SHS

General Chemistry 1
Quarter 4: Week 1 - Module 1
Thermodynamics
 Development Team of the Module

Author: Jovy B. Licos, MT-II

Editor: SDO La Union, Learning Resource Quality Assurance Team

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Claire P. Toluyen, Librarian II

GENERAL CHEMISTRY 2
Quarter 4: Week 1 – Module 1
Thermodynamics

Target
 In the previous lesson, how fast reactions take place and what properties
can be used to change reactions rate was discussed. But how do we know
whether the processes will occur or not? When does change occur? In this
module, thermodynamics will allow us to predict whether s process will take
place or not. When a process is considered spontaneous and
nonspontaneous?

After reading this learning material, you are expected to:

1.predict the spontaneity of a process based on entropy
STEM_GC11CTIVa-b-140

2.Explain the second 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

JUMPSTART
 Before going on, check how much you know about this topic.
Answer the pretest on the next page and write your answer in
¼ sheet of paper.
Direction: Select the letter of the correct answer and write in ¼ sheet of paper.

1. Which of the following is NOT a spontaneous process?

A. Sugar dissolving in hot coffee

B. Coffee freezing while you drink it on a warm summer day
C. A nail rusting over the course of years
D. Ripening of fruits

2. Which one of the following is always positive when a spontaneous process

occurs?
A. ΔSsystem B. ΔSuniverse
C. ΔSsurroundings D. ΔHuniverse

3. Which of the following processes is NOT a spontaneous?

A. cooling of a hot flat iron B. black hair turning grey

C. drop of ink dispersing in water D. straightening curly hair

4. Which of the following law of thermodynamics states that the total entropy of the
universe is continually increasing?
A. First law of thermodynamics.
B. Second law of thermodynamics.
C. Third law of thermodynamics.
D. None of these.

5. If the value of AG is less than zero, it indicates that the reaction is ___________.
A. Spontaneous B. reaction is at equilibrium
C. nonspontaneous D. none from the choices.
 Discover

Spontaneity and Entropy

Consider the following examples: a waterfall flows downhill, but never up, heat
flows from a warmer object to a cooler one, but the reverse never happens
spontaneously. Iron exposed to water and oxygen forms rust, but rust does not
spontaneously change back into iron. Chemical processes can be spontaneous as
well. An example is spontaneous combustion, wherein a flammable substance
burns by itself even without direct application of spark or flame. The spontaneous
reaction between magnesium ribbon and hydrochloric acid wherein the magnesium
metal instantly disappears with the evolution of heat and gas is irreversible. This
type of process does not need the application of energy to take place is said to be
spontaneous process.

Conversely, a nonspontaneous process cannot proceed unless there is a

driving force or outside help that acts on the system. For example, a ball cannot
be brought uphill unless someone pushes it. Spontaneity of a process can be
determined from the change in entropy and change in free energy of a system.

The driving force for a spontaneous process is an increase in the entropy of

the universe. Entropy, S, can be viewed as a measure of randomness, or disorder.
Nature spontaneously proceeds toward the states that have the most “spread out
energy”, or the highest probabilities of existing. In other words, towards an
arrangement where energy can be contained in the greatest number of ways.
Everyone will agree that a person usually spends more time and effort in arranging
or organizing things as compared to creating a mess. An orderly room becomes
messy with time. Neatly arranged items on a shelf do not stay orderly for long. They
tend to become disordered as time passes by. This is inevitable, because creating a
mess is a more natural and spontaneous process. Hence, if we will compare the
entropies of 1 mole of a substance in the three physical states based on the kinetic
molecular theory theory, molar entropy of the gaseous state will be highest, molar
entropy of the liquid state will be intermediate, and molar entropy of the solid state
will be the lowest. The change in entropy, ∆S, depends only on the entropies of the
final and initial states of the system.

∆S = Sfinal-Sinitial

A positive value of ∆S (∆S>0), indicates that the final state is more random or
disordered than the initial state. A negative ∆S value (∆S<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. The direction in which a chemical reaction
proceeds is governed by the tendency to attain a state that is statistically more
probable. In other words, an increase in disorder or entropy is thermodynamically
favorable for a reaction to proceed spontaneously. This is simply implies that
entropy change is the factor that can account for the spontaneity of endothermic
processes. There are several factors that influence the amount of entropy present in
a system at a particular state. These factors are the following:

1.Change in Phase. Solid particles are confined to fixed positions or compactly

arranged so that they can hardly move, thus, entropy is relatively low. In liquids,
the particles are slightly far from each other, allowing limited movement, which
results in higher entropy as compared to solids. Whereas in gases, the particles are
very far apart, hence, there is a great freedom of movement and increase kinetic
energy, giving rise to greater entropy as compared to liquids. On the other hand,
conversion of gas to liquid, and from liquid to solid, result in a decrease in entropy.

2. Change in Temperature. Rising the temperature increases the average

kinetic energy of molecules. With an increase in temperature, solid particles vibrate
more energetically, while liquid and gas particles move about more rapidly. Hence,
increasing the temperature increases the entropy of a system while a decrease in
temperature results in lowering of entropy.

3. Number of particles. The phrase “ the more the merrier” can certainly be
applied to entropy. It is definitely “merrier” when there are more people in
gathering. When a lot of people are present, there will be more movement, more
noise, more wastes, and definitely greater disorder.

Consider a chemical system presented by the following equation,

A2 B 2A + B

At the left arrow, only one particle is present as reactant, but at the right side, a
total of two particles are produced from the reaction. Since there are more particles
in products as compared to the reactants, there is a corresponding increase in
disorder. Generally, an increase in the number of particles, increase the entropy.

Example. Predict whether the entropy increases or decreases, and consider the
degree of disorder, from initial to final state or form.

1. Sublimation of solid carbon dioxide (dry ice):

CO2 (s) CO2 (g)

Solution: Entropy increases and ∆S is > 0, because once the solid is converted to
gas, the particles are more scattered and are no longer confined to a limited volume
of space, thus leading to greater disorder.
A numerical value for entropy can be possibly determined for any substance under
a given set of conditions. The change in entropy is related to heat transferred
during the process. The relationship of ∆S and the heat transferred under constant
pressure. For processes occurring at constant temperature and pressure, the
change entropy can be calculated using the equation, ∆S = q rev/T where: is 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), q= heat transferred at a particular temperature, in
J and T= temperature in Kelvin, (K). However, this equation applies only to
processes that are almost reversible. Any process that can go back to its original
state due to a very slight change in condition is reversible. A typical example is the
melting and freezing.

Example: Calculate the entropy change, ∆Svap, when 1 mole water in liquid state is
converted to 1 mole stam at 1 atm pressure?

Given: q= heat of vaporization, ∆Hvap (amount of heat transferred to the system),

equal to + 40.7kJ/mol

T= temperature at which the process occurs is the boiling point (100 0C or

373 K)

∆Svap= ∆Hvap/ T

= (1mol)(40.7kJ/mol)(1000J/kJ

373K

= +109 J/K

Note that the change in entropy is positive, thus indicating that water molecules in
gaseous state are more disordered than the liquid state. It is also possible to
calculate entropy change for various processes that occur under standard
conditions using standard entropy values of substances. Standard molar entropy
or standard entropy, S0, is defined as the entropy of one mole of a substance at
standard condition, 250C and 1 atm pressure. The entropy of a substance can be
obtained from the tabulated values of standard molar entropies, and entropy
change can be calculated using this equation,

∆So = ∑ySo products - ∑zSo reactants

The superscript o in the symbol indicates standard conditions (25oC and 1 atm
pressure) while letters y and z, represent the number of moles.

Table of Standard Molar Entropies

From ChemPRIME

Compound Smo /J K-1mol-1 Compound Smo /J K-1mol-1

Solids Diatomic Gases

C (diamond) 2.377
C (graphite) 5.74 H2 130.
7
145.
Si 18.8 D2
0
186.
Ge 31.1 HCl
9
198.
Sn (gray) 44.1 HBr
7
206.
Pb 64.8 HI
6
191.
Li 29.1 N2
6
205.
Na 51.2 O2
1
202.
K 64.2 F2
8
223.
Rb 69.5 Cl2
1
245.
Cs 85.2 Br2
5
260.
NaF 51.5 I2
7
197.
MgO 26.9 CO
7
Triatomic
AlN 20.2
Gases

NaCl 72.1 H2O 188.8

KCl 82.6 NO2 240.1

Mg 32.7 H2S 205.8

Ag 42.6 CO2 213.7

I2 116.1 SO2 248.2

MgH2 31.1 N2O 219.9

AgN3 99.2 O3 238.9

Liquids Polyatomic Gases( >
3)

Hg 76.0 CH4 186.3

Br2 152.2 C2H6 229.6

H2 O 69.9 C3H8 269.9

H2 O2 109.6 C4H10 310.2

CH3OH 126.8 C5H12 348.9

C2H5OH 160.7 C2H4 219.6

C6H6 172.8 N2O4 304.3

BCl3 206.3 B2H6 232.0

Monatomic Gases BF3 254.0

He 126.0 NH3 192.5

Ne 146.2

Ar 154.8

Kr 164.0

Xe 169.6

This table shows molar entropies for the standard conditions of 298.15 K
(25°C) and 101.3 kPa. Such conditions need to be specified, since entropy is
proportional to substance amount, and dependent on temperature, pressure.
Entropy is also dependent upon volume, but since the amount, n, temperature, and
pressure are given, volume is implicitly defined. This table is taken from
CoreChem:Standard Molar Entropies, and is also used on CoreChem:Dependence
of S on Molecular Structure as well as CoreChem:Some Trends In Entropy Values.

Example:

Calculate the entropy change when graphite burns in sufficient supply of oxygen as
shown in the equation below,

C graphite (s) + O2 (g) CO2 (g)

Solution:
Given: So of C graphite (s) =5.7 J/mol-K

So O2 (g) = 205J/mol-K

So CO2 (g) = 213 J/mol-K

∆So = ∑ySo products - ∑zSo reactants

= [ So of CO2 (g) ]- [So of C graphite (s) + So O2 (g) ]

= [ ( 1mol)(213.6J/mol-K) ]-( 1mol)(5.7J/mol-K)+(1 mol)(205J/mol-K) ]

= +2.97 J/K

Since the entropy change is positive, there is an increase in entropy from reactants
to products.

What is Second Law of Thermodynamics and Its Significance?

The second law of thermodynamics expresses the relationship between spontaneity

of a process. It states that the 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. In principle, the second law can be used
in predicting the spontaneity of a process. This law is one of the most powerful
tools that helps explain everything in the physical world. It enables us to
understand why things work as they do, why gasoline makes the engine run, why
hot pans cool down, or why our bodies stay warm even when it is cold. In industry
or engineering, the second law can help to determine which reaction will favor the
formation of desired products to obtain better economic yield. It is important to
note that sponataneity is also affected by changes in temperature and
concentrations.

In predicting the spontaneity of a process, the enthalpy factor is considered in

conjunction with the entropy factor. The balance between these two quantities is
given by another state function called free energy or Gibbs free energy, represented
by G, named after the proponent, William Gibbs. This is a more convenient method
to assess spontaneity is to use a single thermodynamic function that serves the
same purpose, a function that is associated with the system only. Therefore, there
is no need to assess surroundings. This state function where both enthalpy and
entropy factors are taken into consideration, is called Gibbs free energy, G, is
defined mathematically as

G=H−TS

Where H is enthalpy, T is temperature in Kelvin, and S is entropy. Gibbs free

energy is represented using the symbol G and typically has a unit of KJ/mol-
reaction. Free energy, G, 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
nonspontaneous process, free energy is a measure of the minimum amount of work
that must be done on the system in order to drive the reaction. In this equation,
G,H, and S, all refer to the system. Every substance possesses free energy, but the
actual amount is seldom known, hence, what will be considered is the change free
energy, of a system. For a process occurring at constant temperature, the change
in free energy of the system is given by the expression

AG = ∆H - T∆S

This equation is valid in all conditions. If both temperature and pressure are
constant, the relationship between the sign of AG and spontaneity of a reaction is
as follows:

AG < 0, reaction is spontaneous in the forward direction

AG > 0, nonspontaneous in the forward direction, work must be

supplied to make it occur

AG = 0, reaction is at equilibrium

If application is limited to standard condition, 25 oC and 1 atm pressure, the new

equation will be in the form:

AGo = ∆Ho - T∆So

Standard state means that solid and liquid substance are pure, gaseous substance
is at 1 atm pressure, and for substances in solution, concentration is normally 1M.
AGo can readily be calculated from the tabulated values of ∆H f o and So at 25oC.

Sample Problem.

A drying agent has the chemical composition CaSO 4. Calculate the AGo at 25oC, for
the following reaction, which has ∆So value of -139.7 J/K.

CaSO4 (s) Ca-2 (aq) + SO4-2 (aq) ∆Ho = -18.0 KJ Solution:

Given: ∆Ho = -18.0 KJ

∆So = -139.7 J/K

 Required: AGo for the reaction
Strategy: Convert J to KJ and 25oC to K

∆So = (-139.7 J/K) (1Kj/1000J)

= -0.1397 kJ/K

K = OC + 273 K

= 25 + 273 = 298K

Substitute the given values into the equation,

AGo = ∆Ho - T∆So

=
-18.0 kJ- (298K)(-0.1397 kJ/K

= 18.0 kJ - (-41.6 kJ)

= -59.63 kJ

Since AGo > 0 or positive, the reaction is not spontaneous at 25 oC. In other words,
at this temperature, CaSO4, does not dissolve in water to produce a 1M solution.
The table below shows the relationship between temperature, AG o, and spontaneity.

∆H ∆S ∆G =∆H-TAS Characteristic 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 temperature
_ _ -at low T Spontaneous a low temperature
_ _ + at high T Nonspontaneous at high temperature
 EXPLORE

Here are some enrichment activities for you to strengthen the

basic concepts you have learned from this lesson

Exercise. Given the equation, calcite the standard free energy change. Answer what
is being asked.

1. N2(g)+3H2(g) --->2NH3(g)

If ΔH = -92.2kJ and ΔS= -0.1987kJ/K, what is ΔG for the reaction at 475°C

and at 5°C? Provide the answer in kJ. In each case, is the reaction
spontaneous?

2. The enthalpy and entropy change of a reaction are -3.9

kJ/mole and +56.6 J/mole K respectively at 25o C. What is
the free energy change in kJ/mole? Is this reaction always
spontaneous, never spontaneous or does it depend on the
temperature?
 You are really doing great! That’s amazing!

Deepen

At this point, continue assessing your learning by accomplishing the activity

below.

Enrichment Activity: “SLOGAN MAKING”

The world is presently saddled with a variety of environmental problems and the
Philippines is one country that is heavily saddled with such problems. Prepare a
slogan on how one environmental problem can be solved by the application of the
principles of energetics and chemical reactions.

SLOGAN RUBRIC

Beginning Developing Accomplished Exemplar

(7 pts) (8 points) (9 pts) (10 pts)
Organization The The sequencing The sequencing The sequencing
sequencing of of words and of the words of words and
words and phrases is very and phrases is phrases is
phrases is confusing, and somewhat logical, and the
random. The the reader may logical, and the reader is able
reader can need to use his reader is able to follow the
find no or her own to to follow the ordering of
evidence of knowledge to ordering of ideas easily
thoughtful determine the ideas with
ordering of ordering of
minimal efforts
ideas. ideas.
Word Choice The slogan The slogan uses The slogan uses The slogan uses
and Main uses general general or several many precise,
Idea or ordinary ordinary terms descriptive and
terms to to develop main words to descriptive
describe the idea. develop a main words to
object; the idea or develop a main
words do not
message idea or
develop main message.
idea.
Spelling Numerous Numerous There are There are very
spelling errors spelling errors spelling errors, few spelling
impede impede the which may or errors. They
the reader reader from may not be are
from understanding developmentall developmentall
understandin the slogan’s y appropriate. y appropriate
g the slogan’s message. Some However, they and do not
message. of the errors do not impede impede the
Errors are the reader’s reader’s
are developmentall understanding understanding
developmenta y appropriate, of the slogan of the slogan
but others
lly
should have
appropriate
been noticed
and should and corrected.
have been
noticed and
corrected.

Gauge
Direction: Read carefully each question. Use a separate sheet of paper for your
answer. Write the letter of the best answer.(15 pts)

1. What is a spontaneous process? A. is reversible.

B. Is irreversible
C. may be reversible or irreversible depending on the value of ΔS.
D. may be reversible or irreversible depending on whether equilibrium is
maintained throughout the process.

2. If a chemical reaction is spontaneous, the total entropy of the chemical systems

and its surroundings _______________.
A. increases only if the reaction is exothermic
B. increases only if the reaction is endothermic
C. always increases
D. always decreases

3. Which of the following is NOT a spontaneous process?

A. Sugar dissolving in hot coffee
B. Coffee freezing while you drink it on a warm summer day
C. A nail rusting over the course of years
D. Ripening of fruits

4. Which one of the following processes produces a decrease in the entropy of the
system?
A. boiling water to form steam
B. dissolution of solid KCl in water
C. mixing of two gases into one container
D. freezing water to form ice

5. Which of the following is NOT a processes of spontaneous?

A. cooling of a hot flat iron B. black hair turning grey
C. drop of ink dispersing in water D. straightening curly hair

6. Which of the following law of thermodynamics states that the total entropy of
the universe is continually increasing?
A. First law of thermodynamics
B. Second law of thermodynamics
C. Third law of thermodynamics
D. None of these

7. What is the statistical measure of entropy?

 A. disorder of a system B. heat of a system
C. order of a system D. cooling of a system

8. The second law of thermodynamics relates to ___________________________.

A. enthalpy B. entropy
C. free energy D. heat

9. Standard entropy is measure at ____________________________.

A. 25oC and 1.o atm B. 25oC and 2.0 atm
C. 100oC and 1 atm D. 25oC and 2.5 atm

10. What is the correct equation in solving for the entropy of a chemical reaction?
A. ∑entropy of the products - ∑ entropy of the reactants.
B. ∑entropy of the reactants - ∑ entropy of the products.
C. entropy of products X entropy of the reactants.
D. entropy of the products divided by entropy of the reactants.

11. If the ∆S is calculated to be positive, there is greater disorder in the

____________, which would drive the reaction in the __________________ reaction.
A. reactant (s), forward C. product (s), reverse
B. product (s), forward D. reactant (s), reverse

12. What will happen to the temperature and entropy if heat is added to a pure
liquid?
A. the temperature increases and the entropy is unchanged.
the temperature increases and the entropy increases.
B. the temperature increases and the entropy decreases.
C. the temperature is unchanged and the entropy increases.

13. What is the definition of standard condition when working with free energy?
A. ions or molecules in solution at one molar concentration.
B. both gases at one atmospheric and ions or molecules in solution at one
molar concentration.
C. gases at one atmosphere, ions or molecules in solution at one molar
concentration and 0 K temperature.
D. There’s no such thing as standard condition.

14. If Delta G standard is zero, what does it mean?

A. the reaction is spontaneous at standard condition.
B. the reaction is nonspontaneous at standard condition.
C. the system is at equilibrium at standard condition.
D. the reaction is both nonspontaneous and at equilibrium.
15. What is the characteristic of reaction if the calculated delta G is negative, the
A. the reaction is always spontaneous at all temperature.
B. The reaction is always nonspontaneous at all temperature
C. the reaction is spontaneous at high temperature.
D. The reaction is nonspontaneous at high temperature.
 JUMPSTART
1. B 2. D 3. D 4. B 5.A
EXPLORE:
1. ∆G for the reaction at 475 oC = 56 kJ (not
spontaneous)
2. ∆G for the reaction
37.0 atoC5 = - kJ (spontaneous)
20.86 3. ∆G = - kJ ( spontaneous)
Since, ∆So is +, ∆H o ,and ∆Go, the reaction is always
spontaneous
DEEPEN
Answers may vary
GAUGE
1 .B
2 .C
3 .B
4 .D
5 .D
6 .B
7. A
8. B
9 .A
10 .A
11 . B
12 . B
13 . B
14 . C
15 . A
Answer Key
References
A. Books

Ayson, Marissa F. and De Borja, Rebecca S. General Chemistry 2. Araneta

Avenue, Quezon City, Manila: Vibal Group, Inc.2016.

Ilao, Lacsamana V., Betty M.Lontoc, and Edwehna Elinore S. Paderna-Gayon.

General Chemistry 1. Sampaloc, Manila: Rex Bookstore, Inc. 2017.

B. Website

https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemistry_
-
The_Central_Science_(Brown_et_al.)/19%3A_Chemical_Thermodynamics/19.4%3A_
Entropy_Changes_in_Chemical_Reactions.

https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Principles_
of_Modern_Chemistry_(Oxtoby_et_al.)/UNIT_4%3A_EQUILIBRIUM_IN_CHEMICAL_
REACTIONS/13%3A_Spontaneous_Processes_and_Thermodynamic_Equilibrium/1
3.5%3A_Entropy_Changes_and_Spontaneity
https://www.chem.tamu.edu/class/fyp/mcquest/ch15.html

https://www.cliffsnotes.com/studyguides/chemistry/chemistry/
thermodynamics/quiz-energy-and-entropy

http://williamwithin.com/worksheet/entropy-and-gibbs-free-energy-
worksheetanswers.html

https://www.clarkchargers.org/ourpages/auto/2017/5/4/38070320/EntropyFree
%20Energy%2001%20Answers.pdf