Chapter 19

Chemical
Thermodynamics
Masego Ramonyai

Office GH851
Gate House

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 THERMODYNAMICS

Heat “Not static”

Temperature from
Energy the Greek
Word
for “power”
Thermodynamics is the study of energy and its
transformation.

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 FIRST LAW OF THERMODYNAMICS

• You will recall that energy cannot be created

nor destroyed.

• Therefore, the total energy of the universe is a

constant.

• Energy can, however, be converted from one

form to another or transferred from a system
to the surroundings or vice versa.

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 FIRST LAW OF THERMODYNAMICS

Two ways for energy to be transferred

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 U is a state function

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 What the first law doesn’t tell us

• Whether or not a reaction will occur

(spontaneously)

• The extent to which a reaction will occur (i.e.,

the position of the equilibrium).

• The First Law is an incomplete description of

the energy changes occurring during a
chemical reaction.

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 SPONTANEOUS PROCESSES

• Spontaneous processes are

those that can proceed
without any outside
intervention, i.e. without
ongoing input of energy
from outside the system.

• The gas in vessel B will

spontaneously effuse into
vessel A, but once the gas is
in both vessels, it will not
spontaneously return to
vessel B.
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 SPONTANEOUS PROCESSES

• Processes that are

spontaneous in one
direction are
nonspontaneous in the
reverse direction.

• Spontaneity does not

predict the rate (speed) of
the reaction.

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 SPONTANEOUS DOESN’T MEAN FAST

• Rusting of an iron nail is spontaneous and

slow.

Fe + O2 → Fe2O3

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 • Acid-base neutralisation is spontaneous and
fast.

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• When H2(g) is ignited, it combines with O2(g)
in air to form water in a spontaneous and fast
reaction.

http://iopscience.iop.org/00319120/48/1/22/downloadFigure/figure/ped435834f3
 SPONTANEOUS PROCESSES

• Processes that are spontaneous at one temperature may be

nonspontaneous at other temperatures.

• Above 0 oC, it is spontaneous for ice to melt.

• Below 0 oC, the reverse process is spontaneous.

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 WHAT MAKES A PROCESS SPONTANEOUS?
• The First Law of Thermodynamics accounts for the energy
involved in a process and the size of the energy change.

• However it does not tell us in what direction a chemical

change spontaneously occurs.

• Example: Ice melts in your hand.

 The First Law of Thermodynamics explains that heat is
transferred from your hand to the ice and the ice melts,
i.e. energy is converted and is therefore conserved.
 But this law does not explain why the melted ice does not
refreeze in your hand.

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 WHAT DETERMINES THE SPONTANEITY OF A
PROCESS?

• There must be some other quantity other than internal

energy (U) and enthalpy (H) that determines if a process
is going to occur i.e. whether a process is spontaneous in
a particular direction.

• This quantity is called entropy.

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 Irreversible processes

• Irreversible processes cannot be undone by exactly

reversing the change to the system.
• Spontaneous processes are irreversible.

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 Reversible processes

In a reversible process the system changes in such a way

that the system and surroundings can be put back in their
original states by exactly reversing the process.

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 The Second Law of
Thermodynamics: Entropy

• To understand spontaneity we
consider the thermodynamic
quantity called entropy.

• Entropy (S) is a term

introduced by Rudolph
Clausius in the 19th century.

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 ENTROPY

• Entropy is a thermodynamic quantity that measures

disorder, chaos and randomness.

• The symbol for entropy is S.

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 ENTROPY

The second law of thermodynamics

states that the entropy of the universe
increases for spontaneous processes,
and the entropy of the universe does
not change for reversible processes.

Recall: Universe = System + Surroundings

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 ENTROPY

In other words:

For reversible processes:

∆Suniv = ∆Ssystem + ∆Ssurroundings = 0

For irreversible processes:

∆Suniv = ∆Ssystem + ∆Ssurroundings > 0

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 ENTROPY

These last truth mean that as a result of all

spontaneous processes, the entropy of the universe
increases.

ENTROPY IS NOT CONSERVED

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 ENTROPY

Like total Energy, E, and Enthalpy,

H, Entropy is a state function:

ΔS = Sfinal - Sinitial

Clausius believed that the ratio of heat delivered and

the temperature q/T at which it is delivered was
important.

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 ENTROPY

For a process occurring at constant temperature (an

isothermal process), the change in entropy is equal
to the heat that would be transferred if the process
were reversible divided by the temperature:

ΔS = qrev
T

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 Entropy on the Molecular Scale

• Ludwig Boltzmann described the concept of entropy

on the molecular level.
• Temperature is a measure of the average kinetic
energy of the molecules in a sample.

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 Entropy on the Molecular Scale

• Molecules exhibit several types of motion:

 Translational: Movement of the entire molecule from one
place to another.
 Vibrational: Periodic motion of atoms within a molecule.
 Rotational: Rotation of the molecule about an axis or
rotation about σ bonds.

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 Entropy on the Molecular Scale

• Boltzmann envisioned the motions of a sample of molecules at a

particular instant in time.
 This would be akin to taking a snapshot of all the molecules.

• He referred to this sampling as a microstate of the

thermodynamic system.

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 Entropy on the Molecular Scale

• Each thermodynamic state has a specific number of microstates,

W, associated with it.
• Entropy is
S = k ln W
where k is the Boltzmann constant, 1.38 x 1023 J/K.

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 Third Law of Thermodynamics

The entropy of a pure, perfect, crystalline

substance (i.e., with no defects) at absolute
zero (T = 0 K) is equal to 0.

At T = 0 K there is only one

microstate
W=1
S = klnW = 0
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 Entropy on the Molecular Scale

o The change in entropy for a process, then, is

∆S = k ln Wfinal - k ln Winitial

∆S = k ln Wfinal
ln Winitial

o Entropy increases with the number of microstates in

the system.

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 Entropy on the Molecular Scale

• The number of microstates and, therefore, the entropy,

tends to increase with increases in
 Temperature
 Phase change
 Volume
 The number of independently moving molecules.

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 Entropy and Physical States
• Entropy increases with the increase of freedom of motion of molecules.
• Therefore….. S(g) > S(l) > S(s)

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 Entropy and Physical States

The entropy of a pure crystalline substance at absolute zero is 0.

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 Solutions

Generally, when a
solid is dissolved in a
solvent, entropy
increases.
(the disorder or
randomness increases)

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 Entropy Changes

• In general, entropy
increases when
 Gases are formed from
liquids and solids;
 Liquids or solutions are
formed from solids;
 The number of gas
molecules increases;
 The number of moles
increases.

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 PREDICTING ∆S FOR A REACTION

ΔSreaction = Sproducts – Sreactants

• An increase the number of moles of gas results

in an increase in entropy so ΔSreaction > 0.

• An decrease the number of moles of gas results

in a decrease in entropy so ΔSreaction < 0.

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 STANDARD ENTROPIES

Larger and more complex molecules have greater

entropies because they have more degrees of freedom
(independent ways of moving) and, hence, microstates.

Estimate the standard entropy of butane ~ 310–315 J mol-1K-1

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 STANDARD MOLAR ENTROPY S°

The standard molar entropy of a substance is the entropy

per mole of the substance at a pressure of 1 atm at a
specified temperature (usually 298 K).

•Other symbols that are used for standard molar

entropy are: Sθ, Sm θ, S298°.
•Standard molar entropies are positive.
•Elements and compounds have non-zero entropy
values.
•S°H+(aq) = 0 by convention.

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 TABLE OF
STANDARD
MOLAR
ENTROPIES Gases have
higher S°
values

See also the

table at the
back of the
pink student
booklet.
Solids have
lower S°
values
CALCULATING STANDARD ENTROPY CHANGES

• One can calculate the standard entropy change, ΔS°,

for a reaction using standard molar entropy values.

ΔS° = ΣnS°(products) - ΣmS°(reactants)

n and m are coefficients of the balanced

equation.
 Example

Consider the following reaction:

4Fe(s) + 3O2(g) 2Fe2O3(s)

a) First predict whether the ΔS of the reaction will be

positive or negative.

b) Then calculate the ΔS° for the above reaction.

ΔS° [Fe(s)] = 27.23 J/mol-K

ΔS° [O2(g)] = 205 J/mol-K
ΔS° [Fe2O3(s) = 87.4 J/mol-K
 WHY IS THIS REACTION SPONTANEOUS?

• ΔS°reaction was predicted and calculated as less than zero,

ΔS°< 0.
• ΔH° reaction for the oxidation of iron is known to be less
than zero, ΔH°< 0 (exothermic reaction) (-842 kJ/mol).

• The increase in temperature results in an increase in

thermal motion resulting in an increase in entropy in the
surroundings.

• ∴ overall ΔSuniverse = ΔSsystem + ΔSsurroundings > 0

• A greater disorder is created in the surroundings than in

the system. Therefore the overall (total) entropy increases
and the process is spontaneous.
• Calculate ∆S° for the equation below using the standard
entropy data given:

2NO(g) + O2(g) 2NO2(g)

S° values (JK-1mol-1):
NO2(g) = 240,
NO(g) = 211,
O2(g) = 205.

1. +176 JK-1mol-1 3. - 147 JK-1mol-1

2. +147 JK-1mol-1 4. - 176 JK-1mol-1
 REACTION SPONTANEITY

• Spontaneous processes that result in a decrease in the

entropy of the system are always exothermic.

• Thus, the spontaneity of a reaction seems to involve two

thermodynamic concepts, enthalpy and entropy.
 GIBBS FREE ENERGY

Gibbs free energy (G) is defined as:

• The thermodynamic state function that gives a criterion
for spontaneous change in terms of enthalpy (H) and
entropy (S).
G = H - TS

• Temperature is absolute temperature (i.e. temperature is

in kelvin).
• Remember a state function is a property of a system that
is defined by the state or condition of the system and not
how it got to that state.
 CHANGE IN FREE ENERGY

• For a process taking place at constant temperature, the

change in free energy of the system is:

ΔG = ΔH - TΔS

• The change in free energy, ΔG, is the portion of the energy

change that is free to do work (w).
ΔG = -wmax
•A process is spontaneous if ΔG is negative,
i.e. ΔG < 0.
 STANDARD FREE ENERGY CHANGES ∆G°

• ΔG° is the free energy change for a reaction under standard

conditions.
• ΔG° for a reaction can be calculated from tabulated ΔGf°
(standard free energy of formation) values.

ΔG°reaction = ΣnΔGf°(products) - ΣmΔGf°(reactants)

• n and m are coefficients of the balanced equation.

FREE ENERGY OF FORMATION CHANGES (∆Gf°)

ΔGf° is the Gibbs free energy change for the formation of 1

mole of substance from its elements in their standard state
at a specified temperature (usually 25 °C) and 1 atm
pressure.

• ΔGf° of an element in its standard state is zero.

• The standard state for:
 a solid is a pure solid.
 a liquid is a pure liquid.
 a gas is 1 atm pressure.
 a solution is 1M concentration.
 THE SIGN OF ∆G AND SPONTANEITY

• The sign of ΔG provides information about the

spontaneity of a process at constant temperature and
pressure.

∆G -ve Reaction is spontaneous in the

forward direction.
∆G = 0 Reaction is at equilibrium.
Free energy has reached a minimum and
system can do no work.
Forward reaction is not
∆G +ve spontaneous.
Reaction is spontaneous in reverse
direction.
 EXAMPLE

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• If the reaction mixture has too much N2 and H2
relative to NH3, the equilibrium lies too far to the left
(Q < K) and NH3 forms spontaneously i.e. ΔG is
negative in the forward direction.

• If there is too much NH3 in the mixture, the

equilibrium lies too far to the right (Q > K) and NH3
decomposes spontaneously into N2 and H2 i.e. ΔG is
negative in the reverse direction.

• At equilibrium ΔG = 0
EXAMPLE: THE OXIDATION OF IRON (RUSTING)
• Calculate the ΔG° at 25 °C for the oxidation (rusting) of iron to
show the spontaneity of the reaction.

4Fe(s) + 3O2(g) 2Fe2O3(s)

 STANDARD FREE ENERGY CHANGES

a) Calculate ∆G for the equation below using the Gibbs

free energy data given.
b) What is ∆G for the reverse of this reaction?

2SO2(g) + O2(g) 2SO3(g)

∆G° values (kJmol-1):

SO2(g) = -300.4,
SO3(g) = -370.4
 CALCULATING ∆G USING ∆H AND ∆S

• We can also calculate ΔG by first calculating ΔH and ΔS and

then using the equation:

ΔG = ΔH - TΔS

• See tutorial 10 problems.

 FREE ENERGY AND TEMPERATURE
• Lets consider temperatures other than 25°C.
• How does ΔG change with temperature?
ΔG = ΔH - TΔS
• There are two parts to the free energy equation:
 ΔH— the enthalpy term
 TΔS— the entropy term
• The temperature dependence of free energy, therefore
comes from the entropy term.
• ΔH and ΔS do not change much with temperature provided
there is no phase change.
 DEPENDENCE OF ∆G ON TEMPERATURE

• The dependence of ΔG on temperature is governed by the

value of T in the expression.
ΔG = ΔH - TΔS

ΔH ΔS - TΔS ΔG Behaviour of reaction

- + - - Spontaneous at all temperatures
+ - + + Non-spontaneous at all temperatures
- - + +/- Spontaneous at only low temperatures
+ + - +/- Spontaneous at only high temperatures

• Systems tend towards the lowest possible G values.

 EXAMPLE
Consider the reaction:
CH4(g) + H2O(g) 3H2(g) + CO(g)

Using tables of ΔHf° and S°, calculate:

a) ΔG° at (i) 600 K
(ii) 1200 K
b) The temperature at which ΔG = 0.

FROM TABLES (∴ at 298 K):

ΔH°(298) = 206.1 kJmol-1

ΔS°(298) = 212.8 Jmol-1 K-1 = 0.2128 kJmol-1 K-1

NOTE: Be aware of the units of ΔH° and ΔS°!

 Gibbs Free Energy and Temperature

• Consider the signs ΔH and ΔS

• Some reactions that are not spontaneous at low

temperature can become spontaneous on heating.

ΔG = ΔH - TΔS
 Gibbs Free Energy and Temperature

• Decomposition of CaCO3 has ∆H° = 178.3 kJ mol-1 and ∆S°

= 159.0 JK-1 mol-1.
At what temperature does this reaction become
spontaneous?

CaCO3(s) → CaO(s) + CO2(g)

 COUPLED REACTIONS

• A non-spontaneous process can be made to occur if it is

coupled to a spontaneous process.
• Consider:

ΔG° (kJ mol-1) Type of reaction

A B +23 Non spontaneous
B C -30 Spontaneous
A C -7 Overall reaction is spontaneous

• Coupled reactions have a common substance that is the

product of one step and the reactant for the next step.
 COUPLED REACTIONS IN NATURE

Coupled reactions are widely used in nature to drive

biochemical processes.

Example:
An important reaction is the hydrolysis of adenosine
triphosphate (ATP) to adenosine diphosphate (ADP).

ATP4- + H2O ADP3- + HPO42- + H+

ΔG° = -30 kJ ∴ reaction is spontaneous.

The conversion of ADP back to ATP is not spontaneous,

ΔG° = +30 kJ.
 DRIVING THE FORMATION OF ATP
• One of the steps in the oxidation of glucose is the
formation of phosphoenolpyruvate.
• This compound can lose a HPO42- ion spontaneously and
drive the synthesis of ATP from ADP in a coupled process.

phosphoenolpyruvate + H2O pyruvate + HPO42- (ΔG° = -62 kJ)

ADP3- + HPO42- + H+ ATP4- + H2O (ΔG° = +30 kJ)
phosphoenolpyruvate + ADP3- + H+ pyruvate + ATP4-
ΔG° = (-62+30) kJ = -32 kJ ∴ overall reaction is spontaneous.

• The complete oxidation of one molecule of glucose results

in the formation of 38 molecules of ATP.
 Gibbs Energy and Equilibrium

• Most chemical reactions occur under non-standard

conditions.
• Under any conditions, standard or non-standard, the Gibbs
energy change can be found from

Ideal-gas
Reaction
constant
quotient

∆G = ∆G° + RT lnQ

(Under standard conditions, all concentrations are 1 M, so Q =

1 and ln Q = 0 and the last term drops out.)
 Gibbs Energy and Equilibrium

• Calculate ∆G at 298 K for a mixture of 0.5 atm N2, 0.75

atm H2 and 2.0 atm NH3

N2(g) + 3H2(g) 2NH3(g)

Given ∆G° = -33.3 kJ/mol

 Gibbs Energy and Equilibrium
• At equilibrium, Q = K, and ∆G = 0.

• The equation becomes

0 = ∆G° + RT lnK

• Rearranging, this becomes

∆G° = - RT lnK
or,

K = exp(-∆G° /RT)
 Gibbs Energy and the Equilibrium Constant

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 Gibbs Energy and Equilibrium

If the temperature of the reaction is decreased, what is the

effect on the equilibrium constant and ∆G° (e.g.see table
15.2)?

N2(g) + 3H2(g) 2NH3(g) ∆H° = -92.4 kJ/mol

See p810 12th Edition also Table 15.2

 Gibbs Energy and Equilibrium
The overall reaction for the corrosion (rusting) of iron is given
below. Use the data given to calculate the equilibrium
constant for the reaction.

4Fe(s) + 3O2(g) 2Fe2O3(s)

 Practice Exercise
Predict whether ∆S is positive or negative for each of the following processes,
assuming each occurs at constant temperature:

a) H2O(l) H2O(g)
b) Ag+(aq) + Cl-(aq) AgCl(s)
c) 4Fe(s) + 3O2(g) 2Fe2O3(s)
d) N2(g) + O2(g) 2NO(g)
e) 2SO3(g) 2SO2(g) + O2(g)

Answer:
(a) = positive
(b) = negative
(c) = negative
(d) = Same number of moles on both sides, thus end
change will be small. ∆S will be close to zero.
(e) = positive
 Practice Exercise

Indicate whether each of the following processes produces an increase or

decrease in the entropy of the system?

(a) CO2(s) CO2(g)

(b) CaO(s) + CO2(g) CaCO3(s)
(c) HCl(g) + NH3(g) NH4Cl(s)
(d) 2SO2(g) + O2(g) 2SO3(g)

Answer:
(a) Increase
(b) Decrease
(c) Decrease
(d) Decrease
 Practice Exercise

Which one of the following processes involves a decrease in entropy?

a) The decomposition of NH3(g) to H2(g) and N2(g).

b) The condensation of steam to liquid water.
c) The sublimation of CO2 from solid to gas.
d) The evaporation of ethanol.
e) The dissolution of NH4NO3(s) in water.