CHEMICAL

THERMODYNAMICS

Prepared by
JOJI C. VICTORIANO, MChem
Master Teacher II
Roxas Stand-Alone Senior High School
 Recall
If ΔH < 0 : the process is exothermic
If ΔH > 0 : the process is endothermic

Note: The existence of energy balance is

not enough to answer questions
about a chemical reaction, such as,
to what extent will it proceed, or
whether the reaction would be
spontaneous or not.
Content Standard
The learners demonstrate an
understanding of spontaneous change,
entropy, and free energy.
Most Essential Learning
Competency

Predict the spontaneity of a process

based on entropy
(STEM_CG11CT-IVa-b-140)
Specific Objectives
Explain the spontaneity of a process
based on entropy
Determine whether entropy increases or
decreases if the following are changed:
temperature, phase, number of particles
Activity 1: COMPARE ME!

What can you say about the pictures?

How do you compare the pictures
Which one is more spontaneous? Why?
What can you
say about the
pictures?
How do you
compare the
pictures
Which one is
more
spontaneous?
Why?
 Spontaneous Processes
A spotaneous process is one that takes
place without energy from an external
source.
For a chemical reaction to be
spontaneous, it should proceed as
written (fom left to right), without an
input of energy.
 Spontaneous Processes
Examples:
➢ Biological processes
(movement of the heart,
expansion and
contraction of the lungs)
Examples:
➢Natural processes
(ripening of fruits,
dissolving of sugar in
water, waterfalls)
Example:

If a ball that is thrown

upwards, it will fall
spontaneously back to
the ground
Example:
Whenever two objects with different
temperatures are brought into contact,
heat is transferred from the hotter to the
cooler objects spontaneously
 Spontaneous Process
➢ Chemical processes can be
spontaneous as well.
➢ These are chemical reactions that
occur without any intervention in a
given set of condition
Examples of chemical
processes:
➢ spontaneous combustion,
wherein a flammable
substance burns by itself
even without direct
application of spark or
flame
➢ spontaneous reactions
such as burning of coal or
gasoline go to completion
even without further input
of energy once tiggered
➢ The spontaneous
reaction between
magnesium ribbon
and hydrochloric
acid
➢ rusting of iron to
iron (III) oxide when
exposed to
moisture

➢ conversion of
graphite to
diamond)
Nonspontaneous Processes
A nonspontaneous process cannot
proceed unless thereis a driving force or
outside help that acts on the system.
Nonspontaneous Processes
Examples:
➢ a rock cannot be brought uphill unless
someone pushes it
➢ conversion of water
to hydrogen gas and
oxygen gas, which
cannot take place
unless electric
current is applied on
the system

➢ crystallization of
salt out of water
Exercises: (5.1 Spontaneous Processes
on Page 131 – 132)
1. Which of the following processes are
spontaneous?
a. Cooling of a flat iron
b. Drop of ink dispersing in water
c. Straightening curly hair
d. Cold water warming to room temperature
e. Sorting names alphabetically
f. Black hair turning grey
g. Wind scattering leaves in a pile
h. Shoveling snow
i. Removing stain from a cloth
j. Sublimation of naphthalene at room
temperature
Note:
➢ Exothermic processes in general are
thermodynamically favored to occur
spontaneously due to the decrease in
enthalpy.
➢ Nearly all exothermic changes are
spontaneous.
➢ Endothermic reactions often become
spontaneous at high temperature such
as melting of ice and decomposition of
limestone.
 Entropy (S)
➢ It is a measure of randomness or
disorder of a system.
➢ The greater the degree of disorder, the
greater the entropy.
➢ The change in entropy, ΔS, depend
only on the entropies of the final and
initial states of the system.
ΔS = Sfinal – Sinitial
 ΔS = Sfinal – Sinitial
➢ A positive value of ΔS (ΔS > 0),
indicates that the final state if more
random or disordered than the initial
state.
➢ A negative value of ΔS (ΔS < 0),
indicates that the final state is more
ordered than the initial state.
➢ Spontaneity of a process is not solely
determined by the tendency of a system
to proceed to a state of lower energy. It
is also dependent on the state of
disorder.
➢ An increase in disorder or entropy is
thermodynamically favorable for a
reaction to proceed spontaneously.
➢ This simply implies that entropy change
is one factor that can account for the
spontaneity of endothermic processes.
 Factors Affecting Entropy
1. Change in Phase or Physical State
❖ In general, a liquid has a higher entropy than
the solid from which it is formed, while a gas
has a higher entropy than the liquid
counterpart.
 Factors Affecting Entropy
2. Change in Temperature
❖ Raising the temperature increases the
average kinetic energy of molecules.
❖ Greater translational, vibrational, and
rotational motion lead to a more
disorderly state.
❖ Increasing the temperature increases
the entropy of a system.
 Factors Affecting Entropy
3. Change in Concentration or Number
of Particles
❖ When there more particles present,
there will be more movement and
greater disorder.
❖ Generally, an increase in number of
particles, increases the entropy.
❖ Consider a chemical system
represented by the following equation,

A2B → 2A + B
Left : one particle is present
Right : three particles are produced

Since there are more particles in the

products as compared to the reactants,
there is a corresponding increase in
disorder.
Sample Exercise: (Page 118)
Predict whether the entropy increases or
decreases for each of the following
processes. Consider the degree of
disorder, from initial to final state or from
reactants to products.
1. Sublimation of dry ice :
CO2(s) → CO2(g)
Solution:
Entropy increases and ΔS>0, because
the solid is converted into a gas, the
particles are more scattered and are no
longer confined to a limited volume, thus
leading to greater disorder.
2. Na+1(aq) + Cl-1(aq) → NaCl(s)
Solution:
Entropy decreases and ΔS<0, since the
ions in the crystalline solid are confined in
a highly ordered position as compared to
the ions in aqueous solution which have
greater freedom of movement.
3. 2NH3(g) → N2(g) + 3H2(g)
Solution:
Entropy increases and ΔS>0, because
there are more particles in the products
as compared to the reactants, and more
particles leads to a more disorderly state.
4. Lowering the temperature of ethyl
alcohol from 30ºC to 10ºC.
Solution:
Decrease in entropy and ΔS<0, because
decreasing the temperature decreases
the kinetic energy of the molecules
causing them to move less rapidly
resulting in a less random final state or
less entropy.
5. Dissolving food color in water
Solution:
Increase in entropy and ΔS>0, since a
solution of two different molecules is more
random compared to only one kind of
molecule.
Answer 5.2 Entropy on Page 132
1. How does entropy change when the
following oocur? Predict whether there is
an increase or decrease in entropy?
Briefly state the reason for each answer.
a. ice cream melts
b. water vapor deposits as ice crystals on
a cold window pane
c. iodine crystals undergo sublimation
d. sugar dissolves in a cup of water
e. water is heated until lukewarm
f. 2SO2(g) + O2(g) → 2SO3(g)
g. NH3(g) + HCl(g) → NH4Cl(s)
h. MgCO3(s) → MgO(s) + CO2(g)
2. Choose the substance in each pair with
the higher entropy
a. 1 mole N2(l) or 1 mole N2(g)
b. 3 moles CH4(g) at 25ºC or
2 moles of CH4(g) at 25ºC
c. aqueous solution of CaCl2 or solid
CaCl2
d. 1 mole of HCl at standard conditions or
1 mole HCl at 60ºC and 0.8 atm
1. a. Increases, due to phase change
from solid to liquid
b. Decreases, due to phase change
from gas to solid
c. Increases, due to phase change
from solid to gas
d. Increase, since more particles of
different kinds are now present
e. Increases, due to increased kinetic
energy as temperature rises, hence,
more disorderly
f. Decreases, less particles are present
in the products as compared to the
reactants
g. Decreases, since both reactants
exist in gaseous phase which have
higher entropy as compared to the
product which is a solid
h. Increases, since there are more
particles in the product compared to
the reactant and one of the products
is gaseous while the reactant is solid
2. a. 1 mole of N2(g)
b. 3 moles of CH4(g) gas at 25ºC
c. aqueous solution of CaCl2
d. 1 mole of HCl at 60ºC and 0.8 atm
 SUM UP!
1. What characterize a spontaneous
process?
A spotaneous process is one that
takes place without energy from an
external source. It is characterized by
an increase in entropy.
 SUM UP!
2. How do entropy changes occur?
Increasing the temperature will
increase the entropy. Generally, an
increase in number of particles,
increases the entropy.
Change in phase or physical state
such as melting and vaporization can
lead to an increase in entropy of the
system.
 Correct Me If I,m Wrong!
Directions:
Write TRUE if the statement is correct but
if it is false, change the underlined word
or group of words to make the whole
statement true.
1. If heat flows into the surroundings, the
random motion of the molecules in the
surroundings decreases.
2. In a chemical reaction, the change is
positive if the heat product is lower than
the heat reactant.
3. The heat change is negative if the heat
product is greater than heat reactant.
4. Spontaneous process is reversible
reaction.
5. Entropy changes occur when gas
molecules inside the LPG tank escape
and spread out into room.
6. Heat flows from hotter objects to a
colder one is a spontaneous process.
7.Burning of fuel is an example of
exothermic reaction.
8. Coffee granules dissolve faster in hot
water than in cold water.
9. Melting of ice cream left on top of a
table is an example of exothermic
reaction.
10. For a chemical reaction to be
spontneous, it shoud proceed without an
input of energy.
Entropy Change Determination
Entropy change can be measured by a
calorimeter, the same instrument used
in determining enthalpy change.
The changed in entropy is related to the
heat transferred during the process.
The relationship between ΔS and the heat
transferred is similar to that of ΔH and heat
transferred under constant pressure.
Entropy Change Determination
For processes occurring at constant
temperature and pressure, the change in
entropy can be calculated using the
following equation,
ΔS = Qrev / T
where:
ΔS = change in entropy in J/K (it is
negative if heat is released by the
system and positive if heat is
absorbed by the system)
 ΔS = Qrev / T
Q = heat transferred at a particular
temperature, in J
T = temperature in Kelvin, K
➢ The equation applies only to processes
that are almost reversible.
➢Any process that can go back to its
original state due to a vey slight change
in conditions is reversible.
Sample Problem on Page 120
Calculate the entropy change, ΔSvap when
1 mole of water in liquid state is converted
to 1 mole steam at 1 atm pressure.
(ΔHvap = +40.7 kJ/mol)

Refer solution on Page 120

Answer 5.2 Entropy on Page 132
Number 3. a – c
Standard Molar Entropy or
Standard Entropy (S°)
➢ the entropy of one mole of a substance
at standard conditions, 25ºC and 1 atm
pressure

Note: The third law of thermodynamics

which states that a pure crystalline
solid has an entropy of zero at 0 K,
allows the determination of the
entropy of the substance without
reference to its constituent elements.
The entropy change can be calculated
using the equation,

ΔS = ∑yS°products - ∑zS°reactants
Sample Problem 1 (Page 121)
Calculate the entropy change when
graphite burns in sufficient supply of
oxygen as shown in the following
equation,
Cgraphite(s) + O2(g) → CO2(g)
S°of Cgraphite(s) = 5.7 J/mol-K
S°of O2(g) = 205 J/mol-K
S°of CO2(g) = 213.6 J/mol-K
Required: ΔS° of the reaction
Solution:
ΔS°= ∑yS°products - ∑zS°reactants
= [(1mol)(213.6 J/mol-K)] –
[(1mol)(5.7 J/mol-K) + (1 mol)(205 J/mol-K)]
= 213.6 J/K – 210.7 J/K
ΔS° = +2.97 J/K
Answer 5.2 Entropy on Page 133
Number 4. a & b
 Second Law of
Thermodynamics
It states that natural processes
proceed in the direction that
maintains or increases the total
entropy of the universe, and in any
spontaneous change, there is a net
increase in entropy
 The entropy change of the universe is the
sum of the changes in entropy of the
system and the surroundings.

ΔSuniverse = ΔSsystem + ΔSsurrounding

Under standard conditions, the entropy

change for the universe, ΔS°universe is
ΔS°universe = ΔS°system + ΔS°surrounding
ΔS°universe > 0 for spontaneous process
Sample Problem (Page 123)
1. Calculate the ΔS°universe for the prcess
of dissolving NaCl in water at 25ºC.
NaCl(s) → NaCl(aq)
S° NaCl(s) = 72.1 J/mol-K
S° NaCl(aq) = 115.5 J/mol-K
ΔHf° NaCl(s) = -411.1 kJ/mol
ΔHf° NaCl(aq) = -407.3 kJ/mol
T = 25ºC = 298 K
❖Refer the solution on Page 123
2. A 6.25-kg block of ice is placed on a
concrete floor which has a constant
temperature of 25.5°C. The ice
melts as it absorbs 2.09 x 10^6 J of
heat. What is the change in entropy
of the
a. ice
b. floor
c. universe
Given:
Tice = 0ºC (temperature at which the
ice begins to melt)
Tfloor = 25.5ºC
Q = 2.09 x 10^6 J
Find:
a. ΔSice
b. ΔSfloor
c. ΔSuniverse
Solution:
a. ΔSice = Q (positive since heat flows into it)
T
= 2.09 x 10^6 J
273 K
ΔSice = 7655.68 J/K
b. ΔSfloor = -Q (negative since heat flows from it)
T
= -2.09 x 10^6 J
298.5 K
ΔSfloor = -7001.68 J/K
c. ΔSuniverse = ΔSice + ΔSfloor
= 7655.68J/K + (-7001.68 J/K)
ΔSuniverse = +654 J/K (therefore the
entropy of the
universe has
increased)
Answer 5.3 The Second Law of
Thermodynamics on Page 133
Number 1. a – b
Number 2.
 Gibbs Free Energy and
Chemical Equilibrium
Gibbs Free Energy or Free Energy (G)
➢ It was named after William Gibbs.
➢ it is a portion of energy change in spontaneous
reactions that is available to do useful work.
➢ It is the maximum amount of work that can be
done by the system on its surroundings at
constant temperature and pressure.
➢ In a nonspontaneous process, it is a measure of
the minimum amount of work that must be done
on the system in order to drive the reaction.
Gibbs Free Energy or Free Energy (G)
➢It is defined mathematically as
G = H – TS
where: G = Gibbs free energy
H = Enthalpy
T = Kelvin temperature
S = Entropy
In the equation, G, H, and S all refer to
the system.
 Change in Free Energy (ΔG)
❖ For a process occurring at constant
temperature, the change in free energy
of the system is given by the expression
ΔG = ΔH – TΔS
❖ This equation is valid in all conditions.
❖ If both temperature and pressure are
constant, the relationship between the
sign of ΔG and spontaneity of a reaction
is as follows:
ΔG < 0, reaction is spontaneous in
the forward direction
ΔG > 0, nonspontaneous in the
forward direction, work must
be supplied to make it occur
ΔG = 0, reaction is at equilibrium
❖ If application is limited to standard
conditions, 25°C and 1 atm pressure, the
new equation will be in the form of:
ΔG°= ΔH°– TΔS°
❖ Standard state means that solid and
liquid substances are pure, gaseous
substance is at 1 atm pressure, and for
substances in solution, concentration is
normally 1 M.
❖ ΔG°can be calculated from the tabulated
values of ΔHf° and S° at 25ºC.
Sample Problem (Page 125)
A drying agent has the chemical composition
CaSO4. Calculate ΔG°at 25ºC for the
following reaction which has a ΔS°value of –
139.7 J/K.

CaSO4(s) → Ca+2(aq) + SO4 -2(aq) ΔH=-18.0kJ

Given:
ΔH° = –18.0 kJ
ΔS° = –139.7 J/K
Required:
ΔG° for the reaction
Solution:
ΔG°= ΔH°– TΔS°
= (–18.0 kJ) – (298 K)(–0.1397 kJ/K)
= –18.0 kJ + 41.6 kJ
ΔG° = +23.6 kJ
❖ Since ΔG° > 0 or positive, the reaction is not
spontaneous at 25ºC.
 The table shows the relationship between
temperature, ΔG°, and spontaneity.
ΔH ΔS ΔG = ΔH – TΔS Characteristics of Reaction

_ + Always – Spontaneous at all

temperatures

+ _ Always + Nonspontaneous at all

temperatures

+ + – at high T Spontaneous at high

temperature

+ + + at low T Nonspontaneous at low

temperatures

_ _ – at low T Spontaneous at low

temperature

_ _ + at high T Nonspontaneous at high

temperatures
Answer 5.4 Gibbs Free Energy and
Chemical Equilibrium on Page 134
Number 1. a – c
 Effect of Temperature on the
Spontaneity of Reactions

Sample Problem: (Page 126 – 127)

Calculate the standard free energy
change for the following reaction at 25ºC.
2HgO(s) → 2Hg(l) + O2(g)
Given:
From tabulated standard entropy values,
S°values at 25ºC are as follows:
S°Hg(l) = 76.0 J/mol-K
S°O2(g) = 205.0 J/mol-K
S°HgO(s) = 70.3 J/mol-K
From the tabulated standard enthalpy
values, ΔHºf of HgO(s) = -90.8 kJ
Required:
ΔG° for the reaction
Solution:
A. Calculate ΔS°at 25ºC using the formula
ΔS°= ∑yS°products - ∑zS°reactants

B. Calculate ΔH° at 25ºC using the formula

ΔH°= ∑yΔHºf products - ∑zΔHºf reactants

C. Calculate ΔG°at 25ºC using the formula

ΔG°= ΔH°– TΔS°
 Standard Free Energy of
Formation
Standard Free Energy of Formation
➢ the free energy change when one mole of
a compound is formed from the constituent
elements in their stable states at 1 atm
pressure
➢ Free energies of elements in their
standard states are also set to zero.
ΔG°= ∑yΔGºf products - ∑zΔGºf reactants
Sample Problem:
Calculate the ΔG°for the following
reaction at 25ºC, using the tabulated ΔGºf.
CaSO4(s) → Ca2+(aq) + SO4-2(aq)
Given:
ΔGºf CaSO4(s) = -1321.8 kJ/mol
ΔGºf Ca2+(aq) = -553.6 kJ/mol
ΔGºf SO4-2(s) = -744.5 kJ/mol
Required:
ΔG° for the reaction
Solution:
ΔG°= ∑yΔGºf products - ∑zΔGºf reactants
= [(1 mol)(-553.6 kJ/mol) +
(1mol)(-744.5 kJ/mol)] –
[(1mol)(-1321.8 kJ/mol)]
= -1298.1 kJ + 1321.8 kJ
ΔG° = +23.7 kJ
 Free Energy and Chemical
Equilibrium
For any chemical process, the relation between
the free energy change under standard
conditions, ΔG°, and the free energy under
nonstandard conditions, ΔG, is given by the
following equation,
ΔG = ΔG° + RT ln Q
where: R = gas constant
T = temperature in Kelvin
Q = the “reaction quotient” which
corresponds to the equilibrium
constant expression, K
For a chemical reaction represented by
the following equation,
aA + bB → cC + dD

Q = [C]^c [D]^d
[A]^a [B]^b

ΔG = ΔG° + RT ln K
At equilibrium, ΔG = 0, and substituting
this value, the result is,
0 = ΔG° + RT ln K
After rearranging, the next equation
clearly expresses the relationship
between the standard free energy change
and the equilibrium constant K.
ΔG° = - RT ln K
 ΔG° = - RT ln K
This equation readily shows that ΔG° is
negative when K is greater than 1. This
means that the more negative ΔG° is,
the larger is the value of K and, therefore,
the forward direction leading to the
formation of products is favored.
Conversely, if ΔG° is positive, the K is
less than 1.
Thank you!!!