplicity S= 2s+1
Forbidden transitions : S→T and T→S. Spin paired S= 2x 0 +1 = 1 (singlet)
Spin Parallel S= 2x 1 +1 = 3 (Triplet)

Ground states are usually singlets (S0)

• Thus most excitations are to singlet excited states,
• like S0→S1, S0→S2, …
2. Laporte selection rule:
Centro-symmetric molecules,
▪ Gerade (symmetrical) g
▪ Ungerade (anti symmetrical) u
Only, transition between states of opposite parity (symmetry w.r.to center of inversion) is
allowed
• Allowed transitions: g → u & u → g
• Forbidden transitions: g → g & u → u
Parity (symmetry)of Atomic orbitals
 Parity (symmetry)of Molecular orbitals
Parity of s molecular orbitals

Parity of  molecular orbitals

➢ Allowed transitions: g → u & u → g

➢ Forbidden transitions: g → g & u → u
What are the allowed transitions if the selection rules are strictly obeyed

Symmetry Allowed Transitions

σ → σ* (High Energy) > π → π*
Symmetry Forbidden Transitions
σ → π * > π → σ * > n → σ * > n → π* (depends)

The electronic transitions modify the charge distribution of the absorbing molecule
 UV transition type
1.σ→σ* transitions:
➢ For compounds with σ bond only (alkanes)
➢ High ΔE, short λ (< 170 nm).
➢ Appears in far-UV region.

• Appears in saturated hydrocarbons with σ orbital and transition to antibonding σ* or to molecular Rydberg orbital
(higher valence shell orbitals, 3s, 3p, 4s, …),

• This is usually a symmetry allowed and high intensity transition.

• Eg: cycloalkane λmax 135 nm. (vacuum UV)

2. π→π* transitions (K band; konjugierte):
• For compounds containing double, triple bonds, or aromatic rings; a π electron is excited to an antibonding π* orbital.
• This is usually a symmetry allowed and high intensity transition.
In Alkenes:
❖ σ ➔ σ* , π ➔ π *,
h Alkenes and alkynes :
170nm Absorbs at 172 nm (10000), in vacuum UV.
photon

• Extended conjugation lowers the ΔE, and increase in λmax

• If extended beyond 5 double bonds absorption occurs at visible region.
 Effect of conjugation:
Conjugation lowers the energy or increases the wavelength of absorption: Bathochromic shift

LUMO(ES)

Transition
2 → 3
2 → 4
HOMO(GS)

Ethylene Ethylene Phenolphthalein is colorless when pH

Butadiene
= 0-8.2 and pink when pH = 8.2-12
Effect of conjugation: conformation and Steric effect
Effect of Substituent: Conformation

➢ Repulsion between terminal lobes of Ψ2

increases energy of HOMO in s-cis form.

➢ Hence, less energy (ie. Higher wavelength) is

Steric effect
required for Ψ2 Ψ3* transition.

➢ Substitution force a molecule to take s-cis form,

➢ Absorbs energy from a longer wavelength (shows a
red shift) than usual s-trans conformer. Q: Which of the compound absorb from longer wavelength? And why?

➢ Tertiary Group on A impart steric effect on Methyl group( Loss of

planarity)
➢ Compound B is more planar than A as two methyl groups are less
crowded
3. n→π* transitions (R band; radikalartig) :
• The excitation of an electron on a nonbonding (lone pairs) orbital on O, N, S,..to an
antibonding π*,
• Ex: C=O, C=S, N=O, etc absorb between 280-290 nm
• A symmetry forbidden and low intensity transition ( = 15).
• Available transitions of aldehydes and ketones
π → π* (  188 nm with  = 900); > n → π* (280-290 nm with  = 15).

4. n → s* transition :
• appear in the near UV or visible region.
• compounds containing non-bonding or lone-pair electrons
• R OH 175-200 nm
• Thiols 200-220 nm
• MeI ( in hexane) 258 nm
 Terms describing UV absorptions
Wavelength change
➢Bathochromic shift: shift to longer λ, also called red shift.
eg: Increasing conjugation
➢Hypsochromic shift: shift to shorter λ, also called blue shift.

Intensity change
➢Hyperchromism: increase in ε of a band
➢Hypochromism: decrease in ε of a band.
 Terms describing UV absorptions
Chromophores: Covalently unsaturated groups responsible for electronic transitions, C=C, C=O,
Triple bonds, NO2 etc.
Auxochromes:
➢ Substituents with unshared pair e's like OH, NH2,
SH, Cl, etc.
➢ When attached to π chromophore they generally
move the absorption max. to longer λ.
➢ Changes the intensity of the band
Effect of Solvents
➢ Should not absorb in UV region
➢ Should not contain conjugated systems
➢ Should not interact with solute
➢ Non polar solvent : does not form H-bonding
❖ The position and intensity of an absorption band may shift if the
spectrum was recorded in different solvents.
Ex: Acetone in MeOH
Ex: Acetone in Hexane

As solvent polarity increases:

➢ π→π* band red shifts
➢ n→π* band blue shifts

Effect of Solvents on the UV spectrum

Effect of solvents on the spectrum

➢ Red shift
➢ If the excited state is polar, but the ground state is
neutral
➢ Polar solvent will only interact with the excited state.
➢ The excited state and lower its energy by solvation.

➢ Blue shift
➢ If both excited and ground states are polar
➢ Polar solvent will interact with the both state.
➢ The ground state and lower its energy by solvation.
➢ Excited state increases its energy
General applications: Identification of chromophore (Functional group)
General applications
✓ Detection of chromophore in an unknown compound:
Color of compounds

If some light is absorbed and the rest is transmitted through

a substance, the substance is called a transparent medium
with respect to the transmitted radiation.
Lemon yellow food colorants Blue food colorants

Tartrazine

Orange-Red food colorants

Single beam instrument
Double beam instrument
 Electronic Spectroscopy or UV-Visible spectroscopy
Woodward-Fieser rule for predicting the lmax Polyenes

• Summarized by R.B. Woodward, L.F. Fieser and others

• Predict lmax for π → * in extended conjugation systems

References : 1. Spectroscopy by Lampman, Pavia, Kriz, Vyvyan

Woodward-Fieser rule for predicting the lmax Polyenes

Heteroannular & Homoannular

➢ Repulsion between terminal lobes of Ψ2 increases energy of HOMO in s-cis form.

➢ Hence, less energy (ie. Higher wavelength) is required for Ψ2 → Ψ3* transition.

➢ Substitution may force a molecule to take s-cis form,

➢ Absorbs energy from a longer wavelength (shows a
red shift) than usual s-trans conformer.
 Woodward-Fieser rule for predicting the lmax Polyenes

Some Worked Examples

Base value 214
Acyclic, 2 x alkyl subst. 10
Heteroannular, Homoannular, exo DB 5
Base 214 nm
Base 214 nm Base 253 nm total 229
==================
Attached group Increment, (nm) Obs. 227

Extend conjugation +30 Base value 214

Addn exocyclic DB +5 3 x alkyl subst. 15
exo DB 5
Substituent effect total 234
Alkyl +5 Obs. 235

O-Acyl 0
S-alkyl +30 Base value 253
4 x alkyl subst. 20
O-alkyl +6 2 x exo DB 10
NR2 +60 total 283
Obs. 285
Cl, Br +5
Woodward–Fieser Rules for Diene
Woodward–Fieser Rules for Diene

Base value 214

Base value 214 5 x alkyl subst. 25
6 x alkyl subst. 30 4 x Ext. Conjugation 120
5 x Ext. Conjugation 150 2 x exo DB 10
2 x exo DB 10 OR substitution 6
NR2 substitution 60 Halogen 5
Total 464 Total 380
Woodward–Fieser Rules for Diene
Woodward–Fieser Rules for Diene Distinguish Isomers!

HO2C HO2C

Base value 214 Base value 253

4 x alkyl subst. 20 4 x alkyl subst. 20
exo DB 5
exo DB 5
total 239
total 278
Obs. 238
Obs. 275
Problems

HO2C
Woodward–Fieser Rules for Diene
 Raman Spectroscopy

C. N. Banwell and E. M. McCash,

Fundamentals of Molecular Spectroscopy, (4th edition),
New Delhi: Tata McGraw Hill, New Delhi, 2010

When light falls on a material?

Transmission
Reflection
Absorption
Luminescence

Elastic Scattering
Inelastic Scattering
➢ Radiation at a certain frequency is scattered by the molecule with shifts in the
wavelength of the incident beam.
Raman spectroscopy: complementary to IR spectroscopy.
➢ Radiation at a certain frequency is scattered by the molecule with shifts in the wavelength of the incident
beam.
➢ Elastic collision leads to no change in energy between scattered light and incident light
➢ Inelastic collision leads to no change in energy between scattered light and incident light

➢Raman Scattering Spectrum Resembles IR absorbance spectrum

IR Raman
1 Vibrational Modes Vibrational Modes
2 Change in dipole Change in polarizability
3 extend compress

d- 2d+ d-

4 Excitation of molecules to the higher vibrational state Momentary distortion of electrons

distributed around the bond
5 Asymmetric Vibrations are active Symmetric vibrations are active
The Raman Effect → Inelastic Scattering (Quantum theory)
Conservation of Energy: Total energy [Energy of photon + Energy of molecule] before
and after collision will be same

hex + E
(before collision)
= h’+E’
(after collision)
V’ = 2
V’ = 1
{
V’ = 0
[E’ - E]/h = ex- ’ =  (Raman shift) Vibrational Levels at
Excited Electronic
State (E1)

Case I, ex = ’; E = E’ Virtual state

Rayleigh line ( = 0)

Scattered

Scattered
Scattering
Excitation

Excitation
Excitation
Case II, ex < ’: E > E’ Vibrational Levels at
Ground Electronic
Raman (Anti stokes) Line;  = +ve V” = 2
{ State (E0)
v” = 1


Case III, ex > ’: E < E’

v” = 0
Infrared Raman Rayleigh Raman
Raman (stokes line) Line  = -ve (absorption) (anti stoke)) (scattering) (Stoke line))
Quantum theory of Raman effects

➢ Stokes: photon strikes an atom or molecule in the

virtual ground state, a part of its energy may be
used to excite the atoms and rest is scattered,
➢ ( ‘ <  )  is +ve

Lower energy higher energy

➢ Anti-Stokes: photon strikes the molecule already
in the virtual excited state, the photon will get energy
(higher energy ’ >  )  is - ve

Raman Effect
❖ Does not depend on frequency of incident light
❖ Depends only on the characteristic of the substance
❖ Intensity of stoke like is always greater
 Instrumentation
Major Instrumental Setup Differences:
➢ IR has multiwavelength lamp source,
➢ Raman has single wavelength laser source.
➢ Monochromator is absent in IR and required in Raman.
➢ Raman signals are week (long time)

Raman spectroscopy uses a single wavelength laser

source to excite the electrons in a sample.
Raman Effect: classical explanation
Molecular polarizability
A molecule in static electric field experiences a distortion in the
electronic clouds, induced dipole,
µ = α . E, where is the polarizability of the molecule

A molecule will be Raman Active, only when molecular rotation or vibration must cause some change in a
component of the molecular polarizability. (direction or magnitude of polarizability ellipsoid)

➢ 𝑇ℎ𝑟𝑒𝑒 𝑑𝑖𝑎𝑚𝑒𝑛𝑡𝑖𝑜𝑛𝑎𝑙 𝑠𝑢𝑟𝑓𝑎𝑐𝑒

➢ Distance from the electrical center α 1/ 𝑎𝑖
➢ When polarizability is maximum the axis is minimum

Anisotropic distortion

Do not confuse polarizability with electron cloud

All diatomic molecules have similar trends in distortion,
Eg: H2, HCl, CO & linear molecules CO2, CH≡CH
 Raman Effect : importance of shape of molecules
Spherical Top Molecules
➢ Polarizability ellipsoid for this molecules are spherical surface
➢ Rotation will produce no change in polarizability. Eg.: CH4, SiH4, silane….
Symmetric Top Molecules
Asymmetric Top Molecules
➢ Possess axial symmetry,
➢ Polarizability ellipsoid is similar to linear ➢ Possess axial symmetry,
molecules, Eg.: CHCl3, NH3 ➢ Polarizability is different in all axis

Symmetrical molecules: IR active vibrations are Raman Non-symmetrical molecules: Vibrations can be active in both,
inactive and vice versa (Mutual exclusion principle) one, or neither IR and Raman
➢ Strong bands in IR (polar bonds) = Weak bands in Raman
➢ Strong bands in Raman (nonpolar bonds) = Weak bands in IR
 Raman Spectroscopy
Symmetrical molecules:

- comparison of Raman and IR Spectra

Non-symmetrical molecules:
Molecular polarizability
The electric field experienced by each molecule,
E = E0 sin 2 t
Induced dipole, µ = α . E, µ = α .E0 sin 2 t ------------(1)
During molecular rotation and vibration,
✓ the polarizability (α) changes periodically
✓ The change can either be in magnitude or direction
Consider Molecular Vibration α0 = equilibrium polarizability
 = rate of change of polarizability with time
α = α0 +  sin 2vib. t vib.= Vibrational frequency
µ = (α0 +  sin 2vib. t ) E0 sin 2 t

µ = α0 E0 sin 2 t + ½  E0 cos 2 (-vib.) t - cos 2 ( +vib.) t 

Thus oscillating dipole has a frequency component of ν±νvib

µ = α0 E0 sin 2 t + ½  E0 cos 2 (-vib.) t - cos 2 ( +vib.) t 

If the molecule undergoes rotation and vibration, which do not changes the polarizability (α)periodically
 Water

Water is colorless, odorless, tasteless liquid…

Water is polar. ...

Water has high surface tension
Water has high heat of vaporization. ...
Water is an excellent solvent. ...
Water has cohesive and adhesive properties. ...
Water has high heat capacity. ...
Water is less dense as a solid than as a liquid.
Water has high heat capacity. ...
Water has low electrical conductivity
Sources of water
Rain
Rivers and lakes (Surface water)
Wells and springs (Underground water)
Sea water

Imputities
Metal salts, Bicarbonates, Carbonates, Sulphates,
Chlorides, Fluorides, Sulphides, suspended solid
Physical impurities of Water

➢ Color: Dissolved metal complexes, Biological species

➢ Turbidity: insoluble fine suspensions of salts, soil, microorganisms
➢ Taste: Presence of dissolved salts
➢ Odour: living or dead organisms

Chemical impurities of Water

Inorganic and organic impurities from industries, agriculture, drugs, insecticides
➢ Acidity: Dissolved gases like CO2 etc
➢ Alkalinity: Presence of minerals
➢ Dissolved Gases: CO2, SO2, Nitrogen oxides

Biological impurities of Water

Micro organisms like Algae, Fungai, bacteria
Water bodies
Hardness of water
Hard and soft water : Lather forming ability
Lather formation

Cause of Hardness

Effect of Hardness

Effect of Hardness
 Commercial classification of water on the basis of degree of hardness

Types of Hardness: The hardness of water is two types;

1. Temporary hardness. 2. Permanent hardness.
Caused by Caused by dissolved
❖ Bicarbonates of Ca, Mg and heavy metals ❖ Chlorides, sulphates, nitrates of Ca, Mg and heavy
❖ Carbonates of Iron metals
Removed by boiling ➢ Does not remove by boiling
➢ Only chemical treatment can remove this hardness.

Total Hardness = Temporary hardness + Permanent hardness

Expression of hardness:
Hardness of water is expressed in terms of calcium carbonate equivalents.
1. The Molecular Weight of CaCO3 is 100, which is easy for calculation.
2. CaCO3 is an insoluble salt, and
3. All the dissolved salts of calcium are precipitated as CaCO3

➢ The weights of different salts causing hardness are converted to weights equivalent to that of CaCO3
Thus, 120 parts by weight of MgSO4 would react with the same amount of soap as 100 parts by weight of CaCO3.
Hence, weight in terms of CaCO3 = weight of MgSO4 in water multiplied by 100/120.
The method of calculating hardness will be clear from the following formula.

Amount of the hardness causing salt x 100

Hardness of hardness causing salt in terms of CaCO3 =
Molecular weight of hardness causing salt
Mass of the hardness causing salt x Chemical equivalent of CaCO3
=
Chemical equivalent of hardness causing salt
Chemical equivalent of CaCO3 = 50
➢ If a sample of water contains two or more than two salts,
Hardness causing Mol. Weight Multiplication Equi.
their quantities are converted in equivalent to CaCO3 salt factor Weight
➢ Then the sum will give the total hardness. Ca(HCO3)2 162 100/162 81

Mg(HCO3)2 146 100/146 73

CaSO4 136 100/136 68

Units of hardness:
There are five units in which the hardness of water is expressed.
1. Parts per million (ppm).
2. Milligrams per litre (mg/L).
3. Degree Clark (0Cl).
4. Degree French (0F).
5. M.eq per litre (meq/L).
1. Parts per million (ppm): the parts of calcium carbonate equivalent hardness per 106 parts of water.
i.e. 1ppm = 1 part of CaCO3 eq hardness in 106 parts of water.
2. Milligrams per liter (mg/L): the number of milligrams of calcium carbonate equivalent hardness present per liter of water.
Thus, 1 mg/L = 1 mg of CaCO3 eq hardness per 1 L of water
But 1 L water = 1 kg = 1000g = 106 mg
1 mg/L = 1 mg of CaCO3 eq per 106 mg of water = 1 part of CaCO3 eq per 106 parts of water = 1 ppm
3. Degree Clark (0Cl): the number of grains of CaCO3 equivalent hardness per gallon of water.
It is the parts CaCO3 equivalent hardness per 70,000 parts of water.
1 0Cl = 1 grain of CaCO3 eq hardness per gallon of water
10Cl = 1 part of CaCO3 eq hardness per 70,000 parts of water
4. Degree French (0F): the parts of calcium carbonate equivalent hardness per 105 parts of water.
i.e. 1 0F: = 1 part of CaCO3 eq hardness in 105 parts of water.
4. M.eq per litre (meq./L).: number of milliequivalents of hardness present per liter
i.e. 1 meq./L : = 1 meq of CaCO3 eq hardness per liter of water= 50mg of CaCO3 eq per liter = 50ppm

1ppm = 1 mg/L = 0.1 0F = 0.07 0Cl = 0.02 meq/L

 Estimation of hardness by EDTA method:

➢ EDTA is Ethylene diamine tetra acetic acid Ca2+

➢ Hexadentate ligand and usually occurs a disodium salt.
➢ EDTA forms a colorless stable complex with Ca2+ and Mg2+ ions
in water at pH 10.

➢ Ammonia buffer is used to maintain the pH (NH4Cl + NH4OH).

End point
➢ EBT (Eriochrome Black-T) is used as an indicator.
Ca2+
➢ Initially EBT forms an unstable complex with Ca2+ and Mg2+ ions,
(Ca-EBT or Mg-EBT complex) giving wine red color to the solution.
Procedure
1. Standardization of EDTA
(i) Pipette out 20 ml of standard metal ion solution into a conical flask.
(ii) Add 5 ml of buffer solution and few drops of Eriochrome Black-T.
The indicator, which is originally blue color would acquire a wine-red color.
(iii) Titrate with EDTA solution taken in the burette, till the wine red color changes to blue
Let the burette reading of EDTA be V2 ml.
2. Determination of Total hardness
(i) Pipette out 20 (10) ml of well water ion solution into a conical flask.
(ii) Add 5 ml of buffer solution and few drops of Eriochrome Black-T.
(iii) Titrate with EDTA solution taken in the burette, till the wine red color changes to blue
Let the burette reading of EDTA be V3 ml.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑥 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐸𝐷𝑇𝐴

Molarity of the sample (M3) = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒

Total hardness = 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 water sample x 100 x 1000 𝑝𝑝m (as CaCO3 eq)

Multiply M3 with 105 to covert hardness into parts per million (ppm).
3. Determination of Permanent hardness
➢ Take 100 ml of sample hard water in 250 ml beaker.
➢ Boil it to remove temporary hardness to about half of this volume and cool to room temperature.

➢ Filter through filter paper to remove insoluble CaCO3 and MgCO3. Make up the volume to the original 100 ml by adding
distilled water.
➢ Now pipette out 20 ml of this solution into a clean conical flask and repeat the process for determining molarity

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑥 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐸𝐷𝑇𝐴 Multiply M3 with 105 to covert hardness into
Molarity of the sample (M4) = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 parts per million (ppm).

Determination of Temporary hardness

Temporary hardness = Total hardness – Permanent hardness
Disadvantages of hard water:
1. In domestic use.
2. In industrial use.
3. In steam generation

1. In domestic use:
(a) Washing and Bathing:
(a) Causes wastage of soap
(b) It produces sticky and scummy precipitates of calcium and magnesium
(c) Presence of iron salts may cause stains on cloth.

(c) Cooking and Drinking

a) Presence of dissolved hardness causing salts, the boiling point of water is elevated causing more fuel.
b) Certain foods do not cook soft in hard water.
c) Also, tea or coffee, prepared in hard water has an unpleasant taste and muddy- looking extract.
d) Hard water causes bad effect on our digestive system.
e) Moreover, the possibility of forming calcium oxalate crystals in urinary tracks is increased.
2. In Industrial use:
(a) Textile industry:
(a) Hard water causes much of the soap to go as waste.
(b) Metal stain precipitated by soaps adhere to the fabrics causing staining
WATER TECHNOLOGY
(b) Sugar industry:
a) Water containing sulphates, nitrates, alkali carbonates, etc.,
b) If used in sugar refining, it causes difficulties in the crystallization of sugar.
c) Moreover, the sugar so-produced may be deliquescent.

(c) Pharmaceutical industry:

a) Hard water, if used for preparing pharmaceutical product like drugs, injections and ointments etc. may produce certain
undesirable products in them.

3. In Boilers during steam generation:

If the hard water is fed directly to the boilers, there arise many troubles such as:
(i) corrosion
(ii) Scale and sludge formation
(iii) priming and foaming
(iv) caustic embrittlement.
i). Boiler corrosion:
Boiler corrosion is “the decay of boiler material by a chemical or electro-chemical attack by its environment”.
Main reasons for boiler corrosion are:
(i) Dissolved oxygen:
❖ Water usually contains about 8 ppm of dissolved oxygen at room temperature.
❖ At high temperature this D.O. can attack boiler material.

Removal of dissolved oxygen: by adding

calculated quantity of sodium sulphite,
hydrazine or sodium sulphide

(i) Dissolved carbon dioxide:

❖ Carbon dioxide is released by Ca(HCO3)2 inside the boiler,
dissolves in water to form acidic environment
Removal of dissolved CO2: by adding calculated quantity of
ammonium hydroxide.

(i) Acids from dissolved salts:

❖ Acids are liberated inside boilers by the decomposition of Metal chlorides
and sulfides etc
ii). Scale and Sludge formation:
➢ In boilers, water evaporates continuously and the concentration of the dissolved salts increase progressively.
➢ When their concentration reach saturation point, salts gets precipitated
➢ The precipitates sticks on the inner walls of the boiler leads to the formation of Scales and sludge
a). Sludge
❖ The soft, loose and slimy precipitate formed within the boiler.
❖ Sludge is formed by substances which have greater solubilities in hot water than cold water.
E.g. MgCO3, MgCl2, CaCl2, MgSO4, etc.
❖ It is formed at colder portions of the boiler.
❖ Sludge can easily be scrapped off with a wire brush.
Disadvantages of sludge formation:
(a) Sludges are poor conductors of heat, so they tend to waste a portion of heat generated.
(b) Excessive sludge formation disturbs the working of the boiler as it settles in the regions of poor water
circulation
(c) Sludge can get entrapped in scale if formed together and deposits as scale.
WATER TECHNOLOGY
Prevention of sludge formation:
(a) By using well softened water which is free from MgCO3, MgCl2, CaCl2, MgSO4 salts.
(b) By frequent “blow-down” operation, i.e. drawing off a portion of the concentrated water.
b). Scale:
❖ The hard precipitate formed within the boiler.
❖ These will stick very firmly to the inner surfaces of the boiler.
Formation of scales may be due to:
(a) Decomposition of calcium bicarbonate:
Due to high temperature and pressure present in the boilers, the calcium
bicarbonate salt decomposes in to insoluble CaCO3 scale.
Ca(HCO3)2 CaCO3 + H2O + CO2
(scale)
(b) Deposition of calcium sulphate:
The solubility of calcium sulphate in water decreases with rise of temperature.
solubility of CaSO4 is 3,200 ppm at 150C
55 ppm at 2300C
27 ppm at 3200C.
Consequently, CaSO4 gets precipitated as hard scale on the heated portions of the boiler.

(c) Hydrolysis of magnesium salts:

Dissolved magnesium salts undergo hydrolysis to form Mg(OH)2 precipitate, which forms a soft type of scale.
MgCl2 + 2H2O Mg(OH)2 + 2HCl

(d) Presence of silica:

SiO2, even present in small quantities, deposits as calcium silicate (CaSiO3) and magnesium silicate (MgSiO3).
These deposits stick very firmly on the inner side of the boiler surface and are very difficult to remove.
Disadvantages of scales:
a) Wastage of fuel: Scales have a low thermal conductivity, so the rate of heat transfer gradually decreased.
In order to provide a steady supply of heat, over-heating should be done
The wastage of fuel depends upon the thickness of scale.

b) Lowering of boiler safety

c) Danger of explosion

Removal of scales:
(i) With the help of scraper or wire brush, we can remove the scales, if they are loosely adhering.
(ii) By giving thermal shocks, we can remove the scales, if they are brittle.
(ii) Calcium carbonate scales can be dissolved by using 5-10% HCl.
(iv) Calcium sulphate scales can be dissolved by adding EDTA, with which they form soluble complexes.
(v) By frequent blow-down operation, if the scales are loosely adhering.
 iii) Priming and foaming:
Priming (process of ‘wet steam’ formation):
➢ When a boiler is producing steam rapidly, some particles of
the liquid water are carried along with the steam.
Priming is caused by:
(i) The presence of large amount of dissolved solids.
(ii) High steam velocities.
(iii) Sudden boiling.
(iv) Improper boiler design.
(v) Sudden increase in steam-production rate.
Priming can be avoided by:
(i) Fitting mechanical steam purifiers.
(ii) Avoiding rapid change in steam rate.
(iii) Maintaining low water levels in boilers.
(iv) Efficient softening and filtration of boiler- feed water.
Foaming:
➢ Foaming is “the production of persistent foam or
bubbles in boilers, which do not break easily”.
➢ Foaming is due to the presence of substances like oils,
which greatly reduce the surface tension of water.
Foaming can be avoided by:
(i) Adding anti- foaming chemicals like castor oil.
(ii) Removing oil from boiler water by adding
compounds like sodium aluminate.

Dis-advantages of priming and foaming:

(i) Dissolved salts in boiler water are carried by the wet steam to turbine blades, where they get deposited as water evaporates.
This deposit reduces their efficiency.
(ii) Dissolved salts may enter the parts of other machinery, where steam is being used, thereby decreasing the life of the machinery.
(iii) Actual height of the water levels cannot be judged properly, thereby making
The maintenance of boiler pressure becomes difficult
Softening methods:The process of removing hardness producing salts from water
➢ Water used for industrial purpose should be sufficiently pure (Free from hardness producing salts).
In industry, main methods employed for softening of water are two types.
1. Internal treatment
2. External treatment:
1. Internal treatment : the process of softening water inside the boiler

In this process the hardness causing salts are removed by

➢ Adding appropriate reagents for complexing the hardness causing salt to soluble compounds
➢ Precipitating the scale forming impurities in the form of sludge which can be removed by blow down operation.
➢ Converting the scale forming salts into other compounds which stay in ‘dissolved form’ and do not cause any
trouble to the boilers.
The important internal conditioning methods are;
(a) Colloidal conditioning (b) Phosphate conditioning

(c) Carbonate conditioning (d) Calgon conditioning:

(e) Treatment with sodium aluminate (NaAlO2):

(a) Colloidal conditioning

➢ The scale formation in low pressure boilers can be prevented by the addition of kerosene, tannin, agar-agar etc.
➢ The compound will be get coated over the scale forming precipitates.
➢ These forms loose, non-sticky deposits (sludge) that can be removed by blow down.

(b) Phosphate conditioning:

➢ The permanent hardness causing salts in high pressure boilers will be removed by reacting with Sodium phosphate.
3 CaCl2 + 2 Na3PO4 ------→Ca3(PO4)2 + 6 NaCl
➢ The complex formed is soft, non-adherent and easily removable.
➢ The three phosphates employed in this process are
Na3PO4 – tri-sodium phosphate (alkaline),
Na2HPO4 – disodium hydrogen phosphate (weakly alkaline) and
NaH2PO4 – sodium di-hydrogen phosphate (acidic).
(c) Carbonate conditioning:

By the addition of Sodium carbonate to boiler water, the hard and strong adherent scales formed due to CaSO4 are avoided
The CaSO4 is converted to CaCO3, which is loose sludge and it can be removed by blow down.
CaSO4 + Na2CO3 ------→CaCO3↓ + Na2SO4

(d) Calgon (Sodium hexameta phosphate Na2[Na4(PO3)6 or (NaPO3)6) conditioning:

➢ This involes the treatment of boiler water with calgon.
➢ Calgon forms soluble complex compounds with CaSO4.
Na2[Na4(PO3)6 ] -------→2Na+ + [Na4P6O18]2-
2 CaSO4 + [Na4P6O18]2- --------→[Ca2P6O18]2- + 2Na2SO4

(e) Treatment with sodium aluminate (NaAlO2):

➢ Sodium aluminate is hydrolyzed in boiler to give NaOH.

NaAlO2 + H2O-----→ Al(OH)3 + NaOH

➢ The formed NaOH immediately react with Magnesium salts and precipitates Mg(OH)2
MgCl2 + 2 NaOH ------→Mg(OH)2↓ + NaCl

➢ Mg(OH)2 and Al(OH)3 forms a flocculent precipitate with colloidal particles and silica
Caustic embrittlement: a type of boiler corrosion
➢ Caustic embrittlement is caused by using highly alkaline water in the boiler”.
➢ During softening of water by lime-soda process, free Na2CO3 is usually present in small proportion in the softened water.
➢ In high pressure boilers, Na2CO3 decomposes to give NaOH and CO2, makes the boiler water ‘caustic or alkaline’.
Na2CO3 + H2O 2NaOH + CO2

➢ Water containing NaOH flows into the minute hair-cracks present in the inner side of boiler, by capillary action.
➢ At the cracks, water evaporates and the dissolved caustic soda (NaOH) concentration increases progressively.
➢ This caustic soda attacks the surrounding area, thereby corroding the iron of boiler as sodium ferrate.

Caustic embrittlement can be explained by considering the following concentration cell

Prevention of caustic embrittlement:

(i) By using sodium phosphate or sodium sulphate as softening reagent, instead of sodium carbonate.
(ii) By adding tannin or lignin to boiler water, which blocks the hair-cracks, thereby preventing infiltration of caustic soda
solution in cracks.
Caustic embrittlement can be prevented, if Na2SO4 is added to boiler water so that the ratio:
Na2SO4
Na2CO3 = 1:1, 2:1 or 3:1
External treatment:
The treatment given to water for the removal of hardness causing salts before it is taken into the boiler is called
‘external treatment’.
External treatment are
1. Zeolite process (Or) Permutit process
2. Ion exchange process (or) de- ionisation (or) de-mineralization process

1. Zeolite (hydrated sodium alumina silicate) process (Or) Permutit process

➢ Zeolite are microporous materials
➢ Zeolites are capable of exchanging reversibly its Na+ for hardness-producing ions in
water.
➢ Chemical formula of sodium zeolite may be represented as;
Na2O.Al2O3. x SiO2. y H2O where x = 2 – 10 and y = 2 – 6

Zeolites are two types;

(i) Natural zeolites:
These are non-porous.
Eg: Natrolite Na2O.Al2O3. 4 SiO2. 2 H2O
(ii) Synthetic zeolites:
These are porous and prepared by heating china clay with
feldspar and soda ash.
Treated zeolites possess higher exchange capacity per unit
weight than natural zeolites.
The Process:
➢ Hard water is percolated at a specified rate through a bed of zeolite, kept in a cylinder.
➢ The hardness causing ions (Ca2+, Mg2+) are retained by the zeolite as CaZe and MgZe,
while the outgoing water contains sodium salts.
➢ Reactions taking place during the softening process are;

Regeneration:
➢ Zeolites gets exhausted when all Na2Z are converted to MZ
➢ Exhausted zeolite is no longer good for softening.
➢ At this stage, the supply of water is stopped

➢ The exhausted zeolite is reclaimed by treating the bed with brine solution
(10% NaCl solution).
CaZe (or MgZe) + 2NaCl Na2Ze + CaCl2 (or MgCl2)

➢ The washings (containing CaCl2 or MgCl2) are drained off and the regenerated
zeolite bed.
➢ Thus obtained is used again for softening purpose.
Advantages of zeolite process:
➢ It removes the hardness almost completely, and water of about 10 ppm hardness is produced.
➢ The equipment used is compact, occupying a small space.
➢ No impurities are precipitated, so there is no danger of sludge formation in the treated water at a large scale.
➢ The process automatically adjusts itself for variation in hardness of incoming water.
➢ It requires less time for softening.
Limitations of Zeolite process:
➢ Turbid water may clog the pores of zeolite bed thereby making it inactive.
➢ Colored ions such as Mn2+ and Fe2+ produce manganese and iron zeolites, which cannot be easily regenerated.
➢ Mineral acids destroy the zeolite bed (they must be neutralized with soda) before admitting the water to the zeolite
softening plant.
Disadvantages of zeolite process:
➢ The treated water contains more sodium salts than in lime-soda process.
➢ The method only replaces Ca2+ and Mg2+ ions by Na+ ions, but leaves all the acidic Ions (HCO3- and CO3-2) as such in
the softened water.
➢ When softened water (containing NaHCO3 and Na2CO3) is used in boilers for steam generation, sodium bicarbonate
decomposes producing CO2, which causes corrosion
➢ Sodium carbonate undergoes hydrolysis to sodium hydroxide, which causes caustic embrittlement.
 Ion exchange process (or) de-ionization (or) de-mineralization process:
Ion exchange resins are, Insoluble, Cross- linked, Long chain organic polymers with a micro porous
structure, and acidic or basic functional groups attached to the polymer chains

Ion-exchange resins may be classified as follows;

❖ Cation exchange resins (R-H+): Resins containing acidic
functional groups (-COOH, -SO3H) are capable of
exchanging their H+ ions with other cations, which comes
in their contact.
These are mainly styrene-divinyl benzene copolymers with
a suphonic or carboxylic acid group

❖ Anion Exchange resins (R+OH-): Resins containing basic functional

groups (hydroxyl groups) are capable of exchanging their anions with
other anions, which comes in their contact.
➢ These are styrene-divinyl benzene or amine-formaldehyde copolymers,
with amino or quaternary ammonium, quaternary phosphonium, tertiary
sulphonium groups as an integral part of resin matrix.
➢ These, after treatment with dil. NaOH solution, become capable to
exchange their OH anions with anions in water.
http://www.frotecfilter.com/info/?105.html
Step 1.
➢ The hard water is passed first through cation exchange column, which removes the cations like Ca2+ and Mg2+ etc,
➢ Equivalent amount of H+ ions are released from the column to water.
2RH+ + Ca2+ -------→ R2Ca2+ + 2H +
2RH + + Mg2+ ------→ R2Mg2+ + 2H +

Step 2
➢ Water from cation exchange column, is passed through anion
exchange column, which removes all the anions like SO4 2- , Cl-,
CO32- etc. present in the water
➢ Equivalent amount of OH- ions are replaced from this column to
water.
R + OH- + Cl- -------→ R + Cl- + OH-
2R + OH- + SO4 2- ------------→R2 + SO4 2- + 2OH-
2R + OH- + CO32- ----------→ R2 + CO32- + 2OH-

➢ H+ and OH- ions (released from cation exchange and anion exchange
columns respectively) get combined to produce water molecule.
H+ + OH--------→ H2O
Regeneration of exhausted resins:
➢ The exhausted cation exchange column is regenerated by passing a
solution of dil. HCl or dil. H2SO4.
R2Ca2+ + 2H+--------→ 2RH+ + Ca2+
➢ The exhausted anion exchange column is regenerated by passing a
solution of dil. NaOH.
R2 + SO4 2- + 2OH- ---------→2R+OH- + SO4 2-
➢ The regenerated ion exchange resins are then used again.

Advantages of ion-exchange process:

1. The process can be used to soften highly acidic or alkaline waters.
2. It produces water of very low hardness (about 2 ppm).
So it is very good for treating water used in high – pressure boilers.
Disadvantages:
1. The equipment is costly and more expensive chemicals are needed.
2. If water contains turbidity, then the output of the process is reduced.
The turbidity must be below 10 ppm. If it is more, it has to be removed first by coagulation and filtration.
The Bureau of Indian Standards (BIS) For Safe Drinking Water

Treatment
➢ The processes and technologies
used to remove the contaminants
from water to improve its quality.
The choice of treatment depends
on
➢ The source & purpose of use of
water.
➢ Characteristics of the water.
➢ Type of the water.
➢ Quality problems to be present.
➢ Costs of different treatments.
Comparison of WHO and BIS standard for drinking water
Overall process A. Removal of suspended impurities B. Removal of Micro organism (Disinfection)
a) Screening a) Boiling
b) Filtration b) By adding bleaching powder
c) Sedimentation c) By Chlorination
➢ Plain sedimentation e) Disinfection by ozone
➢ Sedimentation by coagulation
REMOVAL OF SUSPENDED IMPURITIES
a) Screening : The process of removing floating matter from water
➢ In this process, water is passed through a screen.
➢ The floating matter is arrested by the screen and the water is free from floating matter.

b) Filtration:
➢ The process of passing a liquid containing suspended impurities through a suitable porous material so as to
effectively removed suspended impurities. Eg: Sand, Gravel
➢ It is a mechanical process.
➢ When water flows through a filter bed, many suspended particles are unable to pass through the gaps and settle in the
bed.
C) Sedimentation
Plain sedimentation : The process of removing big sized suspended solid particles from water
➢ In this process, water is stored in big tanks for several hours.
➢ 70% of solid particles settle down due to force of gravity.

Sedimentation by coagulation :
➢ This is the process of removing fine suspended and colloidal impurities by adding coagulants
➢ When coagulant is added to water, flocculant precipitate formation takes place due to hydroxide formation which can
gather tiny particles together to form bigger particles and settle down quickly.

1. Alum as coagulant: (sufficient amount of lime is added in the absence of natural alkalinity)
K2SO4. Al2(SO4)3 24 H2O + Ca(HCO3)2 → 2Al(OH)3  + 3CaSO4 + 6 CO2.

2. Sodium aluminate as coagulant: (good in the absence of natural alkalinity best for pH range 5-8.5)
NaAlO2 + H2O → 2Al(OH)3  + NaOH For best result pH range should be less than 7
NaOH + Mg SO4 → Mg(OH)2  + NaSO4

3. Copperas or Ferrous sulphate coagulant: (good for pH above 8.5)

FeSO4 + Ca(HCO3)2 → Fe(OH)2  + 3CaSO4 + CO2 + H2O

Fe(OH)2 + O2 + H2O → Fe(OH)3 
B. Removal of Micro organism: Disinfection or sterilization

➢ The process of killing pathogenic bacteria and other microorganisms is called disinfection or sterilization.
➢ The water which is free from pathogenic bacteria and safe for drinking is called potable water.
➢ The chemicals used for killing bacteria are called disinfectants.
i) Boiling
ii) By adding bleaching powder
iii) Chlorination
iv) Ozonisation

ii) By adding bleaching powder

Water is mixed with required amount of bleaching powder, and the mixture is allowed to stand for several hours.
The disinfection action of bleaching powder is due to available chlorine in it.
It forms hypochlorous acid which acts as a powerful germicide (disinfectant).
ii) Chlorination:

➢ Chlorine is mixed with water in a chlorinator, (high tower having a number of baffle plates).
➢ Water and required quantity of concentrated chlorine solution are introduced from the top of the tower.
➢ They get thoroughly mixed and then sterilized water is taken out from the bottom. Factors affecting:
1. Temperature.
2. pH
3. Time of contact

iii) Ozonisation
➢ Ozone is an excellent, disinfectant which can be prepared by passing silent Advantage:
electric discharge through pure and dry oxygen. Remove color, Odor and Taste
➢ Ozone is highly unstable and breaks down, liberating nascent oxygen.
Disadvantage:
Costly
Desalination of Barkish water (dissolved salt with a peculiar salty taste)
➢ Brackish water is a broad term used to describe water whose salinity is between that of fresh and marine water (3.5 %
salt and unfit for drinking) 1. Electro dialysis
2. Reverse osmosis

1. Electro dialysis: Dialysis under electric field

➢ Electro Dialysis (ED) is a membrane process,
➢ Ions are transported through semi permeable membrane, under the influence of an
electric potential.
➢ Passage of an electric current through a salt solution results in migration of cations
towards the cathode & anions towards the anode.
➢ Cation-selective membranes consist of sulphonated polystyrene permits the passage of
cations only
➢ Anion-selective membranes consist of polystyrene with quaternary ammonia permits the
passage of anions only

➢ An electro dialyzer consists of a chamber carrying a series of compartments fitted with

closely spaced alternate cation (C) & anion (A) exchange semi permeable membranes
between the electrodes.
➢ An electrodialyzer unit will have 200 to 1000 compartments.
➢ The feed water is taken in the dialyzer & the electrodes are connected to a source of an
electric current.
Reverse osmosis: superfiltration or hyper-filtration

➢ When two solutions of unequal concentrations are separated by a

semipermeable membrane, flow of solvent takes place from dilute to
concentrated sides, due to osmosis.
➢ If, however, a hydrostatic pressure in excess of osmotic pressure is
applied on the concentrated side, the solvent flow reverses, i.e. solvent
is forced to move from concentrated side to diluted side across the
membrane. This is the principle of reverse osmosis.

➢ Thus, in reverse osmosis method, pure solvent is separated from its contaminates, rather than removing
contaminates from water.

Advantages:
➢ This process removes, ionic as well as non- ionic, colloidal and high molecular weight organic matter.
➢ It removes colloidal silica, which is not removed by demineralization process.
➢ The life time of membrane is quite high, about 2 years.
➢ The membrane can be replaced within a few minutes, thereby providing nearly uninterrupted water supply.
➢ Due to low cost, simplicity and high reliability, the reverse osmosis is gaining ground at present for converting sea water
into drinking water.
Differentiate between Sludge & Scale
Sludge
1 Due to heating, the salt containing water will get
concentrated and changes into loose and slimy
precipitates called sludge.
2 Sludge is not harmful for boiler.
3 Sludge can be removed from the bottom of the
boiler time to time.
4 Sludge doesn’t cause clogging and corrosion.
5 Sludge increases the discarding cost of waste.
Differentiate between Priming & Foaming
Priming
1 When boiler is producing steam very rapidly some
particles of the water carried along with the steam.
This process of “Wet Steam” formation is called
priming.
2 Priming is caused by dissolved salts, high steam
velocity, sudden heating, improper design etc.
3 Priming can be prevented by improving the boiler
design, adding mechanical purifier, maintaining
low water level and decreasing the salt
concentration.
4 Priming reduces the boiler efficiency, life of
machinery parts.
5 Due to priming one can’t judge the water level
properly.
Scale
1 When these precipitates becomes hard and
adherent called scales.
2 Scales is harmful for boiler.
3 Scale can be removed by either external or internal
treatment or hammering.
4 Scale causes clogging and corrosion.
5 Scale increases the maintenance and operation
cost.
Foaming
1 Foaming is the persistent formation of bubbles or
foam in the boiler.
2 Foaming is caused by the presence of oily
substances in water.
3 Priming can be prevented by addition of anti-
foaming agents such as castor oil, Gallic acid,
Tannic acid, sodium aluminate etc.
4 Foaming reduces the boiler efficiency and
damages machinery parts.
5 Due to foaming boiler pressure can’t be
maintained and water level also can’t be judged.
Differentiate between Proximate analysis & Ultimate analysis
Proximate analysis
1 Proximate analysis is an empirical analysis.
2 In Proximate analysis, the values are not accurate
but approximate as the data varies with the
procedure adopted.
3 The analysis performed are: Moisture content,
Volatile matter content, Ash content and Fixed
carbon content.
4 Proximate analysis is more physical analysis.
5 Proximate analysis is bulk analysis.
Differentiate between Aniline point & Steam emulsion number (SEN)
Aniline point
1 The minimum equilibrium solution temperature
for equal volumes of aniline and oil sample is
called aniline point.
2 Aniline point gives an idea about the quality of
lubricating oil.
3 Aniline point should be high for a good quality of
lubricating oil.
4 The unit of Aniline point is degree Celsius (°C)
5 Higher Aniline point indicates the lower
percentage of aromatic hydrocarbons in
lubricating oil.
Ultimate analysis
1 Ultimate analysis is an absolute analysis.
2 In Ultimate analysis, the values are accurate.
3 The analysis performed are: Percentage of C, H,
N, S, O elements.
4 Ultimate analysis is more chemical analysis.
5 Ultimate analysis is an elemental analysis.
Steam emulsion number (SEN)
1 The number of seconds required for oil to separate
when it is emulsified and separated under
specified conditions is called Steam emulsion
number (SEN).
2 SEN gives an idea of stability of emulsion.
3 SEN should be low for a good quality of
lubricating oil.
4 The unit of SEN is time (sec).
5 Higher SEN indicates the high stability of
emulsion.
Differentiate between Viscosity & Viscosity index
Viscosity
1 The property of a liquid by virtue of which it
opposes relative motion between its difference
layers is known as viscosity or internal friction of
liquid.
2 Viscosity is the property of liquid.
3 The unit of viscosity is centipoise or centistokes.
4 Viscosity should be moderate (neither too high nor
too low) for a good quality of lubricating oil.
5 Viscosity can be measured by Redwood, Engler or
Saybolt viscometers.
Differentiate between LDP & HDP
LDP
1 Full form: Low density polythene
2 Temperature require for the synthesis is about
350-570 K.
3 Pressure require for the synthesis is about 1000-
2000 atm.
4 Chain initiator required for the synthesis is traces
of Oxygen or a Peroxide which initiate the
polymerization.
5 LDPs are branched polymers.
6 LDP is chemically inert tough but flexible and
poor conductor of electricity.
7 LDP is used in manufacturing of squeeze bottles,
toys, flexible pipes etc.
Viscosity index (VI)
1 Viscosity index is an empirical number indicating
the effect of change of temperature on viscosity of
oil.
2 Viscosity index is the property of lubricants.
3 Viscosity index is unit less property.
4 Viscosity index should be higher for a good
quality of lubricating oil.
5 Viscosity index can be determined graphically.
HDP
1 Full form: High density polythene
2 Temperature require for the synthesis is about
330-350 K.
3 Pressure require for the synthesis is about 1 atm.
4 Catalyst required for the synthesis is Zeigler-Natta
catalyst (ZNC).
5 HDPs are linear polymers.
6 HDP is chemically inert but relatively tough and
hard with high tensile strength.
7 HDP is used in manufacturing of containers,
drums, durable pipes, water tanks, bottles etc.
Differentiate between Starch & Cellulose
Starch
1 Molecular formula: (C6H10O5)n
2 Source: Wheat, Corn, Rice, Potatoes etc.
3 Starch is a condensation polymer.
4 Monomer: -D (+) Glucose
5 Starch contains 20% Amylose (water soluble) and
80% Amylopectin (water insoluble)
6 Starch is a mixture of linear (Amylose) and
branched-helix (Amylopectin) polymers.
7 In Amylose C1-C4 and in Amylopectin C1-C4 as
well as C1-C6 glycosidic linkages present.
8 The shape of glycosidic linkage is “U” shape in
Amylose and “Zigzag” shape in Amylopectin.
Differentiate between Graphite & Molybdenum disulphide
Graphite
1 Graphite is a planner structure.
2 It is a network structure.
3 The distance between two layers is 3.4 °A.
4 C-C bond length is 1.42 °A. (SP2 hybridization)
5 In air, it can be used up to 375 °C.
6 Graphite is being used as solid as well as Oildag
and Aquadag (mixture with oil and water as semi
solid lubricant).
7 Application: Railway tracks joints, Printer roller,
Internal combustion engines, Cast iron bearings,
Heavy chains, Air compressors etc.
Cellulose
1 Molecular formula: (C6H10O5)n
2 Source: Wood, Plant fibers, Cotton etc.
3 Cellulose is condensation polymer.
4 Monomer: -D (+) Glucose
5 There is a single component only as cellulose
(water insoluble).
6 Cellulose is a linear polymer.
7 C1-C4 glycosidic linkage present.
8 The shape of glycosidic linkage is “Z” shape.
Molybdenum dishulphide (MoS2)
1 MoS2 is a sandwich structure.
2 It is a network structure.
3 The distance between two layers of Mo is 6.26 °A.
4 Mo-Mo bond length is 3.08 °A and S-S bond
length is 3.15 °A.
5 In air, it can be used up to 400 °C.
MoS2 is being used as a mixture of 70% MoS2, 7%
Graphite and 23% Silicates.
7 Applications: Nuclear reactors, Low pressure and
extreme temperature applications, Space vehicles
etc.
6/7/2021 Top 5 Basic Industrial Boiler Problems & Their Solutions | Thermodyne Boilers

Home » Boiler Blog » Steam Boiler » Top 5 Basic Industrial Boiler Problems & Their Solutions

Top 5 Basic Industrial Boiler Problems & Their

Solutions
Steam Boiler

Table of Contents 

Five Basic Boiler Problems

Boiler efficiency can be increased upto 90% by proper maintenance of the systems.

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Some of the common problems hinder the boiler’s ability to produce output to its full
capacity.

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They are as under-

 1. Priming:

                                                  Priming

When the steam is produced in the boiler, some droplets of water get carried away with the
steam resulting in the formation of ‘wet steam’. This phenomenon is termed as priming.

Problem:
1. Deposits on the valves which may cause overheating and corrosion
2. Reduced product quality which affects the heat transfer rates
3. Higher steam consumption for the same power output
4. Life of boiler and its components are subjected to danger

Cause:
There are two main causes for priming to occur in a boiler:

Mechanical Causes:
1. Improper design of boiler shell
2. Too high a water level

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3. Incorrect firing rate

4. Boiler operating at a steam pressure below the design pressure

Chemical Causes:
1. Presence of oil and organic matter in the boiler water.
2. Suspended solids in boiling water.
3. Highly alkalinity
4. Soap-like structures in boiler water

Solution:
1. Maintain low levels of salts in the water
2. Efficient filtration of water used in the boiler
3. Blow-off the sludge from time to time
4. Controlling rapid changes in the flow velocity

2. Foaming

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Formation of a layer of froth or stable foam on the surface of the water is termed as foaming.

Problem:

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1. Formation of soap like structures reduces the surface tension of water significantly, thus
decreasing the boiler efficiency.
2. Fluctuation in water levels.
3. Water hammer problem.
4. Can lead to contamination and scaling.

Cause:
1. Presence of various chemical (especially alkalis and oils) and solid constituents in the
boiling water. These oil and alkali constituents react to form soaps, which in turn lowers
the surface tension thus increasing the foaming tendency.
2. The lubrication used in boilers serves as a source of oil, which is the primary source
behind the effect of foaming.
3. Formation of small bubbles at the water surface, which do not break easily.

Solution:
1. Use of Anti-foaming agents such as castor oil. (Anti-foaming agents neutralize the
effects of surface tension)
2. Proper treatment of water before entry into the boiler in order to remove the foaming
agents (such as oil, alkali)
3. Addition of sodium aluminates has proved to be an effective way to remove oil traces
by entrapping oil drops.

3. Carry-over

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Carrying away of water containing soluble salts into the distribution system is termed as
carry-over. The salts essentially have an alkaline nature.

Problem:
1. The decrease in the efficiency of a boiler as the dissolved salts and solid particles have
chances of getting carried away into the turbine blades and finally getting deposited
over the blades.
2. Life of different parts of a boiler subjected to such water-soluble salts is at stake.
3. A judgment of actual height of water column becomes difficult, making maintenance
procedure quite troublesome
4. Carry-over poses a serious problem to the parts such as turbine blades, steam traps,
valve bodies, etc.

Cause:
1. Presence of soluble alkaline salts in the boiler water

Solution:
1. Ensure proper feed water treatment

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2. Expert advice of a chemist should be considered regarding the boiler and feed water
treatment
3. Main steam stop valve should be opened gradually.
4. Maintain lower water levels.
5. Use anti-priming baffles.
6. Leakage of any ‘foreign’ material into the boiler feed water system should be avoided.
7. Alignment of gauge glasses should be properly done.

4. Scale

A layer of water formed over the metal surfaces of the boiler is termed as scale. Scales are
salts of Calcium and Magnesium (existing primarily in the form of sulphates or carbonates),
which are highly insoluble in water.

Problem:
1. If there is scaling in the boiler, then the amount of fuel required to produce the same
amount of steam may increase considerably in comparison to a boiler without scales.
2. Sodium sulphate is a strong electrolyte so it dissociates with water   Its conductivity is
about one hundredth to that of steel thus causing hindrance in the heat flow. Even a
thin layer of this scale on the metallic surfaces may reduce the boiler efficiency by, upto
20%.
3. The scaled boiler becomes increasingly hotter due to resistance in heat flow, so this
metal will become more prone to deformation and rupturing.
4. The heat transfer in the boiler is reduced due to the layers of scale that act as an
insulator.

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Cause:
1. Hard water is the reason for scale formation in boilers.

Solution:
1. If the scales are adhered loose to the surface, a wire brush or scraper can remove
them.
2. Thermal shocks may remove the “brittle” natured scales.
3. Frequent blow-down operations can be benefic in removing scale which is loosely held
on to the surface of the boiler.
4. Hard scales require chemical treatment. For e.g. Calcium Sulphate scales can be
removed by adding EDTA(Ethylenediaminetetraacetic acid).

5. Corrosion:

Corrosion

The active destruction of the boiler material through pitting action is termed as corrosion. It is
the process of continuous ‘decay’ or ‘disintegration’ of the boiler material due to the
electrochemical action of the dissolved oxygen with the boiler metal. Corrosion leads to
rusting of ferrous metals, tools which are not regularly oiled and steel windows which are not
regularly painted.

Problem:

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1. The boiler metal gets eaten up quickly due to the action of dissolved oxygen leading to
complete failure of the boiler system.
2. Increase in cost of maintenance and repairs.
3. Leaking of rivets and joint areas.
4. Reduced boiler life and possible chances of failure of the entire system.

Cause:
1. The dissolved oxygen (about 8ppm at room temperature) sets free as the water is
heated. This dissolved oxygen then reacts with the iron of the boiler to form a ferric
oxide (known as rust).

Solution:
1. Addition of Hydrazine/ Sodium Sulphite/Sodium Sulphide.
2. By mechanical aeration under high temperature and vacuum conditions.

Thermodyne boilers advises all the boiler users to thoroughly read this write up so that they
can use their boilers effectively and efficiently. 

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https://www.thermodyneboilers.com/boiler-problems/ 11/11
 UNIT-IV
POLYMER and COMPOSITES

Dr. Baby Viswambharan 1

Introduction Polymer

Degree of
Monomer Polymer Functionality
polymerization

Monomer should have DP = Number of repeat

at least two reactive sites units in a chain OR Ratio of
Ex: olefin, functionality = 2 Avg. Mol. Weight of polymer
Therefore, it is “Bifunctional” to Mol. Weight of monomer
Oligomer M n
Short polymer DP =
chain m

➢Type of Polymers
Heteropolymer
Homopolymer (Co-Polymer – ➢Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
A-A-A-A-A-A-A-A-A-A-A- 2 monomer units) ➢Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
A-A-A-A-A-A-A-A-A-A-A-A A-B-B-A-A-B-A-B-A-B-B- ➢Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B
B-A-A-B

2
 Classification of Polymers

Source Structure Intermolecular forces Synthesis

❖ Thermoplastic 1. Addition polymerization: the

1. Natural ❖ Thermosetting reactive site in the monomer is
❖ Elastomers responsible for chain-growth
2. Synthetic ❖ Fibres polymerization is associated with
addition of consecutive monomer
units to a single molecule.
2. Condensation polymerization: Step
polymerizations involve successive
reactions between pairs of reactive
functional groups on the monomers
.
3. Copolymerization
What Makes Polymers Unique?
• Really big molecules (macromolecules) like polymers have very different properties than small molecules
Chain entanglement: Long polymer chains get entangled with each other.
• When the polymer is melted, the chains can flow past each other.
• Below the melting point, the chains can move, but only slowly.
– Thus the plastic is flexible, but cannot be easily stretched.
• Below the glass transition point, the chains become locked and the polymer is rigid
Linear Polymer

Stretch

The chains can be stretched, which causes

them to flow past each other. When released,
the polymer will not return to its original form.
Cross-Linked Polymer

Stretch

Relax
The cross-links hold the chains together.
When released, the polymer will return to it's
original form.
Polymer properties and macrostructure
Why Tacticity (geometrical arrangement) is important?
Tacticity affects the physical properties

more crystalline, thus harder and less flexible ➢ amorphous,

Isoatactic Polyproylene
➢ high melting (176º),
➢ crystalline,
➢ tough material
➢ that is industrially useful
➢ soft,
➢ flexible materials
Syndiotactic PP has similar
Atactic Polypropylene
properties,
➢ a low melting,
➢ but is very clear.
➢ gooey material
➢ It is harder to synthesize
Natural Polymers
Monomer Polymer

Isoprene Polyisoprene:
Natural rubber n

H OH H OH
HO H HO
HO O
HO OH HO OH
H OH Poly(ß-D-glycoside): H OH
H H cellulose H H n

ß-D-glucose

O O O O
H H
H3N H3N N N OH
O Polyamino acid:
protein R1 Rn+1 n Rn+2
R
Amino Acid
O O
DNA
O P O Base O P O
O Base
O O O
oligonucleic acid
OH DNA
O
Nucleotide DNA
Monomer Functionality (The number of bonding sites ) for polymer Synthesis:
➢ Monomer should have at least two functionalities. Eg: OH, COOH, NH2, Diol, Amino acids, amino alcohol etc
➢ Bi functional → long chain polymers → Individual chains are held by van der Waals forces →movement in one direction

➢ Mixing bi and tri functional → Branched

→ Individual chains are held by van der Waals forces
→movement is restricted

➢ Poly functional →3D network

→ Individual chains are held by van der Waals forces
→movement is prevented by cross links
Polymer Synthesis
• There are two major classes of polymer formation mechanisms
➢ Addition polymerization: The polymer grows by sequential addition of monomers to a reactive site
• Chain growth is linear
• Maximum molecular weight is obtained early in the reaction

➢ Co-Ordination polymerization Zeigler Natta polymerization

➢ Step-Growth polymerization: Monomers react together to make small oligomers. Small oligomers
make bigger ones, and big oligomers react to give polymers.
Condensation polymerization and Co-polymerization
• Chain growth is exponential
• Maximum molecular weight is obtained late in the reaction

Three major steps in polymerization

1. Initiation
2. Chain Propagation
3. Chain termination
 Addition Polymerization ➢ Instigated by the application of
A heat
A A
In* InIn* A* A In A A*
In* A In A A A A* light
Initiation Initiation Initiation pressure or
Propagation
by catalyst

➢ There are three types of initiation Anionic

➢ Anionic
➢ Radical n
Ph Li+ Ph Li+
➢ Cationic C4H9 C4H9
C3H7 Li n
Ph Ph Ph
Radical

n
Ph Ph
PhCO2• PhCO2 PhCO2
n
Ph Ph Ph
➢ Addition polymerization may Cationic
results in Atactic polymers mostly

n
Ph Ph
Cl3Al OH2 H H HOAlCl3
n
Ph Ph Ph
HOAlCl3
Chain termination in Addition Polymerization

A nA
In* In A A A A* In A A A A A*
Initiation Propagation n

*A A A A A
A *A A A A A m
m

In A A A A A In A A A A A A A A A A
In A A A A A n
n n m

A* Combination
B A A A A
m
Chain Transfer Disproportionation
New reactive site
is produced
Termination
Reactive site is consumed
MW

k propagation
MW 
k ter mination

0 100
% conversion
Zeigler-Natta Polymerization : catalyzed by transition metal complexes

• In 1955, Ziegler and coworkers reported that a combination of TiCl4 and Al(C2H5)3 in hydrocarbon solvents are
good catalyst for polymerizing ethylene
• For getting isotactic polymers

➢ Lead to a revolution in polymer industry

A typical Ziegler Natta (ZN) catalyst system usually contains two parts:

➢ A transition metal (Group IV metals, like Ti, Zr, Hf) compound

➢ And an organo-aluminum compound (co-catalyst).
e.g. TiCl4 + Et3Al or TiCl3 + AlEt2Cl.

➢ The active species is TiCl 3 (solid Polymeric form)

➢ The TiCl3 has a crystal structure in which each Ti atom is
coordinated to 6 chlorine atoms.
➢ On the crystal surface, a Ti atom is surrounded by 5 chlorine
atoms with one empty orbital to be filled.
➢ Alkene can co-ordinate with this 5th site
 Mechanism of Zeigler-Natta Polymerization
1. Initiation, 2. Propagation 3. Termination

Initiation (Active site generation)

1. Initiation (chain)

Ti Ti Ti Ti

2. Propagation
Migratory Insertion

Stereo-selectivity
CH2=CH2
CH2=CH2
Stereochemistry of polymers made from ZN-catalyst can be well
Ti regulated by rational design of ligands.
Ti
By using different ligand system, either syndiotactic or isotactic
polymers can be obtained.
Termination step
Termination is the final step of a chain-growth polymerization, forming
desired polymers products.
Common Polyolefins
➢ Radical polymerization yields Low density polythene(LDPE)
➢ Ionic polymerization yields High density polythene (HDPE)
➢ Rigid and waxy with high chemical resistance

➢ Zeigler Natta polymerization yields isotatic polymers

➢ Better hardness, strength and stiffness

➢ Radical polymerization using benzyl or hydrogen peroxide

➢ Colorless, non flamable and inert
➢ Soluble in chlorinated solvents
➢ High softening point at 148 0C

➢ Radical polymerization using benzoyl or hydrogen peroxide

➢ High attractive forces between chains give toughness
➢ Insulating material
Common Polyolefins
➢ Radical polymerization using benzoyl or hydrogen peroxide
➢ Transparent with low softening point
➢ Inert and harmless (glue or gum making)

➢ Radical polymerization using Acetyl peroxide

➢ Hard and rigid with high softening point
➢ Resistance to sunlight
➢ Artificial bone, eye adhesives

➢ Radical polymerization using Acetyl peroxide

➢ Moisture resistant and lite with high softening point
➢ Resistance to sunlight
➢ Battery case, electrical insulators, indoor lighting panels

➢ Radical polymerization using peroxide

➢ High melting and hard
➢ Making fibers
Step-Growth Polymerization
Step-polymers are made by allowing difunctional monomers with complementary functional groups to react with one
another

Stage 1
n n
Consumption
of monomer

Stage 2

Combination
of small fragments

Stage 3

Reaction of
oligomers to give
high molecular
weight polymer
Condensation polymers Polymerization: Condensation between two molecules

Polyesters
HO
O O O O
+ C C OCH2CH2O
MeO OMe
OH
n

ethylene glycol Poly(ethylene terephthalate)

https://omnexus.specialchem.com/selection-guide/polyethylene-terephthalate-pet-plastic

O O O O
H
Amides, HO 4
Adipic Acid
OH H2N 4
NH2
1,6-Diaminohexane Nylon 6,6
HO 4
N
H
4 N
H n
Amide
O O
H H
HO2C CO2H H2N NH2 HO N N H
Kevlar n
Terephthalic 1,4-Diamino
acid benzene
Urethanes
H2
OCN C NCO OH
HO
Ethylene Spandex
4,4-diisocyantophenylmethane
glycol
O O
H H2 H H2 H2
HO N C N O C C O H Urethane linkage
n
Determination of Molecular Weight of a polymer
❖ The interesting and useful mechanical properties that are uniquely associated with polymeric materials are a
consequence of their high molecular weight.

❖ A few properties may increase with molecular weight to a maximum value and then decrease with further increase in
molecular weight.

❖ High molecular weight determine the ability to process polymers

into useful articles and forms (e.g., film, sheet, pipe, fiber).

❖ Processability begins to decrease past some molecular weight as

the viscosity becomes too high and melt flow too difficult.

Synthetic macromolecules are Polydisperse

1. Having different molecular weight for each chain
2. Different way of expressing molecular weight (based on the method of determination) 20
Number-average molecular weight Mn

❖ Based on methods of counting the number of molecules in a given weight of polymer

❖ Total mass of all the molecules in a polymer sample divided by the total number of molecules present.

❖ Number Average Molecular Weight: obtained by multiplying each molar mass by number fraction (Ni/N) of
molecules of that mass of the sample.


w M N i i
Mn = 
= i =1


N
i =1
i N i =1
i

Ni = number molecules with molar mass M i

❖ Each Molecule contributes to total molar mass

❖ Or simply the arithmetic mean of all molar mass
❖ It is determined by the measurement of colligative properties.
Weight-average molecular weight Mw
❖ Determination of molecular weight based on size rather than the number of molecules
❖ Greater the mass, the greater the contribution to the measurement
❖ Weight Average Molecular Weight: obtained by multiplying molar masses of molecules by mass fraction (mi/m)
of each one present in the sample
 

 wi M i  Ni M i
2

Mw = i =1

= i =1


w i =1
i N M
i =1
i i

mi = total mass molecules with molar mass Mi and m is total mass of the sample wi = weight fraction
Mi = molecular weight
Ni = number of molecules

❖ Each Molecule contributes according to their massess

❖ It is determined by the measurement of light scattering method.
Molecular weight of Polymer Solution Viscosity
When a polymer solution is subjected to flow through a narrow capillary it exerts a resistance to that flow.
This resistance is very informative.
– It provides information on the size of the polymer
– Its Flexibility and shape in solution
– Its interactions with the solvent it is dissolved in.

Viscosity-average molecular weight (Mu )

❖ Viscosity is greater for the larger-sized polymer molecules than the smaller ones.
❖ Mv is much closer to Mw than Mn
1a
 
a +1 

1a
  Ni M i  w = (mi/m) weight fraction
a

M u =  wi M i  =  i =1  N = number of moles
 i =1    M = molecular weight

 
N M a = A constant
i =1
i i

– When a = 1, Mu= Mw , usually a ~ 0.5-0.9
– a is a measure of the hydrodynamic volume of the polymer
– varies with polymer, solvent and temperature
A Typical Molecular Weight Distribution Curve
polydispersity index (PI) = Mw/Mn ≥ 1 for
104 w i heterogeneous polymers

4.0 Mw > Mn

3.0
Mw > Mv > Mn

2.0

1.0

200 000 400 000 600 000 800 000 1 000 000
Mi (g mol-1)
Polymer Solution Viscosity Ostwald Viscometer
For dilute solutions, the ratio between flow time of a polymer solution (t) to that of the pure
solvent (t o) is effectively equal to the relative viscosity (h rel)
t h
hrel = = h is the viscosity of polymer solution
t o ho ho is the viscosity of solvent
Relative viscosity h rel has a limiting value of unity

A more useful quantity is specific viscosity, hsp = hrel − 1 =

(t − to )
to
Intrinsic viscosity ([h]) or viscosity number is used to eliminate concentration effects,
Intrinsic viscosity ([h]) is defined as the specific viscosity (hsp ) divided by concentration and extrapolated to
zero concentration h
sp
[h] =
𝑐
Intrinsic viscosity ([h]) is related to the molecular weight of macromolecules by Mark-Kuhn-Houwink equation

hsp ➢ K and a are constant .

[h] = = K[Mv]a ➢ The values are determined by viscosity measurements of a series of
𝑐 polymer sample whose Mv has been determined by other method
Value of K and a
PROCEDURE
➢ 20 mL of the solvent is measured out into a clean viscometer using a measuring cylinder.
➢ The solution is sucked up to the mark and released. The time of flow between the two marks is noted.
➢ Now fill the viscometer with 20 mL of the polymer solution (say 1) into the viscometer and determine the flow
time of the polymer solution to flow from the upper mark to lower mark.
➢ Using the same procedure, determine the flow time of the various concentrations of the polymer solution.

➢ From the flow times, reduced viscosity (ηsp/C) can be calculated.

➢ Graph is plotted between ηred vs. concentration, a straight line is obtained
➢ The intercept called intrinsic viscosity (ηi )
[h] = K[Mv]a
Molecular weight of Polymer Solution Osmometry
Osmosis: the selective passage of solvent molecules through a porous membrane from a dilute solution to a more
concentrated one
➢ The osmotic pressure ( = MRT for ideal solution) of a solution is the pressure required to stop osmosis.
➢ For a dilute solution, change in Osmotic Pressure () is larger when compared to the change in other
colligative properties

The Van’t Hoff equation relating osmotic pressure () and molecular molar mass (M) of a polymer
(non-ideal)solution is given by

𝝅 𝑹𝑻
= + 𝑩𝟐𝑪
𝑪 𝑴 𝝅 𝑺𝒍𝒐𝒑𝒆 = 𝑩𝟐
𝜋
= Reduced osmotic pressure 𝑪
𝐶
R = 0.08206 dm3 atm K-1 mol-1 𝑹𝑻
Y intercept =
𝑴
𝐵2 = Virial coefficient
𝑪
Osmotic pressure measurements leads to Number averaged molecular weight
 Light Scattering of Polymers
➢ Light when passes through a colloidal medium of particle size less
than 1/10th the wavelength () of light undergo scattering
➢ The components of the coherent incident radiation (a laser) interacts
with polymer backbone in a small scattering volume (induced vibrating
dipole formation: changes the polarizability)
➢Excitation and re-emission of the radiation at the same wavelength and frequency but at variable intensity
➢Intensity measurement of the scattered radiation allows the calculation of molecular weight
➢If intensity of the incident (I) and scattered (I )light at an angle ()
I 𝟖𝟒𝒂a𝟐 𝟐] 𝒏𝟎�̅𝒎 𝒅𝒏
𝒏𝟎= refractive index of the solvent
= [𝟏 + 𝑪𝒐𝒔 a = ( )
𝒅𝒏
= change in refractive index with
𝑰 𝟒𝒓𝟐 𝟐𝑵𝑨 𝒅𝒄 𝒅𝒄
r = distance between source and detector concentration
a = number of scattering particle per unit volume
a = electrical polarizability of the polymer molecule

𝑰 𝒓𝟐 𝟐𝟐𝒂𝒏𝟎𝟐 𝒅𝒏 2 =
R = K Mm C R =
𝑰 [𝟏+𝑪𝒐𝒔 ]
= Rayleigh Ratio K= Optical constant
𝑵𝑨
𝟐
𝟒
𝒅𝒄
(instrumental)
Effect of structure and molecular weight on properties of Polymer
➢ The properties are decided by the magnitude and strength of forces between the polymer chains
1. Strength of a polymer
➢ Intermolecular forces increases with chain length viz
➢ Controlling chain length, it is possible to vary the physical properties
➢ Chain length above 150-200 atoms per chain have more strength and are usually
heat resistant and tougher

➢ Intermolecular forces increases with polar groups (OH, Cl, F, Carboxyl) eg: Nylon6,6, TEFLON, Polyesters atc
➢ Controlling chain length, it is possible to vary the physical properties
➢ Chain length above 150-200 atoms per chain have more strength and are usually heat resistant and tougher

➢ Strength depends on slipping power between the chains (presence of bulky group lowers the slipping)

Long chain polymers forms thermo plastics while cross linked polymers for thermosetting plastic
2. Chemical resistance
➢ Chemical attaches cause swelling, softening and loss of strength
➢ Polar group in polymer can interact with polar solvents and chemicals

➢ Higher molecular weight polymers are resistant towards swelling and softening
➢ Yield high density solutions → high viscosity

➢ Denser packing in crystalline polymer prevents from chemical attacks

➢ Crosslinking increases chemical resistance

3. Crystallinity: degree to which the chains are arranged orderly in a polymer

➢ Long chain polymers are more crystallin than short chain(amorphous)

➢ Cross linking increases crystallinity
Rubber (Elastomers)
➢ Polymers having elastic properties in excess of 300 %
➢ Stretched up to 4 to 10 times, Restore the original position when released
➢ Unstretched rubber is amorphous a chain folded (coiled spring) structure
➢ Stretching causes aligned structure(more crystalline)
Draw backs:
1. Plastic in nature (10-60 oC) 4. Non resistant to polar solvents
2. It is weak (Tensile strength 200kg/m2) 5. Not enough chemical resistant
3. Large water absorbing capacity 6. Little durability
4. Swelling in organic solvents 7. May undergo permanent deformation
Vulcanization: Process of strengthening the rubber by cross linking the chain
➢ Heating rubber at 100-140 oC with Sulphur, Hydrogen sulphide, benzoyl chloride etc
➢ The extend of stiffness depends on the percentage of sulphur present
➢ Tires contain 3-5 % but battery case contain 30 %
Advantage:
1. Good tensile strength and extensibility (bare up to 2000kg/m2)
2. Has excellent resilience
3. Low water absorbing capacity
4. Resistance to oxidation, abrasion and wear & tear
5. Low electrical conductivity
6. Resistance to organic solvents
7. Use full temperature range -40-100 oC
 Conducting polymer
Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa
"discovery and development of conductive polymers”
➢ Mostly conjugated polyenes
➢ The conductivity depends on the number of charge carriers (number of electrons)
➢ And their speed.(metal it’s the valance electron) The Nobel Prize in Chemistry 2000
➢ Conductivities up to 1.5 x 107ohm-1m-1
2. Doped conducting polymers
1. Intrinsic conducting polymers 3. Extrinsic conducting polymers
➢ Exposing conjugated polymer to a charge
➢ Conductivity increased by foreign
➢ Mostly -conjugated back bone transfer agent (Oxidant or reductant)
material (C, Ag, C-ntube)
➢ Forms valance and conduction band ➢ Doping increases conductivities by
➢ Polymer is filled with conducting
➢ Delocalized electron pairs creating positive or negative backbone
element
➢ Electrons gets excited under electric P-doping: treating with Lewis acid(oxidation) ➢ Act as binder
field Eg: I2, Br2, As, F2, PF6 ➢ Bulk conductivity is increased
➢ Conductivities up to 10-10ohm-1m-1
➢ Conductivity increased by
addition of charge transfer
10-10ohm-1cm-1 103ohm-1cm-1 complex
n-doping: treating with Lewis base(reduction)
Eg: I2, Br2, As, F2, PF6
Applications
➢ Conducting polymers have many uses.
➢ anti-static substances for photographic film
➢ Corrosion Inhibitors
➢ Compact Capacitors
➢ Anti Static Coating
➢ Electromagnetic shielding for computers Smart windows
➢ A second generation of conducting polymers have been developed for industrial uses Solar cell
➢ Transistors Light-emitting diodes
➢ Light Emitting Diodes (LEDs)
➢ Pintable elastic conductors for wearable electronics and prosthetics
➢ Solar cells
➢ Displays in mobile telephones and mini-format television screens

https://onlinelibrary.wiley.com/doi/10.1002/aelm.201900681