LEARNING ACTIVITY SHEET

QUARTER: 4th/ SEMESTER: 2nd / WEEK: 1-2

Name: ________________________________________________ Score: _______

Grade & Section: _______________________ Subject: GENERAL CHEMISTRY 2
Name of Teacher: EDWARD HENRY M. CAOILE Date: _____________
I. Title: The Three Laws of Thermodynamics
II. Type of Activity: Concept notes with formative activities

LAS for summative assessment ( Written Work Performance Task)

III. MELC: Predict the spontaneity of a process based on entropy,

STEM_GC11CTIVa-b-140. Explain the second law of thermodynamics and its
significance, STEM_GC11CTIVa-b-142. Use Gibbs’ free energy to determine the
direction of a reaction, STEM_GC11CTIVa-b-143.

IV. Learning Objective/s:

• Identify spontaneous process.
• Predict the spontaneity of a process based on entropy and Gibbs free
energy.
• Calculate entropy change and Gibbs free energy change using
thermodynamic data.
V. Reference/s:

Print Material/s:
Chang, R. (2010). Chemistry Tenth Edition, pp: 801

Patalinghug, W. C., et al. (2016). Teaching Guide for Senior High School
General Chemistry 2, pp: 409-.

Online Resource/s:
Chemistry LibreTexts (2021). Entropy and Free Enregy. Retrieved from
https://chem.libretexts.org/Courses/University_of_Arkansas_Littl
e_Rock/Chem_1403%3A_General_Chemistry_2/Homework/18
%3A_Entropy_and_Free_Energy on May 05, 2021.
VI. Concept Notes

THE THREE LAWS OF THERMODYNAMICS

The first law of thermodynamics says that energy can be converted from one
form to another, but it cannot be created or destroyed. One measure of these changes
is the amount of heat given off or absorbed by a system during a constant-pressure
process, which we define as a change in enthalpy (ΔH).
In this lesson, we will discuss the second law of thermodynamics which explains
why chemical processes tend to favor one direction, and the third law which is an
extension of the second law. We will also give emphasis on the concepts of
spontaneous process, entropy, and Gibb’s free energy.

SPONTANEOUS PROCESS
A reaction that does occur under the given set of conditions is called a
spontaneous reaction. If a reaction does not occur under specified conditions, it is said
to be nonspontaneous. We observe spontaneous physical and chemical processes
every day, including many of the following examples:
• A waterfall runs downhill, but never up, spontaneously.
• A lump of sugar spontaneously dissolves in a cup of coffee, but dissolved sugar
does not spontaneously reappear in its original form.
• Water freezes spontaneously below 0°C, and ice melts spontaneously above
0°C (at 1 atm).
• Heat flows from a hotter object to a colder one, but the reverse never happens
spontaneously.
• The expansion of a gas into an evacuated bulb is a spontaneous process (see
Figure 1a). The reverse process, that is, the gathering of all the molecules into
one bulb, is not spontaneous (see Figure 1b).
• A piece of sodium metal reacts violently with water to form sodium hydroxide
and hydrogen gas. However, hydrogen gas does not react with sodium
hydroxide to form water and sodium.
• Iron exposed to water and oxygen forms rust, but rust does not spontaneously
change back to iron.

Figure 1. (a) A spontaneous process. After the valve is opened, the molecules distribute
evenly between the two bulbs. (b) A nonspontaneous process. After the valve is opened, the
molecules preferentially gather in one bulb.

These examples show that processes that occur spontaneously in one direction
cannot, under the same conditions, also take place spontaneously in the opposite
direction.
 Many exothermic reactions are spontaneous. An example is the combustion of
methane:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH° = – 890.4 kJ/mol

Another example is the acid-base neutralization reaction:

H+(aq) + OH–(aq) → H2O(l) ΔH° = – 56.2 kJ/mol

But not all spontaneous processes are exothermic reactions. Consider the following
examples:

Solid-to-liquid phase transition of water:

H2O(s) → H2O(l) ΔH° = 6.01 kJ/mol

Dissolution of ammonium nitrate in water:

NH4NO3(s) → NH4+(aq) + NO3–(aq) ΔH° = 25 kJ/mol

Decomposition of mercury (II) oxide is an endothermic reaction that is

nonspontaneous at room temperature, but it becomes spontaneous when the
temperature is raised:

2HgO(s) → 2Hg(l) + O2(g) ΔH° = 90.7 kJ/mol

Meaning, exothermicity favors the spontaneity of a reaction but does not

guarantee it. Just as it is possible for an endothermic reaction to be spontaneous, it is
possible for an exothermic reaction to be nonspontaneous. In other words, we cannot
decide whether a chemical reaction will occur spontaneously solely on the basis of
energy changes in the system. To make this kind of prediction we need another
thermodynamic quantity, which turns out to be entropy.
ENTROPY
We need entropy to predict the spontaneity of a process. Entropy (S) is a
thermodynamic quantity often described as a measure of how spread out or dispersed
the energy of a system. The greater the dispersal, the greater is the entropy. Most
processes are accompanied by a change in entropy.
A cup of hot water has a certain amount of entropy due to the dispersal of
energy among the various energy states of the water. If left standing on a table, the
water loses heat to the cooler surroundings. Consequently, there is an overall increase
in entropy because of the dispersal of energy over a great many energy states of the
air molecules.
As another example, consider the situation depicted in Figure 1. Before the
valve is opened, the system possesses a certain amount of entropy. Upon opening
the valve, the gas molecules now have access to the combined volume of both bulbs.
A larger volume for movement results in a narrowing of the gap between translational
energy levels of the molecules. Consequently, the entropy of the system increases
because closely spaced energy levels lead to a greater dispersal among the energy
levels.
 THE SECOND LAW OF THERMODYNAMICS
The Second Law of Thermodynamics deals with entropy and the spontaneity
of reactions. It tells whether a process or chemical reaction can occur. It states that
the entropy of the universe increases in a spontaneous process and remains
unchanged in an equilibrium process. Because the universe is made up of the system
and the surroundings, the entropy change in the universe (ΔSuniv) for any process is
the sum of the entropy changes in the system (ΔSsys) and in the surroundings (ΔSsurr).
Mathematically, we can express the second law of thermodynamics as follows:

For a spontaneous process: ΔSuniv = ΔSsys + ΔSsurr > 0

For an equilibrium process: ΔSuniv = ΔSsys + ΔSsurr = 0

For a spontaneous process, the second law says that ΔSuniv must be greater
than zero, but it does not place a restriction on either ΔSsys or ΔSsurr. Thus, it is possible
for either ΔSsys or ΔSsurr to be negative, as long as the sum of these two quantities is
greater than zero. For an equilibrium process, ΔSuniv is zero. In this case, ΔSsys and
ΔSsurr must be equal in magnitude, but opposite in sign. What if for some hypothetical
process we find that ΔSuniv is negative? What this means is that the process is not
spontaneous in the direction described. Rather, it is spontaneous in the opposite
direction.

Entropy Changes in the System

To calculate ΔSuniv, we need to know both ΔSsys and ΔSsurr. Let us focus first on
ΔSsys. Suppose that the system is represented by the following reaction:

aA + bB → cC + dD

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

ΔS°rxn = [cS°(C) + dS°(D)] - [aS°(A) + bS°(B)]

or, in general, using Σ to represent summation and m and n for the stoichiometric
coefficients in the reaction:
ΔS°rxn = ΣnS°(products) - ΣmS°(reactants)

The standard entropy values of a large number of compounds have been measured
in J/K · mol. To calculate ΔS°rxn or ΔS° (which is ΔSsys), we look up their values in
https://web.facebook.com/groups/290989511714323.

Example 1: Calculate ΔS° for the reaction: H2(g) + I2(s) → 2HI(g)

Solution: First, write the standard entropy below each formula. See to it that the
equation is balance.

H2(g) + I2(s) → 2HI(g)

130.6 116.7 206.3 (From the Thermodynamic Data Table, S°(J/K·mol)

Then use the equation for the standard entropy of reaction (ΔS°rxn)
 ΔS°rxn = ΣnS°(products) - ΣmS°(reactants)
ΔS°rxn = ΣnS°(products) − ΣmS°(reactants)
= [(2)So HI] – [(1)SoH2 + (1) SoI2]
= [(2) (206.3 J/K·mol)] – [(1) (130.6 J/K·mol) + (1) (116.7 J/K·mol)]
= +165.3 J/K·mol

Thus, the formation of 2 moles of gaseous Hl from 1 mole of gaseous H2

and 1 mole of gaseous l2 results in an increase in entropy equal to 165.3
J/K · mol.

Example 2: N2(g) + 3H2(g) → 2NH3(g)

192 131 193 (J/K·mol)

Expected Answer: -199 J/K·mol

Example 3: SO3(g) + H2O(l) → H2SO4(l)

256.2 69.9 156.9 (J/K·mol)

Expected Answer: -169.2 J/K·mol

General Rules for Predicting Entropy Change of the System

1. If the reaction produces more gas molecules than it consumes, ΔS° is
positive.
2. If the total number of gas molecules diminishes, ΔS° is negative.
3. If there is no net change in the total number of gas molecules, ΔS° may be
positive or negative, but will be relatively small numerically.

Examples:
1. N2(g, 10 atm) → N2(g, 1atm).
Answer: POSITIVE. Decrease in pressure of the system will increase
entropy.

2. 6CO2(g) + 6H2O(g) → C6H12O6(g) + 6O2(g)

Answer: NEGATIVE. Decrease in number of gas particles.

3. 2H2(g) + O2(g) → 2H2O(l)

Answer: NEGATIVE. Net deceases in number of molecules and gases
are converted to liquid.
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.
Consequently, the entropy of the surroundings increases. Conversely, an endothermic
process in the system absorbs heat from the surroundings and so decreases the
entropy of the surroundings because molecular motion decreases (see Figure 2).

Figure 2. (a) An exothermic process transfers heat from the system to the surroundings and
results in an increase in the entropy of the surroundings. (b) An endothermic process
absorbs heat from the surroundings and thereby decreases the entropy of the surroundings.

For constant-pressure processes, the heat change is equal to the enthalpy

change of the system(ΔHsys). Therefore, the change in entropy of the surroundings,
(ΔSsurr) is proportional to ΔHsys:

ΔSsurr α – ΔHsys

The minus sign is used because if the process is exothermic, ΔHsys is negative and
ΔSsurr is a positive quantity, indicating an increase in entropy. On the other hand, for
an endothermic process, ΔHsys is positive and the negative sign ensures that the
entropy of the surroundings decreases.

The change in entropy for a given amount of heat absorbed also depends on
the temperature. If the temperature of the surroundings is high, the molecules are
already quite energetic. Therefore, the absorption of heat from an exothermic process
in the system will have relatively little impact on molecular motion and the resulting
increase in entropy of the surroundings will be small. However, if the temperature of
the surroundings is low, then the addition of the same amount of heat will cause a
more drastic increase in molecular motion and hence a larger increase in entropy.

From the inverse relationship between ΔSsurr and temperature T (in kelvins),
that is, the higher the temperature, the smaller the ΔSsurr and vice versa. We can
rewrite the above relationship as
−ΔHsys
ΔSsurr =
T
 Let us now apply the procedure for calculating ΔSsys and ΔSsurr to the synthesis
of ammonia and ask whether the reaction is spontaneous at 25°C:
N2(g) + 3H2(g) → 2NH3(g) ΔH°rxn = -92.6 kJ/mol
From Example 2 we have ΔSsys = -199 J/K·mol, and ΔHsys = -92.6 kJ/mol, we obtain
92.6kJ
−(− mol )
ΔSsurr =
298 K
J
−(−92600mol)
ΔSsurr =
298 K
= 311 J/K·mol
The change in entropy of the universe is
ΔSuniv = ΔSsys + ΔSsur
= -199 J/K·mol + 311 J/K·mol
= 112 J/K·mol
Because ΔSuniv is positive, we predict that the reaction is spontaneous at 25°C. It is
important to keep in mind that just because a reaction is spontaneous does not mean
that it will occur at an observable rate. The synthesis of ammonia is, in fact, extremely
slow at room temperature. Thermodynamics can tell us whether a reaction will occur
spontaneously under specific conditions, but it does not say how fast it will occur.
Reaction rates are the subject of chemical kinetics.
THE THIRD LAW OF THERMODYNAMICS AND ABSOLUTE ENTROPY
According to the 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 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 enables us
to determine the absolute entropies of substances. Starting with the knowledge that
the entropy of a pure crystalline substance is zero at absolute zero, we can measure
the increase in entropy of the substance when it is heated from 0 K to, say, 298 K. The
change in entropy, ΔS, is given by

ΔS = Sf - Si
ΔS = Sf

because Si is zero. The entropy of the substance at 298 K, then, is given by ΔS or Sf,
which is called the absolute entropy because this is the true value and not a value
derived using some arbitrary reference as in the case of standard enthalpy of
formation. Thus, the entropy values quoted so far and those listed in the
Thermodynamic Table are all absolute entropies. Because measurements are carried
out at 1 atm, we usually refer to absolute entropies as standard entropies. In contrast,
we cannot have the absolute energy or enthalpy of a substance because the zero of
energy or enthalpy is undefined.

GIBB’S FREE ENERGY

The second law of thermodynamics tells us that a spontaneous reaction
increases the entropy of the universe; that is, ΔSuniv > 0. In order to determine the sign
of ΔSuniv for a reaction, however, we would need to calculate both ΔSsys and ΔSsurr. In
general, we are usually concerned only with what happens in a particular system.
Therefore, we need another thermodynamic function to help us determine whether a
reaction will occur spontaneously if we consider only the system itself.

The thermodynamic function we need is the Gibb’s free energy (G) or simply
free energy.
G = H – TS

All quantities in this equation pertain to the system, and T is the temperature of
the system. G has units of energy (both H and TS are in energy units). Like H and S,
G is a state function.

The change in free energy (ΔG) of a system for a constant-temperature process

is ΔG = ΔH – TΔS.

Free energy is the energy available to do work. Thus, if a particular reaction is

accompanied by a release of usable energy (that is, if ΔG is negative), this fact alone
guarantees that it is spontaneous, and there is no need to worry about what happens
to the rest of the universe.

ΔG < 0 The reaction is spontaneous in the forward direction.

ΔG > 0 The reaction is nonspontaneous. The reaction is spontaneous in

the opposite direction.

ΔG = 0 The system is at equilibrium. There is no net change.

Standard Free-Energy Changes

The standard free-energy of reaction (ΔG°rxn) is the free-energy change for a

reaction when it occurs under standard-state conditions, when reactants in their
standard states are converted to products in their standard states.

The standard free-energy change for this reaction is given by

ΔG°rxn = [cΔG°f(C) + dΔG°f(D)] - [aΔG°f(A) + bΔG°f(B)]

or, in general,
ΔG°rxn = ΣnΔG°f(products) - ΣmΔG°f(reactants)

where m and n are stoichiometric coefficients. The term ΔG°f is the standard free
energy of formation of a compound, that is, the free-energy change that occurs when
1 mole of the compound is synthesized from its elements in their standard states.
Example 1: The old camera flash bulb used Mg metal sealed in a bulb with oxygen.
Is the reaction spontaneous at STP? The reaction is:

Mg(s) + ½ O2(g) →MgO(s)

ΔS° (J/K·mol): 32.7 205.0 26.9
ΔHo f (kJ/mol): 0 0 - 601.2

Solution: First, calculate ΔS and ΔH.

ΔS° = ΣnS°(products) − ΣmS°(reactants)
= [(1)SoMgO] – [(1)SoMg + (½)SoO2]
= [(1) (26.9)] – [(1) (32.7) + (½) (205.0)]
ΔS° = - 108.3 J/K mol

ΔH° = ΣnΔH°f(products) – ΣmΔH°f (reactants)

= [(1)ΔH°fMgO] – [(1)ΔH°fMg + (½) ΔH°f O2]
= [(1) (- 601.2) ] – [(1) (0) + (½) (0)]
ΔH° = - 601.2 kJ/mol

Then, to know whether the reaction is spontaneous, solve for ΔG using

the equation

ΔG°rxn = ΔG = ΔH – TΔS
= - 601.2kJ - (298 K) (-108.3 J/K)
Convert -108.3 J/K to kJ/mol.
= - 601.2kJ - (298 K) (-0.1083 kJ/K)
= - 601.2 kJ + 32.3 kJ (-108.3 J/K) (1 kJ/1000J) = -0.1083 kJ/K
ΔG°rxn = - 568.9 kJ

Since ΔG is negative, the reaction will form MgO.

Take Note: We can also solve the problem using the equation
ΔG°rxn = ΣnΔG°f(products) - ΣmΔG°f(reactants)

Try it! Check the necessary data in the Thermodynamic Data Table
that can be accessed in
https://web.facebook.com/groups/290989511714323.

Example 2: Ozone (O3) in the atmosphere can react with nitric oxide (NO):
O3(g) + NO(g) → NO2(g) + O2(g)

Calculate the ΔG for this reaction at 25oC.

Expected Answer: - 198 kJ/mol
 YOU CAN DO THIS!
Task 1. Spontaneity. Write S if it is spontaneous at STP and NS if not.
1. Dissolving table salt (NaCl) in hot soup.
2. Climbing Mt. Everest.
3. Spreading fragrance in a room by removing the cap from a perfume bottle.
4. Separating helium and neon from a mixture of the gases.
5. Sugar dissolves in a cup of coffee.

Task 2. Increase or Decrease. Write IE if entropy increases and DE if entropy

decreases.
1. Molecules of gas at high pressure spread to lower pressure regions.
2. Gas in the balloon spreads out into the room and deflates.
3. Heat always goes from high temperatures into cooler regions.
4. Hot coffee in a room gets cooler and the heat spreads out into the room.
5. Liquid water turns into ice.
6. Boiling water.
7. A vapor is converted to a solid.
8. A vapor condenses to a liquid.
9. Sublimation.
10. Melting

Task 3. Check Point. Consider the gas-phase reaction of A2 (blue) and B2 (orange)
to form AB3.
(a) Write a balanced equation for the reaction.
(b) What is the sign of S for the reaction?

YOU CAN DO MORE!

Task 4. Express Me Mathematically. Write the appropriate equations for the
following concepts.

1. The second law of thermodynamics for equilibrium process.

2. Standard entropy change of a reaction.
3. Free-energy change at constant temperature.
4. Standard free-energy change of reaction.
5. Enthalpy change of a reaction.
Task 5. TRUE or FALSE. Identify the following statements as True or False.
1. Entropy change is negative if the reaction produces more gas molecules than
it consumes.
2. Entropy change is negative if there is a decrease in the total number of gas
molecules.
3. All spontaneous reactions are exothermic.
4. The reaction is spontaneous if the standard free energy of the reaction is
negative.
5. The reaction is spontaneous if the entropy change in the universe is greater
than zero.

Task 6. Check your Concepts. Predict whether the entropy change of the system in
each of the following reactions is positive or negative.
1. 2H2(g) + O2(g) → 2H2O(l)
2. NH4Cl(s) → NH3(g) + HCl(g)
3. H2(g) + Br2(g) → 2HBr(g)
4. I2(s) → 2I(g)
5. 2Zn(s) + O2(g) → 2ZnO(s)

CHALLENGE YOURSELF!
Task 7. Entropy Changes in the System. Using the data, calculate the standard
entropy changes for the following reactions at 25°C. Show your solutions.
1. CaCO3(s) → CaO(s) + CO2(g)
2. N2(g) + 3H2(g) → 2NH3(g)
3. H2(g) + Cl2(g) → 2HCl(g)
4. 2CO(g) + O2(g) → 2CO2(g)
5. 3O2(g) → 2O3(g)
Task 8. Entropy Changes in the Surroundings. Calculate the entropy of the
surroundings for the following reactions at 25°C. Show your solutions.

1. C2H8(g) + 5O2 → 3CO2(g) + 4H2O(g) ΔH = -2045 kJ

2. H2O(l) → H2O(g) ΔH = +44kJ
3. A + B → AB ΔH = +100 kJ
For item no. 3, if ΔSsys is -50 J/K·mol, do you think the reaction is spontaneous
at 25°C? Prove your answer.
Task 9. Gibb’s Challenge. Calculate the standard free-energy changes for the
following reactions at 25°C. Show your solutions.
1. CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
2. 2MgO(s) → 2Mg(s) + O2(g)
3. H2(g) + Br2(l) → 2HBr(g)
4. 2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l)
 5. H2O(l) → H2O(g)
LEVEL UP!
Task 10. Let’s Analyze. Solve the problem following Polya’s principle.
From the values of ΔH and ΔS, predict which of the following reactions would be
spontaneous at 25°C:

Reaction A: ΔH = 10.5 kJ/mol, ΔS = 30 J/K·mol

Reaction B: ΔH = 1.8 kJ/mol, ΔS = -113 J/K·mol

If either of the reactions is nonspontaneous at 25°C, at what temperature might it

become spontaneous?

Principle 1 (1pt) Principle 2 (2pts) Principle 3 (4pts) Principle 4 (3pts)

What is asked: What will you use Carry out your Do you think you
to solve the plan did it correctly?
What are the problem?
given: Why do you think
so?

Task 11. Check your Understanding. Find the temperatures at which reactions with
the following ΔH and ΔS values would become spontaneous:

1. ΔH = -126 kJ/mol, ΔS = 84 J/K·mol

2. ΔH = -11.7 kJ/mol, ΔS = -105 J/K·mol.

Task 12. Give It Some Thought. For each pair of substances listed here, choose the
one having the larger standard entropy value at 25°C. The same molar amount is used
in the comparison. Explain the basis for your choice.

1. Li(s) or Li(l)
2. Ar(g) or Xe(g)
3. CO(g) or CO2(g)
4. O2(g) or O3(g)
5. NO2(g) or N2O4(g)