LIST OF GROUP MEMBERS

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8 JACOB YOTHAM NTILINIGA T23-03-20040
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 ELECTRODE POTENTIAL
• Electrode potential, also known as electrode potential difference or electrode
voltage. It refers to the potential difference or voltage that develops at an
electrode surface when it is immersed in an electrolyte solution and
subjected to an electrochemical reaction.
• When an electrode is immersed in an electrolyte solution, it can either gain
or lose electrons depending on the redox reaction occurring at the electrode.
The electrode potential is a measure of the tendency of an electrode to gain
or lose electrons and is defined as the potential difference between the
electrode and the electrolyte solution.
• The electrode potential is often measured with respect to a reference electrode, which has
a known and stable potential. The most commonly used reference electrode is the
standard hydrogen electrode (SHE), which has an assigned electrode potential of 0 volts.
By comparing the potential of the electrode of interest to the potential of the reference
electrode, the electrode potential can be determined.

• The electrode potential is influenced by various factors, including the nature of the
electrode material, the concentration of ions in the electrolyte solution, temperature, and
pressure. These factors can affect the redox reactions occurring at the electrode and,
consequently, the potential difference between the electrode and the electrolyte solution.
 CONT……..
• Electrode potential plays a crucial role in understanding and predicting the
behavior of electrochemical cells. It helps determine the direction of
electron flow, the feasibility of redox reactions, and the overall cell
potential. Electrode potentials are often tabulated in a standard electrode
potential table, which provides a reference for comparing the reactivity
and tendencies of different electrode materials
 DEVELOPMENT OF ELECTRODE POTENTIAL

•Electrode potential, also known as electrode potential difference, It is a

fundamental concept in electrochemistry and plays a crucial role in
understanding and predicting the behavior of electrochemical cells.
The development of electrode potential is influenced by several factors,
including the nature of the electrode material, the concentration of ions in
the electrolyte solution, and the temperature. Let's explore these factors in
more detail:
 FACTORS

•1. Electrode Material:

• The type of material used for the electrode greatly affects its electrode
potential. Different materials have different tendencies to gain or lose
electrons. Electrodes can be broadly classified into two categories: Standard
Hydrogen Electrode (SHE) and Non-Standard Electrodes.
 FACTORS
• - Standard Hydrogen Electrode (SHE):
The SHE is often used as a reference electrode to measure the electrode potential of other
electrodes. It consists of a platinum electrode immersed in an acidic solution with a known hydrogen
ion concentration. The electrode potential of the SHE is defined as zero volts by convention.

• - Non-Standard Electrodes:
Non-standard electrodes are made from various materials like metals, metal oxides, or conducting
polymers. The electrode potential of these materials is measured relative to the reference electrode
(SHE).
 FACTORS

•2. Concentration of Ions:

The concentration of ions in the electrolyte solution surrounding the electrode can significantly influence
its electrode potential. According to the Nernst equation, the electrode potential is directly proportional
to the logarithm of the ratio of ion concentrations. This relationship reflects the fact that the movement
of ions across the electrode-electrolyte interface is influenced by the concentration gradient.
- For example, consider a metal electrode immersed in a solution containing its own ions. If the
concentration of metal ions in the solution is higher than the concentration on the electrode surface, the
electrode potential will be positive. Conversely, if the concentration of metal ions on the electrode
surface is higher, the electrode potential will be negative.
 FACTORS
• 3. Temperature
Temperature also affects the electrode potential. Higher temperatures generally increase the
rate of electrochemical reactions, leading to changes in the electrode potential. The
relationship between temperature and electrode potential is described by the Nernst equation,
which incorporates a temperature-dependent term.
In summary, the electrode potential is a measure of the voltage difference between an
electrode and its surrounding electrolyte solution. It is influenced by the electrode material, the
concentration of ions in the solution, and the temperature. Understanding electrode potential
is crucial for predicting and controlling electrochemical reactions in various applications,
including batteries, corrosion prevention, and electroplating.
 WHY USE OF PLATINUM?
•Platinum is used in the standard hydrogen electrode for the following reasons.

•Platinum is an inert catalyst. So, it doesn’t corrode during the electrochemical and speeds up the rate
of the reaction.
•Platinum is a less reactive metal. So, it doesn’t easily react with other metals. As a result, it provides
the surface for the redox reaction.
•Being a good absorber of hydrogen, platinum improves the chemical kinetics of the electrochemical
reaction at the interface.
•Unlike other metals such as gold, silver, copper, mercury; platinum doesn’t poison the electrode of
another half-cell.
•Owing to its catalytic properties, platinum promotes the proton reduction reaction
 Measurement of electrode potential
• In order to measure the electrode potential, a second electrode is needed.
• A voltmeter has to be connected to the external circuit across the two
electrodes. The reading on the voltmeter will be the sum of the electrode
potentials of the two electrodes.
 CONT……….
• Therefore in order to obtain electrode potential of the particular half cell, a
reference electrode with known potential is used
• The standard hydrogen electrode has been choosed as the standard
electrode against which electrode potentials of the others
 ELEMENTS TO BE MEASURED
An electrode potential for the hydrogen electrode is arbitrarily assigned a
value of 0.00V
Hence, when a standard hydrogen electrode is connected to other electrode
the reading on the voltmeter will be equal to the electrode potential of the
electode
 STANDARD HYDROGEN POTENTIAL
•Standard hydrogen potential is abbreviated as SHE, the Standard Hydrogen
Electrodes, a redox electrode, is the foundational basis of the scale of the
oxidation-reduction potential. Moreover, it is the main electrode where the
electrochemical reaction takes place. It consists of a platinum electrode
immersed in a solution of 1 M HCl and surrounded by a gaseous atmosphere
of hydrogen at a pressure of 1 bar.
 STANDARD HYDROGEN POTENTIAL
•To compare hydrogen’s potential with other electrochemical reactions, it is
said to have a zero volts potential (E°) at a certain temperature (298 K). At a
given temperature, the potential of any electrode is compared to the potential
of a hydrogen electrode. It is referred to as the standard hydrogen electrode
because it acts as a reference electrode.
•
DIAGRAM OF SHE
RELATIONSHIP BETWEEN FREE ENERGY AND CELL POTENTIAL

•In galvanic cell chemical energy is converted to electrical energy, the

electrical energy that is generated as the results of the chemical reaction is
equal to the products of the emf of the cell and the total charge that posses
through the electrochemical cell
 CONT…..
•Thus,
•Electrical energy (J)= maximum cell potential (V)x total electrical charge (C)
•The total charge is obtained by multiplying the number of moles (n) of the elections that pass through the
circuit by the electrical charge contained in 1 mole of electrons
•Total electric charge= nF
•Electrical energy = -Ecell x nF
•Negative sign indicate that the system does work on the surrounding
•In accordance with the Gibbs the energy released by the chemical reaction and which is used to perform a
certain work is called Gibbs free energy
 CONT…..
• G. =nF xE0
•The free energy of the system at the initial state
Gi =-RTlnQ

•The final or equilibrium state is

Gf = -RTlnK

•Change in ∆G = Gf -Gi = RT( lnQ - ln K).....................(I)

 CONT…….
•When the initial state is at standard conditions,
∆ G= G0 and Q = 1
∆ G= RT lnQ - RTlnK
∆G0 = -RTlnK.................................................(ii)
•Then take equation (ii) into equation (I)
∆G = RTlnQ - RTlnK
 CONT…….
• ∆G = RTlnQ - ∆G0
∆G0= -nFE0 but also ∆G = -nFE
∆G = ∆G0 + RTlnQ
-nFE = -nFE0 + RTlnQ
E = E0 - RTlnQ/nF
•Where R, T ,and T are constant with ther values equal to 8.314J/molK , 298K and 965900C/mol
respectively, The equation is known as the Nernst Equation
E = E0 - 0.0591/n logQ
•For electrode reaction
Cu(aq)2+ + 2e- -------------------->Cu(s)

• E(Cu2+/Cu)= E0(Cu2+/Cu) - 0.0591/2 log([Cu]/[Cu2+])

•E(Cu2+/Cu) = E0(Cu2+/Cu) - 0.0591/2 log(1/[Cu2+])..................(iii)

Zn2+ + 2e+ ------------------------------->Zn

 CONT……..
•E(Zn2+/zn) = E0(Zn2+/Zn) - 0.0591/2 log(1/[Zn2+].....................(iv)
•Ecell = {E0(Cu2+/Cu)- 0.0591/2 log (1/[Cu2+])}- {E0(Zn2+/Zn) -0.0591/2 log (1/[Zn2+])}
•Ecell = (E0(Cu2+/Cu) -E0(Zn2+/Zn)) +0.0591/2 {log(1/[Zn2+]) - log(1/[Cu2+])}
•Ecell = ∆E0. +0.0591/n log{[Cu2+]/[Zn2+]}
OR
•Ecell = ∆E + 0.0591/n log {[reduced species]/[oxidized species]}
 CALCULATION OF EMF
• ,
 EMF
•The emf of the cell is obtained as the difference between the EO
Value of the cathode and the anode electrode which is given by
EOcell=EoCathode-Eoandode
 AT CATHODE AND ANODE
• At the cathode is where reduction takes place
example Cu2+(aq)+2e→cu(s) EO=0.34V
• At the anode is where oxidation takes place
example H2(g)→2H +(aq)+2e_ Eo=0.00v
the overall redox reaction
H2(g)+cu2+(aq)→2H++cu(s)
Ecell o
=E cathode -EOAnode
0.34V-0.00V

0.34v
• example
• Calculate the emf of the cell below
•Ni(s) +2Ag(aq) → N2+(aq)+2Ag(aq)
•Given that
• Eo(Ag+/ag)=0.8v
• Eo(Ni+/Ni(s)=-0.23v
•Answer=+1.03v
 examples
• Calculate the standard emf of the cells formed by different combination of
the following half cells
• zn(s)/Zn2+(aq) ,cu(s)/cu2+ , Ni(s)/Ni+(aq) , Ag(s)/ag+(ag)
• Eo zn/zn2+=0.76v, E0cu/cu2+=0.34v
• E0Ni/Ni2+=0.23v, EoAg/ag+=0.8v
• anwer=1.1v (when zinc combine with copper)
• answer=0.46v (when copper combine with silver)
 EQUILBRIUM CONSTANTS OF EMF
 The potential of the cell depend one equilibrium constant of cell.
When the cell has established equilibrium constant
 The potential of the cell
 The reaction quotient become equal to equilibrium constant,Kc=Q
 From Nernst Equation we can calculate equilibrium constant by
considering the above condition
 CONT…….
• ∆E=E°cell-0.0591/𝑛 logQ
• But At equlibrium, ∆E=O and Q=Kc

• 0=E°cell-0.0591/𝑛logKc

• (𝑛𝐸°𝑐𝑒𝑙𝑙)/0.0591 =logKc

• Kc= 〖𝑙𝑜𝑔〗 ^(−1) [(𝑛𝐸°𝑐𝑒𝑙𝑙)/0.0591]

CONT……
 GIBBS FREE ENERGY
• Gibbs free energy (G) is a thermodynamic potential that measures the maximum amount of work
that can be extracted from a closed system at constant temperature and pressure. It is defined as:

G = H - TS

where:

* G is the Gibbs free energy

* H is the enthalpy
* T is the absolute temperature
* S is the entropy
 SIGNIFICANCE OF GIBBS FREE
ENERGY
• Significance of Gibbs Free Energy

Gibbs free energy is a crucial concept in thermodynamics because it:

* Determines the spontaneity of a reaction: A reaction is spontaneous if ΔG is

negative.
* Predicts the equilibrium state of a system: At equilibrium, ΔG = 0.
* Relates to the work that can be done by a system: The maximum work that can
be extracted is equal to -ΔG.
 SPONTANEITY AND EQUILBRIUM
• Spontaneity and Equilibrium

* Spontaneous Reactions (ΔG < 0): Reactions that occur without the need for
external energy input. The system loses free energy and does work on the
surroundings.
* Non-Spontaneous Reactions (ΔG > 0):Reactions that require external energy
input to occur. The system gains free energy from the surroundings.
* Equilibrium (ΔG = 0): The system is in a state where the forward and
reverse reactions occur at the same rate. There is no net change in free energy.
 APPLICATION OF GIBBS FREE
ENERGY
• Applications of Gibbs Free Energy

Gibbs free energy has numerous applications in various fields, including:

* Chemical Reactions: Predicting the spontaneity and equilibrium of chemical reactions.

* Phase Transitions: Determining the conditions under which a substance undergoes a phase
change (e.g., melting, freezing).
* Electrochemistry: Calculating the electromotive force (EMF) of electrochemical cells.
* Biological Systems:Understanding the energetics of biological processes, such as enzyme
catalysis and muscle contraction.
* Engineering: Designing processes that maximize energy efficiency and minimize waste.
 FACTORS AFFECTING GIBBS FREE
ENERGY
• Factors Affecting Gibbs Free Energy

The value of Gibbs free energy is influenced by several factors:

* Temperature:ΔG decreases with increasing temperature for exothermic reactions and increases with
increasing temperature for endothermic reactions.
* Pressure:ΔG decreases with increasing pressure for reactions that involve a decrease in volume and
increases with increasing pressure for reactions that involve an increase in volume.
* Concentration: ΔG decreases with increasing concentrations of reactants and decreases with
increasing concentrations of products.
* Entropy: ΔG decreases with increasing entropy.
 STANDARD GIBBS FREE ENERGY
• Standard Gibbs Free Energy

The standard Gibbs free energy change (ΔG°) is the change in Gibbs free energy under standard conditions
(298 K, 1 atm). It provides a reference point for comparing the spontaneity of different reactions.

Additional Notes:

* Gibbs free energy is also known as the free enthalpy.

* The change in Gibbs free energy (ΔG) is related to the equilibrium constant (K) by the equation: ΔG = -
RT ln K
* Gibbs free energy can be used to calculate the work done by a system in isothermal and isobaric
processes.