Electrochemical

Techniques
Presented By:-
Himanshu Patil (1132220033)
Atharva Kulkarni (1132220456)
Sakhi Pingle (1132220518)
Shweta Kulkarni (1132220512)
What is Electrochemistry?
● Electrochemistry is the study of chemical processes that causes
electrons to move across the two interfaces

● This transfer of electrons provides a means for converting chemical

energy to electrical energy, or vice versa.

● Thus, it is the branch of physical chemistry concerned with

interrelation between the chemical changes and electricity

● It has been widely used in chemical, metallurgy,

electronics, aerospace, medicine, energy,
environmental science, etc.
Redox Reaction
• A reduction–oxidation reaction—commonly called a redox reaction—is one
that occurs between a reducing and an oxidizing agent:
Ox1 + Red2 Red1 + Ox2
• Ox1 is reduced to Red1, and Red2 is oxidized to Ox2. Ox1 is the oxidizing
agent, and Red2 is the reducing agent. The reducing or oxidizing tendency
of a substance will depend on its reduction potential, described below. An
oxidizing substance will tend to take on an electron or electrons and be
reduced to a lower oxidation state:
Ma+ + ne− → M(a−n)+
for example, Fe3+ + e− → Fe2+. Conversely, a reducing substance will tend
to give up an electron or electrons and be oxidized:

for example, 2I− → I2 + 2e−. If the oxidized form of a metal ion is

complexed, it is more stable and will be more difficult to reduce; so its
tendency to take on electrons will be decreased if the reduced form is not also
complexed to make it more stable and easier to form.
Electrochemical cells
● A device that make use of a chemical change to produce electricity or
electricity to produce chemical change
● It consists of two electronic conductors such as metal plates or carbon
rods dipped into an electrolytic or ionic conductor which is an
aqueous electrolytic solution or a pure liquid of an electrolyte

Electrochemical Reactions:

Redox reaction

Reduction Oxidation
- gain of e - loss of e
- Oxidation No. - Oxidation no.
increases decreases
- at cathode - at anode
 Components of electrochemical cell
Any electrochemical cell consists of these two major components:
a. Electrode: It is a solid electrical conductor made of metal (sometimes non-
metal like graphite). A cell consists of two electrodes, Anode and Cathode
Anode : The electrode where oxidation (loss of electron) takes place.
Metal → Metal ion + electron (e-)

Cathode : The electrode where reduction(gain of electron) takes place.

Metal ion + electron (e-) → Metal
b. Electrolyte: It is made up of solutions of ions or molten salts which can
conduct electricity.

c. Salt bridge : A chamber of electrolytes necessary to complete the circuit in a

electrochemical cell
Electrode potential (E)
1. If the metal rod is dipped into the aqueous solution of it salt, the rod
become either positively or negatively charged with respect to solution.

2. Thus a potential difference get developed between metal rod and solution,
this potential difference is called electro potential
Standard Electrode Potential (𝑬°)
Measurement of Electrode Potential
It is assigned a zero potential at all temperatures corresponding to the reaction
Cell Potential or EMF of cell
The potential difference between the two electrodes of an electrochemical cell
is called the cell potential and is measured
in volts. The cell potential is the difference between the electrode potentials
(reduction potentials) of the cathode and anode.
 Types of Electrochemical Cells
Based on the nature of the energy conversion, electrochemical cells are
broadly classified as below:
Electrochemical Cell

Galvanic Cell Electrolytic Cell

a. Chemical energy into Electrical a. Electrical energy into Chemical
energy Energy (Electrolysis)
b. Anode is negative in nature b. Anode is positive
c. Cathode is positive in nature c. Cathode is negative
d. Electrons flow from Anode to d. Electrons flow from Cathode to
Cathode Anode
e. Reaction is Spontaneous e. Reaction is Nonspontaneous
f. No external voltage source f. Requires external voltage source
required g. One single complete cell
g. Two half cells (Two containers
with a salt bridge)
 Galvanic Cell
Electrolytic Cell

Cu(s)│Cu2+(aq,1M)║Ag+(aq,1M)│Ag(s)
 Uses of Electrochemistry:
• It has been used to discover important technical processes for the production
and purification of non-ferrous metals, and for the electro- synthesis of organic
compounds.
• Electrochemistry has been used to predict whether a particular reaction will
occur or not.
• The detection of alcohol in drunken drivers is possible through the
electrochemical redox reaction of ethanol.
• Production of metals like aluminum and titanium from their ores involve
electrochemical reactions.
• Diabetes blood sugar metres measure the amount of glucose in the blood
through its redox potential.
• Lead acid batteries, lithium-ion batteries and fuel cells are based on
electrochemical cells. Fuel cell is used to bring about direct conversion of
chemical energy into electrical energy.
POTENTIOMETRY
Principle - Potentiometry is a technique that is used in analytical chemistry,
usually to find the concentration of a solute in solution.
In this technique, the potential between two electrodes is measured using a
voltmeter. Use of voltmeter ensures that current flow is negligible. Hence, the
system is in equilibrium.

Potentiometric Electrochemical cells:

*The electrochemical cell consists of two
Cell, each containing an electrode immersed in a
Solution of ions whose activity determine the
Electrode potential.

*Salt bridge is used to neutralize ionic disbalance.

If Salt bridge is not used the current will not flow
Through the circuit.
Instrumentation
1. Reference Electrodes – The electrode that remains stable and maintains its
potential in the presence of the sample solution.

TYPES OF REFERENCE ELECTRODE

A. Standard Hydrogen electrode {SHE}.
B. Saturated Calomel electrode.
C. Silver Chloride Electrode. i,e Ag-AgCL Electrode
Standard Hydrogen Electrode
*Reference is an electrode that has the half-cell
potential is known, constant and completely
insensitive to the composition of solution that is under
study,

*It Obeys Nernst equation and exhibit a potential that

is constant with time. And exhibit little changes with
temperature cycling.

*Standard condition is 25C. At 1 Atmospheric

pressure in 1 Molar solution.

*In Non standard condition we calculate electrode

potential by Nernst equation.
NERNST
EQUATION:-
2. Indicator electrode- Indicator electrode used to determine the concentration of
analyte in the sample solution. Because it respond to the changes in the activity of
analyte.
*It is used in conjugation with reference electrode.

Types Of Indicator Electrode

a.Nobel Metal Electrode. Example: Platinum electrode.
b.Metal indicator Electrodes. Example Cu For CuSO4, Zn For ZnSO4.
c.Ion Selective/Membrane Electrode. Two types ,
1. Glass membrane electrode.
2. Polymer membrane electrode.

Glass Membrane Electrode

Sensitive to a specific ion.It is transducer or sensor that coverts the activity
Of specific ion dissolved in a solution into an electric potential.
Which can be measured by PH meter or Voltameter.
*Used in PH meter
Fig: Glass membrane electrode
 ADVANTAGES DISADVANTAGES
More complex than simple acid- base
Simple titration method
titration

It requires special assembly to carry out

Require less amount of time for completion of process
process

This does not require any indicator Galvanic cell is used to carry out the process

Require electrodes of metal like silver,

End result of the reaction is easily visible.
hydrogen.

Reaction is not interfered by reaction poison like

Overall cost of the process is high
mercury etc.

Continuous supply of electricity is

Equilibrium of the reaction achieved quickly
mandatory

Electrolyte used in the reaction must be

Accuracy of the end result is good.
freshly prepared.
This titration can be performed even in the presence of
a small amount of solute whose concentration is to be Variation in electrolyte pH alters the result of
determined.
Applications
* It is used in clinical chemistry for the analysis of metals. 
* It is used for the analysis of cyanide, ammonia etc., in water or wastewater. 
* It is used in agriculture for the detection of different elements in soils, fertilizers etc. 
* It is used in detergent manufacturing, food processing etc.

Environmental chemistry:
* Environmental chemistry is used to quantify CN-, NO3, F3, and NH3 in water and wastewater.

Agriculture:
* NO3, NH4, I, Ca, K, and CN are all elements found in soils, plant materials, feed, and
fertilisers.

Detergent production:
* Studying the effects of calcium, barium, and fluorine in detergent manufacturing.

Clinical chemistry:
* They are useful sensors because analytes in complex matrices are selective for ion-selective
electrodes in clinical chemistry. Analytes including sodium, potassium, calcium, hydrogen, and
chlorine, as well as dissolved gases like CO₂, are commonly used.
CONDUCTOMETRY
❖ It is an electrochemical method of analysis used for the
measurement of the electrical conductance of an electrolytic
solution by means of a conductometer.

❖ It is a measurement of electrolytic conductivity to monitor a

progress of chemical reaction.

❖ Conductance of an electrolyte solution can be measured by a

suitable instrument which consists of conductivity cell and
conductometer.
Conductance
The flow of electricity through electrolytic solution due to migration of ions by
applying potential difference between two electrode is known as ‘conductance’
(G). Unit siemens /meter (S/m)
‘Conductance is reciprocal of resistance’
By Ohm’s law,
I =V/R Therefore, I/V = G
I: current, V: P.D., R: resistance
Current flows between the electrode due to migration of ions known as
conductance.

Factors affecting conductance:

- Temperature
- Nature of electrolyte
- Concentration of ions
- Size of ions
Instrumentation
• Conductivity cell-
Electrode type (two/four electrodes)
Induction type- used in case of high conductivity levels
(Low conc. Measurement, for precipitate type reaction, dipped type)

• Conductivity meter- It is made by using Wheatstone’s bridge

 Principle
Wheatstone’s bridge calculates unknown resistance (S) by balancing two legs of bridge
circuit.

W. bridge works on principle of null deflection, (point B on meter bridge)

.…….1

Resistance ‘r’ of a wire of length ‘l’ , area of cross-section ‘A’ and resistivity ‘ρ’ is,
r = ρl/ A ….….2
As, length of side AB= l1, Length of side BC = l2 = (100- l1) .…….3
Equation 1 becomes, R/ ρl1/A = S/ ρl2/A
Thus, the unknown resistance of conductivity cell ‘S’= (100- l1)R/l1
Conductivity cell is dipped into electrolyte solution of interest and connected to test
Applications
❏ Conductometric titration is one of the most important
applications of conductometry. It is based upon the
principle of substitution of ions of different mobilities
which affects conductance.
❏ Kinetic studies
❏ Degree of dissociation of weaker electrolytes
solubility of sparingly soluble compound
❏ To find basicity of organic acids
❏ Determination of concentrations
 Advantages
• Conductivity measurement is simple
• It provides accurate results with minimum errors
• Suitable for the analysis of strong/weak acids and strong/weak
bases.

Disadvantages
• Accuracy of conductometric titration is low when conversion of
electrolytes is high.
• Only few specific redox titrations can be done.
VOLTAMMETRY
What is Voltage ?
Voltage describes the “pressure” that pushes electricity.

What is Current ?
Current is the rate at which electrons flow past a point in a complete
electrical circuit.

What is Electric Potential energy ?

Electric potential energy is the energy that is needed to move a
charge against an electric field.
Voltammetry
Voltammetry is any experiment where we expose a solution of an analyte to an electrode, we change the
electrode potential, and observe the current that flows in response.

Cyclic Voltammetry
If sweep or change in electrode potential is only in one direction, then it is referred as
“linear sweep voltammetry”. If the potential reverses the direction and return to the starting
potential, then it is “cyclic” voltammetry and collecting a “cyclic voltammogram”.
Components of the voltammetric cell
The cell consists of the following,

a. Working electrode
Eg. Hg, Au, Ag, etc.

b. Reference electrode
Eg. Calomel electrode, Ag/AgCl

c. Auxillary / Counter electrode

Eg. Pt wire

d. Supporting Electrode : A salt added in excess to the analyte solution. It reduces,

migrates and lowers the resistance of the solutions
 Applications and Types of
Voltammetry
Voltammetry is excessively used for

1. the study of the redox processes

2. Understanding reaction intermediates
3. Obtaining stability of reaction
4. Study of reaction mechanism

Types of Voltammetry:

Linear Sweep Voltammetry

Polarography Voltammetry

Striping Voltammetry

Etc.
COULOMETRY
• Coulometric method of analysis measures the current
required to exhaustively oxidize or reduce the analyte.
• It is based on the strict proportionality between the extent of
chemical change & the quantity of electricity involved
• The sample which is to be determined undergoes the reaction
at electrode which is measured at the electrode.

Coulometer - used to measure amount of current that is

required to bring the chemical change of the analyte
• It determines the total amount of decomposition resulting
from the passage of the charge through the cell
 Principle
• The main principle involved in the coulometry is the measurement of the quantity of the
electricity which is directly proportional to the chemical reaction at the electrode.
• This is given by Faraday’s law :-

where, Q is the total charge

n is the number of electrons per mole of analyte,
F is Faraday’s constant (96487 C mol–1),
NA is the moles of analyte.

• A coulomb is equivalent to an Ampere-sec; thus, when passing a constant current, i, the

total charge is

where, te is the electrolysis time.

• If the current varies with time, as it does in controlled-potential coulometry, then the total
charge is
Instrumentation
• Working electrodes: Platinum electrode (to apply a positive potential) or
a Mercury Hg pool electrode (for an analyte requiring a negative
potential)
• The auxiliary electrode, which is often a Pt wire, is separated by a salt
bridge from the analytical solution.
• A saturated calomel or Ag/AgCl electrode serves as the reference
electrode.
• Modern instruments use electronic integration to monitor charge as a
function of time.
• The completion of the reaction is indicated by the decrease in the current
which can be measured by the coulometer
1. Gasometric Coulometer (Hydrogen- Oxygen coulometer)
2. Silver Coulometer (a Gravimetric Coulometer)
 Types of Coulometry
1. Potentiostatic Coulometry
• Constant electric potential
• Consists of a three-electrode
potentiostat, an electrolysis cell &
a chemical coulometer
• 100% current efficiency required
• Constant potential ∝ analyte conc.

2. Amperostatic Coulometry

• Constant electric current

• Consists of a amperostat, working or generator electrode, a salt
bridge & a counter electrode
• More rapid analysis
• Current does not decrease over time therefore total charge is
product of current (I) & time (t)
Applications
⮚ Inorganic Analysis
• Determination of several metal ions. Eg iron, calcium etc.
• To Determine purity & impurity of Inorganic compound.

⮚ Analysis of radioactive materials

• Determination of uranium and plutonium.

⮚ Micro analysis
• Determination of small amounts of analyte (0.01– l mg) with an accuracy
of (± 0.5 %)

⮚ Electrolytic determination of organic compounds:

• Controlled potential coulometry offers a new step for the electrolytic
determination of organic compounds.
 Advantages Disadvantages
• Provides accuracy, sensitivity • Difficult to ensure 100%
and good selectivity current efficiency
• Use of volatile compounds • Long time in determination
does not affects may yield false results
• Easy to detect presence of • Departure and variation in
moisture in liquids current causes errors
• No standards are required • Interference of other ions
• Detectable to trace amounts
• Can use unstable reagents
• Relatively inexpensive
• Readily automated technique
• Singe coulometric titration
apparatus is enough for
analysis
REFERENCES
• ANALYTICAL CHEMISTRY by Gary D. Christian, Purnendu K. (Sandy) Dasgupta,
Kevin A. Schug, 7th edition, ISBN 978-0-470-88757-8
• https://www.brainkart.com/article/Electrochemical-Cell_39966

• https://gpatindia.com/conductometry-definition-principletheory-and-mcq-for-gpat-gate-
and-csir-net-jrf
• https://www.scribd.com/document/458389190/Principle-and-Instrumentation-of-Coulo
metry
Thank
You!