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WESTERN LEYTE COLLEGE

SENIOR HIGH SCHOOL- SCIENCE, TECHNOLOGY,
ENGINEERING AND MATHEMATICS (STEM)
K to 12 CURRICULUM

SPONTANEOUS CHANGE,
ENTROPY, AND FREE
ENERGY

Instructor: Elton Jhon M. Meridor

Principal: Isabelita T. Peroso

General Chemistry I
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General Chemistry I
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Thermodynamic Data at 1 atm and 25 ˚C

General Chemistry I
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Thermodynamic Data at 1 atm and 25 ˚C

General Chemistry I
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Thermodynamic Data at 1 atm and 25 ˚C

General Chemistry I
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Thermodynamic Data at 1 atm and 25 ˚C

General Chemistry I
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Thermodynamic Data at 1 atm and 25 ˚C

General Chemistry I
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Thermodynamic Data at 1 atm and 25 ˚C

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Thermodynamic Data at 1 atm and 25 ˚C

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SPONTANEOUS CHANGE, ENTROPY, AND FREE ENERGY

Objective
Explain spontaneous change, entropy, and free energy

Overview
In this lesson, learners are expected to describe and explain the energy changes in a chemical
reactions under second and third laws of thermodynamics. Specifically, students are expected to explain
the origin of the spontaneity of physical and chemical change in terms of entropy.

Background
The first law of thermodynamics is concerned with the conservation of energy which cannot
determine the feasibility or spontaneity of a process. The spontaneity of a process is decided by the
second law of thermodynamics. This law helps to predict whether a given process or chemical reaction
can occur spontaneously or not also help to assess how far the reaction will proceed or the stage at
which equilibrium will be established.
Spontaneous Processes
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. Spontaneous
physical and chemical processes are observed every day such as (Chang, 2010):
 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.

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 (Chang, 2010).

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Entropy
To predict the spontaneity of a process, a new thermodynamic quantity called entropy, S, must
be introduced. Entropy is defined in a simple ways as a measure of the degree of randomness of the
particles, how spread out or dispersed the energy of a system. The greater the dispersal, the greater is the
entropy.
To understand the concept of entropy, consider solids, liquids, and gases. In a solid, the particles
are fixed in position in their small regions of space but are vibrating back and forth. The degree of
randomness is low, so the entropy is low. When the solid melts, the particles are still close but can move
about somewhat. The system is more random, the entropy is higher. It is more difficult to describe the
location of the particles. When the liquid evaporates, the particles are moving rapidly and are much
farther apart. The entropy of the gas is still higher than that of the liquid because the location of the
particles is much more difficult and the system is much more random. A general but not an absolute rule
is that the entropy of the system increases from solid to gas.

Figure 1. Processes that lead to an increase in entropy of the system: (a) melting: S liquid > Ssolid; (b) vaporization:
Svapor > Sliquid; (c) dissolving: Ssoln > Ssolute + Ssolvent; (d) heating: ST2 > ST1. (Chang, 2010).

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The Second Law of Thermodynamics

The second law of thermodynamics states that the entropy of an isolated system tends to increase
and reaches a maximum value. This means that the most stable state of an isolated system is the state of
maximum entropy. Since the universe may be considered an isolated system, it might be said that “the
entropy of the universe is always increasing”. Because the universe is made up of the system and the
surroundings, the entropy change in the universe (∆S univ) for any process is the sum of the entropy
changes in the system (∆Ssys) and in the surroundings (∆Ssurr). Mathematically, the second law of
thermodynamics can be expressed as follows:
For a spontaneous process: ∆Suniv = ∆Ssys + ∆Ssurr > 0
For an equilibrium process: ∆Suniv = ∆Ssys + ∆Ssurr = 0
There are several other equivalent statements of the second law:
1. Clausius postulated that it is impossible to transfer heat from a cold reservoir to a hot reservoir
without doing some work.
2. Kelvin postulated that it is impossible to take heat from a source and convert all of it into work,
by a cyclic process, without losing some of it to a colder reservoir.
3. Caratheodory postulated that in neighborhood of every equilibrium state of a closed system,
there are states which cannot be reached from the first state along any adiabatic path.

Entropy Changes in the System

The standard entropy of reaction, ∆S˚rxn, is given by the difference in standard entropies between
products and reactants. Consider the reaction below:
aA + bB cC + dD
∆S˚rxn = [cS˚(C) + dS˚(D)] - [aS˚(A) + bS˚(B)]
In general, Ʃ can be used to represent the summation, and m and n for stoichiometric coefficients
in the reaction.
∆S˚rxn = ƩnS˚(products) - ƩnS˚(reactants)

Entropy Change during Phase Transition

The change of matter from one state into another is called phase transition. Such changes occur
at definite temperatures and are accompanied by absorption or evolution of heat. The entropy change:

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q trans ∆ Htrans ∆ Hfusion ∆ Hevap

∆S = = ; ∆Sfusion = ; ∆Sevap =
T Ttrans Tfusion Tevap
Entropy Changes for an Ideal Gas
In going from state 1 to state 2, the entropy change (∆S) is given by the following reactions:
a. When temperature (T) and volume (V) are the two variables:
T2 V2
∆S = n Cv,m ln + n R ln (Cv,m is independent of temperature)
T1 V1
b. When temperature (T) and pressure (p) are the two variables:
T2 p2
∆S = n Cp,m ln - n R ln (Cp,m is constant)
T1 p1
For an isothermal process (Temperature is constant)
V2 p2
∆S = n R ln = - n R ln
V1 p1
For an isobaric process (Pressure is constant)
T2
∆S = n Cp,m ln (Assume Cp,m is independent of Temperature)
T1
For an isochoric process (Volume is constant)
T2
∆S = n Cv,m ln (Assume Cv,m is independent of Temperature)
T1
Entropy Change during Adiabatic Expansion
In such processes, q = 0 at all stages. Hence, ∆S = 0. Thus, reversible adiabatic processes are
called isoentropic processes.

The Third Law of Thermodynamics

The third law of thermodynamics deals with the entropies of perfect crystalline substances at
absolute zero of temperature. According to this law, the entropies of all pure crystalline solids may be
taken as zero at the absolute zero of temperature. However, if there are imperfections of any type in the
perfect crystalline arrangement at 0 ˚K, the entropy will be larger than zero. The common limitations of
the third law are noticed in the following cases:
1. Glassy solids in which arrangement is less regular than in crystalline solids such as glassy
glycerin.
2. Solids containing mixtures of isotopes like chlorine which exists as Cl 35-Cl35, Cl37-Cl37, and Cl35-
Cl37 molecules.

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3. Crystals of pure substances which fail to attain perfect order at 0 ˚K.

The importance of this law lies in the fact that it helps to calculate the absolute entropies of pure
substances at different temperatures. The entropy of the substance at different temperatures may be
calculated from measurements of heat capacities (Cp) at a number of temperatures.
Free Energy Functions
In order to express the spontaneity of a reaction more directly, another thermodynamic function
is introduced and is called free energy. Helmholtz and Gibbs free energy functions predict the feasibility
and equilibrium conditions at constant temperature and at constant volume or pressure. Free energy
functions are define by the relations:
Helmholtz free energy : A = U – TS
Gibbs free energy : G = H – TS
The changes in A and G when the system goes from state 1 to sate 2 at constant temperature, are
expressed by:
Helmholtz free energy : ∆A = ∆U – T∆S
Gibbs free energy : ∆G = ∆H – T∆S
It is not possible to determine the absolute values of the Gibbs free energy as the absolute values
of enthalpy (H) and internal energy (U) are unknown. The Gibbs free energy of elements in their most
stable form are arbitrarily fixed equal to zero at one atmospheric pressure at a specified temperature. For
compounds, standard Gibbs free energy of formation is defined as the free energy change when one
mole of the substance is formed at 1 atm from the elements in their standard states at the specific
temperature. This is denoted by ∆G˚f. The values of the standard free energy of formation of various
compounds help in determining the free energy change for various reactions at standard conditions. It is
mathematically expressed as:
∆G˚rxn = Ʃ(n∆G˚f)products - Ʃ(n∆G˚f)reactants

Examples
1. From the standard entropy values, calculate the standard entropy change for the reaction below:
CaCO3 (s) CaO (s) + CO2 (g)
Solution:
∆S˚rxn = ƩnS˚(products) - ƩnS˚(reactants)
∆S˚rxn = [(39.8 J/K ۰ mol) + (213.6 J/K ۰ mol)] – [92.9 K/J ۰ mol]

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∆S˚rxn = 160.5 J/K ۰ mol

2. Calculate the entropy change when 2 mol of an ideal gas expand isothermally and reversibly
from and initial volume of 1 dm3 to a final volume of 10 dm3 at 300 K.
Solution:
V2
∆S = n R ln
V1
n = 2.0 mol R = 8.314 J/K ۰ mol V1 = 1 dm3 V2 = 10 dm3
3
10 dm
∆S = (2.0 mol) x (8.314 J/K ۰ mol) x ln 3
1 dm
∆S = 38.29 J/K
3. Two moles of an ideal gas (Cv,m = 12.5 J/K ۰ mol) are at 300 K and occupy 2 dm3. If the gas is
heated to 325 K and the volume is changed to 4 dm3, calculate the entropy change.
Solution:
T2 V2
∆S = n Cv,m ln + n R ln
T1 V1
n = 2.0 mol R = 8.314 J/K ۰ mol V1 = 2 dm3 V2 = 4 dm3
Cv,m = 12.5 J/K ۰ mol T1 = 300 K T2 = 325 K
3
325 K 4 dm
∆S = [(2.0 mol) (12.5 J/K ۰ mol) ln ] + [(2.0 mol) (8.314 J/K ۰ mol) ln 3]
300 K 2 dm
∆S = 13.53 J/K
4. Calculate the standard Gibbs free energy change of the reaction below from the free energies of
formation data.
15
C6H6 (l) + O2 (g) 3H2O (g) + 6CO2
2
(g)

∆G˚rxn = Ʃ(n∆G˚f)products - Ʃ(n∆G˚f)reactants

∆G˚rxn = [(n CO2) + (n H2O)] – [(n C6H6) + (n O2)]
∆G˚rxn = {[6 x (-394.4)] + [3 x (-228.6)] – {[172.8] + (15 x 0)]
∆G˚rxn = -3225 kJ

REFERENCES

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CHANG, R. 2010. Chemistry, 10th ed. McGraw-Hill Companies, Inc.

SMITH, J. 2011. Organic Chemistry, 3rd ed.

USC Chemistry Review Center. 2016. Chemistry Review Manual.

WHITTEN, K., DAVIS, R., PECK, M. L. and G. STANLEY. 2010. Chemistry, 9th ed.

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Name: ______________________________ Section: ________________________________

Date Received: _______________________ Date Submitted: _________________________
Score: ____________
Instructions: Answer the following problems by showing a step-wise solution and enclosed in a box the
final answer.
1. From the standard entropy values, calculate the standard entropy changes for the following
reactions at 25 ˚C.

A. N2 (g) + 3H2 (g) CO2 (g)

B. H2 (g) + Cl2 (g) 2HCl (g)

C. 2CO (g) + O2 (g) 2CO2 (g)

D. 3O2 (g) 2O3 (g)

E. 2NaHCO3 (s) Na2CO3 (s) + CO2 (g) + H2O (l)

2. Predict whether the entropy change of the system in each of the following reaction is positive or
negative. Justify your answer.

A. 2H2 (g) + O2 (g) 2H2O (l)

B. NH4Cl (s) NH3 (g) + HCl (g)

C. H2 (g) + Br2 (g) 2HBr (g)

D. 2Zn (s) + O2 (g) 2ZnO (s)

E. N2 (g) + O2 (g) + 2NO (g)

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3. From the thermodynamic data, calculate the Gibbs free energy changes of the following
reactions:.

A. Fe2O3 (s) + 3H2 (g) 2 Fe (s) + 3H2O (l)

B. 4NH3 (g) + 5O2 (g) 4NO (g) + 3H2O (l)

C. C6H12O6 (s) + 6O2 (g) 6H2O (g) + 6CO2 (g)

4. Helium, weighing 4 g, is expanded from 1 atm to one-tenth of the initial pressure at

30 ˚C. Calculate the change in its entropy, assuming it to be an ideal gas.

5. Fifty four grams of water are heated from 17 ˚C to 27 ˚C at constant pressure.

Calculate the increase in entropy for this process. The molar heat capacity at
constant pressure for water 75.3 J/K ۰ mol.

6. Calculate the entropy changes for the fusion and vaporization of 1 mol of water at
normal melting point (273 K) and boiling point (373 K). The molar enthalpy of
fusion is 6.01 kJ/mol and the molar enthalpy of vaporization is 40.79 kJ/mol.

7. A block of copper weighing 200 g is heated from 27 ˚C to 127 ˚C. What is the
increase in its entropy if the average specific heat of copper over this range is taken
to be equal to 0.09 cal/g ۰ K.

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8. Calculate the entropy change for the conversion of 1 mol of alpha-tin (at 13 ˚C, 1
atm) to 1 mol beta-tin (at 13 ˚C, 1 atm), if the enthalpy of transition is 2.095
kJ/mol.

9. Calculate the change in entropy when two moles of ice are heated from -10 ˚C to
10 ˚C, given that Cp,m of ice is 37.7 J/mol ۰ K, Cp,m of water is 75.3 J/mol ۰ K, and
molar enthalpy of fusion is 6.01 kJ/mol. Assume heat capacities to be constant in
this temperature range.

10.One mole of water evaporates at 100 ˚C and 1 atm pressure, by transferring heat
from a source only infinitely greater than 100 ˚C. Calculate the entropy changes in
the system and the surroundings. Enthalpy of vaporization of water is 40.7 kJ/mol.

11. Calculate the change in entropy when 100 g of hot water at 90 ˚C are added to 100
g of water at 10 ˚C in an insulted vessel. The molar heat capacity of water at
constant pressure is 75.48 J/mol ۰ K.

12.The Gibbs free energy values of a reaction at 300 K and 310 K are -121 kJ and -
123.5 kJ, respectively. Determine its ∆H and ∆S in this temperature range.

Assignment
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Create a research report about “Biology of Ageing and Senescence”. The content
of the report should relate the principles and concepts of entropy (Second and Third Laws
of Thermodynamics).
Format
Introduction
Body
-Other related topics (highlight the subtopics)
Conclusion

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