CHM 101

ELECTROCHEMISTRY
st
1 Lecture
BY
DR. S.O. SANUSI
Department of Chemistry,
Obafemi Awolowo University, Ile-Ife
Outline of the topic and relevant texts:

a. Relevant textbooks: Physical chemistry textbook by – P.W. Atkins, J.H. Noggle, L.M. Raff, K.J. Laidler and J.H.

Meiser or any other physical chemistry textbooks. Specialized electrochemistry texts are also useful.

b. The following areas are to be discussed under this topic – electrical units, Ohm’s law, Faraday’s laws of electrolysis,

Galvanic cells, standard half-cell potentials and reactions. Concentration effects (Nernst equation). Redox reactions,

oxidation potential treated in terms of free energy change, cells and batteries.

Introduction

The branch of chemistry that studies the reactions which occur at the electrodes and relates electricity to chemical

reactions is known as electrochemistry. Such chemical reactions may occur to generate electric current as in

electrochemical cell or an application of electric current may initiate chemical reactions as in an electrolytic cell.

Electrochemistry can be subdivided into five broad segments:

i.) The production of an electromotive force, e.m.f. and generation of current by chemical reactions. Areas covered under
this segment are the studies of the galvanic primary cells, commercial secondary cells, batteries, fuel cells and electrode
potentials.

ii.) The application of potential difference or electric current to an electrolyte. Electrolysis, electrodepositing etc.

iii.) Equilibria in electrolyte (in the absence of the application of potential difference or e.m.f.). Ionic activities, pH,
hydrolysis of salts, buffer solutions etc.

iv.) Mechanism of reactions at electrode surface (electrodics). Electron transfer processes. Anodic and cathodic currents,
exchange current density etc.

v.) Applications of electrochemistry. Electro-analytical techniques such as potentiometry, voltammetry, polarography and
corrosion.
Electrical Units
The electrostatic force F between two charges 𝑄1 and 𝑄2 separated by a distance r in a vacuum is
𝑄1 𝑄2
𝐹=𝑘 (1)
𝑟2
1
where the constant k = 4𝜋𝜖 (𝜖0 = permittivity of a vacuum with value 8.854 × 10−12 C 2 J −1 m−1 ).
0

If the charges are in a medium having a relative permittivity, or dielectric constant 𝜖, Eq. 1 becomes:
 𝑘 𝑄1 𝑄2
𝐹= (2)
𝜖 𝑟2
For example, water at 25°C has a dielectric constant (𝜖) of about 78, with the result that the electrostatic forces between ions
are reduced by this factor.
Equations 1 and 2 are referred to as the Coulomb’s inverse-square law, or simply Coulomb’s law.
The Electric field E at any point is the region around a unit charge (1 C) particle, within which a force would be exerted on
other charged particles or objects. The field strength at a distance r from a charge Q, in a medium of dielectric constant 𝜖, is
thus:
𝑘 𝑄 𝐹
𝐸= =𝑄 (3)
𝜖 𝑟2

The SI unit of charge Q is the coulomb, C, and that of distance r is the metre, m. The unit of force F is the newton, N, which
is J m-1. The SI unit of field strength is newton per coulomb (N C-1 ≡ J m-1 C-1). However, since joule = volt coulomb (VIt) =
newton metre (F × distance), the SI unit of field strength is usually expressed as volt per metre (V m-1).
The field strength E (calculated from electric potential) at a distance r from a charge Q is given by Eq. 4:
𝑑𝜙
𝐸 = − 𝑑𝑟 (4)
E is the negative gradient of an electric potential 𝜙 (electrostatic potential) according to Eq. 4. The electric potential is
obtained by integration according to Eq. 5:
𝑘𝑄
𝜙 = − ‫= 𝑟𝑑𝐸 ׬‬ (5)
𝜖𝑟
𝜙 is the amount of work energy required per unit of electric charge to move the charge from a reference point to a specific
point in an electric field.
The electric potential energy with the SI unit of joule is the potential energy resulting from the coulombic interaction between
two charges, Eq. 6.
𝑘 𝑄1 𝑄2
𝑉= (6)
𝜖 𝑟
There is an important fundamental difference between the electrostatic (electrical) units and the SI units for electricity and
magnetism. In the electrostatic system, all electrical and magnetic quantities can be expressed in terms of not more than three
base units, which means they are expressed in three-dimensional base units. In SI, however, quantities are expressed in terms
of four base units, namely, metre, kilogram, second and ampere. The SI base units of electricity and magnetism are therefore
said to be four dimensional. For example, the ohm, in SI units is:
𝑉 𝑣𝑜𝑙𝑡
𝑅 Ω =
𝐼 𝐴
Ω = 𝑣𝑜𝑙𝑡𝐴−1
𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 J = 𝐼 𝐴 𝑡(𝑠) 𝑉(𝑣𝑜𝑙𝑡)
𝑣𝑜𝑙𝑡 = J𝐴−1 𝑠 −1
Recall that J = kg m2 𝑠 −2 , then 𝑣𝑜𝑙𝑡 = kg m2 𝑠 −2 𝐴−1 𝑠 −1 = kg m2 𝑠 −3 𝐴−1
Finally, Ω = 𝑣𝑜𝑙𝑡𝐴−1 = kg m2 𝑠 −3 𝐴−1 𝐴−1 = kg m2 𝑠 −3 𝐴−2 (a four-dimensional base units: SI base).
Exercise 1:

2
a. What would be the value of the electric potential 𝜙 for an electric field strength described by the function 𝐸(𝑟) = 3 𝑟 at

𝑟 = 2.0 cm and 2.0 m?

b. What is the magnitude of electric force produced by an electric potential energy 𝑉 𝑟 = 3𝑟 2 at 𝑟 = 1.5 m?
c. Given that in a box containing two charged particles, the product of the charges and the relative permittivity of the
𝑘
medium in the box, 𝜖 𝑄1 𝑄2 , is 8.85 × 10-10 J-1 m-1, calculate the electrostatic force produced in this box at a radius of

2.0 cm from the two-point charges.

𝑘 𝑄1 𝑄2
d. Calculate the electric force produced by two-point charges with electrostatic potential energy 𝑉(𝑟) = at 2.0 cm
𝜖 𝑟

𝑘
radius from the charges, given that 𝜖 𝑄1 𝑄2 = 8.85 × 10-9 J-1 m-1.

e. Is it correct to write A2 kg m as the unit of 𝜖0 ? Is it correct to classify it as a SI base unit or an electrical base unit?