8 Chemical

thermodynamics
8.1 Introduction to chemical
thermodynamics
• Chemical thermodynamics allows us
to predict both the direction and the
extent of spontaneous chemical and
physical change under particular
conditions using a property called the
Gibbs free energy, G.
8.2 Gibbs free energy
• Chemical reactions and physical
changes almost always either absorb or
release energy as heat.

• Energy may be distributed throughout a

chemical system in a large number of
different ways, some of which have
significantly higher probabilities than
others
8.2 Gibbs free energy
G = H – TS
• H enthalpy of the system
– Function related to the heat absorbed or
evolved by a chemical system

• S entropy of the system

– Measure of number of ways energy is
distributed throughout a chemical system

• T temperature in kelvin
8.2 Gibbs free energy
ΔG = ΔH – TΔS
• ΔG allows us to determine whether a
particular chemical reaction or physical
change is spontaneous
• If ΔG < 0, the process is spontaneous
• If ΔG > 0, the process is
nonspontaneous
• If ΔG = 0, the system is at equilibrium
 8.2 Gibbs free energy
• System refers to the particular
chemical species being studied
• Surroundings are everything else
 8.2 Gibbs free energy
• Universe refers to the system and the
surroundings
• Boundary defined as region across
which heat flows
8.2 Gibbs free energy
• Open systems
– Can gain or lose mass and energy across
their boundaries
• Closed systems
– Can absorb or release energy, but not
mass, across the boundary
• Isolated systems
– Can not exchange matter or energy with
their surroundings
8.2 Gibbs free energy
• SI unit of energy
– Joule
– 1 J = 1 kg m2 s-2
– 1 kJ = 103 J

• Thermodynamic equations require the

temperature in kelvin
– Temperature difference (ΔT) of 1 K is
numerically equal to ΔT of 1 °C
 8.3 Enthalpy
• Internal energy (U)
– The sum of energies for all of the individual
particles in a sample of matter

– Interested in the CHANGE in internal energy that

accompanies a process

ΔU = Ufinal – Uinitial
ΔU = Uproducts – Ureactants
 8.3 Enthalpy
• Internal energy
– Chemical system can exchange energy with
its surroundings in two ways
– Either absorbing heat from or emitting heat to
the surroundings
– Doing work on the surroundings of having the
surroundings do work on it
– Work may be defined simply as motion against
an opposing force
 8.3 Enthalpy
• Internal energy
– Type of work most
often encountered in
chemical systems is
the compression or
expansion of gas
– Often called pressure-
volume or pV work
– w = –pΔV
 8.3 Enthalpy
• First law of thermodynamic
ΔU = q + w
– q - heat
– w - work
– Energy can be transferred between
systems as either heat or work
– It can never be created or destroyed
– Law of conservation of energy
 8.3 Enthalpy
• State functions
– Value is dependent only on the current
state of the system
– ΔX = Xfinal – Xinitial
– Independence from the method or
mechanism by which a change occurs is
the important feature of all state
functions
 8.3 Enthalpy
• State functions
– q and w are NOT state functions
– The values of q
and w are
dependent on
the path
of change
 8.3 Enthalpy
• Heat Capacity
– Heat and temperature are not the same
thing
– Heat is a transfer of energy due to a
temperature difference
q = CΔT
– q - heat (J)
– C - heat capacity (J K-1)
 8.3 Enthalpy
• Heat Capacity
– Heat capacity depends on the size of the
sample
– A property with a value that depends on
the size of the sample is an extensive
property
– A property with a value independent of
the size of the sample is an intensive
property
 8.3 Enthalpy
• Heat Capacity
– Divide heat capacity (extensive property) by
the mass of the sample to form specific heat
capacity (intensive property)

C
c=
m
– c - specific heat capacity (J g-1 K-1 )
– Divide by amount instead of mass to form
molar heat capacity (J mol-1 K-1 )
 8.3 Enthalpy
• Heat Capacity
q = cmΔT
If a gold ring with a mass of 5.50 g changes
in temperature from 25.0 to 28.0 °C, how
much heat has it absorbed?
m = 5.50 g c = 0.129 J g–1 K–1 ΔT = 3 K
q = cmΔT
= (0.129 J g-1 K-1 ) × (5.50 g) × (3 K)
= 2.1 J
 8.3 Enthalpy
• The determination of heat
– Calorimeter
• Apparatus designed to
minimise heat loss
between the system
and surroundings
– Bomb calorimeter
• System remains at
constant volume
• ΔU = q + w
• ΔU = qv
 8.3 Enthalpy
• Enthalpy: the heat of reaction at
constant pressure
ΔU = q + w
ΔU = qp – pΔV
– Inconvenient as need
to know ΔV
– Define a new thermodynamic property
called enthalpy (H)
ΔH = qp
 8.3 Enthalpy
• Enthalpy: the heat of reaction at
constant pressure
H = U + pV
ΔH = ΔU + pΔV

– Substituting ΔU = qp – pΔV gives

ΔH = qp – pΔV + pΔV
ΔH = qp
 8.3 Enthalpy
• Enthalpy: the heat of reaction at constant
pressure
– The heat of reaction at constant pressure is
equal to ΔH
– The heat of reaction at constant volume is
equal to ΔU
– ΔH > 0 reaction is endothermic
– ΔH < 0 reaction is exothermic
– The difference between ΔH and ΔU for a
reaction is pΔV
 8.3 Enthalpy
• Standard enthalpy change
– Standard states
• Pressure of 105 Pa
• Concentration of 1 M

– Standard enthalpy of reaction

• Value of ΔH for a reaction occurring under
standard conditions (ΔHθ (kJ or kJ mol–1)
• Involves the actual numbers of MOLES
specified by the coefficients of the equation
 8.3 Enthalpy
• Standard enthalpy change
N2(g) + 3H2(g)  2NH3(g) ΔHθ = –92.38 kJ
– The above is a thermochemical equation
– Always gives the physical states of the
reactants and products
– Its value of ΔHθ is only true when
coefficients of reactants and products
are numerically equal to the number of
moles of the corresponding substances
 8.3 Enthalpy
• Hess’s law
– Method for combining known thermochemical
equations in a way that allows us to calculate ΔHθ
for another reaction
– One step
C(s) + O2(g)  CO2(g) ΔHθ = –393.5 kJ
– Two step
Step 1: C(s) + ½O2(g)  CO(g) ΔHθ = – 110.5 kJ
Step 2: CO(g) + ½O2(g)  CO2(g)ΔHθ = – 283.0 kJ
 8.3 Enthalpy
• Hess’s law
2Fe(s) + 3CO2(g)  Fe2O3(s) + 3CO(g) ΔHθ = +26.7 kJ
3CO(g) + O2(g)  3CO2(g) ΔHθ = -849.0 kJ
2Fe(s) + O 2 (g) 
Rules for manipulating
Fe O
2 3 (s)
thermochemical equations:
ΔHθ
= -822.3 kJ
–
1. When an equation is reversed the sign of ΔHθ must also be reversed.

Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g) ΔHθ = -26.7 kJ

2Fe(s) + 3CO2(g)  Fe2O3(s) + 3CO(g) ΔHθ = +26.7 kJ
 8.3 Enthalpy
• Hess’s law
2Fe(s) + 3CO2(g)  Fe2O3(s) + 3CO(g) ΔHθ = +26.7 kJ
3CO(g) + O2(g)  3CO2(g) ΔHθ = -849.0 kJ
2Fe(s) + O2(g)  Fe2O3(s) ΔHθ = -822.3 kJ
– Rules for manipulating thermochemical
equations:
2. Formulae can be cancelled from both
sides of an equation only if the substance
is an identical physical state.
 8.3 Enthalpy
• Hess’s law
2Fe(s) + 3CO2(g)  Fe2O3(s) + 3CO(g) ΔHθ = +26.7 kJ
3CO(g) + O2(g)  3CO2(g) ΔHθ = -849.0 kJ
2Fe(s) + O2(g)  Fe2O3(s) ΔHθ = -822.3 kJ
– Rules for manipulating thermochemical
equations:
3. If all the coefficients of an equation are
multiplied or divided by the same factor,
the value of ΔHθ must likewise be
multiplied or divided by that factor.
CO(g) + ½O2(g)  CO2(g) ΔHθ = -283.0 kJ
3CO(g) + 3/2O (g)  3CO (g) ΔHθ = -849.0 kJ
 8.3 Enthalpy
• Standard enthalpy of combustion
– ΔcHθ
– Enthalpy change at temperature T when
1 mole of a substance is completely burned
in pure oxygen gas
– Combustion reactions are always
exothermic
– ΔcHθ always negative
– kJ mol–1
 8.3 Enthalpy
• Standard enthalpy of formation (ΔfHθ)
– Enthalpy change when 1 mole of substance is formed
at 105 Pa and the specified temperature from its
elements in their standard states
– An element is in its standard state when it is in its
most stable form and physical state at 105 Pa and the
specified temperature
– ΔfHθ for the elements in their standard states are 0
 8.3 Enthalpy
• Standard enthalpy of formation
aA + bB  cC + dD
∆H θ = c ∆f HCθ + d ∆f H Dθ − a ∆f H Aθ + b ∆ f H Bθ 
 
– Hess’s law equation
– Use either enthalpies of combustion or enthalpies of
formation
 8.3 Enthalpy
• Bond enthalpies
– A bond enthalpy is the enthalpy change on
breaking 1 mole of a particular chemical
bond to give electrically neutral fragments
– Atomisation enthalpy (ΔatH) is the enthalpy
change that occurs on rupturing all the
chemical bonds in 1 mole of gaseous
molecules
 8.3 Enthalpy
• Bond enthalpies and Hess’s law
 8.3 Enthalpy
• Lattice enthalpies and Hess’s law
– Lattice enthalpies for ionic solids calculable
using Hess’s law and thermodynamic data
 8.4 Entropy
• Entropy and probability

No energy is transferred

Two units of energy

One unit of energy is are transferred
transferred

Three units of energy

are transferred
– Spontaneous processes tend to proceed from states of low
probability to states of higher probability.
– Spontaneous processes tend to disperse energy
 8.4 Entropy
• Entropy and entropy change
– Entropy (S) describes the number of equivalent
ways that energy can be distributed in the system
– Entropy is a state function
ΔS = Sproducts – Sreactants

– Any event that is accompanied by an increase in

the entropy of the system has a tendency to
occur spontaneously
 8.4 Entropy
• Entropy and entropy change
 8.4 Entropy
• Factors that affect entropy
– Often possible to predict whether ΔS is positive or
negative for a particular change
– Volume
• For gases the entropy increases with increasing volume
 8.4 Entropy
• Factors that affect entropy
– Temperature
• The higher the temperature the higher the entropy
 8.4 Entropy
• Factors that affect entropy
– Physical state
• One of the major factors that affects the entropy of a
system is its physical state
 8.4 Entropy
• Factors that affect entropy
– Number of particles
• When all other things are equal, reactions that
increase the number of particles in the system tend
to have a positive entropy change
 8.4 Entropy

qsuroundings
∆S surroundings =
T

−∆Hsystem
∆S surroundings =
T
 8.4 Entropy
• Absolute entropy and the third law of
thermodynamics
– At absolute zero, the entropy of a perfectly
ordered pure crystalline substance is 0
S = 0 at T = 0 K

– Point at which entropy equal to 0 is known,

hence by experimental measurement and
calculation entropy can be determined for a
substance at temperatures above 0 K
 8.4 Entropy
• Absolute entropy and the third law of
thermodynamics
– Standard entropy (Sθ) – entropy of
1 mole of a substance determined under
standard conditions at temperature
of 298 K
– Standard entropy of reaction
aA + bB  cC + dD
∆S θ = c ∆f SCθ + d ∆f SDθ −  a ∆f S Aθ + b ∆f SBθ 
 
 8.5 Gibbs free energy and
reaction spontaneity
• The sign of ΔG

ΔGθ = ΔHθ – TΔSθ

ΔG < 0 reaction
spontaneous
8.5 Gibbs free energy and
reaction spontaneity
• Standard Gibbs free energy change
– When ΔG is determined at 105 Pa, this is
called the standard free energy change
(ΔGθ)
– There are several ways for determining
ΔGθ for a reaction
• ΔGθ = ΔHθ – TΔSθ
• aA + bB  cC + dD
∆G θ = c ∆f GCθ + d ∆f GDθ −  a ∆f GAθ + b ∆f GBθ 
 
 8.5 Gibbs free energy and
reaction spontaneity
• Gibbs free energy and work

– Maximum conversion of chemical energy to work occurs if a

reaction is carried out under conditions that are said to be
thermodynamically reversible
8.5 Gibbs free energy and
reaction spontaneity
• Gibbs free energy and work
– The maximum amount of energy produced by a
reaction that can be THEORETICALLY harnessed
as work is equal to ΔG
– ΔG = 0 the system is in a state of equilibrium
Gproducts = Greactants
– When ΔG = 0 the amount of work available is 0
8.5 Gibbs free energy and
reaction spontaneity

∆H ∆H
∆S = T =
T ∆S
 8.5 Gibbs free energy and
reaction spontaneity

• Gibbs free
energy and
work