SECOND & THIRD LAW
OF THERMODYNAMICS
Prepared by: Emelyn E. Gimotea
T-II NOHS SHS
Preparation:
Prayer
Checking of Attendance / Energizer
Rules and Regulations (Reminders)
What is chemical
kinetics?
RECAPITULATION
How does collision theory
affect rate of reactions?
Learning Competencies:
• Predict the spontaneity of a process based on entropy.
(STEM_GC11CTIVa-b-140 )
• Determine whether entropy increases or decreases if the
following are changed: temperature, phase, number of
particle. (STEM_GC11CTIVa-b-140 )
• Explain the second law of thermodynamics and its
significances. (STEM_GC11CTIVa-b-142)
• Use Gibb’s free energy to determine the direction of a
reaction. (STEM_GC11CTIVa-b-143)
Objectives:
the concept of entropy (ΔS) and Gibb’s free
Describe
energy(ΔG)
Predict the spontaneity of the reaction based on ΔS and ΔG.
the use of second and third law of
Appreciate thermodynamics in predicting the spontaneity
and direction of a chemical reaction.
Concept Map:
Write something that comes to your mind
when you hear the word thermodynamics.
Motivation:
THERMODYNAMICS
ACTIVITY 1: How is my coffee?
Write your comments in a paragraph
form based on the guide questions
below:
1. Is the coffee hot or cold?
2. What will happen to the
temperature of the coffee after
sometime?
3. Is the process spontaneous?
Consider the hot coffee placed
on top of the table.
We can observe that the hot coffee after some
time changes its temperature and becomes
cold. This occurrence has something to do with
thermodynamics.
Analysis:
Chemical thermodynamics is a branch of science that
studies the relationships between heat, temperature,
energy, and work in chemical systems. It focuses on
understanding the behavior of energy in chemical
reactions, including changes in energy levels, entropy,
and the ability of a system to perform work.
ABSTRACTION
Introduction to Spontaneity
Spontaneous process
• occurs without the addition of
external energy
• the process or action may take
place quickly or slowly as long
as it occurs and it is not
directly related to rate
Examples:
Heat transfer (activity 1) Corrosion of iron nails Melting of Ice
ENTROPY AND THE SECOND
LAW OF THERMODYNAMICS
What is entropy?
• defined as the measure of a system's thermal energy
per unit temperature that is unavailable for doing useful
work
• thesecond law of thermodynamics describes the
entropy (ΔS), the unit is in terms of J/K or J/mol●K for
1 mol of a substance
•a measure of the molecular disorder, or randomness of
a system
• the system favors disorder than order
Therefore: Ssolid < Sliquid <<Sgas
∆S = Sf – Si
If the change results in an
increase in randomness, or
disorder, then Sf > Si or ∆ S > 0.
Activity 2: Try this….
Predict whether the entropy change is greater than or less than
zero for each of the
following processes:
(a) freezing ethanol
(b) evaporating a beaker of liquid bromine at room temperature
(c) dissolving sucrose in water
(d) cooling nitrogen gas from 80°C to 20°C.
Second Law of Thermodynamics
The entropy of the universe increases in a spontaneous process
and remains unchanged in an equilibrium process.
For spontaneous process: ∆Suniverse = ∆ S system + ∆ S surrounding > 0
For equilibrium process : ∆Suniverse = ∆ S system + ∆ S surrounding = 0
Entropy Change in the System
aA + bB cC + dD
∆ S0rxn = [ cS0 (C) + dS0 (D) ] - [ aS0 (A) + bS0 (B) ]
For general equation: ∆ S0rxn = σ 𝒏S0 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 - σ mS0 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
Example:
Calculate the standard entropy changes for the following reactions at 25°C:
1. CaCO3(s) CaO(s) + CO2(g)
Given: S0 CaCO3 = 92.9 J/K.mol S0 CaO = 39.8 J/K.mol
S0 CO2 = 213.6 J/K.mol
2. N2(g) + 3H2(g) 2NH3(g)
Given: S0 N2 = 192 J/K.mol S0 NH3 = 193 J/K.mol
S0 H2 = 131 J/K.mol
1.
2.
General Rule:
• If a reaction produces more gas molecules than it
consumes ∆ S0 is positive.
• If the total number of gas molecules diminishes ∆ S0
is negative.
• If there is no net change in the total number of gas
molecules, then ∆ S0 may be positive or negative, but
will be relatively small numerically.
Activity 3:
Predict whether the entropy change of the system in
each of the following reactions is positive or negative.
(a) 2H2(g) + O2(g) 2H2O(l)
(b) NH4Cl(s) NH3(g) + HCl(g)
(c) H2(g) + Br2(g) 2HBr(g)
ENTROPY CHANGES IN THE SURROUNDINGS
• When an exothermic process takes place in the system, the heat
transferred to the surroundings enhances motion of the molecules in the
surroundings thus an increase in disorder at the molecular level, and the
entropy of the surroundings increases.
• An endothermic process in the system absorbs heat from the surroundings
and so decreases the entropy of the surroundings because molecular
motion decreases (Figure 18.4).
• For constant pressure processes the heat change is equal to the enthalpy change
of the system, ∆Hsys. Therefore, the change in entropy of the surroundings, ∆ Ssurr,
is proportional to ∆Hsys:
ACTIVITY 4:
ENTROPY IN REAL LIFE SETTING
What is climate change?
How does it affect life including those in
Guide the indigenous communities?
Questions: How do you relate climate change with
the second law of thermodynamics?
Suggest ways to help reduce the impact
of climate change in our society.
THIRD LAW OF
THERMODYNAMICS
• the entropy of a perfect crystalline substance is zero at the
absolute zero of temperature
• as the temperature increases, the freedom of motion also
increases
• thus, the entropy of any substance at a temperature above 0 K is
greater than zero
“The important point about the third law of thermodynamics is
that it allows us to determine the absolute entropies of
substances. Starting with the knowledge that the entropy of a
pure crystalline substance is zero at 0 K, we can measure the
increase in entropy of the substance when it is heated to, say,
298 K.”
∆S = Sf – Si ∆S = Sf
GIBBS FREE
ENERGY
• was developed in the 1870’s by Josiah Willard Gibbs
• originally termed this energy as the “available energy” in a system
• combines the first and second law of thermodynamics, enthalpy
and entropy into a single value
• the change in free energy, ΔG, is equal to the sum of the enthalpy
plus the product of the temperature and entropy of the system
• ΔG can predict the direction of the chemical reaction under two
conditions; a.) constant temperature and b.) constant pressure.
• If ΔG is positive, then the reaction is nonspontaneous (i.e., the input
of external energy is necessary for the reaction to occur)
• if
it is negative, then it is spontaneous (occurs without external
energy input)
“Since the changes of entropy of chemical
reaction are not measured readily, thus,
entropy is not typically used as a criterion. To
obviate this difficulty, we can use ΔG. The sign
of ΔG indicates the direction of a chemical
reaction and determine if a reaction is
spontaneous or not.”
Below are the possible values of Gibbs free energy:
ΔG < 0: (negative value) reaction is spontaneous in the direction
written or forward reaction (i.e., the reaction is exergonic)
ΔG = 0: the system is at equilibrium and there is no net change
either in forward or reverse direction.
ΔG > 0: (positive value) reaction is not spontaneous, and the
process proceeds spontaneously in the reverse direction. To drive
such a reaction, we need to have input of free energy (i.e., the
reaction is endergonic).
Example:
Calculate the standard free-energy changes for the
following reactions at 25°C.
Application:
Classify the following as spontaneous or non-
spontaneous.
1. Freezing of water at room temperature.
2. Breakdown of liquid water into hydrogen gas and
oxygen gas at room temperature.
3. Evaporation of liquid water at room temperature.
4. Rolling a ball downhill.
Practical Applications of Concepts and Skills in Daily Living:
Collage Making (Group Activity)
Identify at least 5 occurrences in the surroundings that
obey the 2nd law of thermodynamics. Create a collage
using those phenomena.
Generalization:
• The laws of thermodynamics provide a framework for understanding
the transfer of energy and the direction of chemical reactions.
• They play a crucial role in fields such as chemical engineering,
materials science, and biochemistry.
• The second law of thermodynamics helps us understand the
underlying processes and energy dynamics involved in climate
change and global warming affecting everyone (including the
indigenous people and even persons with disabilities). These
occurrences can be viewed as a consequence of violating the
principles of equilibrium, leading to a more disordered state in the
global climate system.
Evaluation:
