CO QAH + MELC LW

Course Outline & Quality Assured HANDOUT No. 8

Handouts paired with MELC- in GENERAL CHEMISTRY 2
Based Learner’s Worksheet

MELC:
23. Predict the spontaneity of a process based on entropy. (STEM_GC11TCIVg-a-b--140)
24. Explain the second law of thermodynamics and its significance (STEM_ GC11TCIVg-a-b-142)
25. Use Gibb’s free energy to determine the direction of a reaction (STEM_GC11TCIVa-b-143)
Semester: 2 Week No. 8 Day: 1-4
LESSON 1: SPONTANEOUS PROCESSES

Spontaneity is generally associated with natural occurrences or those that proceed even without
an external triggering factor.
Examples:
• Hot objects tend to cool down to room temperature over a certain period of time. However,
cool objects cannot react spontaneously without heat.
• Bush fires spontaneously occur in the presence of an oxidant to form water and carbon
dioxide, but bushes don’t form spontaneously through reaction of carbon dioxide and water
at higher temperature.
• Iron sheets spontaneously undergo corrosion in the presence of air and moisture to form
iron (III) oxide.

Chemical reactions can be either fast or slow as explained by kinetics. Spontaneous reaction can
also go in both forward and reverse directions or in either way only. A spontaneous process is
physical or chemical change that occurs by itself. These processes occur without requiring an outside
force and continue until equilibrium is reached.

What is entropy? How does it relate to spontaneity of a process?

Entropy(S), is a thermodynamic quantity that is measure of how spread out or dispersed the energy
of a system is among the different possible ways that system can contain energy. It is a quantity that is
generally used to describe the course of a process, that is, whether it is a spontaneous process and has a
probability of occurring in a defined direction, or a non-spontaneous process and will not proceed in the
defined direction, but in the reverse direction.
The SI unit of entropy is joules per Kelvin (J/K) and, like enthalpy, is a state function.

How do entropy changes occur?

Most processes are accompanied by entropy change. The following are processes that lead to an
increase in entropy of the system.

Process Order —> Disorder

Melting Solid —> Liquid
Vaporization Liquid —> Vapor
Dissolving Solute —> Solution
Heating System at T1 —> System at T2 (T2 > T1)

The spreading out of more concentrated molecules and the spreading out of more concentrated
energy are changes from more order to more random. The changes that occur are the ones that lead
to an increasing randomness of the universe. Entropy is sometimes referred as the measure of
randomness and disorder.
At high enough temperature, the spontaneous change is from Solid Liquid Gas; gas is more random
than liquid and liquid is more random than solid. There is an increase in entropy (S) of the system by
going from solid to liquid to gas.

Entropy and the Second Law of Thermodynamics

The Second Law of Thermodynamics deals with entropy. It tells whether a process or chemical
reaction can occur. The connection between entropy and the spontaneity of a reaction is expressed
by the second law of thermodynamics: It states that: “The entropy of the universe increases in a
spontaneous process and remains unchanged in an equilibrium process.” Because the universe is
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 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 (ΔSsur).

ΔSuniv = ΔSsys + ΔSsur > 0 Process is spontaneous.

ΔSuniv = ΔSsys + ΔSsur = 0 Process tends not to occur; equilibrium is attained.
ΔSuniv = ΔSsys + ΔSsur < 0 Reverse process occurs spontaneously.

Calculating Entropy Changes in the System: Standard Entropy of Reaction, ΔS°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° = ΣnS° (products) − ΣmS° (reactants)

• Where m and n are the stoichiometric coefficients in the reaction.

ΔS° rxn = [cSo (C) + d So (D)] ‒ [aSo (A) + bSo (B)]

The standard entropy values of compounds have been measured in J/K mol. To calculate the ΔS°
rxn (which is the ΔSsys), the values may be found in the Thermodynamic Data Table. Thermodynamic
tables have absolute entropy of substances at 25°C and 1atm.
• For convenience, ΔS° will be used instead of ΔS° rxn in the proceeding discussion.
• Remember, the greater the value of ΔS then the greater is the increase in the randomness of the
system.

Sample Problem 1:
From the standard entropy values in the Thermodynamic Data table, calculate ΔS° for the
following reaction.
H2(g) + I2(s) —> 2HI(g)
Step 1. Write the standard entropy below each formula.

H2(g) + I2(s) —> 2HI(g)

From the table, S°(J/K·mol): 130.6 116.7 206.3

Step 2: Using the equation for the standard entropy of reaction

ΔS° = ΣnS° (products) − ΣmS° (reactants)

= [(2) So HI] – [(1) So H2 + (1) So I2]

Tracking the units:

• The units (mol) for the number of moles of reacting substances and (J/ K mol) for the S° results to the
unit (J/K) for the ΔS° = ((mol) (J/ K mol) = J/K.
• We expect a positive value for ΔS for the system because the change involved 1 mole gas + 1 mole solid
2 moles gas should increase randomness (entropy).
• Gas is more random than solid. In general, there is more randomness in a gas or if the temperature is higher
or if a much larger molecule rather than smaller.

Step 3: Substitute the entropy values.

= [ (2) (206.3) ] – [ (1) (130.6) + (1) (116.7) ] = [ 412.6 ] – [ 247.3 ] ΔS° = +165.3 J/K

What general rules apply to predicting whether an entropy change is negative or positive?

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.
Practice Problem 1: Predict whether the entropy change of the system in each of the following is
positive or negative.

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 a. O2(g) —> 2O(g)
b. N2 (g, 10 atm) —> N2 (g, 1atm).
c. 6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g).
d. 2 H2 (g) + O2 (g) —> 2 H2O (l)
e. NH4Cl (s) —> NH3(g) + HCl (g)
ANSWER:
O2(g) —> 2O(g) Positive
Increase in number of gas molecules
N2 (g, 10 atm) —> N2 (g, 1atm) Positive
Decrease in pressure of the system will increase entropy
6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g). Negative
Decrease in number of gas particles
2 H2 (g) + O2 (g) —> 2 H2O (l) Negative
Net decrease in number of molecules and gases are converted to solids
NH4Cl (s) —> NH3(g) + HCl (g) Positive
A solid is converted to two gaseous products

Practice Problem 2:
1. Determine S for the reaction: SO3(g) + H2O(l) —> H2SO4(l)
Given: S°(J/K·mol): 256.2 69.9 156.9

2. Calculate S for the reaction SO2(s) + NO2(g) —> SO3(g) + NO(g)

Given: S°(J/K·mol): 248.5 240.5 256.2 210.6

3. Calculate S at 250C for the reduction of given these absolute entropies:

2PbO(s) + C(s) —> 2Pb(s) + CO2(g)
Given: S°(J/K·mol): 69.54 5.7 64.89 213.6
Expected answers:
1. -169.2 J/K·mol
2. -22.2 J/K·mol
3. +198.8 J/K·mol

Calculating the Entropy Changes in the Surroundings, ΔSsur

How is entropy change in the surrounding determined? What conditions are involved in the
calculations? How can the spontaneity of a reaction be predicted using entropy change in the
surrounding, ΔSsur?
• For constant-pressure process the heat change is equal to the enthalpy change of the system
ΔHsys,. Then the change in entropy of the surroundings ΔSsurr is proportional to the ΔHsys.
ΔSsurr —> − ΔHsys
• The minus sign is used because, if the process is exothermic, ΔHsys is negative and the
ΔSsurr is a positive quantity, indicating an increase in entropy.
• For an endothermic process, ΔHsys is positive and the negative sign ensures that the entropy
of the surroundings ΔHsurr 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 the motion of the molecules 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.

−ΔHsys
ΔSsurr =
𝑇

Sample Problem 2: Applying the procedure for calculating the ΔSsys and ΔSsurr to the synthesis of
ammonia: Is the reaction spontaneous at 25 0C?

N2 (g) + 3 H2 (g) —> 2 NH3 (g) ΔH°rxn = - 92.6 kJ/mo

Calculating the ΔSsurr

−ΔHsys
ΔSsurr =
𝑇

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 = − (− 92.6 kJ/mol)(1 kJ/1000 J) 298 K
ΔSsurr = 311 J/K ·mol

Calculating the ΔSsys

N2 (g) + 3 H2 (g) —> 2 NH3 (g)
From the table, S°(J/K· mol): 192 131 193

ΔS° = ΣnS° (products) − ΣmS° (reactants)

= [(2) So NH3] – [(1) So N2 + (3) So H2]
= [ (2) (193) ] – [ (1) (192) + (3) (131) ]
ΔS° = −199 J/K· mol

Determining Spontaneity of Reaction Using ΔSuniv

ΔSuniv = ΔSsys + ΔSsurr

= −199 J/K· mol + 311 J/K ·mol
ΔSuniv = 112 J/K ·mol
* Because the ΔSuniv is positive, we predict that the reaction is spontaneous at 25 0C.

Why is the second law of thermodynamics so important?

The second law of thermodynamics is one of the most fundamental laws of nature, having
profound implications. In essence, it says this:
The second law - The level of disorder in the universe is steadily increasing. Systems tend to
move from ordered behavior to more random behavior.
One implication of the second law is that heat flows spontaneously from a hotter region to a cooler
region, but will not flow spontaneously the other way. This applies to anything that flows: it will
naturally flow downhill rather than uphill.
The second law also predicts the end of the universe: it implies that the universe will end in a
"heat death" in which everything is at the same temperature. This is the ultimate level of disorder;
if everything is at the same temperature, no work can be done, and all the energy will end up as
the random motion of atoms and molecules.

LESSON 2: GIBBS FREE ENERGY,G

.
What is Gibbs free energy? How does it relate to the spontaneity of a reaction?

Another thermodynamic function is used in order to express the spontaneity of a reaction more
directly. This is called Gibbs free energy, G. The use of G predicts changes that are focused on the
system.
Gibbs free energy is defined as: G = H – TS

• All the quantities in the equation pertain to the system; the temperature T is the temperature
of the system.
• G has units of energy; both H and TS are in energy units.
• H, S and G are all state functions.

If the entropy of the universe increases then the ΔG of the system will decrease. The
direction of spontaneous change is negative ΔG for system. The ΔG tells us if a
change can occur for a chemical reaction.
If ΔSuniv is (+) for universe then ΔG for system is ( - ). The ΔG for the system is a
convenient way to predict a change.

ΔSuniv ΔG ΔSuniv Reaction

+ - increase Spontaneous, will go
Stay the same No change at
0 0
equilibrium
decrease Not spontaneous, will
- +
not go, the reverse will

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 Summary of conditions for spontaneity and equilibrium at constant temperature and pressure in
terms of
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.
Methods to determine change in Gibbs Free Energy (ΔG)

How is Gibbs free energy change determined when ΔH and ΔS are available?

ΔG = ΔH – TΔS

ΔH TΔS ΔG Effects
Reaction proceeds spontaneously at all temperatures
- + - Example:
2 H2O2 (aq) —> 2 H2O (l) + O2 (g)
Reaction is spontaneous in the reverse direction at all temperatures
+ - +
Example: 3 O2 (g) —> 2 O3 (g)
Reaction proceeds spontaneously at high temperatures. At low
+ + ? temperatures, the reverse reaction becomes spontaneous.
Example: 2 HgO (s) —> 2 Hg (l) + H2O (g)
Reaction proceeds spontaneously at low temperatures. At high
- - ? temperatures, the reverse reaction becomes spontaneous.
Example: NH3 (g) + HCl (g) —> NH4Cl (s)

Sample Problem:
Should 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
½ N2(g) + O2 (g) —> NO2(g)

Evaluate using thermodynamics ½ N2(g) + O2 (g) —> NO2(g)

S° J/K mol: 191.5 205.0 240.5
ΔHfo kJ/mol: 0 0 +34
Calculate enthalpy change
ΔH° = Σ nΔHf° (products) – Σ mΔHf° (reactants)
= [(1 ) ΔHf o NO2] – [(½)ΔHf o N2 + (1) ΔHf o O2]
= [(1)(+34)] – [((½) (0) + (1)(0)]
ΔH° = +34 kJ
* No heat given off only taken in.

Calculate entropy change

ΔS° = ΣnS° (products) − ΣmS° (reactants)
= [(1 ) So NO2] – [(½) So N2 +(1) So O2]
= [(1) (240.5) ] – [(½) (191.5) + (1) (205.0)]
= 240.5 - 300.8 ΔS°
= -60.3 J/K mol

Calculate Gibbs Free Energy change from above

ΔG = ΔH - TΔS
= +34kJ – (298K) (-60.3J/molK) (1kJ/1000J)
= 34 kJ + 18.0 kJ
ΔG = +52 kJ
* The reaction will NOT occur and NO heat is given off. Neither ΔH which is + or ΔS which is − favors reaction.

Effect of Temperature Effect on Chemical Reactions

How does temperature affect the direction of a chemical reaction?

The ΔG can be found for different temperature values.

ΔG = ΔH - TΔS

The values for ΔS° from S° and ΔH° from ΔHf° can be derived from the Thermodynamic Data
Table for both reactants and products at 25 oC and 1 atm. ΔH and ΔS will vary with temperature but

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 the variation is frequently small. In the calculations, it will be assumed that there is no variation in ΔH
or ΔS but only in T and ΔG.

Determining temperature when a reaction can occur

How can we determine the temperature that will cause a reaction to occur?

Calcium oxide (CaO), also called quicklime is prepared by decomposing limestone (CaCO 3) in a kiln
at high temperature and the reaction proceeds as:

CaCO3 (s) ⇆ CaO (s) + CO2 (g)

It is a reversible reaction, where CaO readily combines with CO2 to for CaCO3. To promote the
formation of CaO, CO2 is constantly removed from the kiln to shift the equilibrium from left to right.

Sample Problem:The important determination for the decomposition process to occur is the
temperature that will promote the forward reaction. Here we can use the thermodynamics
data for the standard states of the reactants and products at 25 °C.
CaCO3 (s) ⇆ CaO (s) + CO2 (g)
S° J/K mol: 92.9 39.8 213.6
ΔHf o kJ/mol: -1206.9 -635.6 -393.5

First we apply the equation for the enthalpy change in the reaction
ΔH° = Σ nΔHf° (products) – Σ mΔHf° (reactants)
= [(1 ) ΔHf o CaO + (1) ΔHf oCO2] – [(1) ΔHf oCaCO3]
= [(1)( -635.6) + (1)( -33.59) ] – [(1)( -1206.9)]
ΔH° = 177.8 kJ/mol
Then we apply the equation for the entropy change in the reaction
ΔS° = ΣnS° (products) − ΣmS° (reactants)
= [(1 ) So CaO + (1) So CO2] – [(1) So CaCO3]
= [(1)( 39.8) + (1)( 213.6)] – [(1)(92.9)]
ΔS° = 160.5 J/K mol
Calculating Gibbs Free Energy change from the data obtained above
ΔG = ΔH - TΔS
= 177.8 kJ/mol – (298K) (160.5 J/K mol) (1kJ/1000J)
ΔG = 130.0 kJ/mol
Because the ΔG° is a large positive value, we conclude that the reaction is not favored for the product
formation at 25 °C (298 K). In order to make the ΔG° negative, we need to find the temperature at
which ΔG° is zero (at equilibrium).
ΔG° = ΔH° - T ΔS° = 0
0 = ΔH° - T ΔS°
T = ΔH°/ΔS°
= (177.8 kJ/mol)(1000 J/ 1kJ) /160.5 J/K·mol
T = 1108 K or 835 °C

At a temperature higher than 835 °C, ΔG° is now negative, indicating that the reaction now favors
the formation of CaO and CO2.

For example, at 840 °C (1113 K):

ΔG = ΔH – TΔS
= 177.8 kJ/mol – (1113 K) (160.5 J/K·mol) (1kJ/1000J)
ΔG = 0.8 kJ/mol

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 REFERENCES

Apocada, Dahlia 2017. “General Chemistry 2.” DIWA Learning System Inc., Makati City, pages 141-149.

Chang, Raymond. 2010. “ Chemistry” 1oth Edition. McGrawHill, New York, pages 802-808.

Ilao, Luciana V., LONTOC, Betty M.,Paderno-Gayom, Edwehna Elinore S.,”General Chemistry 2.” 1 st Edition.
REX Bookstore,Inc.,pages 134-141.

Teaching Guide for Senior High School “General Chemistry 2”. Commission on Higher Education. Quezon
City, 2016, pages 418-453.

Prepared by: KAREN J. YU

CCNHS