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General Chemistry 2
Quarter 4 – Module 1
Entropy and Gibbs’ Free Energy

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 Module
1 Entropy and Gibbs’ Free Energy
What I Need to Know
This module was designed and written with you in mind. It is
here to help you master the concepts behind Entropy and Free energy.
The scope of this module permits it to be used in many different learning
situations. The language used recognizes the diverse vocabulary level of students.
The lessons are arranged to follow the standard sequence of the course. But the
order in which you read them can be changed to correspond with the textbook you
are now using.

After going through this module, you are expected to:

1. Predict the spontaneity of a process based on entropy
(STEM_GC11CTIVa-b-140);
2. Explain the 2nd Law of Thermodynamics and its significance
(STEM_GC11CTIVa-b-142);
3. Use Gibbs’ free energy to determine the direction of a reaction
(STEM_GC11CTIVa-b-143).

Have you ever wondered why it is easy to make a mess of your room than to
keep it neat and clean? You may think that not cleaning your room has been the
culprit all along, but it may have been more than that. Entropy and the 2 nd Law of
Thermodynamics will tell you that keeping things disordered is the natural law of
the universe.

What’s New
Activity 2: Spontaneous Processes all Around Us
This activity will help you realize that spontaneous changes are widespread
in our daily lives. Identify if the changes or situations indicated happen naturally without
human intervention. Write Spontaneous if it happens naturally or Non-
spontaneous if not.
1. Souring of milk
2. A ball rolling from the top of Rotunda Hills
3. Spoiling of the left-over rice in your lunch box
4. Rusting of nail
5. Crumpled papers inside your bag
6. Spilling of water from your cup
7. An iPhone with a broken screen
8. Melting of ice in your winter melon flavored milk tea
9. A cut of star-shaped colored paper for your project
10. Denting of a metal due to applied force
11. A hot drink turning cold
12. Water flowing downhill
 13. Carbon atoms turning to a diamond at high pressure
14. A water fetched from a nearby well
15. A paper plane made from scratch papers.

What is It
SPONTANEOUS PROCESSES and ENTROPY

From the activity you have answered, you now have a gist of what a
spontaneous process is! Spontaneous processes are the physical or chemical
changes that occur by themselves, without needing constant help from external energy, and will
continue until an equilibrium state is reached. Please take note that the word
spontaneous does not mean instantaneous nor does it tell anything about how long
the process occurs; it means that the process will take place by itself, given enough
time. The common burning of woods is a perfect example of a spontaneous and fast
reaction; once started, we can guarantee that it will proceed by itself. Many processes
are spontaneous yet slow – aging and ripening are excellent examples.

Combustion of methane (Chemical)

CH4 + 2O2  CO2 + 2H2O ΔH°= - 890.4 kJ/mol
(Exothermic)

Solid to liquid phase transition of water

(Physical)
H2O (s)  H2O (l) ΔH°= 6.01kJ/mol
(Endothermic)

Note: The  sign in a chemical equation signifies a spontaneousreaction

and hence no input of energy is needed.

Figure 1. Examples of spontaneous processes

From the examples given in Figure 1, both endothermic and exothermic

reactions can be spontaneous, meaning that the change in energy (ΔH) does not tell
us if the reaction will occur spontaneously. Even physical and chemical changes can
be spontaneous, so how will we predict if the reaction can happen spontaneously?
The answer lies with another thermodynamic quantity – Entropy.

Entropy (S), with the SI unit of joules per Kelvin (J/K), is a thermodynamic
quantity that is a measure of how spread out or dispersed a system’s energy is, among the
different possible ways that a system can contain energy. It is the measure of
disorder or randomness of a reaction. We will use the word entropy in exchange for
the words disorder and randomness in this module. The melting of ice from solid to
liquid and the vaporization of water from liquid to vapor are common examples that
show an increase of entropy in the system. These processes are spontaneous and do
not need continuous output of energy for it to occur. We can see how spontaneous
processes and entropy are related from these two examples.
 Most process leads to entropy change, given below
are processes that leads to a higher disorder
(increase in entropy):

Process Order  Disorder

Melting Solid Liquid
Vaporization Liquid Vapor

Note: ENTROPY = measure of molecular

DISORDER or RANDOMNESS
Figure 2. Example of physical processes that leads to higher entropy

Some factors affect whether an entropy of a reaction increases or decreases, namely:

a. temperature, b. phase, c. number of particles, d. volume or pressure, and e. size.
Table 1 below summarizes how these factors affect entropy change.

FACTORS How Entropy Changes

Temperature Higher T  Greater ∆S
Phase Solid < liquid <<< gas
Number of
More particles  Greater ∆S
Paticles
Volume/Pressure Higher V (Lower P)  Greater ∆S
Size Larger  Greater ∆S

Table 1. How the following factors affect Entropy

THE 2nd LAW OF THERMODYNAMICS

Disorder and randomness are a big deal in Chemistry and has great
importance that our 2nd Law of Thermodynamics is all about entropy. The law states
that: “The entropy of the universe increases in a spontaneous process and remains unchanged in
an equilibrium process.” Entropy is also a state function like enthalpy, which means it
does not depend on the system’s path to reach its current state. We can calculate the
change in entropy (∆S) that occurs during the reaction exactly like we can, for the
change in enthalpy (∆H).

Processes Change in Entropy

Spontaneous Entropy increases
Equilibrium Entropy remains unchanged

Table 2. What does the 2nd Law of Thermodynamics mean?

CALCULATING THE STANDARD ENTROPY OF THE REACTION ∆S°rxn

Suppose that the system is represented by the following reaction: aA

+ bB  cC + dD

As in the case for the enthalpy of a reaction, the standard entropy of reaction
(ΔS°rxn) is given by the difference in standard entropies between the products and the
reactants.

ΔS° rxn = ΣnS° (products) − ΣmS° (reactants) (where m and n are the stoichiometric coefficients in the reaction)
ΔS° rxn = [c S°(C) + d S°(D)] ‒ [a S°(A) + b S°(B)]

EXAMPLE #1
To determine the ΔS° of the reaction, we must first know the standard entropy
values (S°) from the thermodynamic values table available online or even attached in
your chemistry books. For our modules, the S° values are given below the reaction.
Here are the steps to guide you in calculating the ΔS° of the reaction:

1. Before setting up the mathematical equation, make sure to balance the

chemical equation first to get the stoichiometric coefficients (a, b, c, and d)
needed for solving the entropy.
2. Write the complete mathematical equation given above to guide you on what
values to plug. Remember the keywords “products minus reactants” always.
3. Plug in the values and do not forget the correct coefficients from the balanced
equation. In the example given below, a=2, b=1, c=1, and d=2. Refer to the
color scheme of each values to know where the values are taken.
4. After ensuring that all plug-in values are correct, do the math to find ΔS°.
Figure 3 shows how to do a comprehensive calculation of your work. Do not
forget to write the units of the entropy after the final answer.

(Unbalanced) PbO(s) +
(Balanced) 2PbO(s) +

S° value is in J/mol∙K

ΔS° = Σn S°(products) – Σm S°(reactants)

ΔS° = [c S°(C) + d S°(D)] ‒ [a S°(A) + b S°(B)]
ΔS° = [213.6 + 2(64.89)] – [ 2(69.54) + 5.7]

ΔS° = 343.38 – 144.78

Note: Only do rounding off in the final answer.

Figure 3. Sample calculation for Example 1
EXAMPLE #2
For this example, the reaction is already balanced, and the standard entropy
(S°) values are given. The same steps from example 1 but we only have 1 product
which means that only [c S°(C)] will be on the product side equation.

(Balanced) H2SO4(l)

S° values is in J/mol∙K

ΔS° = Σn S°(products) – Σm S°(reactants)

ΔS° = [c S°(C)] ‒ [a S°(A) + b S°(B)]
ΔS° = [156.9] – [ 256.2 + 69.9]

Figure 3. Sample calculation for Example 2

When we look at the two values from Example 1 and Example 2, we have 198.6
J/mol∙K and -169.2 J/mol∙K, respectively. What does a negative ΔS° in example 2
means? What about the positive ΔS° in example 1? In Chemistry, there is a big
difference between a negative and a positive value. Knowing what your calculated
values means, will be a whole new world of understanding.

In Example 1, we have a calculated ΔS° value of 198.6 J/mol∙K. This positive

value is reasonable just looking at the balance chemical equation alone. We have
defined entropy (S) as the disorder of a system and looking at the reactant side, we
have solids, but our products have gas. We can therefore see why we have a positive
value of entropy since the system is increasing its disorder, from an ordered solid to
a relatively disordered gas. From our 2nd Law of Thermodynamics, a reaction that
increases its entropy (ΔS°>0) will most likely be spontaneous.

Example 1
(Balanced) 2PbO(s) + C(s)  CO2(g) + 2Pb(s) ΔS° = 198.6
J/mol∙K
Solid + Solid  Gas + Solid (Most likely
Spontaneous)

In Example 2, we have a calculated ΔS° value of -169.2 J/mol∙K. From what

we can see in the chemical equation, we have a gas as reactant and liquid as the
product, from a disordered gas to a relatively ordered liquid. The negative value of
entropy therefore means that we have a decrease in disorder for this chemical
reaction. From our 2nd Law of Thermodynamics, reactions that has ΔS° < 0, will not
occur spontaneously.

Example 2
(Balanced) SO3(g) + H2O(l)  H2SO4(l) ΔS° = -169.2 J/mol∙K
Gas + Liquid  Liquid
 Of course, there are exceptions to this general rule of observing from the
balanced chemical reactions alone and calculating the ΔS° values will be more
accurate in determining if the system increases or decreases its entropy.
GIBBS FREE ENERGY, G
Even though we know the entropy of a system and can predict whether it will
proceed spontaneously based on that alone, we are still merely predicting. It does not
guarantee a 100% that the process will occur spontaneously. Entropy (S) and
enthalpy (H) alone does not directly explain why reaction proceeds spontaneously but
Josiah Willard Gibbs found a way to explain it. This is called the Gibbs free energy,
G.

In thermodynamics, the Gibbs free energy (or standard free energy) is a

thermodynamic potential that can be used to calculate the maximum reversible work that
may be performed by a thermodynamic system at a constant temperature and pressure. In other
words, the free energy available within a system or process. These values are readily
available on the internet and most chemistry books and we can then calculate the
standard free energy of the reaction by the equation:

ΔG° = Σ nΔGf° (products) − Σ mΔGf° (reactants)

Remember that the ΔGf° is the standard free energy of formation at 25 °C and 1atm
for 1 mol of compound formed from its elements. The ΔGf° can be used to get the ΔG of a
reaction just like using ΔHf° to get ΔH for reaction. The standard free energy ΔG° of
element in the standard state is 0.

But for those values not listed, we can calculate the Gibbs free energy through
the equation:

ΔG° = ΔH° – TΔS° in standard Temperature and Pressure (STP)

Spontaneous, reaction will proceed to

∆G < 0
form products
∆G = 0 At Equilibrium, no change
Non-spontaneous, the reverse reaction
∆G > 0
will proceed forming the reactants

Table 3. How the reaction proceeds based on Gibbs’ free energy

What’s More
Activity 3: Predict It
Directions: Underline the compound with the higher entropy in each of the following
pairs, and justify your choice based on the factors affecting entropy in Table 1 at
What Is It:

3 mol of O2(g) or 2 mol of O3(g)
(EXAMPLE)
Based on what Factor?
Number of Particles. The two samples contain
same number of oxygen atoms but different numbers
of molecules. The greater number of molecules
dominates for 3 mol of O2 than for 2 mol of O3.

Phase. The two samples have the same number

Example: of molecules, but as we know from the table, we
1 mol of KBr(s) or 1 mol of KBr(aq) have greater entropy for compounds in aqueous
(aq) or in liquid state than in solid state.

1 mol of SO2(g) or 1 mol of SO3(g)

1 mol of CO2(s) or 1 mol of CO2(g)

1 mol of CF4(g) or 1 mol of CCl4(g)

Seawater at 2°C or at 23°C

1 mol of CaF2(s) or 1 mol of BaCl2(s)

INDEPENDENT PRACTICE

The old camera flash bulb used Mg metal sealed in a bulb with oxygen. The
reaction is:
Mg + ½ O2  MgO
S° (J/K mol): 32.7 205.0 26.9
ΔHf° (kJ/mol): 0 0 -601.2

A. Calculating ΔH° ΔH° = Σ nΔHf° (products) – Σ mΔHf° (reactants)

ΔH° = -601.2 - 0
ΔH° = -601.2 kJ/mol

B. Calculating ΔS° ΔS° = Σ nΔS° (products) – Σ mΔS° (reactants)

ΔS° = 26.9 – [32.7 + ½ (205.0)]
ΔS° = 26.9 – [32.7 + 102.5]
ΔS° = 26.9 – 135.2
ΔS° = -108.3 J/K mol = -0.1083 kJ/K mol

C. Calculating ΔG° ΔG° = ΔH° – TΔS°

kJ
 ΔG° =
−601.2
kJ/mol
– 298 K
(−0.108
3
mol) K
ΔG° = -601.2 kJ/mol + 32.2734 kJ/mol
ΔG° = -568.9266 kJ/mol
ΔG° ≈ -568.9 kJ/mol

The ΔGf°(MgO) ≈ -568.9 kJ/mol is highly negative which means that the
reaction will proceed to form the product (MgO) once initiated.

What I Have Learned

ENTROPY: LIFE IS CHAOS!

To let us understand entropy more, James Clear has a perfect example of how
to do it. Imagine that you take a box of puzzle pieces and dump them out on a table.
In theory, it is possible for the pieces to fall perfectly into place and create a completed
puzzle when you dump them out of the box. But that never happens in real life.
Why? Simply because the odds are overwhelmingly against it. Every piece
would have to fall in just the right spot to create a completed puzzle. There is only
one possible state where every piece is in order, but there are a nearly infinite number
of states where the pieces are in disorder. Mathematically speaking, an orderly
outcome is incredibly unlikely to happen at random. That is why our everyday life is
in chaos naturally because we cannot maintain applying energy to keep things in
order. Sometimes, you just have to let things occur.
But this disorder or Entropy is extremely important in Chemistry to calculate
the free energy to do work from Gibbs free energy equation ΔG° = ΔH° – TΔS°. Enthalpy
alone cannot determine if the reaction is spontaneous but coupled with entropy, one
can know how the reaction proceeds.

What I Can Do
Activity 4: Think about it!

Calculate the change in free energy (ΔG°) for the combustion of 1 mol of
propane at 25 °C and answer the follow up questions:

C3H8(g) + 5O2(g)  + 4H2O(l)

S° (J/K mol): 269.9 205.0 213.7 70
Hf° (kJ/mol): -105 0 -393.5 -285.8

What is the calculated value?

Is the reaction spontaneous?

Propane is one of the gas mixed in our Gasul (LPGs). Does your calculated
value of ΔG°, tells you anything about how easily flammable Gasul is? Will you be
careful the next time you are dealing with propane and other similar gases? Why or
why not?

Activity 5: Would you?

Would you invest in an engine that is said to burn air at room temperature?
You are told that a special chamber allows O2 to combine with N2 to form NO2
(nitrogen dioxide) using reaction. Calculate the ΔG° of the reaction from your
calculated ΔS° and ΔH°.

½ N2(g) + O2(g)  NO2(g)

S° (J/K mol): 191.5 205.0 240.5
ΔHf° (kJ/mol): 0 0 34

Calculating ΔH° ΔH° = Σ n ΔHf° (products) – Σ m ΔHf° (reactants)

ΔH° = -0
ΔH° = kJ/mol

Calculating ΔS° ΔS° = Σ nΔS° (products) – Σ mΔS° (reactants)

ΔS° = 240.5 – [205.0 + (191.5)]
ΔS° = 240.5 –
ΔS° = J/K mol = kJ/K mol

Calculating ΔG° ΔG° = ΔH° – TΔS°

ΔG° = kJ/mol – 298 K ( kJ/mol)
ΔG° = kJ/mol + kJ/mol
ΔG° = kJ/mol
ΔG° ≈ kJ/mol

Assessment
Direction. Write the letter of the best answer.

1. The second law of thermodynamics states that .

a. ΔH° = Σ n ΔHf° (products) – Σ m ΔHf° (reactants)
b. ΔS = qrev/T at constant temperature
c. for any spontaneous process, the entropy of the universe increases
d. the entropy of a pure crystalline substance at absolute zero is zero
 2. A reaction that is spontaneous .
a. is very rapid
b. will proceed without outside intervention
c. is also spontaneous in the reverse direction
d. has an equilibrium position that lies far to the left

3. The thermodynamic quantity that expresses the degree of disorder in a

system is .

a. enthalpy b. internal energy c. heat flow d. entropy

4. For a reaction to be spontaneous under standard conditions at all

temperatures, the signs of ΔH° and ΔS° must be and , respectively. (Hint:
Look at Gibbs’ Free Energy equation and determine what signs of ΔH° and ΔS° will
always make the calculated values of ΔG° negative)

a. +, + b. +,- c. -, + d. -, -

5. At equilibrium, what happens to a system’s entropy?

a. increases
b. decreases
c. remains the same
d. twice the ΔG°

6. A2(g) + B2(g) → 2AB(g) [ΔG°= -3.4 kJ/mol], what can we say about this
reaction?
a. Proceeds to form the products
b. Non-spontaneous reaction
c. No conclusion can be made
d. At equilibrium and entropy increases

7. Which of the following is NOT true?

a. When a process is spontaneous, entropy increases.
b. We can always predict how a reaction proceeds just by examining the
given chemical reaction.
c. Entropy is the disorder of a system.
d. Gases have the highest entropy relative to both liquid and solid state.

8. The entropy will usually increase when

I. a molecule is broken into two or more smaller molecules.
II. a reaction occurs resulting in an increase in the number of moles of gas.
III. a solid change to a liquid.
IV. a liquid change to a gas.
a. I, II, III only
b. II and III only
c. I only
d. I, II, III, and IV
 9. Which one of the following thermodynamic quantities is NOT a state
function?
a. Gibbs free energy
b. enthalpy
c. entropy
d. work
10. All of the following have a standard free energy value of zero at 25°C and
1.0 atm except:
a. N2(g) b. Fe(s) C) Ne(g) D) H(g)

11. Which statement is INCORRECT?

a. At constant pressure, H = E + PV
b. The thermodynamic symbol for entropy is S.
c. Gibbs free energy is a state function.
d. For an endothermic process, H is negative.

12. Chemical changes that occur by themselves without external force

a. Non-spontaneous processes
b. Enthalpy
c. Entropy
d. Spontaneous processes

13. From the equation ΔG° = Σ nΔGf° (products) − Σ mΔGf° (reactants), which
of the following statements is true?
a. The calculated value is not in standard temperature and pressure.
b. To get the standard free energy of a system, we must subtract the products
from the reactants.
c. Gf° is not readily available in the standard Thermodynamic Values
d. n and m are the stoichiometric coefficients seen in a balanced chemical
equation.
14. Which of the following factors does NOT affect entropy?
a. Temperature b. Phase c. Size d. Time

15. Which of the following statement is true?

a. Small compounds have higher entropy than bigger compounds
b. The higher the temperature, the greater the entropy.
c. Solid has the highest entropy relative to a compound’s phase
d. Pressure does not affect entropy
 References

Books:
Silberberg, M. (2012). Principles of General Chemistry. In Thermodynamics:
Entropy, Free Energy, and the Direction of Chemical Reactions (3rd ed. , Vol. 1,
pp. 653—660). McGraw-Hill Education.
https: / /www.mheducation.com / highered /product / principles-general-chemistrV-
silberberg / M9780073402697.html

Electronic Resources:
Clear, J. (2020, February 4). Entropy: Why Life Always Seems to Get More
Complicated. James Clear. https:/ /jamesclear. com/entropy