SECOND AND THIRD LAW OF

THERMODYNAMICS
for GENERAL CHEMISTRY 2/Grade 12
Quarter 4 / Week 1

1
NegOr_Q4_GenChem2-12_SLK Week1_v2 1
 FOREWORD

This self – learning kit will serve as a guide in understanding

the concepts of second and third law of thermodynamics. It will be
your aid as you learn to describe the energy and spontaneity of a
chemical reaction. Moreover, learning the thermodynamic
concepts have important implication in understanding the real
world.

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OBJECTIVES
At the end of the lesson, the learners are expected to:
K : describe the concept of entropy (ΔS) and Gibb’s free energy
(ΔG)
S : predict the spontaneity of the reaction based on ΔS and ΔG
A : appreciate the use of second and third law of
thermodynamics in predicting the spontaneity and direction
of a chemical reaction.

LEARNING COMPETENCIES
- Predict the spontaneity of process based on entropy
(STEM_GC11CTIVa-b-140)
- Explain the second law of thermodynamics and its significance
(STEM_GC11CTIVa-b-142)
- Use Gibb’s free energy to determine the direction of a reaction
(STEM_GC11CTIVa-b-143)

I. WHAT HAPPENED
Pre-activity/Pre-test

A. Directions: From the given word pool below, choose the word that
matches the given definition. Write your answer in your notebook.

- Specific heat - Adiabatic - Enthalpy

- Heat of reaction - Exothermic - Internal energy

____________ 1. It is the amount of heat per unit mass required to raise

the temperature by one degree Celsius.
____________ 2. It is the change in the enthalpy of a chemical
reaction that occurs at a constant pressure.
____________ 3. A type of system where no heat and matter
exchange.
____________ 4. A reactions or processes that release energy.
____________ 5. A thermodynamic system which is the energy
contained within it.

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II. WHAT I NEED TO KNOW
DISCUSSION:

Introduction to Spontaneity
In the previous module, you have learned that energy cannot
be created nor destroyed it can only be transferred from one form
to another. In addition, a discussion of energy as a form of heat and
work and in relation to internal energy. For a chemical reaction,
energy in the form of heat (measured in enthalpy) can either be
exothermic or endothermic process.
In this module we will be discussing spontaneity or spontaneous
process. A spontaneous process is one that 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. Example of a spontaneous process is heat transfer. Heat always
transfer from a hotter body to a colder body until such a thermal
equilibrium is reach between them. Another is corrosion of iron nails
exposed in the atmosphere. The iron in the nail spontaneously reacts
with oxygen in the air to form rust or iron oxide. Another is ice melting
at room temperature.

The Degree of Disorder or Entropy

The second 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. Entropy
is defined as the measure of a system's thermal energy per unit
temperature that is unavailable for doing useful work. Because work
is obtained from ordered molecular motion, the amount of entropy
is also a measure of the molecular disorder, or randomness of a
system. In simplest meaning, the system favors disorder than order.
Entropy is different than enthalpy, entropy is the degree of disorder
and enthalpy is the total heat at constant temperature (see Figure
1). The more disorder the system is the higher the entropy value.

4 NegOr_Q4_GenChem2-12_SLK Week1_v2
 H2O(s) H2O(l)
Figure 1. Enthalpy is the total heat content in a thermodynamic system whereas entropy
is the degree of disorder in the same.

Source: https://byjus.com/physics/differences-between-enthalpy-and-entropy/

As solid water is place left outside at room temperature, it

spontaneously converted into liquid water at room temperature. This
is also consistent with the experimental data of H2O(s) 41= J/mol●K
and H2O(l) = 69.95 J/mol●K (note that molecules in liquid is more
disordered than solid water and at room temperature so the process
is spontaneous). In figure 2, it shows the differences in the entropy of
solid, liquid and gas.

Figure 2. The comparison of the different values of entropy of water (not to scale) notice
that the ΔS(solid) < ΔS(liquid) < ΔS(gas).

Source: https://opentextbc.ca/introductorychemistry/chapter/measuring-entropy-and-
entropy-changes-2/

Another way to explain entropy, through statistical

thermodynamics, which was first proposed by Ludwig Boltzmann, an
Austrian physicist. He was the first person who used statistics in
calculating entropy using the equation;
5 NegOr_Q4_GenChem2-12_SLK Week1_v2
 S = k ln Ω
Where: S = entropy, k = Boltzmann Constant (1.38 x 10-23 J/K),
Ω is the microstates. Microstates is a term used to describe the
number of different possible arrangements of molecular position and
kinetic energy at a particular thermodynamic state. A process that
gives an increase in the number of microstates therefore increases
the entropy.
The Gibbs Free Energy.
The Gibbs free energy (denoted by ΔG) 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)
and if it is negative, then it is spontaneous (occurs without external
energy input). Gibbs energy was developed in the 1870’s by Josiah
Willard Gibbs. He originally termed this energy as the “available
energy” in a system. his quantity is the energy associated with a
chemical reaction that can be used to do work, and is the sum of its
enthalpy (H) and the product of the temperature and the entropy
(S) of the system. This quantity is defined as follows:
ΔG = ΔH – TΔS
where ΔG = Gibbs free energy, ΔH = enthalpy, T = temperature,
and ΔS is entropy. 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 (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 reserve direction. To
6 NegOr_Q4_GenChem2-12_SLK Week1_v2
 drive such a reaction, we need to have input of free energy
(i.e., the reaction is endergonic)
The factors affect ΔG of a reaction (assume ΔH and ΔS are
independent of temperature) is summarized below:

ΔH ΔS ΔG Example
+ + at low T = (+), at high T = (-) 2HgO(s) -> 2Hg(l) + O2(g)

+ - at all T = (+) 3O2 (g) -> 2O3(g)

- + at all T = (-) 2H2O2(l) -> 2H2O(l) + O2(g)

- - at low T = (+), at high T = (-) NH3(g) + HCl(g) -> NH4Cl(s)

Note:
• ΔG depends only on the difference in free energy of products and reactants (or
final state and initial state). ΔG is independent of the path of the transformation
and is unaffected by the mechanism of a reaction.
• ΔG cannot tell us anything about the rate of a reaction.

For The standard Gibbs energy change (the standard-state

free energy of reaction (ΔG°) is defined as the free energy of
reaction at standard state conditions) for a reaction in the form of
aA + bB → cC + dD, where A, B, C, and D are substances and a, b,
c, and d are stoichiometric ratio or coefficients; the formula is;
ΔrG° = cΔfG°(C)+ dΔfG°(D) − aΔfG°(A) − bΔfG°(B)
or summation of the total standard Gibbs free energy of the
products minus the total Gibbs free energy of the reactants;
ΔfG° = ∑ΔfG°(products)−∑ΔfG°(reactants)

III. WHAT I HAVE LEARNED

Evaluation/Post-test

A. True or False. Write the statement True if the statement is correct

and False if the statement is incorrect.

_________ 1. There is an increase in entropy if the state changes

from gas to solid.

7 NegOr_Q4_GenChem2-12_SLK Week1_v2
_________ 2. A gas from a container decreases the entropy as it
undergoes diffusion or effusion.
_________ 3. For a chemical reaction if the value of Gibbs free energy
if zero, it means that the reaction does not react.
_________ 4. According the second law of thermodynamics, if the
system is randomly arranged it has much higher entropy
than that of the properly arrange system.
_________ 5. Gibbs free energy can be used to determine how fast
the energy reaction is.

B. Multiple Choice. Choose the correct letter of the answer for the
following questions.

1. Comparing reaction a and b, below;

(a.) O2(g) + N2(g) → N2O(g) (b.) N2O(g) → O2(g) + N2(g).
Which has entropy value?
a. a b. b c. both are equal d. both have low value

2. Which of the following statements will always apply when a

reversible chemical reaction has attained equilibrium?
a. All reactants will convert to products.
b. The reaction proceeds alternately in the forward and
reverse directions.
c. The Gibbs free energy of the system reaches a minimum.
d. The forward reaction will dominate over the reverse
reaction.

3. Which of the following statements best describes the second law

of thermodynamics?
a. The internal energy of the universe is constant.
b. Energy can be neither created nor destroyed.
c. When an isolated system undergoes a spontaneous change,
the entropy of the system will increase.
d. At absolute zero, the entropy of a perfect crystal is zero.

4. The entropy of an isolated system can never ____?

a. increases b. decreases
c. zero d. none of the mentioned

8 NegOr_Q4_GenChem2-12_SLK Week1_v2
5. Which of the following can be considered as an application of
entropy principle?
a. transfer of heat through a finite temperature difference
b. mixing of two fluids
c. maximum temperature obtainable from two finite bodies
d. all of the mentioned

6. The entropy of an isolated system always ____ and becomes a ____

at the state of equilibrium.
a. decreases, minimum b. increases, maximum
c. increases, minimum d. decreases, maximum

7. A system with _________ enthalpy and _________ entropy will never

be spontaneous.
a. positive/positive b. negative/positive
c. positive/negative d. negative/negative

8. Of the following reactions, which of the following is only

spontaneous at high enough temperatures?
a. ∆H +, ∆S + b. ∆H +, ∆S – c. ∆H –, ∆S – d. ∆H –, ∆S +

9. Which of the following transformations most likely involves a

decrease in entropy?
a. 2NaHCO3 (s) → Na2CO3 (s) + H2O (g) + CO2 (g)
b. NH4NO3 (s) → NH4+(aq) + NO3-(aq)
c. N2(g) + 3 H2(g) → 2NH3(g)
d. CO2 (s) → CO2 (g)

10. Which of the phase changes illustrated here illustrates an increase

in the entropy of the substance?

a. b.

c. d.

9 NegOr_Q4_GenChem2-12_SLK Week1_v2
REFERENCES

Chang, R. (2008). General chemistry: the essential concepts. Boston:

McGraw-Hill,

Brown, T. L., LeMay Jr, H. E., Bursten, B. E., Murphy, C., Woodward, P.,
Langford, S., ... & George, A. (2013). Chemistry: The Central
Science. Pearson Higher Education AU.

Peter Atkins, P., & De Paula, J. (2014). Atkins’ Physical Chemistry. OUP
Oxford.

10 NegOr_Q4_GenChem2-12_SLK Week1_v2
 DIVISION OF NEGROS ORIENTAL
SENEN PRISCILLO P. PAULIN, CESO V
Schools Division Superintendent

JOELYZA M. ARCILLA EdD

OIC - Assistant Schools Division Superintendent

MARCELO K. PALISPIS EdD JD

OIC – Assistant Schools Division Superintendent

NILITA L. RAGAY EdD

OIC - Assistant Schools Division Superintendent/CID Chief

ROSELA R. ABIERA
Education Program Supervisor – (LRMDS)

ARNOLD R. JUNGCO
PSDS – Division Science Coordinator

MARICEL S. RASID
Librarian II (LRMDS)

ELMAR L. CABRERA
PDO II (LRMDS)

EUFRATES G. ANSOK JR.

Writer

CLIFFORD JAY G. ANSOK

GERALD T. UBAG
Lay-out Artists

ALPHA QA TEAM
AGUSTINA C. OMAGUING
NILO JAY A. BAYBAY

BETA QA TEAM
ZENAIDA A. ACADEMIA
ALLAN Z. ALBERTO
ROWENA R. DINOKOT
CHRISTINE A. GARSOLA
LESTER C. PABALINAS

11 NegOr_Q4_GenChem2-12_SLK Week1_v2
SYNOPSIS ANSWERS KEY

This Self-Learning Kit deals

with the discussion of the second
and third law of thermodynamics.
Understanding entropy and Gibbs
free energy is useful in predicting if
the reaction is spontaneous or
nonspontaneous at a given
temperature even without
performing an experiment. This is also
very useful in relating equilibrium and
electrochemical reactions.

Pre-activity/Pre-test
ABOUT THE AUTHOR A. 1. Specific heat
2. Heat of reaction
3. Adiabatic
EUFRATES G. ANSOK JR. is a licensed chemist and a
4. Exothermic
licensed teacher. He took his BS Chemistry at NORSU
5. Internal Energy
and BS Secondary Education – Crash Program at
Foundation University. In addition, he is master
Evaluation/Post-test
degree holder of Master of Chemistry at USC with
A. True or False
PhD units in Education1.major
False in Chemistry at UP-OU.
Currently teaching fulltime
2. Falseat Siaton Science High
School Senior High Department
3. False at the same time a
part-time faculty member
4. True of the Chemistry
. Department at NORSU. 5. False
B. Multiple Choice
1. b 2. c 3. c 4. b 5. d
6. b 7. c 8. a 9. c 10. d

12 NegOr_Q4_GenChem2-12_SLK Week1_v2