Electrochemical Energy
JAN KENNEY D. GONZALES
(Chemistry Instructor)
Nature of Redox Reactions
• Electrochemistry is the scientific study of chemical processes that cause
electrons to move.
• Movement of electrons from one element to another is known as
reduction-oxidation (redox) reactions.
• Redox reactions are characterized by the changes in the oxidation
numbers of the elements involved in the process.
• Oxidation number is the charge of the atom would have in a molecule (or
an ionic compound) if electrons were completely transferred.
Nature of Redox Reactions
Oxidation numbers of elements in their compounds
Nature of Redox Reactions
Rules to assign oxidation numbers
Nature of Redox Reactions
Sample Exercise 1.
Assign oxidation numbers to all the elements in the following compounds and ion:
(a) Li2O, (b) HNO3, (c) Cr2O72-.
Answer:
(a) Lithium has an oxidation number of +1 (Li+) and oxygen’s oxidation number is -2 (O2- ).
(b) H has an oxidation number of +1, N has an oxidation number of +5, and oxygen’s
oxidation number of -2
(c) Chromium has an oxidation number of +6 and Oxygen has an oxidation number of -2
Nature of Redox Reactions
• Reduction is defined as: • Oxidation is defined as:
• the loss of oxygen • the gain of oxygen
• the gain of hydrogen • the loss of hydrogen
• the gain of electrons (the most • the loss of electrons (the most
fundamental definition) fundamental definition)
The substance being reduced is the The substance being oxidized is the
oxidizing agent. reducing agent.
Nature of Redox Reactions
Nature of Redox Reactions
Nature of Redox Reactions
• Mnemonic Device:
• GEROA - Gain Electrons, Reduction, Oxidizing Agents
• LEORA - Loss Electrons, Oxidation, Reducing Agents
Nature of Redox Reactions
Sample Exercise 2.
Identify the chemical processes as reduction or oxidation:
1. Cu2+ (aq) + 2e− → Cu(s)
2. Zn(s) → Zn2+ (aq) + 2e−
3. MnO4− (aq) + 8H+ (aq) + 5e− → Mn2+ (aq) + 4 H2O(ℓ)
4. Al3+ (aq) + 3e− → Al(s)
5. NO(g) + 2 H2O(ℓ) → NO3− (aq) + 4H+ (aq) + 3e−
Answer:
Balancing Redox Reactions
The following steps will be used to balance the equation.
• Step 1: Write the unbalanced equation for the reaction in ionic form.
• Step 2: Separate the equations into two half-reactions.
• Step 3: Balance each half-reaction for number and types of atoms and charges. Add H2O to
balance O atoms and H+ to balance H atoms.
• Step 4: Add the two half-reactions together and balance final equation. The electrons on
both sides must cancel. If the oxidation and reduction half-reactions contain different
numbers of elections, multiply one or both half-reactions to equalize the number of
electrons.
• Step 5: Check if the equation has the same type and numbers of atoms and same charges
on both sides of the overall equation.
Balancing Redox Reactions
Example:
Write a balanced ionic equation to represent the oxidation of iodide ion (I-) by
permanganate ion (MnO4-) in basic solution to yield molecular iodine (I2) and
manganese(IV) oxide (MnO2).
Solution:
Step 1: The unbalanced equation is
Step 2: The two half-reactions:
Balancing Redox Reactions
Step 3: Balance each half-reaction for number and type of atoms and charges.
• (a) Oxidation half-reaction: We first balance the I atoms. To balance charges, we add two
electrons to the right-hand side of the equation:
• (b) Reduction half-reaction: To balance the O atoms, we add two H2O molecules on the
right: To balance the H atoms, we add four H+ ions on the left:
There are three net positive charges on the left, so we add three electrons to the same
side to balance the charges:
Balancing Redox Reactions
Step 4: We now add the oxidation and reduction half reactions to give the overall reaction.
In order to equalize the number of electrons, we need to multiply the oxidation half-
reaction by 3 and the reduction half-reaction by 2 as follows:
The electrons on both sides cancel, and we are left with the balanced net ionic equation:
Step 5: A final check shows that the equation is balanced in terms of both atoms and
charges.
Balancing Redox Reactions
Sample Exercise 3.
Balance the following skeleton ionic reaction,
Mn2+ (aq) + Br2 (l) ⟶ MnO4−(aq) + Br−(aq)
Generation of Electrochemical Energy
• Redox reactions are used by electrochemical cells to produce electrical energy.
• There are two types of electrochemical cells:
• Voltaic cell (or galvanic cell): uses a spontaneous reaction to produce an electrical
current.
• Electrolytic cell: uses electrical energy to drive a nonspontaneous reaction.
• By physically separating two substances that undergo redox reaction, the electrons
can be forced to travel through an external circuit as an electric current.
• For example, if zinc metal is immersed in copper solution, a redox reaction occurs.
Zinc undergoes loss of electrons (oxidation) and copper ions gain electron (reduction).
Generation of Electrochemical Energy
• Spontaneous reaction between Zn and copper ion solution
Generation of Electrochemical Energy
(a) Diagram of a voltaic cell, (b) Zn anode loses mass as it is consumed to give Zn 2+ ions while the
Cucathode gains mass as Cu 2+ ions are reduced to copper metal that is deposited on the cathode.
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Generation of Electrochemical Energy
• Anode is the electrode at which oxidation occurs as electrons are lost by some
species.
• Cathode is defined as the electrode at which reduction occurs as electrons are
gained by some species.
• A salt bridge allows electrical contact between two solutions, prevents mixing of
the electrode solutions, and maintains the electrical neutrality in each half-cell as
ions flow into and out of the salt bridge.
• A simple way to remember the name of the electrode is to imagine a "red cat"-
REDuctions always occurs at the CAThode and “anox”- Oxidation always occur at
the Anode.
Generation of Electrochemical Energy
Battery in a form of an electrochemical cell can be constructed by
physically separating the zinc metal and the copper ions, so that the
electrons’ only path from the zinc to the copper is through a wire,
following the preceding chemical reaction.
Generation of Electrochemical Energy
Why batteries have limited lifetime?
• Reactants deplete as the redox reaction proceeds. Over time,
zinc electrode is dissolved and copper ion solution is depleted.
The battery no longer produces electric current and must be
discarded.
Generation of Electrochemical Energy
Notation for Voltaic Cell
The convention is:
• The anode is written on the left;
• The double lines, //, separate the two half reactions;
• The single lines, / , represent phase boundary;
• A comma separates members of the same phase.
For the voltaic cell of Zn and Cu,
Zn(s)/ Zn2+(aq) // Cu2+(aq)/ Cu(s)
or
anode/electrolyte of anode//electrolyte of cathode/cathode
Generation of Electrochemical Energy
Sample Exercise 3.
Give the cell notation of the reaction which present in voltaic cell.
Al(s) + Cu2+(aq) → Al3+(aq) + Cu(s)
Solution
Al(s) + Cu2+(aq) → Al3+(aq) + Cu(s)
Anode
Oxidation: Al(s) → Al3+(aq) + 3e-
Cathode
Reduction: Cu2+(aq) + 2e- → Cu(s)
Al(s) Al3+(aq) Cu2+(aq) Cu(s)
Cell Potential (E°cell)
In a voltaic cell, the potential difference between the two electrodes is the cell potential
(E°cell) or cell emf.
Cell Potential (E°cell)
How to assign which is anode and which is cathode?
• The electrode in any half-cell with a greater tendency to undergo
reduction, therefore the cathode. While the electrode in any half-
cell with a lesser tendency to undergo reduction (or greater
tendency to undergo oxidation), therefore the anode.
Cell Potential (E°cell)
The table shown the lists of the standard
electrode potentials for a number of common
half-reactions.
Cell Potential (E°cell)
Sample Exercise 4.
From the tabulated standard electrode potentials to calculate the positive standard cell potential
for the following system occurring in an electrochemical cell at 25 °C.
• 1. Ni2+/Ni (Eº = -0.23 V) and Mn2+/Mn (Eº = -1.18 V)
• 2. Fe2+ /Fe (Eº = -0.45 V) and Mg2+/Mg (Eº = -2.37 V)
Cell Potential (E°cell)
SOLUTION
1.) Ni2+/Ni (Eº = -0.23 V) and Mn2+/Mn (Eº = -1.18 V)
Cathode: Ni2+ (aq) + 2e- → Ni(s) Eºcathode = -0.23 V
Anode: : Mn (s) + → Mn2+ (aq) + 2e- Eºanode = -1.18 V
Overall: Mn (s) + Ni2+ (aq) → Mn2+ (aq) + Ni(s)
Eºcell = Eºcathode - Eºanode
= (-0.23 V) – (-1.18 V)
= -0.23 V + 1.18 V
= +0.95 V
Cell Potential (E°cell)
SOLUTION
2.) Fe2+ /Fe (Eº = -0.45 V) and Mg2+/Mg (Eº = -2.37 V))
Cathode: Fe2+ (aq) + 2e- → Fe(s) Eºcathode = -0.45 V
Anode: : Mg (s) + → Mg2+ (aq) + 2e- Eºanode = -2.37 V
Overall: Mg (s) + Fe2+(aq) → Mg2+(aq) + Fe(s)
Eºcell = Eºcathode - Eºanode
= (-0.45 V) – (-2.37 V)
= -0.45 V + 2.37 V
= +1.92 V
Corrosion
Corrosion
• Corrosion is the term usually applied to
the deterioration of metals by an
electrochemical process.
• By far the most familiar example of
corrosion is the formation of rust on
iron. Oxygen gas and water must be
present for iron to rust.
Corrosion
• Anode: Fe is oxidized to Fe2+
• Cathode: Another region on the metal
where the electrons from Fe reduce
atmospheric oxygen to water.
• The overall process is
• Rust: Fe2O3 ∙ xH2O
