Chapter 3

Chemical
Thermodynamics
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es%3A_General_Chemistry/Misc/Thermodynamic_Probl
ems

https://www.slideshare.net/sureshss141/thermodynamic
s-exercise-with-solutions
 LESSON OUTCOMES
At the end of this lecture, students should be
able to:
1.Recognize and use thermodynamic terms:
system, surrounding, heat, work, internal
energy, Gibbs Free energy, enthalpy and
entropy
2. Describe the first law and second law of
thermodynamics
3. Calculate the change in internal energy
 SCOPE
Thermochemistry

Chemical
Thermodynamics
 3.1 Thermochemistry
 Forms of Energy and Their Interconversion
 Enthalpy: Heats of Reaction and Chemical
Change
 Calorimetry: Laboratory Measurement of Heats
of Reaction
 Stoichiometry of Thermochemical Equations
 Hess’s Law of Heat Summation
 Standard Heats of Reaction
 3.1.1 Energy
Forms of Energy and Their Interconversion
 All changes in matter - accompany by changes in
the energy/heat content of the matter.
e.g. 1. Snow melts - energy is absorbed
2. H2O vapor condenses to rain - energy is
release

 Thermodynamics: the study of heat & its

transformation.
 Thermochemistry: branch of thermodynamics,
deals with heat involved in chemical reaction.
 3.1.1 Energy
Forms of Energy and Their Interconversion

 All energy (potential or kinetic) - convertible

from one to the other

 An object has:
(i) potential energy by virtue of its position
(ii) kinetic energy by virtue of its motion
 3.1.1 Energy

The System and Its surroundings

 System must be defined - to make a meaningful

observation & measurement of a change in
energy.
 System: part of universe whose change to be
observed.
 Surroundings: everything relevant to the change of
the system
 3.1.1 Energy
The system and Its Surroundings

Contents of the flask: system

Flask & the laboratory: surroundings
 3.1.1 Energy
Forms of Energy and Their Interconversion
 Sum of potential and kinetic energy for all the particles in
the system = internal energy, E

 Change or difference in internal energy,

E = difference between the system’s internal energy
after the change (Efinal) and before the change (Einitial)

E = Efinal - Einitial = Eproducts – Ereactants

 3.1.1 Energy
Forms of Energy and Their Interconversion
 A reacting chemical system can change its internal
energy in either of two ways by:
(i) losing some energy to surroundings:
Efinal  Einitial
(ii) gaining some energy from surroundings:
Efinal > Einitial

 Change in internal energy - a transfer of energy from

system to surroundings & vice versa
 3.1.1 Energy
Energy flow to and from a system

Energy diagrams for the transfer of internal energy (E)

between a system and its surroundings
 3.1.1 Energy
Heat and Work: Two Forms of Energy Transfer
 Energy transfer outward from the system or inward from
the surroundings can appear in two forms; heat & work
 Heat, q (or thermal energy)
 energy transferred between a system and its
surroundings
 as a result of a difference in temperatures between the
system and surroundings
 Work, w
 energy transferred when an object is moved by a force
 3.1.1 Energy
Heat and Work: Two Forms of Energy Transfer

 Total change in a system’s internal energy:

E = q + w

 q & w can be either +ve/-ve:

 energy into the system: +ve
 energy out from the system: -ve
 3.1.1 Energy
Example of energy transfer as heat only
 A system that does no work but transfers energy as heat (q),
work, w = 0.  E = q
 3.1.1 Energy

Example of energy transfer as heat only

 Hot water in a beaker - heat out from a system
System: hot water
q = -ve as heat was lost by the system.
E = -ve

 Ice water in a beaker - Heat into a system

System: ice water
q = +ve as heat was gained by the system.
E = +ve
 3.1.1 Energy
Example of energy transfer as work only
 Heat , q = 0. E = w
 3.1.1 Energy
Example of energy transfer as work only

 Work done by a system

 Reaction between Zn & HCl in an insulated container
attached to a piston-cylinder assembly
 System: atoms making up the substances
Zn (s) + 2H+ (aq)  H2(g) + Zn2+ (aq) + 2Cl-(aq)
 As the H2 gas forms, the system used some of the internal
energy on the surroundings and push the piston outward.
  Energy is lost by the system as work, w = -ve,
E = -ve
 3.1.1 Energy

 q = +ve : system gains heat

 q = -ve: system loses energy

 w = +ve: work done on system

 w = -ve: work done by system
 3.1.1 Energy
The Law of Energy Conservation /
The First Law of Thermodynamics
 Energy
can be converted from one to another
cannot simply appear or disappear
cannot be created or destroyed

 First Law of Thermodynamics: The total energy of the

universe is constant
 3.1.1 Energy
The Law of Energy Conservation /
The First Law of Thermodynamics

 Energy of the system + energy of the surroundings

remains constant: energy is conserved.

 A mathematical expression of the first law of

thermodynamics

Euniverse = Esystem + Esurroundings = 0

 3.1.1 Energy
Units of Energy
 SI unit = Joule (J)
 1 cal (non SI unit) = 4.184 J
 Heat, work, potential energy, kinetic energy are expressed
in Joules

 In the case of work:

kgm
 Work, w = Force (F) x distance (d)
s2
 where F = mass (m) x acceleration (a) in units of
2
 w = kg m kg m
2
xm 2
J
s s
 Example
When gasoline burns in a car engine, the heat
released causes the products CO2 and H2O expand,
which pushes the pistons outward. Excess heat is
removed by the car’s cooling system. If the
expanding gases do 451 J of work on the pistons
and the system loses 325 J to the surroundings as
heat, calculate the change in energy (E) in J.
 Solution
Plan: Define the system and surroundings
System - reactants and products

Surroundings - pistons, cooling system & rest of the car

Heat released by the system, q = -ve, work done by

the system to push the piston outward, w = -ve

Calculating E in J:
q = -325 J, w = -451 J,
E = q + w = -325 J + (-451J) = -776 J
 Exercise 1
Using the First Law of Thermodynamics, calculate the quantity
listed, in J, for the system of one mole of a gas in a cylinder
with moveable piston. The gas heat capacities are: 12.5 J/molK
at constant V and 20.8 J/molK at constant P.

a. The gas absorbs 234 J of heat and is compressed by 534 J of

work. ΔE = ?

b. The gas is cooled by removing 106 J of heat and expands

doing 242 J of work. ΔE = ?

(Ans: a) 768 J and b) -348 J)

By Ms Ayu_August 9 2018
 3.1.1 Energy
State Functions and the Path Independence of
the Energy Change
 System’s internal energy, E - state of function
 property determined by the current state of the
system
 not dependent on the path the system took to
reach the state
 Changes in state function (such as E, P, V)
depend only on the initial and final states of the
system
 3.1.1 Energy
State Functions and the Path Independence of
the Energy Change

 Heat, q and work, w are not state function their

values depend on the path the system takes in
undergoing the energy change

 Note: Symbols for state functions (such as E,P,V)

are capitalized
 3.1.2 Enthalpy
 Enthalphy is a thermodynamic property of a system.

 Enthalpy is defined by H = E + PV

Thus, change in enthalphy, H = E + PV (eq. 1)

 Total change in a system’s internal energy under

conditions of constant pressure, E = qp + w (eq. 2)

 Substituting eq. 2 into eq. 1,

 H = qp + w + PV (eq. 3)
 3.1.2 Enthalpy
 In Chemistry, we are most often concern with the
reactions/systems that occur in solution under conditions of
constant atmospheric pressure. Hence the system is free to
expand or contract and this means that it potentially do work.
Thus work done by the system, w =  PV (eq. 4)
 Substituting eq. 4 in eq. 3,
 H = qp (eq. 5)
 Thus, the heat of reaction at constant
pressure is equal to H (change in enthalpy)
 3.1.2 Enthalpy
Comparing E and H
 For many reactions, H is equal / very close to E. Three
cases:

(i) Reactions that do not involve gases

 e.g. 2KOH(aq) + H2SO4(aq)  K2SO4(aq) + 2H2O(l)
 Liquids & solids undergo very small volume changes,
 V 0, PV  0, H  E
 3.1.2 Enthalpy
Comparing E and H
(ii) Reactions in which the amount (mol) of gas does not
change. Total amount of gaseous reactants = total
amount of gaseous products
 e.g. N2(g) + O2(g)  2NO(g), V = 0, PV = 0,
 H  E

(iii) Reactions in which the amount (mol) of gas does

change. PV  0, qp is usually much larger than PV
 From eq. 1, H = E + PV, H = qp = E + PV
 E = qp  PV = H, E  qp  H,  E  H
 3.1.2 Enthalpy

Exothermic and Endothermic Processes

 Enthalphy is a state function

 The enthalphy change of reaction, H, is also

called the heat of reaction, Hrxn.

H = Hfinal - Hinitial = Hproducts – Hreactants

 3.1.2 Enthalpy
Exothermic and Endothermic Processes
 An exothermic (“heat out”)
process releases heat
results in a decrease in the enthalphy
Exothermic: Hfinal  Hinitial, H  0/-ve

 An endothermic (“heat in”)

process absorbs heat
results in an increase in the enthalphy
Endothermic: Hfinal  Hinitial, H  0/+ve
 Example
In each of the following cases, determine the sign of
H, state whether the reaction is exothermic or
endothermic
(a) H2(g) + 1/2 O2(g)  H2O(l) + 285.8 kJ
(b) 40.7 kJ + H2O(l)  H2O(g)

Solution
(a) Heat is a product (on the right), so H  0 and the
reaction is exothermic
(b) Heat is a reactant (on the left), so H  0 and the
reaction is endothermic
 3.1.2 Enthalpy
Some Important Types of Enthalpy Change

(i) Heat of combustion (Hcomb): when 1 mole of

substance reacts with O2 in a combustion reaction
e.g. C4H10(l) + 13/2 O2(g)  4CO2(g) + 5H2O, H = Hcomb

(ii) Heat of formation (Hf): when 1 mole of compound

is produced from its element
e.g. K(s) + 1/2 Br2 (l)  KBr(s), H = Hf
 3.1.2 Enthalpy
Some Important Types of Enthalpy Change

(iii) Heat of fusion (Hfus): when 1 mole of a substance

melts
e.g. NaCl(s)  NaCl(l), H = Hfus

(iv) Heat of vaporization (Hvap): when 1 mole of

substance vaporize
 3.1.3 Calorimetry
Measurement of Heats of Reaction
 Enthalphy of a system in a given state - cannot be
measured
 Change in enthalphy - can be measured

Specific Heat Capacity

 Quantity of heat (q) absorbed by an object is
proportional to its temperature change
q  T or q = constant x T or q/T = constant
 3.1.3 Calorimetry
Measurement of Heats of Reaction
Specific Heat Capacity

 Heat capacity, C = q/T = quantity of heat

required to change the temperature of substance
by 1K. (Unit: J/K)

 Specific heat capacity, c = q/m T = quantity of

heat required to change the temperature of 1 gram
of a substance by 1K (Unit: J/g.K)
Heat absorbed or released, q = c x mass x T
Example
A welded layer of copper on the bottom of a skillet
weighs 125 g. How much heat is needed to raise the
temperature of the copper layer from 25oC to 300oC?.
The specific heat capacity (c) of Cu is 0.387 J/gK.

Solution
T = Tfinal - Tinitial = 300oC – 25oC = 275oC = 275 K
q = c x mass (g) x T = 0.387 J/gK x 125 g x 275 K
= 1.33 x 104 J
 3.1.3 Calorimetry
The Practice of Calorimetry
 Calorimeter – an equipment used to measure the heat
released/absorbed by a physical or chemical process.
 Two common types:
constant-pressure & constant-volume calorimeters

Constant-Pressure Calorimetry

 A coffee/styroform-cup calorimeter

 Use to measure the heat (qp) of many processes that are

open to the laboratory atmosphere

 Common use - to determine the specific heat capacity of a

solid (does not react/dissolve in water)
 3.1.3 Calorimetry
Constant-Pressure Calorimetry

 A coffee-cup calorimeter
Process:
solid (system) is weighed,
heated to some known
temperature, added to a
sample of water (surroundings)
of known temperature & mass
in the calorimeter
https://www.youtube.com/watch?v=TEqh7E4ccgU
 3.1.3 Calorimetry
A coffee-cup calorimeter
 Continual stirring which distribute the released heat

 Final water temperature (final temperature of the solid)

is measured

 Heat lost by the system (-q) is equal in magnitude but

opposite in sign to the heat gained (+q) by the
surroundings:
 -qsolid = qH2O

 -(csolid x masssolid x Tsolid) = cH20 x massH20 x TH20

 All the quantities are known except csolid
 Example
A 25.64 g sample of solid was heated in a test tube to
100.000C in boiling water and carefully added to a coffee-cup
calorimeter containing 50.00 g water. The water temperature
increased from 25.100C to 28.490C. What is the specific heat
capacity of the solid? (Assume all the heat is gained by the
water)

Solution
Plan -summarize the information given, calculate csolid
J
4.184 x 50.00 g x 3.93 K
c H 2O x mass H 2O x ΔTH 2O gK
c solid = =
masssolid x ΔTsolid 25.64 g x ( 71.51 K)
J
= 0.387
gK
 3.1.3 Calorimetry
Constant-Volume Calorimetry
 Common type: bomb
calorimeter
 Use to measure very
precisely the heat
released in combustion
reaction
 Knowing mass of the
sample and the heat
capacity of the
calorimeter, the
measured T is used to
calculate the heat
released
Example

A manufacturer claims that its new dietetic

dessert has “fewer than 10 Calories per serving”.
To test the claim, a chemist at the Department of
Consumers Affairs places one serving in a bomb
calorimeter and burns it in O2. The temperature
increases 4.937 K. Is the manufacturer’s claim
correct? (Heat capacity of the calorimeter =
8.151 J/K)
Solution
When the dessert burns, the heat released is
gained by the calorimeter:
-qsample = qcalorimeter

Heat is found by mutiplying the heat capacity of the

calorimeter by T
 qcalorimeter = heat capacity x T
= 8.151 J/k x 4.937 K
= 40 J = 9.56 cal
(1cal = 4.184 J)
3.1.4 Stoichiometry of Thermochemical Equations
 Thermochemical equations
 a balanced equation that states the heat of reaction (Hrxn)
 Note: Hrxn value refers to the enthalphy change for the
amounts of substances in that specific reaction

 Two aspects of enthalphy change:

(i) Sign: Sign of H depends on the reaction of the change
 Sign of a forward reaction is opposite that of the reverse
reaction
e.g. Decomposition of 2 mol water (endothermic):
2H2O(l)  2H2(g) + O2(g) Hrxn = 572 kJ
Formation of 2 mol water (exothermic):
2H2(g) + O2(g)  2H2O(l) Hrxn = -572 kJ
3.1.4 Stoichiometry of Thermochemical Equations

(ii) Magnitude
 Magnitude of H is proportional to the amount of
substances in the reaction
e.g. Formation of 1 mol water:
H2(g) + 1/2 02(g)  H20(l) Hrxn = -286 kJ

Formation of 2 mol water

2H2(g) + O2(g)  2H2O Hrxn = -576 kJ
 Exercise 2 (FEQ Mar 2018)
A great amount of heat is released when pure sulfuric acid dissolves in
water. To measure the amount of heat released, 350.0 g of water was
placed in a coffee cup calorimeter and chilled to 10 °C. Then, 10.0 g of
sulfuric acid, also at 10 °C was added and the mixture was quickly
stirred with a thermometer. The temperature rose rapidly to 22 °C.
Assume that the value of the specific heat of the mixture is 4.18 JK-1g-1
and all of the heat released is absorbed by the solution.

a. Calculate the heat released in kJ by the formation of the acidic

mixture.
b. Calculate the heat released per mole of sulfuric acid.

Ans: a) 17.56 kJ b) 172.19 kJ

By Ms Ayu_August 9 2018
3.1.5 Hess’s Law of Heat Summation
 Hess’s law of heat summation: the enthalpy
change of an overall process is the sum of
the enthalpy changes of its individual steps

 Hess Laws - the difference between the

enthalpies of the reactant and the product has
the same value even though the reaction
takes place differently
3.1.5 Hess’s Law of Heat Summation
 Calculating an unknown H involves three steps:
(i) identify the target equation, note the number of moles of
reactants and products.

(ii) manipulate the equations of known H - the target

numbers of moles of reactants and products are on the
correct sides( Slide 45 & 46 punya explanation)
 change the sign of H when reverse an equation
 multiply number of moles and H by the same factor

(iii) Add the manipulated equations to obtain the target

equation. (cancel terms that appear on both sides of
equations). Add their H values to obtain the unknown H
 Example
 Application of Hess’s Law:
Oxidation of sulfur trioxide
eq. 1: S(s) + O2(g)  SO2(g) H1 = -296.8 kJ
eq. 2: 2SO2(g) + O2(g)  2SO3(g) H2 = -198.4 kJ
eq. 3: S(s) + 3/2 O2(g)  SO3(g) H 3 = ?

Solution
 Manipulate eq.1 and/or 2 so that they add up to eq.3
 identify eq. 3 as a target, carefully note the number
of moles of reactants and products
 eq. 1 and 3 contain the same amount of S, so leave
eq. 1 unchanged
 Solution (cont.)
• Eq. 2 has twice as much SO3 as eq.3, so multiply it by
1/2, multiply H2 by 1/2 as well
• Add eq. 1 to the halved eq. 2, cancel terms that appear
on both sides:
Eq. 1: S(s) + O2(g)  SO2(g) H1 = -296.8 kJ
1/2(Eq. 2):SO2(g) + 1/2 O2(g)  SO3(g) 1/2(H2) = -99.2 kJ

Eq. 3: S(s) + O2(g) + SO2(g) + 1/2 O2(g)  SO2(g) + SO3(g)

S(s) + 3/2 O2(g)  SO3(g)

 H3 = H1 + 1/2 (H2)

= -296.8 kJ + (-99.2 kJ)
= -396.0 kJ
 Exercise 3
Given:
(1) N2 (g) + O2 (g) → 2NO (g) ΔH = -180.5 kJ
(2) N2 (g) + 3H2 (g) → 2NH3 (g) ΔH = -91.8 kJ
(3) 2H2 (g) + O2 (g) → 2H2O (g) ΔH = -483.6 kJ

Calculate ΔH for the reaction

4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g)

Is the reaction enthalpy is endothermic or exothermic?

Ans: -1628.2 kJ
By Ms Ayu_August 9 2018
 Exercise 4
Given:

(1) CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)-------H = −890 kJ

(2) C2H4(g) + 3O2(g)  2CO2(g) + 2H2O(g)-----H = −1410 kJ

Calculate H for the reaction:

2CH4(g) + O2(g)  C2H4(g) + 2H2O(g)

Is the reaction results in a decrease (H°<0) or increase (H°>0) in

the enthalpy?

Ans: -370 kJ
By Ms Ayu_August 9 2018
 3.1.5 Hess’s Law of Heat Summation
Standard Heats of Reaction (H0rxn)
 Standard states (a set of specified conditions and
concentration) are used to compare heats of reaction
and other thermodynamic data:
(i) Gas: standard state - 1 atm
(ii) Substance in aqueous solution:
standard state - 1 M
(iii) Pure substance (element or compound): standard
state: usually the most standard at 1 atm and the
temperature of interest (250C)
3.1.5 Hess’s Law of Heat Summation

Standard Heats of Reaction (H0rxn)

 A right superscript zero indicates when
thermodynamics variable has been determined
with all substances in their standard states.
e.g. Standard heat reaction, H0rxn, is the H0rxn
measured with all substances in their standard
states.
3.1.5 Hess’s Law of Heat Summation
Formation Equations and Their Standard
Enthalpy
 In a formation equation, 1 mol of compound forms
from its elements
 Standard heat of formation (H0f) - enthalpy
change accompanying the formation equation
when all the substances are in their standard
states.
e.g.
C(graphite) + 2H2O(g)  CH4(g) H0f = -74.9 kJ
Example
Write balanced equations for the formation of 1 mole of the
following compounds from their elements in their standard
states and include H0f
(i) Silver chloride, AgCl, a solid at standard conditions
(ii) Calcium carbonate, CaCO3, a solid at standard conditions
(iii) Hydrogen cyanide, HCN, a gas at standard conditions

Solution
(i) Ag(s) + 1/2 Cl2(g)  AgCl(s) H0f = -127.0 kJ
(ii) Ca(s) + C(graphite) + 3/2 O2(g)  CaCO3 H0f = -1206.9 kJ
(iii) 1/2 H2(g) + C(graphite) + 1/2 N2(g)  HCN H0f = 135 kJ
 3.1.5 Hess’s Law of Heat Summation
Determining H0rxn from H0f values of
Reactants and Products
 By applying Hess’s Law, H0f values can be used to
determine H0rxn for any reaction:

H0rxn = mH0f (products) - nH0f (reactants)

Suppose we want H0rxn for:
TiCl4(l) + 2H2O(g)  TiO2(s) + 4HCl(g)
H0rxn = {H0f [TiO2(s)] + 4H0f [HCl(g)]} - {H0f [TiCl4(l) + 2H0f H2O(g)]}
(Products) (Reactants)
Example
Nitric acid, with an annual production of about 8 billion kg, is
used to make many products, including fertilizer, dyes and
explosive. The first step in its industrial production is the
oxidation of ammonia:

4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)

Calculate H0rxn from H0f values

Solution
H0rxn = mH0f (products) - nH0f (reactants)
= {4H0f [NO(g)] + 6H0f [H2O(g)]} - {4H0f [NH3(g)] +
5H0f [O2(g)]}
= [4 mol (90. 3 kJ/mol) + 6 mol (-241.8 kJ/mol)] –
[4 mol (-45.9 kJ/mol) + 5 mol (0 kJ/mol)]
= 361 kJ - 1451 kJ + 184 kJ - 0 kJ = -906 kJ
 3.2 Chemical Thermodynamics
 Spontaneous Processes
 Entropy
 Molecular Interpretation of Entropy
 Calculation of Entropy Changes
 Second Law of Thermodynamics
 Entropy Change for a Phase Transition
 Gibbs Free Energy
 Free Energy and Temperature
 Free Energy and the Equilibrium Constant
 3.2 Chemical Thermodynamics
 Area of chemistry that explores energy relationship

 Limitations of First Law of Thermodynamics

only tells the amount of heat released/work done
by the system & the amount of heat gained/work
done on the system
sign of H - not enough to predict whether the
reaction will proceed
 H - not the only factor governs reactants or
products favoured
 3.2 Chemical Thermodynamics

 Reactants or products favoured  In addition to

H, change in randomness or disorder in
chemical reaction is considered

 New aspect in discussion of thermodynamics

 spontaneous process

related to disorder in chemical reaction

 3.2.1 Spontaneous Process
 Spontaneous process: Chemical or physical change
occurs by itself
requires no continuing outside agency / occurs
without any outside intervention
A rock at the top of a hill
rolls down by itself - occur spontaneously / naturally
rolls up - not natural process / non spontaneous:
require work
 3.2.1 Spontaneous Process
 Temperature: have an impact on the spontaneity

e.g. endothermic process of melting ice,

 at T  00C:
ice melts spontaneously (ice  liquid water)
reverse process (liquid water  ice),
non-spontaneous
 But at T 00C:
liquid water converts into ice spontaneously
conversion of ice  liquid water,
non-spontaneous
 3.2.2 Entropy
 Entropy, S
 a thermodynamic quantity - a measure of the
randomness/disorder of a system.
 SI unit: Joules per Kelvin (J/K)
 a state function
quantity of S depends only on variables (such as
T & P) that determine the state of substance
 3.2.2 Entropy
Randomness/disorder of the system
(i) Solids: have much more regular structure than
liquids.
 Liquids > disordered than solids
(ii) Particles in a gaseous state are in random motion.
Gases > disordered than liquids
(iii)Any process that increases the amount of particles,
 disorder
 3.2.2 Entropy
Randomness/disorder of the system
 Consider the melting of ice:
Ice: an ordered crystalline structure
Ice melts  liquid, crystalline structure breaks
down,  resultant a less ordered liquid structure
In ice, H2O molecules occupy regular, fixed
positions; ice has a relatively low S
In liquid water, molecules moves about freely,
disordered structure; liquid water has greater
entropy than ice
 3.2.2 Entropy
Randomness/disorder of the system
 Entropy change, S

S = Sfinal – Sinitial
 S of a system  to the disorder of the system
 Ssystem  0,
 implies the system becomes more disordered
 Ssystem  0,
 implies the system becomes less disordered
 3.2.3 Molecular Interpretation of Entropy
 Structure & behaviour of molecules - affect the
entropy of the system
e.g. Entropy of the system increase (S > 0) when:
(i) gas molecules spread out in a larger volume
(ii) phase changes: solid  liquid, liquid  gas
e.g. Entropy of the system decrease (S < 0) when:
(i) condensing a gas,
(ii) freezing a liquid
 A reaction leads to a decrease in the number of
gaseous molecules
generally leads to a decrease in entropy
 3.2.3 Molecular Interpretation of Entropy
e.g. 2NO(g) + O2(g)  2NO2(g)

 Entropy change = -ve because 3 molecules of gas

react to form 2 molecules of gas

 Formation of new N-O (dari NO2) imposes more

order, atoms are more “tied up” in the products
than in the reactants

 Leads to a decrease in the entropy

 3.2.3 Molecular Interpretation of Entropy
 Formation of the new bonds - decreases the
number of degrees of freedom/forms of motion
atoms are less free to move in random fashion
 In general - the greater the no. of freedom of
system, the greater its entropy
 The degrees of freedom of molecules - associate
with three types of motion for the molecule:
(i) Translational motion
(ii) Vibrational motion
(iii) Rotational motion
 Molecular Interpretation of Entropy
 In general - entropy increasing with increasing
temperature.
 Entropy of the phases of a substance:
Ssolid < Sliquid < Sgas
 In general, the entropy is expected to increase
when:
(i) Liquids or solutions are formed from solids
(ii) Gases are formed from either solids or liquids
(iii) No. of molecules of gas increases during a
chemical reaction
3.2.4 Calculation of Entropy Change
 Standard molar entropies, S0 - molar entropy
values of substances in their standard states
 Entropy change in a chemical reaction, S0:

o
ΔS = ΣmS o
 products  - Σn S reactants 
o

 = “sum of”
m = amounts (mol) of the products
n = amounts (mol) of the reactants
 Example
Calculate S0 for the synthesis of ammonia from
N2(g) and H2(g):

N2(g) + 3H2(g)  2NH3(g)

Solution
S0 = 2S0(NH3) - [S0(N2) + 3S0(H2)]
Substituting the appropriate S0 values
 J    J   J 
ΔS  2 mol1925   1mol191.5   3 mol130.6 
 mol K    mol K   mol K 
J
 - 198.3
K
Example
Choose the substance that has greater entropy in each pair,
and explain your choice:
(a) 1 mol of NaCl(s) or 1 mol of HCl(g) at 250C
(b) 2 mol of HCl(g) or 1 mol of HCl(g) at 250C
(c) 1 mol of N2(s) at 24 K or 1 mol of N2(g) at 298 K

Solution
(a) Gaseous HCl has the higher entropy because gases are
more disordered than solids
(b) The sample containing 2 mol of HCl has twice the
entropy of the sample containing 1 mol
(c) The gaseous N2 sample has the higher entropy because
gases are more disordered than solids
3.2.5 Second Law of Thermodynamics
 Second Law of Thermodynamics: total energy of a
system and its surroundings always increases for a
spontaneous process

 Note: the difference between the entropy & energy

energy - cannot be created or destroyed during
chemical change
entropy-created during a spontaneous or natural
process
 3.2.5 Second Law of Thermodynamics
 For a spontaneous process carried out at a given
temp.
The second law can be restated in a form that
refers only to the system
Consider the changes in entropy that occur in the
system
- Process takes place entropy is created, at the
same time heat flows into/out of the system
- Entropy accompanies that heat flow
When heat flow into the system  entropy
flows into the system
 3.2.5 Second Law of Thermodynamics
 The change in entropy, S, of the system at a
given temperature:
q
ΔS  entropy created 
T

 quantity of entropy created during spontaneous

process cannot be directly measured
quantity of entropy created = +ve, by deleting it
from the right side of equation:
S > q/T for a spontaneous process
3.2.5 Second Law of Thermodynamics

The restatement of the second law

For a spontaneous process at a given

temperature, the change in entropy of the
system is greater than the heat divided by
the absolute temperature, q
T
3.2.6 Entropy Change for a Phase Transition
 Certain processes occur closely at equilibrium.
 Under equilibrium conditions, no significant
amount of entropy is created. The S results only
from the absorption of heat.
Thus, entropy change for a phase change:
q
ΔS  equilibrium process
T
 Examples of phase changes under equilibrium:
vaporization of a liquid, fusion of a solid
Example
The heat vaporization, Hvap, of carbon tetrachloride,
CCl4, at 250C is 43.0 kJ/mol.

CCl4(l)  CCl4(g) Hvap = 43.0 kJ/mol

If 1 mol of liquid CCl4 at 250C has an entropy of

214 J/K, what is the entropy of 1 mol of the vapor in
equilibrium with the liquid at this temperature?
Solution

1 mol of CCl4 increases in entropy by 144 J/K when

it vaporizes. Thus, entropy of 1 mol of vapor =
entropy of 1 mol of liquid (214 J/K) + 144 J/K = 358
J/mol.K

3 J
ΔH vap 43.0 ×10 J
ΔS = = mol = 144
T 298 K mol K
 3.2.7 Gibbs Free Energy
 X J Willard Gibbs (1839 -1903) - proposed a way
to use H & S to predict whether a given
reaction will be spontaneous
 Gibbs proposed a new state function  Gibbs
free energy (or just free energy)
 Gibbs free energy, G = H - TS, T = absolute
temp.
 At constant T, the change in free energy of the
system, G = H - TS
 3.2.7 Gibbs Free Energy
G = H - TS
 If T & P are constant, the relationship between
the sign of G and the spontaneity of a reaction:
(i) If G = -ve, reaction is spontaneous in the
forward reaction
(ii) If G = +ve,
 reaction in the forward reaction is non
spontaneous, work must be supplied from the
surroundings to make it occur
 reverse reaction will be spontaneous
 3.2.7 Gibbs Free Energy
Standard Free Energy Change
 Standard free energies of formation, Gof ,are
useful in calculating the standard free energy
change for chemical process
o
ΔG f  Σm ΔG f (products)  Σn
o o
ΔG f (reactants)

 = “sum of”,
m = amounts (mol) of products
n = amounts (mol) of reactants
 3.2.7 Gibbs Free Energy
Standard Free Energy Change
 Quantity of G0 tells whether a mixture of reactants
and products (under standard conditions):
(i) would spontaneously react in the forward
direction to produce more products  G0 < 0
(ii) or in the reverse direction to form more
reactants  G0 > 0
 Example
(a) Calculate the standard free-energy change for the
following reaction at 298 K:

N2(g) + 3H2(g)  2NH3(g)

(b) What is G0 for the reverse of the above reaction?

Solution
   
(a) ΔG o  2 molΔG fo NH3   1molΔG fo N2   3 mol ΔGfo H2 
  kJ    kJ   kJ 
 2 mol  - 16.66 
  1 mol  0   3 mol 0 
  mol    mol   mol 
 - 33.32 kJ

(b) 2NH3(g)  N2(g) + 3H2(g), G0 = +33.32 kJ

 Exercise 5
Calculating ΔG°rxn from Enthalpy and EntropyValues

Potassium chlorate, a common oxidizing agent in fireworks and

matchheads, undergoes a solid-state disproportionation reaction when
heated. Calculate ΔG°rxn ? (T = 25 °C)
Δ
4KClO3 (s) → 3KClO4 (s) + KCl (s)
(Appendix)
ΔH°f (KClO3) -397.7 kJ/mol
ΔH°f (KClO4) -432.8 kJ/mol
ΔH°f (KCl) -436.7 kJ/mol

S° (KClO3) -397.7 J/mol K

S° (KClO4) 151.0 J/mol K
S° (KCl) 82.6 J/mol K (Ans: -133 kJ) *this ans is correct!

By Ms Ayu_August 13 2018
3.2.8 Free Energy and Temperature
 Consider equation :
G = H (enthalpy term) - TS (entropy term)

 Generally H & S change very little with T.

However, the value of T directly affects the
magnitude of -TS

 As T increases, the magnitude of the term -TS

increases. It will become relatively more important
in determining the sign & magnitude of G.
 3.2.8 Free Energy and Temperature
 Example: melting of ice  liquid water (P = 1 atm)

H2O(s)  H2O(l), H > 0, S > 0

 endothermic process, H = +ve
 entropy increases during process, S = +ve, -TS = -ve

 At T < 00C, magnitude of H > magnitude of S

 +ve enthalpy term dominates, leading to a +ve value of G.
Melting of ice is not spontaneous at T < 00C, reverse
process (liquid water to ice) is spontaneous at T < 00C

 When T > 00C, magnitude of -TS > magnitude of H

 -ve entropy term dominates, leading to a negative value of
G
Melting of ice is spontaneous at T > 00C
3.2.8 Free Energy and Temperature

 At normal melting point of water, T = 00C, & the two

phases are in equilibrium.
At T = 0, H & -TS are equal in magnitude.  G = 0

 Under standard conditions (at 250C)

G0 = H0 - TS0
Example
The Haber process for the production of ammonia
involves the following equilibrium:

N2(g) + 3H2(g)  2NH3(g)

Assume that H0 and S0 for this reaction do not

change with temperature
(a) Predict the direction in which G0 for this
reaction changes with increasing temperature
(b) Calculate G0 for the reaction at 500oC
Solution
(a) G0 become less negative (or more positive)
with increasing temperature. Thus the driving
force for the production of NH3 becomes smaller
with increasing temperature

(b) G0 = H0 - T S0

T = 500 + 273 = 773 K
 J  1 kJ 
ΔG  92.38 kJ - 773 K  - 198.3  3 
o

 K  10 kJ 
 - 92.38 kJ  153 kJ
 61kJ
 Exercise 6

A key step in the production of sulfuric acid is the oxidation of SO2(g)

to SO3 (g):
2SO2 (g) + O2(g) → 2SO3(g)

At 298 K, ΔG = -141.6 kJ; ΔH = -198.4 kJ; and ΔS = -187.9 J/K

(a) Use the data to decide if this reaction is spontaneous at 25°C, and
predict how ΔG will change with increasing T.

(b) Assuming ΔH and ΔS are constant with increasing T, is the reaction

spontaneous at 900 °C?

By Ms Ayu_August 13 2018
 3.2.8 Free Energy and the
Equilibrium Constant

 Another two ways to use free energy as a

powerful tool in analysis of chemical
reaction

(i) How to use G0 value to calculate the value

of G under non-standard conditions

(ii) How to directly relate the G0 for a reaction

to the value of the equilibrium constant for
the reaction
 3.2.8 Free Energy and the
Equilibrium Constant
 Most chemical reactions occur under non-standard
conditions
Free-energy change under any other conditions:

G = G0 + RT ln Q

R = ideal gas-constant, 8.314 J/mol-K

T = absolute temperature
Q = reaction quotient that corresponds to the particular
reaction mixture of interest
 3.2.8 Free Energy and the
Equilibrium Constant

 Note: Suppose the general equilibrium equation:

aA + bB → pP + qQ
a, b, p & q = coefficients in balanced chemical
equation (RECALL CHEMISTRY I)

[P] [Q]p q

equilibriu m constant , K = a b
[A] [B]
 3.2.8 Free Energy and the
Equilibrium Constant
 Q is calculated by substituting reactant and product
concentrations in the equilibrium-constant expression

 Under standard conditions: [reactants] & [products] = 1

Q = 1, ln Q = 0,  G = G0

 At equilibrium:
 G = 0, Q = K
 G = G0 + RT ln Q   ΔG o 
 0 = G0 + RT ln K
K  exp  
 G0 = -RT ln K  RT 
 Exercise 7
The oxidation of SO2 (g) is too slow at 298 K to be useful in the
manufacture of sulfuric acid, so the reaction is run at high T.
2SO2 (g) + O2 (g) → 2SO3 (g)

(a) Calculate K at 298 K and at 973 K, (ΔG°298 = -141.6 kJ/mol of

reaction as written; using ΔH° and ΔS° values at 973 K,
ΔG°973 = -12.12 kJ/mol for reaction as written.)

(b) Two containers are filled with 0.500 atm of SO2, 0.0100 atm of O2,
and 0.100 atm of SO3; one is kept at 25 °C and the other at 700 °C. In
which direction, if any, will the reaction proceed to reach equilibrium
at each temperature?

(c) Calculate ΔG for the system in part (b) at each temperature.

By Ms Ayu_August 13 2018
The End