Discussion Outline

• Electrochemistry and Electrochemical Cells

• Nernst Equation and Equilibrium Constant
• Redox Titration
Fundamentals of Electrochemistry • Potentiometric Titration
• Voltammetry
Lecture Chapter 5

Far Eastern University, BIO1103/4 Cluster AY 2021 – 2022

Electrochemistry and Electrochemical Electrochemistry and Electrochemical

Cells
Electrochemistry is the branch of chemistry that deal with the
interconversion of electrical energy and chemical energy.
Electrochemical processes are redox reaction in which the energy
released by spontaneous reaction is converted to electricity, or in which
electrical energy Is used to cause a nonspontaneous reaction to occur.
Cells
An electrochemical cell is a system consisting of electrodes that dip into
an electrolyte and in which a chemical reaction either uses or generates
an electric current.
 Electrochemistry and Electrochemical
Cells
A voltaic, or galvanic, cell is an electrochemical cell in which a
spontaneous reaction generates an electric current. An electrolytic cell is
an electrochemical cell in which an electric current drives an otherwise
nonspontaneous reaction.
Electrochemistry and Electrochemical
Cells
• The electrode at which oxidation occurs is called the anode.
• The other electrode at which the reduction occurs is called the cathode.
• A salt bridge is a tube on an electrolyte in a gel that is connected to the
two half-cells of a voltaic cell; the salt bridge allows the flow of ions but
prevents the mixing of the different solutions that would allow direct
reaction of the cell reactants.

Electrochemistry and Electrochemical Nernst Equation and Equilibrium

Cells Constant
• 
 Nernst Equation and Equilibrium Nernst Equation and Equilibrium
Constant Constant
•  • 

Nernst Equation and Equilibrium Nernst Equation and Equilibrium

Constant Constant
•  • 
 Nernst Equation and Equilibrium
Redox Titration
Constant
•  • 

Solution
Stage Equation for Q
Composition

Initial No equation

Pre-Equival
Mostly analyte
ence
All are A and B are the stoich
Equivalence
equivalent coefficients
Post-Equiva
Mostly titrant
lence

Redox Titration Redox Titration

Redox Titration Indicators Auxiliary Oxidizing/Reducing Agents – used in analytes prior to titration
to convert them into the desired ionic forms
End Point Color
Method Titrant Indicator
Change
Reducing Agents
Iodimetry Starch colorless to blue • Jones Reductor – uses metal amalgams for prereduction of the analytes
• Walden Reductor – uses Ag for prereduction of the analytes
Iodometry Starch Blue to colorless
Oxidizing Agents
none Colorless to
Permanganate
(self indicating) purple • Sodium bismuthate – oxidizing agent used in converting Mn2+ to MnO4-
Colorless to • Ammonium peroxydisulfate
Dichromate Diphenylamine
purple
• Hydrogen peroxide
 Redox Titration Potentiometry

Standard Reducing Agents The principle involved in the Potentiometry is when the pair of electrodes
• Iron (II) solution is placed in the sample solution it shows the potential difference by the
addition of the titrant or by the change in the concentration of the ions.
• Sodium thiosulfate

Standard Oxidizing Agents

• Potassium permanganate
• Cerium (IV) solution

This follows the Nernst Equation.

Potentiometry Potentiometry

The principle involved in the Potentiometry is when the pair of electrodes
is placed in the sample solution it shows the potential difference by the
addition of the titrant or by the change in the concentration of the ions.
Electrodes – These are mainly used to measure the voltages. Mainly two
electrodes are used in the potentiometry. They are as follows: 
• Reference electrode – These are mainly used for the determination of
the analyte by maintaining the fixed potential. Examples include
standard hydrogen electrode, Ag/AgCl electrode, and saturated
calomel electrode.

• Indicator electrode – It is used to measure the potential of the analyte

solution comparing with that of reference electrode. Its potential is
directly proportional to ion concentration. Examples include hydrogen
electrode. glass electrode, and antimony –antimony oxide electrode
This follows the Nernst Equation.
 Potentiometry Potentiometry

Reference Electrodes Indicator Electrodes

1. Primary standard electrodes  There are three classes of indicator electrodes: 
• Standard hydrogen electrode  • Metal indicator electrodes 
• First Kind Electrodes – metal rods
2. Secondary standard electrodes 
• Second Kind Electrodes – metals coated with precipitates
• silver-silver chloride electrode
• Third Kind Electrodes – inert electrodes
• saturated calomel electrode
• Membrane electrodes – used to determine p-values (pH, pCa, pNO3)
• Ion-selective electrodes

Voltammetry Voltammetry

It is an electroanalytical technique that gives information about the It is a three-electrode system. 

analyte.  We can even measure the amount of current by varying the 1. Working electrode 
voltage. 
2. Reference electrode 
3. Auxiliary electrode
The change in current with the varying voltage gives the plot and is
known as voltammogram. There is a minimum potential required to
initiate an oxidation or reduction reaction at an electrode.

(1) working electrode

(2) auxiliary electrode
(3) reference electrode
 Voltammetry Voltammetry

Working Electrode Reference Electrode

• Ranges from small mercury drop to flat platinum disc. • Usually, standard electrode is used as Reference electrode. 
• Other commonly used electrode materials gold, platinum and glassy • Its potential is constant. 
carbon. Glassy carbon Gold electrode • It provides potential to the Working electrode. 
• Depending on the choice of working electrode, the type of voltammetry
is decided. 
Example
Common reference electrode are : 
• We use Dropping Mercury Electrode (DME) in Polarography technique 
• Calomel electrode and Ag/AgCl electrode
• We use Platinum electrode in Cyclic Voltammetry 
• We use Glassy Carbon as electrode in Linear Sweep Voltammetry.

Voltammetry Voltammetry

Auxiliary Electrode Types of Voltammetry

• It is usually a thin platinum wire.  • Linear Sweep Voltammetry 
• It serves merely to carry the current flowing through the cell.  • Staircase Voltammetry 
• Usually, redox reaction occur simultaneously at the auxiliary electrode. • Cyclic Voltammetry 
• Square-wave Voltammetry 
• Anodic Stripping Voltammetry 
• Cathodic Stripping Voltammetry 
• Absorptive Stripping Voltammetry 
• Alternating Current Voltammetry 
• Polarography 

• Rotated Electrode Voltammetry 

• Normal Pulse Voltammetry 
• Differential Pulse Voltammetry 
• Chronoamperometry.
 Voltammetry

Polarography
• Polarography is the branch of voltammetry in which a
dropping mercury electrode (DME) is used as the
working electrode.
• Wide cathodic potential range and a renewable
surface 
• Widely used for the determination of many reducible
species 
• Reduction begins at sufficiently negative potential
• Voltage applied to the polarizable electrode is
increased over the range of 0 - 2V 
• It is known as incomplete electrolysis.