Chemical

Thermodynamics
Prepared by:
STEM-Science Faculty
 Learning Goals
Predict the spontaneity of a
01 process based on entropy;

Explain the second law of

02 thermodynamics and its significance;
and

Use Gibbs’ free energy to determine

03 the direction of a reaction.
 01
RECALL
Direction: Use the clues to
identify the following
questions with the correct
answers.
It is a process that proceeds on its
own, without any outside
intervention.
 The part of the universe
being studied or to which
attention is focused.
 Everything else in the
thermodynamic universe aside
from the system.
Quantitative measure of the
disorder or randomness of a
system.
Capacity to do work or transfer
heat.
 02
LESSON
What do you observe in the picture?
 SPONTANEOUS NON-SPONTANEOUS

A spontaneous process is a A nonspontaneous process, on

physical or chemical change the other hand, will not take
that occurs on its own place unless it is “driven” by
without any outside force. the continual input of energy
from an external source.

GUIDING PRINCIPLES
 Entropy (S)

• Helps to predict the

spontaneity of the process. The entropy change of a reaction is
calculated using the equation:
• It is the quantitative measure
of the disorder, or randomness, ΔS = Sproducts – Sreactants
in the substances involved in a
reaction.
Standard molar entropy
(S°)
• Is the entropy of one mole of
a substance at the standard
conditions (1 atm and 25°C).

Source: moodle.fct.unl.pt
 Standard entropy of reaction (ΔS°)
The standard entropy of reaction (ΔS°) is calculated
using the equation:
ΔS° = ∑S°products – ∑S°reactants

For a general reaction

aA + bB → cC + dD

where a, b c, and d are the coefficients of the substances

in the balanced equations
ΔSO = [cSO(C) + dSO(D)] - [aSO(A) + bSO(B)]
 Sample Problem 1
Calculate the ΔS° of the oxidation of
C2H6(g) to CO2(g) and H20(g). Solution:
The equation is given as:

C2H6(g) + 3 ½ O2(g) → 2 CO2(g) + 3 H20(g)

Substance S° (J/K.mol)
C2H6(g) 229.5
O2(g) 205.0
CO2(g) 213.9
H20(g) 180.0
 Sample Problem 2
Urea hydrolyzes slowly in the
presence of water to produce Solution:
ammonia and carbon dioxide.

CO(NH2)2(aq) + H20(l) → CO2(g) + 2NH3(g)

Substance S° (J/K.mol)
CO(NH2)2(aq) 173.8
H20(l) 69.96
CO2(g) 213.9
NH3(g) 192.5
 2ND LAW OF
THERMODYNAMICS
-explains the relationship
between entropy change and
spontaneity of a process.
2ND LAW OF THERMODYNAMICS
• The entropy of the
universe increases in
a spontaneous
process and remains
unchanged in an
equilibrium process.
This net entropy change of the process is represented
as ΔSuniv.
ΔSuniv = [ΔSsystem + ΔSsurroundings] > 0

The entropy change in the surroundings is directly proportional

to the enthalpy change of the reaction and inversely
proportional to the absolute temperature (K) of the surroundings

ΔSsurr = -ΔHrxn
T
 Sample Problem 1
Calculate the total entropy change
for the decomposition of hydrogen
peroxide (H2O2). Is the reaction Solution: (STEP 1)
spontaneous or not?

2H2O2(l) → 2H2O(l) + O2(g)

Substance ΔH°f S°
(kJ/mol) (J/K.mol)
H2O2(l) -187.8 109.6
H2O(l) -285.8 69.9
O2(g) 0 205.0
 Sample Problem 1
Calculate the total entropy change
for the decomposition of hydrogen
peroxide (H2O2). Is the reaction Solution: (STEP 2)
spontaneous or not?

2H2O2(l) → 2H2O(l) + O2(g)

Substance ΔH°f S°
(kJ/mol) (J/K.mol)
H2O2(l) -187.8 109.6
H2O(l) -285.8 69.9
O2(g) 0 205.0
 Sample Problem 1
Calculate the total entropy change
for the decomposition of hydrogen
peroxide (H2O2). Is the reaction Solution: (STEP 3)
spontaneous or not?

2H2O2(l) → 2H2O(l) + O2(g)

Substance ΔH°f S°
(kJ/mol) (J/K.mol)
H2O2(l) -187.8 109.6
H2O(l) -285.8 69.9
O2(g) 0 205.0
 Sample Problem 1
Calculate the total entropy change
for the decomposition of hydrogen
peroxide (H2O2). Is the reaction Solution: (STEP 4)
spontaneous or not?

2H2O2(l) → 2H2O(l) + O2(g)

Substance ΔH°f S°
(kJ/mol) (J/K.mol)
H2O2(l) -187.8 109.6
H2O(l) -285.8 69.9
O2(g) 0 205.0
 Sample Problem 2
Determine if the decomposition of
potassium chlorate (KClO3) is Solution: (STEP 1)
spontaneous or not.

2KClO3 (s) → 2KCl(s) + 3O2(g)

Substance ΔH°f S°
(kJ/mol) (J/K.mol)
KClO3 (s) -397.7 143.1
KCl(s) -436.7 82.6
O2(g) 0 205.0
 Sample Problem 2
Determine if the decomposition of
potassium chlorate (KClO3) is Solution: (STEP 2)
spontaneous or not.

2KClO3 (s) → 2KCl(s) + 3O2(g)

Substance ΔH°f S°
(kJ/mol) (J/K.mol)
KClO3 (s) -397.7 143.1
KCl(s) -436.7 82.6
O2(g) 0 205.0
 Sample Problem 2
Determine if the decomposition of
potassium chlorate (KClO3) is Solution: (STEP 3)
spontaneous or not.

2KClO3 (s) → 2KCl(s) + 3O2(g)

Substance ΔH°f S°
(kJ/mol) (J/K.mol)
KClO3 (s) -397.7 143.1
KCl(s) -436.7 82.6
O2(g) 0 205.0
 Sample Problem 2
Determine if the decomposition of
potassium chlorate (KClO3) is Solution: (STEP 4)
spontaneous or not.

2KClO3 (s) → 2KCl(s) + 3O2(g)

Substance ΔH°f S°
(kJ/mol) (J/K.mol)
KClO3 (s) -397.7 143.1
KCl(s) -436.7 82.6
O2(g) 0 205.0
Gibbs free energy (G).
-incorporates the concepts of
entropy and enthalpy.
Gibbs free energy (G)
The three thermodynamic
quantities are related by the
equation:
G = H – TS
The equation above can be modified
to give the Gibss-Helmholtz
equation for a reaction occurring at
constant temperature expressed as:
ΔG = ΔH - TΔS
Gibbs free energy (G)
Under standard conditions
of 1 atm and 25 °C, the
standard free energy
change (ΔG°) can be
obtained through:

ΔG° = ΔH° - TΔS°.

 The standard free energy change of a
reaction can also be calculated from the
standard free energy of formation (ΔG°f) of
the reactants and products:

ΔG° = ∑ΔG°f(products) – ∑ΔG°f(reactants).

 Important rules to predict spontaneity of a
reaction
If ΔG is negative, the reaction is spontaneous and will
proceed on its own.
If ΔG is positive, the reaction is nonspontaneous and will
require a sustained input of energy for it to occur.
If ΔG is zero, the reaction is at equilibrium.
 Sample Problem 1

Calculate the ΔG° for the

reaction: Solution:

C2H6(g) → C2H4(g) + H2(g)

Substance ΔG°f (kJ/mol)

C2H6(g) -32.89
C2H4(g) 68.10
H2(g) 0
 Sample Problem 2
Substance ΔH°f (kJ/mol) S° (J/K.mol)
Photosynthesis in plants CO2 (g) -393.5 213.6
converts carbon dioxide H2O(l) -285.8 69.9
and water into glucose and C6H12O6(s) -1273.3 209.2

oxygen according to the O2(g) 0 205.0

equation below. Calculate Solution: (STEP 1)

the ΔH°, ΔS° and ΔG°. Is the
reaction spontaneous at
standard conditions?
6CO2 (g) + 6H2O(l) → C6H12O6(s) + 6O2(g)
 Sample Problem 2
Substance ΔH°f (kJ/mol) S° (J/K.mol)
Photosynthesis in plants CO2 (g) -393.5 213.6
converts carbon dioxide H2O(l) -285.8 69.9
and water into glucose and C6H12O6(s) -1273.3 209.2

oxygen according to the O2(g) 0 205.0

equation below. Calculate Solution: (STEP 2)

the ΔH°, ΔS° and ΔG°. Is the
reaction spontaneous at
standard conditions?
6CO2 (g) + 6H2O(l) → C6H12O6(s) + 6O2(g)
 Sample Problem 2
Substance ΔH°f (kJ/mol) S° (J/K.mol)
Photosynthesis in plants CO2 (g) -393.5 213.6
converts carbon dioxide H2O(l) -285.8 69.9
and water into glucose and C6H12O6(s) -1273.3 209.2

oxygen according to the O2(g) 0 205.0

equation below. Calculate Solution: (STEP 3)

the ΔH°, ΔS° and ΔG°. Is the
reaction spontaneous at
standard conditions?
6CO2 (g) + 6H2O(l) → C6H12O6(s) + 6O2(g)
THANKS
Does anyone have any questions?
[email protected]
+91 620 421 838
yourcompany.com