CHEM 111 Lecture-10

Thermodynamics: Entropy, Free Energy,

and the Direction of Chemical Reactions

Presented by:
Dr. Faizul Azam
faizulazam@gmail.com
 The Nature of Energy

• Capacity to do work or to produce heat.

• Law of conservation of energy – energy can be converted

from one form to another but can be neither created nor
destroyed.

 The total energy content of the universe is constant.

• Potential energy – energy due to position or composition.

• Kinetic energy – energy due to motion of the object and

depends on the mass of the object and its velocity.
Initial Position
• In the initial position, ball A has a higher potential energy
than ball B.

Final Position
• After A has rolled down the hill, the potential energy lost by A
has been converted to random motions of the components of
the hill (frictional heating) and to the increase in the potential
energy of B.
• Heat involves the transfer of energy between two objects
due to a temperature difference.

• Work – force acting over a distance.

• Energy is a state function; work and heat are not

– State Function – property that does not depend in any way on the
system’s past or future (only depends on present state).

Chemical Energy
• System – part of the universe on which we wish to focus
attention.

• Surroundings – include everything else in the universe.

• System – part of the universe on which we wish to focus
attention.

• Surroundings – include everything else in the universe.

• Endothermic Reaction:
– Heat flow is into a system.
– Absorb energy from the surroundings.

• Exothermic Reaction:
– Energy flows out of the system.

• Energy gained by the surroundings must be equal to the

energy lost by the system.
 Classify each process as exothermic or endothermic.
Explain. The system is underlined in each example.

Exo a) Your hand gets cold when you touch ice.

Endo b) The ice gets warmer when you touch it.

Endo c) Water boils in a kettle being heated on a stove.

Exo d) Water vapor condenses on a cold pipe.

Endo e) Ice cream melts.

 First Law of Thermodynamics

 Energy cannot be created or 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.

Enthalpy/Entropy

 Enthalpy is the heat absorbed by a system during a

constant-pressure process.

 Entropy is a measure of the randomness in a system.

 Both play a role in determining whether a process is

spontaneous.
 Spontaneous Processes

• Spontaneous processes proceed without any outside assistance.

• The gas in vessel A will spontaneously effuse into vessel B, but

it will not spontaneously return to vessel A.

• All chemical processes require energy (activation energy) to take

place, but once a spontaneous process has begun, no further
input of energy is needed.

Spontaneous
 A nonspontaneous change occurs only if the surroundings
continuously supply energy to the system.

Nonspontaneous

 A nonspontaneous change occurs only if the surroundings

continuously supply energy to the system.
• If a change is spontaneous in one direction, it will be
nonspontaneous in the reverse direction.

Spontaneous

Non-spontaneous
Experimental factors affect Spontaneous processes

• Temperature and pressure can affect spontaneity.

• An example of how temperature affects spontaneity is ice

melting or freezing.
 Reversible and Irreversible Processes

Reversible process:
 The system changes so that the system and surroundings
can be returned to the original state by exactly reversing the
process.
 This maximizes work done by a system on the surroundings.
Irreversible processes cannot be undone by exactly reversing
the change to the system or cannot have the process exactly
followed in reverse.

Also, any spontaneous process is irreversible!

 The First Law of Thermodynamics Does Not
Predict Spontaneous Change

Energy is conserved. It is neither created nor destroyed, but is

transferred in the form of heat and/or work.

∆E = q + w

q represents heat
w represents work

The total energy of the universe is constant:

∆Esys = −∆Esurr or ∆Esys + ∆Esurr = ∆Euniv = 0

 The law of conservation of energy applies to all changes,

and does not allow us to predict the direction of a
spontaneous change.
 ∆H Does not predict Spontaneous change

A spontaneous change may be exothermic or endothermic.

Spontaneous exothermic processes include:

• freezing and condensation at low temperatures,
• combustion reactions,
• oxidation of iron and other metals.

Spontaneous endothermic processes include:

• melting and vaporization at higher temperatures,
• dissolving of most soluble salts.

The sign of ∆H does not by itself predict the direction of a

spontaneous change.
 Freedom of Particle Motion

All spontaneous endothermic processes result in an increase in

the freedom of motion of the particles in the system.

solid → liquid → gas

crystalline solid + liquid → ions in solution

less freedom of particle motion more freedom of particle motion

localized energy of motion dispersed energy of motion

A change in the freedom of motion of particles in a system is a

key factor affecting the direction of a spontaneous process.
 Microstates and Dispersal of Energy

• Just as the electronic energy levels within an atom are

quantized, a system of particles also has different allowed
energy states.

• Each quantized energy state for a system of particles is called

a microstate.
– At any instant, the total energy of the system is dispersed
throughout one microstate.

• At a given set of conditions, each microstate has the same

total energy as any other.
– Each microstate is therefore equally likely.

• The larger the number of possible microstates, the larger the

number of ways in which a system can disperse its energy.
 Spontaneous expansion of a gas.

• When the stopcock is opened, the gas spontaneously

expands to fill both flasks.

• Increasing the volume increases the number of

translational energy levels the particles can occupy.

The number of microstates – and the entropy – increases.

 The entropy increase due to the expansion of a gas.

Opening the stopcock increases the number of possible energy

levels, which are closer together on average. More distributions of
particles are possible.
 Expansion of a gas and the increase in number of microstates.

When the
stopcock
opens, the
number of
microstates
is 2n, where
n is the
number of
particles.
 Entropy
• Entropy can be thought of as a measure of the randomness of a
system. It is a state function:

The number of microstates (W) in a system is related to the

entropy (S) of the system.

S = k ln W

A system with fewer microstates has lower entropy.

A system with more microstates has higher entropy.

 All spontaneous endothermic processes exhibit an increase in

entropy.
 ∆S for a Reversible Process

It can be found by heat transfer from surroundings at a given

temperature:

∆Ssys = qrev
T

A reversible process is one that occurs in such tiny

increments that the system remains at equilibrium, and the
direction of the change can be reversed by an infinitesimal
reversal of conditions.
 The Second Law of Thermodynamics

The sign of ∆S for a reaction does not, by itself, predict the

direction of a spontaneous reaction.

If we consider both the system and the surroundings, we

find that all real processes occur spontaneously in the
direction that increases the entropy of the universe.

For a process to be spontaneous, a decrease in the

entropy of the system must be compensated by a larger
increase in the entropy of the surroundings.
 Comparing Energy and Entropy

The total energy of the universe remains constant.

∆Esys + ∆Esurr =∆Euniv = 0

∆H is often used to approximate∆E.

For enthalpy there is no zero point; we can only measure
changes in enthalpy.

The total entropy of the universe increases.

∆Suniv =∆Ssys +∆Ssurr > 0

 The Third Law of Thermodynamics

A perfect crystal has zero entropy at absolute zero.

Ssys = 0 at 0 K

A “perfect” crystal has flawless alignment of all its

particles. At absolute zero, the particles have minimum
energy, so there is only one microstate.
S = k ln W = k ln 1 = 0

To find the entropy of a substance at a given temperature, we cool it as

close to 0 K as possible. We then heat in small increments, measure q
and T, and calculate ∆S for each increment. The sum of these ∆S
values gives the absolute entropy at the temperature of interest.
 Standard Molar Entropies

S° is the standard molar entropy of a substance,

measured for a substance in its standard state in
units of J/mol·K.

The conventions for defining a standard state include:

• 1 atm for gases
• 1 M for solutions, and
• the pure substance in its most stable form for
solids and liquids.
 Factors Affecting Entropy

• Entropy depends on temperature.

– For any substance, S° increases as temperature increases.

• Entropy depends on the physical state of a substance.

– S° increases as the phase changes from solid to liquid to gas.

• The formation of a solution affects entropy.

• Entropy is related to atomic size and molecular
complexity.
– Remember to compare substances in the same physical state.
 Visualizing the effect of temperature on entropy.

Computer simulations show each particle in a crystal moving about its

lattice position. Adding heat increases T and the total energy, so the
particles have greater freedom of motion, and their energy is more
dispersed. S therefore increases.
 Visualizing the effect of temperature on entropy.

A system of 21 particles occupy energy levels (lines) in a box whose

height represents the total energy. When heat is added, the total
energy increases and becomes more dispersed, so S increases.
 The entropy change accompanying the dissolution of a salt.

pure solid

MIX

pure liquid
solution

The entropy of a salt solution is usually greater than that of the solid
and of water, but it is affected by the organization of the water molecules
around each ion.
 The small increase in entropy when ethanol dissolves in water.

Ethanol (A) and water (B) each have many H bonds between their own
molecules. In solution (C) they form H bonds to each other, so their
freedom of motion does not change significantly.
The entropy of a gas dissolved in a liquid.
 Entropy and Atomic Size

S° is higher for larger atoms or molecules of the same type.

Li Na K Rb Cs
Atomic radius (pm) 152 186 227 248 265
Molar mass (g/mol) 6.941 22.99 39.10 85.47 132.9
S°(s) 29.1 51.4 64.7 69.5 85.2

HF HCl HBr HI
Molar mass (g/mol) 20.01 36.46 80.91 127.9
S°(s) 173.7 186.8 198.6 206.3
 Predicting Relative Entropy Values

PROBLEM: Choose the member with the higher entropy in each of the
following pairs, and justify your choice [assume constant
temperature, except in part (e)]:
(a) 1 mol of SO2(g) or 1 mol of SO3(g)
(b) 1 mol of CO2(s) or 1 mol of CO2(g)
(c) 3 mol of O2(g) or 2 mol of O3(g)
(d) 1 mol of KBr(s) or 1 mol of KBr(aq)
(e) seawater at 2°C or at 23°C
(f) 1 mol of CF4(g) or 1 mol of CCl4(g)

PLAN: In general, particles with more freedom of motion have more

microstates in which to disperse their kinetic energy, so they
have higher entropy. Raising the temperature or having more
particles increases entropy.
SOLUTION:
(a) 1 mol of SO3(g). For equal numbers of moles of substances with
the same types of atoms in the same physical state, the more atoms
in the molecule the higher the entropy.
(b) 1 mol of CO2(g). For a given substance, entropy increases as the
phase changes from solid to liquid to gas.
(c) 3 mol of O2(g). The two samples contain the same number of
oxygen atoms but different numbers of molecules. Although each
O3 molecule is more complex than each O2 molecule, the greater
number of molecules dominates because there are many more
microstates possible for 3 mol of particles than for 2.
(d) 1 mol of KBr(aq). The two samples have the same number of ions,
but their motion is more limited and their energy less dispersed in
the solid than in the solution. An ionic substance in solution
usually has a higher entropy than the solid.
(e) Seawater at 23°C. Entropy increases with rising temperature.

(f) 1 mol of CCl4(g). For similar compounds, entropy increases with

molar mass.
 Entropy Changes in the Surroundings

A decrease in the entropy of the system is outweighed

by an increase in the entropy of the surroundings.
The surroundings function as a heat source or heat sink.
In an exothermic process, the surroundings absorbs the
heat released by the system, and Ssurr increases.
qsys < 0; qsurr > 0 and ∆Ssurr > 0

In an endothermic process, the surroundings provides the

heat absorbed by the system, and Ssurr decreases.
qsys > 0; qsurr < 0 and ∆Ssurr < 0
 Gibbs Free Energy

The free energy change (∆G) is a measure of the

spontaneity of a process and of the useful energy available
from it.

∆Gsys = ∆Hsys – T ∆Ssys

∆G < 0 (∆G is negative) for a spontaneous process

∆G > 0 (∆G is positive) for a nonspontaneous process
∆G = 0 for a process at equilibrium
Thank You