Chapter 3

Chemical
Thermodynamics
 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
released
 3.1.1 Energy
Forms of Energy and Their Interconversion
 Thermodynamics: the study of heat & its
transformation.
 Thermochemistry: branch of thermodynamics,
deals with heat involved in chemical reaction.
 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:
 Work, w = Force (F) x distance (d)
where F = mass (m) x acceleration (a) in units of kgm
s2
kgm kgm2
w = 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, kJ
and kcal.
 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
 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
 Enthalpy is a thermodynamic property of a system

 Enthalpy is defined by H = E + PV
Thus, change in enthalpy,
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
 Enthalpy is a state function

 The enthalpy 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
 Enthalpy of a system in a given state
- cannot be measured
 Change in enthalpy - can be measured

Heat Capacity & 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
Heat Capacity & 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:
(i)constant-pressure,(ii)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
 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
100.00oC in boiling water and carefully added to a
coffee-cup calorimeter containing 50.00 g water. The
water temperature increased from 25.10oC to 28.49oC.
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
c H 2O x mass H 2O x ΔTH 2O 4.184 x 50.00 g x 3.93 K
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 4.9370C. 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 enthalpy
change for the amounts of substances in
that specific reaction
3.1.4 Stoichiometry of Thermochemical Equations
 Two aspects of enthalpy 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)  H2O(l) Hrxn = 286 kJ
Formation of 2 mol water
2H2(g) + O2(g)  2H2O Hrxn = 576 kJ
 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’s Law - 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
 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) + 1/2O2(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) + 3/2O2(g)  SO3(g)

 H3 = H1 + 1/2(H2)

= 296.8 kJ + (99.2 kJ)
= 396.0 kJ
 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 (25oC)
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)

m & n = no of moles

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 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:

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

o o 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   1 mol 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 25oC
(b) 2 mol of HCl(g) or 1 mol of HCl(g) at 25oC
(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 temperature.
 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 25oC is 43.0 kJ/mol.

CCl4(l)  CCl4(g) Hvap = 43.0 kJ/mol

If 1 mol of liquid CCl4 at 25oC 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
ΔHv ap 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
 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

ΔG  Σm ΔG (products)  Σn ΔG (reactants)
o o
f
o
f

 = “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) ΔGo  2 mol ΔGfo NH3   1 mol ΔGfo 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

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 < 0oC, 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 < 0oC, reverse
process (liquid water to ice) is spontaneous at T < 0oC

 When T > 0oC, 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 > 0oC
 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 normal melting point of water, T = 0oC, & the two

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

 Under standard conditions (at 25oC)

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  1kJ 
ΔG  92.38 kJ - 773 K  - 198.3  3 
o

 K  10 kJ
 - 92.38 kJ  153 kJ
 61kJ
 Question 1
Reaction of carbon (graphite) with hydrogen yields methane:
C(graphite) + 2H2(g)  CH4(g) (reaction 1)
a. Given that the standard enthalpy of combustion for H2, C
(graphite) and CH4 are 285.8, 393.5, and 890.4 kJ/mol
respectively, write the balanced thermochemical equation for the
combustion of H2, C (graphite) and CH4.
b. Calculate the Ho for reaction 1 using the thermochemical
equations in part (a).
c. Calculate So at 25°C for reaction 1.
d. Assume that Ho and So for reaction 1 do not change with
temperature. Predict the driving force to produce CH4 with
increasing of temperature. Explain your answer briefly.
 Question 2
Consider the following thermochemical equations:
Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g) Ho = 26.7 kJ
1
CO(g) + O2(g)  CO2(g) Ho = 283.0 kJ
2

Using the thermochemical equations given,

a. calculate the standard heat of formation (Hof) for iron(III)
oxide

b. Predict the spontaneity of the reaction in (a) with an

increase in temperature. Justify your answer.
 Question 3
a. Given the following thermochemical equations:
2NaCl(s) + H2O(l)  2HCl(g) + Na2O(s) Ho = +507.31 kJ
NO(g) + NO2(g) + Na2O(s)  2NaNO2(s) Ho = 427.14 kJ
NO(g) + NO2(g)  N2O(g) + O2(g) Ho = 42.68 kJ
2HNO2(l)  N2O(g) + O2(g) + H2O(l) Ho = +34.35 kJ

Calculate Ho for the preparation of nitrous acid, HNO2 in the

following reaction:
HCl(g) + NaNO2(s)  HNO2(l) + NaCl(s) (reaction 1)

b. Calculate So for reaction 1. Predict the spontaneity of the reaction

1 with an increase in temperature. Justify your answer.
 Question 4
Ozone (O3) is a gas which can be found in the outer layer of the earth
atmosphere. This gas filter out the dangerous ultra violet light from
the sun. Suppose that ozone is formed from oxygen via the reaction:
3O2(g) → 2O3(g)
a. Determine the enthalpy change of the reaction
b. Based only on the molecular order predict whether the entropy
change of the reaction will increase or decrease. Confirm your
answer by calculation if it is known that standard molar entropy of
oxygen and ozone in the standard gaseous state are 205.138 and
238.930 J/K·mol, respectively.
c. If the standard enthalpy of formation for ozone gas is
+142.70 kJ/mol, predict the spontaneity of the reaction at
T = 600 K. Explain your answer.
The End