2nd Sem Q4 Module 1 Spontaneous Process
2nd Sem Q4 Module 1 Spontaneous Process
SENIOR
SCHOOL
SPONTANEOUS Module
CHANGE, ENTROPY 1
AND FREE ENERGY Quarter 4
ANAMIE T. GALVES
Subject Teacher
For the learner:
Welcome to the General Chemistry 2 (Senior High School) Module 1 on Spontaneous
Process, Entropy and Free Energy.
The hand is one of the most symbolized part of the human body. It is often used to
depict skill, action and purpose. Through our hands we may learn, create and
accomplish. Hence, the hand in this learning resources signifies that you as a learner
is capable and empowered to successfully achieve the relevant competencies and skills
at your own pace and time. Your academic success lies in your own hands!
This module was designed to provide you with fun and meaningful opportunities for
guided and independent learning at your own pace and time. You will be enabled to
process the contents of the learning material while being an active learner.
Learning Goals - These are what you will be able to know after
completing the lessons in the module
Recall - This section will measure what learnings and skills that
you understand from the previous lesson.
Lesson- This section will discuss the topic for this module.
Post-test - This will measure how much you have learned from
the entire module.
LEARNING GOALS
PRE–ASSESSMENT
Read each of the following statements and choose the letter that corresponds to the best
answer.
LESSON
In your previous lesson, it was discussed that the first law of thermodynamics states 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 chemists define as a change in enthalpy (ΔH).
SPONTANEOUS PROCESS
A spontaneous process is a physical or chemical change that occurs by itself. These processes
occur without requiring an outside force and continue until equilibrium is reached
A nonspontaneous process is a process that cannot proceed unless there is a driving force
or outside help that acts on the system.
A B
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.
Iron exposed to water and oxygen forms rust, but rust does not spontaneously
change back to iron.
These examples show that processes that occur spontaneously in one direction cannot, under
the same conditions, also take place spontaneously in the opposite direction.
How does spontaneity apply to chemical reactions?
Chemical processes can be spontaneous as well, these are chemical reactions that occur
without any intervention in a given set of conditions.
In a chemical reaction, ΔHreaction = Hproducts - Hreactants. If it is exothermic, then ΔHreaction = (-). To
get a negative ΔHreaction, the Hproducts must be lower than the Hreactants.
A spontaneous process is one that takes place without energy from an external source. For a
chemical reaction to be spontaneous, it should proceed as written (from left to right), without
an input of energy.
In most cases, exothermicity (example 1 and 2) favors the spontaneity of a reaction but
does not guarantee it. Just as it is possible for an endothermic reaction to be spontaneous
(example 3 and 4), it is possible for an exothermic reaction to be nonspontaneous.
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
Entropy, S, is a measure of the randomness or disorder of the system. This thermodynamic
property is also a measure of how much energy is unavailable for conversion into work.
Entropy is a state function, it is independent of the path or the route taken in attaining the
final state. Therefore, the change in entropy, ∆S, depends only on the entropies of the final and
initial state of the system.
∆𝐒 = 𝑺𝒇𝒊𝒏𝒂𝒍 − 𝑺𝒊𝒏𝒊𝒕𝒊𝒂𝒍
A positive value of ∆S (∆S > 0), indicates that the final state is more random or disorder
than the initial state.
A negative value of ∆S (∆S < 0), indicates that the initial state is more ordered than the
final state.
A. CHANGE IN PHASE
In solids, particles are confined to fixed positions or compactly arranged so 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.
In gases, the particles are very far apart, hence, there is a great freedom of movement and
increased kinetic energy, giving rise to greater entropy as compared to liquids.
Entropy increases as solid changes to liquid and liquid vaporizes to gas.
The gaseous state has a higher degree of disorder.
B. CHANGE IN TEMPERATURE
Raising the temperature increases the average kinetic energy of molecules. Greater
translational, vibrational, and rotational motion lead to a more disorderly state. With an
increase in temperature, solid particles vibrate more energetically, while liquid and gas
particles move above more rapidly.
Increasing the temperature increases the entropy of the system
A decrease in temperature results in lowering of entropy.
C. NUMBER OF PARTICLES
Consider a chemical system represented by the following equation
A2 B 2A + B
At the left of the arrow, only one particle is present as reactant, but at the right side, a total of
three particles are produced from the reaction. Since there are more particles in the product
as compared to the reactant, there is a corresponding increase in disorder.
Increase the number of particles also increase the entropy.
Sample Exercise
Evaluate whether the entropy increases or decreases for each of the following process.
Consider the degree of disorder, from initial to final state or from reactant to product.
Answer: Entropy increases and ∆S > 0, because once the solid is converted into a gas,
the particles are more scattered and are no longer confined to a limited volume of space,
thus leading to greater disorder.
Answer: Entropy decreases and ∆S < 0, since the ions in the crystalline solid are
confined in a highly ordered position as compared to the ions in aqueous solution which
have greater freedom of movement. The change that occurs is from a highly disordered
to a more orderly state.
Answer: Entropy increases and ∆S > 0, because there are more particles in the
products, a total of four, as compared to the reactants with only two particles, and more
particles leads to more disorderly state.
Answer: Entropy decreases and ∆S < 0, decreasing the temperature decreases the
kinetic energy of the molecules causing them to move less rapidly resulting in a less
random final state or less entropy.
Answer: Entropy increases and ∆S > 0, since a solution of two different molecules is
more random compared to only one kind of molecule.
SECOND LAW OF THERMODYNAMICS
The law expresses the relationship between spontaneity and entropy. It states that 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.
Since the universe consists of two parts, the system and the surrounding. 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).
∆𝐒 ° = Σy 𝐒 ° products − Σy 𝐒 ° reactants
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.
When the entropy change is positive, there is an increase in entropy from reactants to
products.
When the entropy change is negative, there is a decrease in entropy in the system and
decrease in the number of particles.
Sample problem:
1. Calculate the entropy change when graphite burns in sufficient supply of oxygen as
shown in the following equation,
∆S ° = Σy S ° products − Σz S ° reactants
= [(1 mol)(S ° CO2 )] − [(1 mol)( S ° Cgraphite ) + (1 mol)( S ° O2 )]
J J J
= [(1 mol)(213.6 )] − [(1 mol)( 5.7 ) + (1 mol)(205.0 )]
K.mol K.mol K.mol
J J
= 213.6 − 210.7
K K
𝐉
= +2.97
𝐊
Since the entropy change is positive, there is an increase in entropy from reactants to
products.
2. Calculate the standard entropy changes, ∆𝑆 ° for the following reaction using the
tabulated standard molar entropies.
Solution:
∆S ° = Σy S ° products − Σz S ° reactants
= [(2 mol)(S ° NO2 )] − [(2 mol)( S ° NO) + (1 mol)( S ° O2 )]
J J J
= [(2 mol)(240.0 )] − [(2 mol)( 210.7 ) + (1 mol)(205.0 )]
K.mol K.mol K.mol
J J
= 480.0 − 626.4
K K
𝐉
= −146.4
𝐊
The result shows decrease in entropy of the system which is consistent with the expected
change dictated by a decrease in the number of particles.
3. The process for dissolving NaCl in water at 25℃, Calculate the entropy change value,
∆S°universe.
𝐉 𝐉
Given: S° NaCl (s) = 72.1 S° NaCl (aq) = 115.5
𝐊.𝐦𝐨𝐥 𝐊.𝐦𝐨𝐥
𝐤𝐉 𝐤𝐉
∆Hf° NaCl (s) = −411.1
𝐦𝐨𝐥
∆Hf° NaCl (aq) = −407.3
𝐦𝐨𝐥
T = 25 + 273 = 298 K
Required: ∆S°universe
Solution:
°
A. Calculate ∆Ssystem
°
∆Ssystem = Σy S ° products − Σz S ° reactants
° °
= SNaCl (aq) − SNaCl (s)
J J
= [(1 mol)(115.5 )] − [(1 mol)(72.1 )]
K.mol K.mol
𝐉
= + 43.4 𝐊
°
B. Calculate ∆Ssurroundings
° −∆H°system
∆Ssurroundings =
T
°
°
∆Hsystem = Σy ∆Hfproducts − Σz ∆Hfreactants
°
kJ kJ
= [(1 mol)(−407.3 )] − [(1 mol)(−411.1 )]
mol mol
= +3.8 kJ
°
Substitute the value of ∆Hsystem
°
to get the value of ∆Ssurroundings
° −∆H°system
∆Ssurroundings =
T
− (+𝟑.𝟖 𝐤𝐉) 1000 J
= x
298K 1 kJ
𝐉
= −12.8 𝐊
The negative sign indicates that the direction of energy transfer for the surroundings is
opposite to that of the system.
°
C. Calculate ∆Suniverse
°
°
∆Suniverse = ∆Ssystem
°
+ ∆Ssurroundings
J J
= + 43.4 K + (−12.8 K
)
𝐉
= + 30.6 𝐊
Since the sum of the entropy change is positive or greater than zero, this indicates that the
entropy of the universe increases. It follows the second law of thermodynamics that the process
is spontaneous under standard conditions.
ΔG = ΔH − TΔS
Where T is the Kelvin temperature, H is enthalpy and S is entropy
This equation is valid in all conditions. If both temperature and pressure are constant, the
relationship between the sign of ∆G and spontaneity of a reaction is as follow.
∆𝐆° = ∆𝐇 ° − T∆𝐒 °
Standard state means that solid and liquid substances are pure, gaseous substance is at 1
atm pressure, and for substances in solution, concentration is normally 1M. ∆𝐆° can readily
be calculated from the tabulated values of ∆Hf° and S° at 25℃.
Sample Problem:
1. A drying agent has the chemical composition CaSO4 . Calculate ∆G° at 25℃, for the
following reaction, which has a ∆S° value of −139.7 J/K.
Required: ∆G°
Solution:
Convert J to kJ and 25℃ to K
J 1 kJ kJ
∆S° = −139.7 x = −0.1397
K 1000 J K
∆G° = ∆H ° − T∆S °
kJ
= −18.0 kJ − (298 K) (−0.1397 K )
= −18.0 kJ − (−41.6 kJ)
= 23.6 kJ
Since ∆G° > 0 or positive, the reaction is not spontaneous at 25℃. In other words, at
this temperature, CaSO4 does not dissolve in water to produce a 1M solution.
The following table shows the relationship between temperature, ∆G° , and spontaneity.
Calculate ΔS°
ΔS° = ΣyS ° (products) − ΣzS ° (reactants)
Calculate ΔH °
= [(1 mol) ΔHf° MgO] – [(1 mol) ΔHf° Mg + (½ mol) ΔHf° O2]
kJ
= [(1 mol) (−601.2 )] – [(1) (0) + (½) (0)]
mol
ΔH° = − 601.2 kJ
Calculate ΔG
ΔG = ΔH - TΔS
J 1 kJ
= −601.2 kJ – [(298 K) (-108.3 x )]
K 1000 J
= −601.2 kJ + 32.3 kJ
ΔG = −568.9kJ
Since ΔG < 0 or negative the reaction will form MgO. Looking up ΔGf (MgO) = −569
kJ based on this reaction occurs rapidly once initiated.
3. 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)
ΔHf° kJ/mol: 0 0 34
ΔH° = + 34 kJ
No heat given off only taken in.
= + 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.
ACTIVITIES
I. Evaluate the following process if it is spontaneous or nonspontaneous. Write S if it is
spontaneous and NS if it is nonspontaneous.
_____ 1. Cooling of a hot flat iron _____ 6. Black hair turning grey
_____ 2. Drop of ink dispersing in water _____ 7. Wind scattering leaves in a pile
_____ 3. Straightening curly hair _____ 8. Shoveling snow
_____ 4. Cold water warming to room temperature _____ 9. Removing stain from a cloth
_____ 5. Sorting names alphabetically _____ 10. Sublimation
II. Determine the entropy change when the following occur? Evaluate whether there is an
increase or decrease in entropy?
III. Solve and analyze the following problems. (Show your solution)
1. Calculate the entropy change, ∆𝐒° , for the following reactions using tabulated standard
entropy values and figure out if the resulting values obtained are consistent with the
expected entropy change as predicted qualitatively.
2. Calculate the entropy change, ∆S°universe for the following reaction, at 25℃
WRAP –UP
o Processes or reaction that are considered spontaneous are those that proceed on their
own in a definite direction, without any outside intervention. They go to completion even
without further input of energy once started.
o Any spontaneous process is irreversible. A change is irreversible if the system cannot
be restored to its original state by the following the same path used in attaining the
final state.
o Entropy is a measure of the randomness or disorder of a system. The greater the degree
of disorder, the greater the entropy.
o The degree of disorder in matter depends on its phase or physical state. Entropy
increases as solid changes to liquid and liquid vaporizes into gas. the gaseous state has
the highest degree of disorder.
o Second Law of Thermodynamics, every spontaneous change is accompanied by an
increase in entropy. The thermodynamic function entropy, S, may be considered to be
measure of disorder, or randomness.
o The total change in entropy (the change in the surroundings as well as in the system)
must be considered to determine spontaneity.
o Gibbs free energy, G, provides a criterion for spontaneity that centers on the system
alone. This thermodynamic function is defined by the equation: G = H – TS. For a
reaction at constant temperature and pressure: ΔG = ΔH – TΔS, and a negative value of
ΔG indicates that the reaction is spontaneous. If the system is in equilibrium, ΔG = 0.
o
POST TEST
Read each of the following statements and choose the letter that corresponds to the best
answer.
1. Which of the following refers to thermodynamic quantity that expresses the degree of
disorder in a system?
A. Entropy C. Enthalpy
B. Internal Energy D. Bond Energy
2. Which one of the following is always positive when a spontaneous process occurs?
A. ∆Huniverse C. ∆Ssurrounding
B. ∆Hsurrounding D. ∆Suniverse
4. Which one of the following processes produces a decrease in the entropy of the
system?
A. Dissolution of solid KCl in water
B. Mixing of two gases into one container
C. Freezing water to from ice
D. Boiling water to form steam
5. Of the following, which one of the gaseous has the largest entropy?
A. H2 C. C2 H2
B. CH4 D. C2 H6
6. Which of the following changes is ruled by the tendency of particles to become more
disordered?
A. Cooling of hot frying pan
B. Dissolving of sugar in water
C. The condensation of water vapor to rain
D. Reaction of iron with oxygen to produce rust
10. What is the entropy change of the reaction below at 298 K and 1 atm
pressure?
N2 (g) + 3H2 (g) 2NH3 (g)
Books:
4. 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.
5. Ayson, M.F., De Borja, R.S., Ysmael, M.C. (2016). General Chemistry 2 ( Teacher’s
Manual). Vibal Group, Inc. Araneta Avenue, Quezon City
6. Licuanan, P.B. (2016). Teaching Guide for Senior High School (GENERAL
CHEMISTRY 2). Commission on Higher Education. Diliman, Quezon City
ANSWER SHEET
2nd SEMESTER - GENERAL CHEMISTRY 2
MODULE - 1
POST TEST
ACTIVITIES
I.
1. _____ 3. _____ 5. _____ 7. _____ 9. ____
2. _____ 4. _____ 6. _____ 8. _____ 10. ____
II.
3. _____ 3. _____ 5. _____ 7. _____ 9. ____
4. _____ 4. _____ 6. _____ 8. _____ 10. ____
III. Solve and analyze the following problems. (Show your solution)