Gen.

Chemistry 2 Q4 Week 1

GROUP 4
 LEARNING COMPETENCIES

1. predict the spontaneity of a process based on entropy;

2. explain the second law of thermodynamics and its

significance; and

3. use Gibbs' free energy to determine the direction of a

reaction.
Lesson 1: Predict the spontaneity of a
process based on entropy
 Spontaneous Reactions
-A spontaneous reaction is a type of process which does not need
the application of energy to take place. There is no need to use
energy to make this process occur.
Examples:

1. Melting of Ice at Room Temperature

Reaction: H₂O(s) → H₂O(l)

Explanation: Ice melts naturally at room temperature because the system moves
toward higher entropy (disorder).
 Spontaneous Reactions
2. Combustion of Methane

Reaction: CH₄(g) + 2O₂(g) → CO₂(g) + 2H₂O(g)

Explanation: Methane burns in oxygen, releasing heat and increasing entropy.

3. Rusting of Iron

Reaction: 4Fe(s) + 3O₂(g) → 2Fe₂O₃(s)

Explanation: Iron reacts with oxygen, forming rust. This process happens
naturally over time.
 Non-Spontaneous Reactions
This type of process which needs the use of energy to make it
happen

Examples:

1. Melting of Ice Below 0°C

Reaction: H₂O(s) → H₂O(l) (at T < 0°C)

Explanation: Ice does not melt below freezing unless heat is supplied.
 Non-Spontaneous Reactions
Examples:

2. Electrolysis of Water

Reaction: 2H₂O(l) → 2H₂(g) + O₂(g)

Explanation: Water does not split into hydrogen and oxygen without an electric current.

3. Formation of Calcium Carbonate

Reaction: CaO(s) + CO₂(g) → CaCO₃(s)

Explanation: This reaction does not occur on its own; it requires external conditions.
 Enthalpy Change and Spontaneity
•melting of ice above O°C (endothermic)
H2O(s) H2O (1)

•dissolution of NH4NO3 at 25°C

The reactions given on the
right are spontaneous. (endothermic) + NH4NO3(s) → NH4+ (aq) +
OH(aq)

The endothermicity or •dissolution of NaOH in water at 25°C

exothermicity of a reaction (exothermic)
does not determine its
NaOH(s) Na+ (aq) + OH (aq)
spontaneity.
•neutralization at 25°C (exothermic) H3O+
(aq) + OH(aq) → 2H2O (1)
Entropy (S) – The Measure of Disorder

Definition:
Entropy (S) is a measure of disorder or randomness in a
system. In thermodynamics, we analyze entropy changes in
three different parts:
Entropy Changes in a Process:
1. Entropy of the System (ΔSsys):

Measures the disorder within the system.

Example: When ice melts, its entropy increases.

2. Entropy of the Surroundings (ΔSsurr):

Measures the entropy change in the surroundings due to energy exchange.

Example: Ice melting absorbs heat, reducing the surroundings’ entropy.

3. Entropy of the Universe (ΔSuniv):

Formula: ΔSuniv = ΔSsys + ΔSsurr

 Rules:

If ΔSuniv > 0, the process is spontaneous.

If ΔSuniv < 0, the process is non-spontaneous.

If ΔSuniv = 0, the system is at equilibrium.

Example:
Ice Melting at Room Temperature

ΔSsys > 0: Ice becomes liquid (more disorder).

ΔSsurr < 0: Heat is absorbed, decreasing the surroundings’ entropy.

ΔSuniv > 0: The total entropy increases, so the process is spontaneous.

 Examples of Entropy Changes:

1. Ice Melting at Room Temperature

ΔS increases because the solid ice turns into liquid water, increasing disorder.

2. Water Freezing in a Freezer

ΔS decreases because liquid water turns into solid ice, reducing molecular movement.

3. Expansion of a Gas in a Vacuum

ΔS increases because gas molecules spread out, increasing randomness.

Entropy Change and Spontaneity:
Examples of spontaneous reactions or processes (ASumiv > 0):

Endothermic phase changes (fusion, evaporation, sublimation) above

melting/boiling/sublimation temperature

Exothermic phase changes (freezing, condensation, deposition) below

freezing/condensation/deposition temperature

Dissolution of a solute in a solvent

Neutralization (acid + base)

Evolution of gaseous products

Conclusion:

Spontaneous reactions occur naturally without external energy.

Non-spontaneous reactions require an energy input.

Entropy helps determine whether a reaction will be spontaneous.

If total entropy (ΔSuniv) increases, the process is spontaneous!

 Lesson 2: Explain the second law of
thermodynamics and its significance
 DEVELOPMENT OF THE SECOND LAW
OF THERMODYNAMICS
Nicolas Léonard Sadi Carnot, the "father of thermodynamics," pioneered the Second Law of
Thermodynamics. He originally described it using caloric theory, realizing that some heat is always
lost in a cycle. This disproved thermodynamic reversibility, proving that all work-involving systems
are irreversible.

Rudolf Clausius, a German physicist, formulated the Clausius statement: heat cannot spontaneously
flow from a colder to a hotter material.

William Thompson, also know as Lord Kelvin's statement says that heat cannot be completely
converted into work in a cyclic process, meaning some energy is always lost.

Constantin Carathéodory stated that some states cannot be reached through adiabatic changes,
offering a mathematical view of the Second Law of Thermodynamics.
 SIGNIFICANCE OF THE SECOND LAW:

Explains Irreversibility: It shows why some processes (like mixing

liquids or burning fuel) are irreversible in nature.

Limits Efficiency: It sets the maximum efficiency for machines and

engines, influencing engineering and energy production.

Governs Natural Processes: It explains phenomena such as why ice

melts, why living organisms require energy input, and why stars
eventually burn out.

Supports the Concept of Time: The increase of entropy provides a

"direction" for time, meaning the universe moves from order to
disorder.
 Lesson 3: Use Gibbs' free energy to
determine the direction of a reaction
 Gibbs Free Energy, G
another thermodynamic property that is used to predict whether the
reaction or process will be spontaneous or non-spontaneous.
Gibbs free energy is defined as:
G = H-TS

where ; H= is enthalphy
T= is temperature ( in Kelvin K ), and
S= is the entropy

The change in free energy ( ∆G) of a system for a constant-temperature

process is
∆G = ∆H-T∆S
 Understanding the Components
of ΔG

Enthalpy (ΔH): The heat content of a system. A negative ΔH indicates

an exothermic reaction (heat is released). A positive ΔH indicates an
endothermic reaction (heat is absorbed).Unit: kJ/mol.

Entropy (ΔS): A measure of disorder or randomness in a system. A

positive ΔS indicates an increase in disorder (more randomness). A
negative ΔS indicates a decrease in disorder (less randomness).Unit:
J/mol·K.

Temperature (T): Always expressed in Kelvin (K). Temperature affects

the spontaneity of a reaction, especially when entropy changes are
significant.(VALUE OF KELVIN IS 273.15)Unit: K
 Gibbs Free Energy Change

Conditions for spontaneity and equilibrium at constant

temperature and pressure in terms of ∆G:

∆G<0 Reaction is spontaneous in forward direction

∆G>0 Reaction is spontaneous in backward direction
∆G=0 Reaction is spontaneous in both forward and
backward directions
 Examples

Problem 1: Calculate ΔG for the reaction N₂(g) + 3H₂(g) → 2NH₃(g)

at 298 K, given that ΔH = -92.2 kJ/mol and ΔS = -198.7 J/mol·K.

Problem 2: Calculate ΔG for the reaction 2SO₂(g) + O₂(g) →

2SO₃(g) at 298 K. given that ΔH = -196 kJ/mol and ΔS = -188
J/mol·K

Problem 3: Determine the Gibbs free energy change (ΔG) for this
reaction at 298 K, given the following standard enthalpies of
formation ( ΔH°f ) and standard entropies (S °) .
 Examples
Reaction:
Standard enthalpies of formation ( ΔH°f )

Standard entropy ( ΔS° )

 Examples
Reaction:
Solution #3.
Solution #3.
Solution #3.
Gibbs Free Energy Change
Energy of Formation

The Gibbs free energy of formation (∆fG) is the

change in Gibbs free energy accompanying the
formation of 1 mole of a substance from
elements in their standard states.

At 1 atm and 25°C, this quantity is called the

standard Gibbs free energy of formation (∆fG°).
 Gibbs Free Energy Change
Energy of Reaction

The Gibbs free energy of reaction (∆rG) is the

change in Gibbs free energy accompanying a
chemical reaction.

At 1 atm and 25°C, this quantity is called the

standard Gibbs free energy of reaction (∆rG°).
 Calculating Gibbs Free Energy of Reaction

Two ways of evaluating ∆rG°:

1. Using ∆rH° and ∆rS°;

2. Using ∆rG° of reactants and products.

Calculating Gibbs Free Energy of Reaction
From Gibbs Free Energy of Formation
 Calculating Gibbs Free Energy of
Reaction

Example 1
 Calculating Gibbs Free Energy of Reaction
Solution ex. 1
 Calculating Gibbs Free Energy of
Reaction

Example 2
 Calculating Gibbs Free Energy of Reaction
Solution ex. 2
 Gibbs Free Energy and
Spontaneity

Example 3
Determine the direction of spontaneity of the
reactions in Examples 1 and 2.
 Gibbs Free Energy and Spontaneity
Solution ex. 3
Thank you!