Electrochemistry

Dr. Md. Abdul Motin

Professor, Department of Chemistry
KUET
 ELECTROCHEMICAL TRANSFORMATION

Electrolysis

Electric energy Chemical energy

Galvanic cell
Electrochemistry is the branch of physical chemistry that studies the relationship

between electricity, as a measurable and quantitative phenomenon, and identifiable

chemical change, with either electricity considered an outcome of a particular chemical

change or vice versa. These reactions involve electric charges moving between electrodes

and an electrolyte (or ionic species in a solution). It deals with the interaction between

electrical energy and chemical change.

Types:
i) Conversion of electrical energy into chemical energy-Electrolytic cell
ii) Conversion of chemical energy into electrical energy-Galvanic cell
 Applications
Electrochemistry is an interdisciplinary branch. Its scope and practical applications
covers several fields of science including
✓Materials science
✓Energy systems
✓Analytical techniques
✓Biological sciences
✓Space research etc.

Sensor , pH meter, Glucometer,

Conductometer, Battery or cell
• Electrochemical cell - combination of two half
reactions to produce electricity from reaction.

E.g. Danielle cell: Zn and Cu electrodes in salts of

these ions.
 Electrolytes

➢ The substance which can carry electricity in solutions. Electrolytes are

substances that form ions in solutions, conduct the electric current. Conduction
takes place by the movement of ions.

Examples: salts, acids and bases

➢ Substances whose aqueous solution does not conduct electricity are called non
electrolytes.
Examples: Solutions of cane sugar, glucose, urea etc.
 Types of Electrolytes
• Electrolytes subdivided further into strong electroytes (hydrochloric acid, sodium sulphate) and
weak electrolytes (ephedrine, phenobarbital).

• Strong electrolytes are substances that are completely ionized when they are dissolved in water.
They conduct electrical currents very efficiently. The classes of strong electrolytes include: (a)
soluble salts e.g. NaCl, (b) strong acids e.g. HCl, HNO3, H2SO4, (c) strong bases e.g. NaOH,
KOH

• Weak electrolytes are substances that exhibit a small degree of ionization in water. That is, they
produce relatively few ions when dissolved in water. Their solutions produce a small current.
The most common weak electrolytes are weak acids (e.g. acetic acid) and weak bases
(ammonium hydroxide – NH4OH).
Difference between electronic & electrolytic conductors

Metallic or electronic conduction Electrolytic conduction

Metallic conduction is carried by the Electrolytic conduction is carried by the

movement of electrons movement of ions
No change in the chemical properties of Chemical reaction take place at the
the conductor electrode surface
It does not involve the mass transfer It involves the transfer of matter as ions
Metallic conduction decreases which Electrolytic conduction increases which
increase in temperature increase in temperature
 Electrolytic Conductance
The reciprocal of the resistance is called conductance. It is denoted by C.

C = 1/R

Conductors allows electric current to pass through them.

Examples are metals, aqueous solution of acids, bases and salts etc.

Unit of conductance is ohm-1 or mho or Siemen(S)

Insulators do not allow the electric current to pass through them.

Examples are pure water, urea, sugar etc.
 Specific Conductance

Conductance of unit volume of cell is specific conductance.

1
Specific conductance =

a
But ρ = R

K =
a.R

 
K =   x Conductance
a

l/a is known as cell constant

Unit of specific conductance is ohm–1cm–1

SI Unit of specific conductance is Sm–1 where S is Siemen
 Equivalent Conductance

It is the conductance of one gram equivalent of the electrolyte dissolved in V cc of

the solution.
Equivalent conductance is represented by Λ

Mathematically, Λ ═ κ × v
𝟏𝟎𝟎𝟎
Λ═κ×
𝒄

Where, κ = Specific conductivity

v = Volume of solution in cc. containing one gram equivalent of
the electrolyte.
 Molar conductance
It is the conductance of a solution containing 1 mole of the electrolyte in V cc
of solution. it is represented as m.

µ=kxV
= k x 1000/M

Where V = volume solution in cc

m = Molar conductance
k = Specific conductance
M=molarity of the solution.
 Conductance depends on

• No. of ions or conducting species present in

solution.
• Charge or charge density of ions.
• Speed or velocity of ions.
• Temperature
 How is conductivity measured?
Conductivity may be measured by applying an alternating electrical current (I) to two electrodes
immersed in a solution and measuring the resulting voltage (V). During this process, the cations
migrate to the negative electrode, the anions to the positive electrode and the solution acts as an
electrical conductor.
Electrical current, I

Voltage, V

+
- +
- +

+
- +
+

Fig: Migration of ions in solution

Conductivity Probe
• 2 metals in contact with electrolyte
solution
• Voltage is applied to electrodes and
resulting current that flows btw
electrodes is used to determine
conductance
• Amount of current flowing depends
on:
• Solution conductivity
• Length, surface area, geometry of
electrodes
Conductivity Probe
• Apply an AC Voltage to Two Electrodes of Exact Dimensions
• Acids, Bases and Salts (NaCl) Dissolve in Solution and Act as Current Carriers
• Current Flow is Directly Proportional to the Total Dissolved Solids in Solution
• Physical Dimensions of a Conductivity Electrode are Referred to as the Cell
Constant
• Cell Constant is Length/Area Relationship
• Distance Between Plates = 1.0 cm
• Area of Each Plate = 1.0 cm x 1.0 cm
• Cell Constant = 1.0 cm-1
Cell Constant
• Cell constant:
• Measure of current response of a
sensor conductive solution
• Due to sensor’s dimensions and
geometry
• Units: cm-1 (length divided by
area)
 The conductivity meter
A typical conductivity meter applies an alternating current (I) at an optimal frequency) to two active electrodes
and measures the potential (V). Both the current and the potential are used to calculate the conductance (I/V).
The conductivity meter then uses the conductance and cell constant to display the conductivity.
Conductivity = cell constant x conductance

current
measurements
R I

I
conductanc e
V

2- pole 4- pole

±200 mV
potential
measurements

reference potential
source Er

current

Fig: Simplified conductivity meter diagram

 Conductivity of Common Solutions

• Solution • Conductivity
• Absolute pure water • 0.055 µS/cm
• Power plant boiler water • 1.0 µS/cm
• Good city water • 50 µS/cm
• Ocean water • 53 mS/cm
• 31% HNO3 • 865 mS/cm
 Illustrative Example
The resistance of 0.01N NaCl solution at 250C is 200 ohm. Cell constant of
conductivity cell is unity. Calculate the equivalent conductance and molar
conductance of the solution.

Solution:
Equivalent Conductance = Specific conductance x (1000/N)
Conductance of the cell=1/resistance
= 0.005 x 1000/0.01
=1/200
= 500 ohm-1cm2eq-1
=0.005 S.

Molar Conductivity = Equivalent conductivity x n-factor

Specific conductance=conductance x cell constant = 500 x 1
=0.005 x 1 = 500 ohm-1mol-1cm2
=0.005 S cm-1
 Effect of type of electrolytes on Conductivity

For strong electrolytes that undergo complete dissociation irrespective of their concentration,
the conductivity increases linearly with dilution as the ions are now more free to move between
the electrodes and hence will carry charge more efficiently.
On the other hand, in case of weak electrolytes which
undergo feeble dissociation when present in large amount
the conductivity varies negligibly until the point of infinite
dilution is reached (which pretty much means like you have
diluted it well below 0.1 M) where the conductivity shows a
steep rise as the in very low concentration the weak
electrolytes will also undergo complete dissociation.
The variation of equivalent conductance with concentration can be studied by plotting
the values of Λ against square root of concentration
 Effect of Dilution on Conductivity
✓ Specific conductivity decreases on dilution.

✓ Equivalent and molar conductance both increase with dilution and reaches a
maximum value.

The conductance of all electrolytes increases with temperature.

KCl (strong electrolyte)

CH3COOH (weak electrolyte)

–1 1/2
concentration, (mole L )
 Effect of dilution on Conductivity

Dilution effects the conductivity of electrolytic solution in the following ways:

1-The electrical conductivity of an electrolytic solution depends upon the number of ions.
2- If we increase in dilution the number of ions per unit volume decreases hence specific
conductivity decreases.
3- On the other hand molar conductivity increases with dilution because it is the product of
specific conductivity and volume.
That is way that increase in volume is much more than decrease in specific conductivity.
Moreover with dilution interionic interactions decrease, this further enhances molar conductivity.
 Effect of temperature on Conductivity
The conductance of a solution of an electrolyte generally increases with rise in temperature. It has been found by experiment that
the conductance of a given solution increases by 2-3 per cent for one degree rise in temperature. For example, the conductances
of 0.1 M KCl at two different temperatures are
1.12 × 10–2 ohm–1 cm–1 at 18ºC
1.29 × 10–2 ohm–1 cm–1 at 25ºC
The conductance of a given electrolyte depends on two factors :
(1) The number of ions present in unit volume of solution
(2) The speed at which ions move towards the electrodes
At a given temperature, the first factor remains the same for a particular electrolyte. Thus the increase in conductance with rise in
temperature is due to the influence of factor (2). With rise in temperature the viscosity of the solvent (water) decreases which
makes the ions to move freely toward the electrodes.
For weak electrolytes, the influence of temperature on conductance depends upon the value of ΔH accompanying the process of
ionisation. If the ionisation is exothermic (–ΔH), the degree of ionisation is less at higher temperature (Le Chatelier’s principle)
and conductance decreases. Conversely, if the ionisation is endothermic (+ΔH), the degree of ionisation is more at higher
temperature and conductance increases.
 Kohlrausch’s Law

The equivalent conductance at infinite dilution is different for different

electrolytes and is equal to the sum of the conductances of the constituent
ions of the electrolytes. Limiting equivalent or molar conductivity of an
electrolyte can be represented as the sum of the individual contributions of
the anion and cation of the electrolyte.

  = a +  c
Where a and c are known as ionic conductance of anion and cation at
infinite dilution respectively.
KOHLRAUSCH’S LAW
 Application of Kohlrausch’s law

1. It is used for determination of degree of dissociation of a weak electrolyte.

v
=

Where,
  represents equivalent conductivity at infinite dilution.
v represents equivalent conductivity at dilution v.

2. For obtaining the equivalent conductivities of weak electrolytes at infinite

dilution of certain electrolytes which can not be or have not been evaluated
from experimental data.
 Determination of concentration of weak electrolytes

Equivalent conductance of NaCl, HCl and C2H5COONa at infinite dilution are

126.45, 426.16 and 91 ohm–1 cm2 respectively. Calculate the equivalent
conductance of C2H5COOH.

  C2H5COOH =   C2H5COONa +  HCl −   NaCl

= 91 + 426.16 – 126.45
= 390.71 ohm–1 cm2
 Conductance of ions
Molar conductance at infinite dilution is the characteristic constant for given electrolyte. Molar
conductances of various ions at infinite dilution at 25℃

ions ( ) 104

m ions ( )  104

m

K+ 73.52 Cl- 76.34

Na+ 50.11 Br- 78.4
Li+ 45.0 OH- 198
H+ 349.82 SO42- 79.8
Ag+ 61.92 CH3COO- 40.9
NH4+ 73.4

Abnormal conductance of ions

 Abnormal Conductivity of H+
H+ has an exceptionally high conductivity. This phenomenon can be explained with an
understanding of the Grotthuss Mechanism. According to this explanation, the proton diffuses
through the hydrogen bond network of the water molecules. The H+ basically is relayed along a
chain of water molecules.

The Grotthuss mechanism, whereby protons tunnel from one water molecule to the next via
hydrogen bonding, is the usual mechanism given for facilitated proton mobility. The process is
similar to that of auto dissociation; the mechanism causing the ions (H+, OH-) to initially
separate.
 Conductivity of OH─ is abnormally high

A similar process to that for hydrogen ions was initially proposed for hydroxide mobility.
However it is now thought that hydroxide ions make use of an entirely different mechanism for
diffusion in an electric field. It has been proposed that the movement of the hydroxyl ion is
accompanied by a hyper-coordinating (that is, a fourth hydrogen bond donor) water molecule.
 Interionic Effects

The electrical attractions among the oppositely charged ions which affect the
speed of an ion in the electric field are called “interionic effects”.

There are two such effects :

❖ Relaxation effect or Asymmetric effect

❖ Electrophoretic effect
RELAXATION EFFECTS OR ASYMMETRY EFFECTS
Undisturbed state Apply potential

- + -
_ - -
- -

- + -
+ - -

- - -
-
-
- (b)
(a)
Symmetrical ionic atmosphere Ionic atmosphere becoming
around a positive ion asymmetrical when central ion moves

FIG:1
ELECTROPHORETIC EFFECT

_
_
_

+
_
_

_ _
FIG:2
 DEBYE-HUCKEL THEORY

• The first successful attempts to explain the variation of equivalent conductance of strong
electrolytes with dilution was made by Debye and Huckel(1923).

• The fundamental idea underlying their work is that because of electrical attraction among the

oppositely charged ions.

• The theory may be considerd as being surrounded by an ionic atmosphere of

opposite sign.
 Debye–Hückel Equation
Onsager was able to derive a theoretical expression to account for the empirical
relation known as Kohlrausch's Law, for the molar conductivity, Λm.
Λm= Λºm - K√c
Λºmis known as the limiting molar conductivity, K is an empirical constant and c is
the electrolyte concentration. Limiting here means "at the limit of the infinite
dilution"). Onsager's expression is
Λm= Λºm – (A+B Λºm) √c
where A and B are constants that depend only on known quantities such as
temperature, the charges on the ions and the dielectric constant and viscosity of the
solvent. This is known as the Debye-Hückel-Onsager equation.

82.4
Electrophoretic force A=
𝐷𝑇 ½ɳ
8.20 x 10⁵
Relaxation force B=
𝐷𝑇 ½

Distribution of ions in a solution

 Debye-Huckel-Onsager equation
• Concentration dependence of equivalent conductance can be explained as due to the changes in the
apparent degree of dissociation. Such an explanation may not be justifiable for strong electrolytes, at
least in more dilute solutions and can only be explained in terms of Debye-Huckel-Onsager theory
for electrical conductance.

• For a univalent electrolyte, the Onsager equation,

assuming complete dissociation, may be written in
the form
Ʌ = Ʌ˳ - (A + B Ʌ˳) √c,
where A and B are constants dependent only on the
nature of the solvent and the temperature, T
Measure of electro-phoretic effect, A = 82.4/(DT)1/2ɳ
and
Measure of asymmetry effect, B =8.20 X 105 /(DT)3/2

38
 DEBYE-HUCKEL-ONSAGER EQUATION
Debye and Huckel (1923)derived a mathematical expression for the variation of equivalent conductance with
concentration. This equation was further improved by Onsager(1926-1927) and is known as Debye-Huckel-
Onsager equation.

Λc = Λ0-[82.4/(DT)1/2 ή +8.20X105/(DT)3/2 λ0]√C

Where Λc = Equivalent conductance at concentration c.
Λ0 = Equivalent conductance at infinite dilution.
D = Dielectric constant of the medium.
ή = Coefficient of viscosity of the medium.
T = Temperature of the solution in degree absolute.
c = Concentration of the solution in moles/litre.
As D and ή are constant for a particular solvent. Therefore, at constant temperature, the above equation can be written in the form:
Λc= Λ0-(A+BΛ0)√c where A and B are constants for a particular solvent
 Transport Number
• During electrolysis the current is carried by the anions and the cations.
• The fraction of the total current carried by the cation or the anion is
termed as its Transport number or Hittorf’s number.

Transport number of cation, t+ = v + /(v+ + v-)

Transport number of anion, t- = v - /(v+ + v-)

Where,
v+ = the speed or velocity of the cation and
v_ = the speed of the anion

t+ + t- = 1 40
Determination transport number by Moving Boundary Method

Suppose the boundary moves a distant x from AA’ to BB’

for the passage of Q coulombs. All the ions, H+, passed
through the boundary AA’.
The amount of substances transported is then Q/F, of
which t+Q/F are carried by the positive ion. If the volume
between the boundaries AA’ and BB’ is V, and the
concentration of HCl is c, then

t+ Q / F = Vc
FVc
t+ =
Q
Determination transport number by Moving Boundary Method
The apparatus used in MBM consists of a long vertical tube fitted with two electrodes at the two ends
(Fig). The tube is filled with a solution of CdCl2 at the lower end and HCl at the upper end in a way that
there is a sharp boundary between the two (due to difference in their refractive indices).

The Pt-cathode dipped in HCl solution is inserted at the top and the anode (Cd stick) is introduced at the
bottom.

On passing electric current through the

apparatus, H+ ions move toward the cathode and H2 gas is
evolved at the cathode .

The H+ ions are replaced by Cd2+ ions and hence the boundary
line moves in the upward direction. By noting the length
through which the boundary moves and the quantity of
electricity passed through the cell, the transport number of H+
ion can be calculated.
Fig: Determination of transport number by moving
42
boundary method.
1. HITTORF’S METHOD
 Migration of ions and Transport no.

The movement of ions towards the oppositely charged electrode is called migration
of ions.

KNO3
SOLUTION

KNO3
SOLUTION
IN JELLY

CHARCOAL
POWDER

CuCr2O7
SOLUTION
Cu2+ (Blue) Cr2O72- (YELLOW)
IN JELLY
(GREEN) FIG: DEMONSTRATION OF THE MIGRATION OF IONS
 Conductometric Titrations
The principle of conductometric titration is based on the fact that during the titration, one of the
ions is replaced by the other and invariably these two ions differ in the ionic conductivity with
the result that conductivity of the solution varies during the course of titration. The equivalence
point may be located graphically by plotting the change in conductance as a function of the
volume of titrant added.
 Conductometric Titrations of Strong Acid with a Strong Base

Strong Acid with a Strong Base, e.g. HCl with NaOH:

Before NaOH is added, the conductance is high due to the
presence of highly mobile hydrogen ions. When the base is
added, the conductance falls due to the replacement of
hydrogen ions by the added cation as H+ ions react with
OH − ions to form undissociated water. This decrease in
the conductance continues till the equivalence point. At the
equivalence point, the solution contains only NaCl.
After the equivalence point, the conductance increases due
to the large conductivity of OH- ions.
Figure : Conductometric titration of a strong acid
(HCl) vs. a strong base (NaOH)
 Conductometric Titrations of Weak Acid with a Strong Base
Weak Acid with a Strong Base, e.g. acetic acid with NaOH: Initially
the conductance is low due to the feeble ionization of acetic acid. On
the addition of base, there is decrease in conductance not only due to
the replacement of H+ by Na+ but also suppresses the dissociation of
acetic acid due to common ion acetate. But very soon, the
conductance increases on adding NaOH as NaOH neutralizes the un-
dissociated CH3COOH to CH3COONa which is the strong
electrolyte. This increase in conductance continues raise up to the
equivalence point. The graph near the equivalence point is curved
due the hydrolysis of salt CH3COONa. Beyond the equivalence
point, conductance increases more rapidly with the addition of NaOH
Figure: Conductometric titration of a weak
due to the highly conducting OH ions. acid (acetic acid) vs. a strong base (NaOH)
 Conductometric Titrations of Strong Acid with a Weak Base

Strong Acid with a Weak Base, e.g. sulphuric acid

with dilute ammonia: Initially the conductance is
high and then it decreases due to the replacement of
H+. But after the endpoint has been reached the
graph becomes almost horizontal, since the excess
aqueous ammonia is not appreciably ionised in the
presence of ammonium sulphate.

Fig: Conductometric titration of a strong acid (H2SO4)

vs. a weak base(NH4OH)
 Conductometric Titrations of Weak Acid with a Weak Base

Weak Acid with a Weak Base: The nature of curve

before the equivalence point is similar to the curve
obtained by titrating weak acid against strong base.
After the equivalence point, conductance virtually
remains same as the weak base which is being
added is feebly ionized and, therefore, is not much
conducting.

Figure: Conductometric titration of a weak acid

(acetic acid) vs. a weak base (NH4OH)
 Electrical Double layer
If we put a charged particle in a suspension with ions, then the primary charge will
attract counter ions (opposite charged ions) by electrostatic attraction. The
primary charge cannot attract an equal amount of counter charge because a gradient
of counter ions is established that drives the counter ions away from the surface.
The formation of the electrical double layer (EDL) then occurs via attraction of
oppositely charged counter ions by the primary surface charge and then a diffusion
of the counter ions away from the surface. The counter ions are mobile, the
primary charge is not.
 Electrical Double layer at Electrode

• Heterogeneous system: electrode/solution interface

• The Electrical Double Layer, electron’s in electrode; ions in solution –
important for voltammetry:
• Compact inner layer: do to d1, E decreases linearly.
• Diffuse layer: d1 to d2, E decreases exponentially.
 Zeta Potential
Zeta potential is a scientific term for electro kinetic potential
in colloidal dispersions. In the colloidal chemistry literature, it is
usually denoted using the Greek letter zeta (ζ), hence ζ-potential.
From a theoretical viewpoint, the zeta potential is the electric
potential in the interfacial double layer (DL) at the location of
the slipping plane relative to a point in the bulk fluid away from the
interface. In other words, zeta potential is the potential difference
between the dispersion medium and the stationary layer of fluid
attached to the dispersed particle. The zeta potential is caused by the
net electrical charge contained within the region bounded by the
slipping plane, and also depends on the location of that plane.

Figure: Schematic representation of zeta potential

 Modes of Mass Transfer

Mass transfer, that is, the movement of material from one location in solution to another, arises
either from differences in electrical or chemical potential at the two locations or from movement
of a volume element of solution. The modes of mass transfer are:

1. Migration. Movement of a charged body under the influence of an electric field (a gradient of
electrical potential).
 2. Diffusion. Movement of a species under the influence of a gradient of chemical potential (i.e., a concentration gradient).

3. Convection. Stirring or hydrodynamic transport. Generally fluid flow occurs because of natural convection
(convection caused by density gradients) and forced convection, and may be characterized by stagnant regions,
laminar flow, and turbulent flow.
 Faradaic current & non-faradaic current
Two types of processes at electrode/solution interface that produce current:
The faradaic current is the current generated by the reduction or oxidation of some chemical
substance at an electrode. The net faradaic current is the algebraic sum of all the faradaic
currents flowing through an indicator electrode or working electrode.
Capacitive current, also called "non-faradaic" or "double-layer" current, does not involve any
chemical reactions (charge transfer), it only causes accumulation (or removal) of electrical
charges on the electrode and in the electrolyte solution near the electrode. The non faradaic
current is due to change in double layer when E is changed; not useful for analysis.
THANKS TO ALL