Lecture Notes: Statistical Thermodynamics
and Electrochemistry
⚡ Electrode Potential
🔹 Definition
Electrode potential is the ability of a metal electrode to lose or gain electrons
when it is in contact with its electrolyte solution.
It represents the tendency of a metal to either oxidize (lose electrons) or reduce
(gain electrons).
🔹 SI Unit
The SI unit of electrode potential is the volt (V).
🔹 Behavior of a Metal in Electrolyte Solution
When a metal is immersed in an electrolyte solution, its electrical properties
change due to interactions at the metal–solution interface.
Some metal atoms dissolve as ions, leaving behind electrons, while some ions from
the solution deposit on the metal surface.
This leads to charge separation and development of an electric potential difference
between metal and solution.
🔹 Conductivity
Conductivity is the movement of charged particles (ions or electrons) that allows
electric current to pass through a substance.
In electrolytes, conductivity occurs through the movement of ions.
In metals, it occurs through free electrons moving in response to an electric field.
🔹 Generation of Electrode Potential
Two ways electrode potential can arise:
1. Between two metals in contact, or
2. Between a metal and an electrolyte solution.
⚙️Atomic and Band Theory Background
🔸 From Atoms to Solids
Metals consist of atoms arranged in a crystal lattice.
Each atom has atomic orbitals with specific energy levels.
When atoms combine or condense to form a solid, their discrete energy levels
broaden into energy bands.
🔸 Formation of Energy Bands
In isolated atoms, electrons occupy discrete (fixed) energy levels.
In solids (crystals), atoms are close together; their outer orbitals overlap, and
individual energy levels merge into continuous energy bands.
Inner shells remain unaffected, but outer shells interact, forming:
o Valence band → occupied by electrons.
o Conduction band → empty or partially filled, allows movement of electrons.
⚡ Why Do Electrons Flow Between Metals?
When two dissimilar metals come into contact:
o Their energy bands interact.
o Electrons flow from the metal with higher energy (lower electron affinity) to
the one with lower energy (higher electron affinity).
This transfer of electrons continues until their Fermi levels (energy levels at
equilibrium) become equal.
The resulting charge separation leads to a potential difference.
This potential difference is the basis of electric current generation in
electrochemical reactions.
🔹 Diagrams (Described Verbally)
1. Energy vs. Interatomic Distance Graph
Shows valence and conduction bands.
As atoms come closer (forming a solid), discrete atomic energy levels spread and
merge into continuous energy bands.
2. Single Atom Diagram
Displays discrete horizontal lines representing individual energy levels of electrons.
3. Two or More Atoms Diagram
When two identical atoms interact → each energy level splits into two.
Adding a third atom → splits further.
In a solid with many atoms → levels merge into bands.
🔹 Key Takeaways
Explanation Concept
Ability of metal to lose/gain electrons when in contact with
Electrode Potential
electrolyte
Volt (V) Unit
Charge separation at metal–solution interface Origin
Reason for Electron
Difference in Fermi levels or electron affinities
Flow
Formed by overlapping atomic orbitals in solids Energy Bands
Occupied energy levels Valence Band
Energy levels that allow electron movement Conduction Band
Potential difference → drives current in electrochemical cells Result
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You said:
A single atom allows specific energy levels for an electron. The energy levels are signified by
the horizontal line within the atomic potential. When two identical atoms interact, each
energy level splits into two. Adding a third atom causes each original level to split into three.
Large number of atoms causes the split energy levels to essentially overlap forming
continuous band of allowed energy separated by a forbidden energy gap. Electron can move
within a partially filled band because there are empty spaces electron can easily excite it to
the next level with a small energy input. Partially filled is good conductors. Electrode
potential, when a piece of metal is placed into an electrolyte solution, into an electrolyte
solution which contains anions and electric potential arises between metal and a solution.
This potential difference occurs not just in metal and electrolyte but any time when two
different conductors when individual atoms balance band this is a band derived from banding
molecular orbital in solids it is generally a filled. This is a band derived from non-bonding
molecular orbital in a solid it is generally a filled. Now the conduction band comes from non-
bonding molecular orbital in metals this band is partially allowing some electrons filled the
freedom to move around. This makes metal as conductors. These free electrons can flow
under electric field under electric current. Electric potential is the amount of potential energy
per unit charge at a point. In a battery one electrode has more electrons than the other this
make potential difference. The force experienced by a charge due to potential difference it
point from higher potential to lower potential for charges. For example, E equals to minus del
V and electric field is a negative gradient of electric potential. The potential difference
between two electrode causes electric field pushing electrode from a negative potential to a
positive potential across a connected external circuit. Only electrons near or at the Fermi
level can move when an electric field is applied and hence since they move. Electricity
electrons must move from one energy level to another gain energy and change velocity and
respond to electric field in a full electrons are stuck in a partially filled electrons are free.
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Excellent — that’s a detailed continuation of your lecture. Based on what you just narrated,
here are complete, structured, and easy-to-study notes combining this new part with your
previous one 👇
📘 Lecture Notes: Statistical
Thermodynamics and Electrochemistry
(Part II)
⚛️Energy Levels and Band Theory
🔹 1. Single Atom
A single atom has discrete (specific) energy levels where its electrons reside.
These energy levels are shown as horizontal lines within the atomic potential well.
Each line represents an allowed energy state for an electron.
🔹 2. Two or More Atoms
When two identical atoms interact, each energy level splits into two.
When a third atom is added, each original level splits into three.
As the number of atoms increases (as in solids), the splitting becomes so dense that:
o The discrete energy levels overlap, forming continuous energy bands.
🔹 3. Energy Bands in Solids
The continuous range of allowed energy levels is called an energy band.
Between two bands lies a forbidden energy gap (band gap) — a range of energy
where no electron states exist.
Role in Conduction Description Band Type
Electrons here are bound and cannot Lower energy band; usually filled
Valence Band
move freely with electrons
Electrons can move freely → electrical Higher energy band; may be Conduction
conduction empty or partially filled Band
Determines whether material is Energy difference between
Band Gap
conductor, semiconductor, or insulator valence and conduction bands
🔹 4. Movement of Electrons
In partially filled bands, some empty states exist → electrons can easily jump to
nearby levels with small energy input.
Hence, partially filled bands = good conductors.
In completely filled bands, no empty levels are available, so electrons cannot move,
making them non-conductors.
⚡ Origin of Electrode Potential
When a piece of metal is placed into an electrolyte solution (containing ions), an
electric potential difference arises between the metal and the solution.
This occurs because:
o Metal atoms may lose electrons and enter the solution as cations, leaving
behind excess electrons (metal becomes negative).
o Or ions in the solution may gain electrons and deposit on the metal surface
(metal becomes positive).
This leads to charge separation and hence an electrode potential.
💡 Relation Between Band Theory and Electrochemistry
In metals:
o The conduction band is partially filled, allowing free movement of
electrons.
o The valence band is usually filled, while the conduction band overlaps or is
close to it.
This overlap allows metals to:
o Conduct electricity easily,
o Develop potential differences when in contact with other materials.
⚙️Electric Potential and Electric Field
🔹 Electric Potential
Definition: Amount of potential energy per unit charge at a point in an electric
field.
Formula:
V=WqV = \frac{W}{q}V=qW
In a battery, one electrode has more electrons than the other → this creates a
potential difference.
🔹 Electric Field and Potential Relationship
The electric field (E) is the negative gradient of electric potential:
E=−∇VE = -\nabla VE=−∇V
This means the electric field direction is from higher potential to lower potential.
🔹 Potential Difference and Electron Flow
The potential difference between two electrodes causes an electric field.
This field pushes electrons through an external circuit from negative to positive
potential.
Only electrons near or at the Fermi level (highest occupied energy level at 0 K) can
move when the field is applied.
These electrons:
o Gain energy,
o Change velocity,
o Move through the conduction band, creating an electric current.
🔹 Summary Table
Key Point Concept
Arises when metal interacts with electrolyte, due to electron transfer Electrode Potential
Formed from overlapping atomic orbitals in solids Energy Bands
Allows free electron movement → good conductor Partially Filled Band
Potential energy per unit charge Electric Potential (V)
Negative gradient of potential; drives electron flow Electric Field (E)
Highest filled energy level; electrons near it conduct current Fermi Level
🔹 Key Idea
The electrode potential of a metal–solution system is a manifestation of microscopic band
interactions and macroscopic charge separation, both governed by how electrons occupy
and move within the energy bands of materials.
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diagrams (energy levels, bands, and electrode–electrolyte interface)? It would visually
capture everything you’ve dictated so far.