CHEMISTRY FOR ENGINEERS

MODULE 3

ELECTROCHEMICAL ENERGY

WHAT IS ELECTROCHEMICAL ENERGY?

The Electrochemical energy is defined as “the energy which converts electrical energy to chemical energy
and vice versa.” The electrochemical energy is related to fuel cells, photo electrochemical, and energy storage
systems such as batteries, super capacitors or ultra-capacitors.

RECALL:

REDOX (REDUCTION-OXIDATION) REACTION

The reaction that happens during the production of electrochemical energy is called REDOX (REDUCTION
OXIDATION) reactions which includes the transfer of electrons.

EXAMPLE:

CHEMICAL EQUATION: 𝐹𝑒(𝑠) + 𝐶𝑢𝑆𝑂4(𝑎𝑞) → 𝐹𝑒𝑆𝑂4(𝑎𝑞) + 𝐶𝑢(𝑠)

IONIC CHEMICAL EQUATION: 𝐹𝑒(𝑠) + 𝐶𝑢(𝑎𝑞)

2+ 2−
+ 𝑆𝑂4(𝑎𝑞) 2+
→ 𝐹𝑒(𝑎𝑞) 2−
+ 𝑆𝑂4(𝑎𝑞) + 𝐶𝑢(𝑠)
2+ 2+
𝐹𝑒(𝑠) + 𝐶𝑢(𝑎𝑞) → 𝐹𝑒(𝑎𝑞) + 𝐶𝑢(𝑠)

THE TWO HALF REACTIONS:

2+
𝐹𝑒(𝑠) → 𝐹𝑒(𝑎𝑞) + 2𝑒 −(OXIDATON/RA)
2+
𝐶𝑢(𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠) (REDUCTION/OA)

REDUCTION – occurs when a specie gains electrons and decreases its oxidation number.

OXIDATION – occurs when a specie loses electrons and increases its oxidation number.

REDUCING AGENT (RA) – ion/molecule that donates electrons

OXIDIZING AGENT (OA) – ion/molecule that accepts electrons

REMEMBER!!!

GEROA- Gain of Electrons Reduction Oxidizing Agent

LEORA- Loss of Electrons Oxidation Reducing Agent

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TYPES OF CELLS

1. VOLTAIC/GALVANIC CELL – the reaction generates current

Anode reaction is OXIDATION Cathode reaction is REDUCTION

Zn atoms are oxidized to Zn2+ Cu2+ ions are Reduced to Cu atoms
𝒁𝒏(𝒔) → 𝒁𝒏𝟐+ (𝒂𝒒) + 𝟐𝒆
−
𝑪𝒖𝟐+ −
(𝒂𝒒) + 𝟐𝒆 → 𝑪𝒖(𝒔)

Balancing HALF CELL REACTION:

Cathode: 𝒁𝒏(𝒔) → 𝒁𝒏𝟐+ (𝒂𝒒) + 𝟐𝒆
−

Anode: 𝑪𝒖𝟐+ −
(𝒂𝒒) + 𝟐𝒆 → 𝑪𝒖(𝒔)

REACTION: 𝒁𝒏(𝒔) + 𝑪𝒖𝟐+ 𝟐+

(𝒂𝒒) → 𝒁𝒏(𝒂𝒒) + 𝑪𝒖(𝒔)

Simplifying it into this notation: |- Phase Boundary

Zn|Zn 2+
|| Cu |Cu
2+
||- Salt Bridge

HOW IT WORKS?

1. At the Zinc anode (- pole), electrons are produced by the oxidation half reaction:
2+
𝑍𝑛(𝑠) → 𝑍𝑛(𝑎𝑞) + 2𝑒 −

2. Electrons generated at the anode move to the Copper cathode (+ pole) thru a wire to voltmeter giving a
reduction reaction:
2+
𝐶𝑢(𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠)

3. To maintain balance or electrical neutrality, Cations (+charged ions) move toward move to Copper Cathode.
Anions (- charged ions) move toward Zinc Anode.

2. ELECTROLYTIC CELL – current drives the reaction

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CELL POTENTIAL, Ecell

Electrons will always flow from a high electric potential to a low electric potential and the difference
between the two is called POTENTIAL DIFFERENCE.

𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒙 + 𝑬𝒓𝒆𝒅

Where the Ered may be obtained from the of STANDARD REDUCTION POTENTIALS TABLE.

The larger the Ecell value, the greater the current it can generate.

GIBB’S FREE ENERGY, ΔG°

The change in Gibb’s Free Energy pertains to the maximum work a voltaic cell is capable of.

∆𝑮° = −𝒏𝑭𝑬°

Where:

n – moles of electrons exchanged in the reaction

𝐽
F – Faraday’s constant, 96,485 𝑉.𝑚𝑜𝑙 𝑒 −

E° – standard cell potential

NERST EQUATION:

The relationship between the cell potential and the standard cell potential
𝑹𝑻 𝐥𝐧(𝑸)
𝑬 = 𝑬° −
𝒏𝑭
Where:

E – Cell Potential

E° - Standard Cell Potential (at standard atmospheric pressure and temperature)

𝐽
R – Universal Gas Constant (8.314 𝑚𝑜𝑙.𝐾)

T – Absolute Temperature (Kelvin)

Q – Reaction Quotient

n – moles of electrons exchanged in the reaction

𝐽
F – Faraday’s constant, 96,485
𝑉.𝑚𝑜𝑙 𝑒 −

PROBLEMS:

1. Consider the following voltaic cell:

3+ 2+
𝐴𝑙(𝑠) | 𝐴𝑙(𝑎𝑞) || 𝐹𝑒(𝑎𝑞) | 𝐹𝑒(𝑠)

a. Which electrode is the anode and which is the cathode?

b. Write the overall reaction.

c. Using the STANDARD REDUCTION POTENTIAL TABLE, calculate the cell potential.

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d. Calculate the Gibb’s Free Energy and the Reaction Quotient (Q).

2. Consider the voltaic cell at 25°C and 1 atm:

+ −
𝑂2(𝑔,0.98 𝑎𝑡𝑚) + 4𝐻(𝑎𝑞,𝑝𝐻=1.24) + 4𝐵𝑟(𝑎𝑞,0.15 𝑀) → 2𝐻2 𝑂 + 2𝐵𝑟2(𝑙)
Solve:

a. Ecell

a. ΔGo

b. Q (search the internet how to calculate for the Reaction Quotient)

REFERENCES:

https://energyfaculty.com/electrochemical-energy/

https://www.youtube.com/watch?v=2VT5rl8P84M

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