UNIT II ENERGY AND

MATTER
PART III: ENTHALPY, ENTROPY, SPONTANEITY, GIBBS FREE ENERGY & LAWS OF
THERMODYNAMICS

RHONA C. ADAJAR
ENTHALPY
• Enthalpy is sometimes known as “heat content”, but “enthalpy” is an interesting
and unusual word, so most people like to use it.
• “enthalpy” is derived from the Greek meaning “warming”
• When a process takes place at constant pressure, the heat absorbed or released is
equal to the Enthalpy change.
ENTHALPY
• Enthalpy(H) is the sum of the internal energy(U) and the product of pressure(P)
and volume(V).
DEFINITIONS
STATE OR POINT FUNCTIONS
• these are functions that depend on
the current state of the system and
not on how the system reaches that
state

PATH FUNCTIONS
• Functions that depend on the path
followed during the process
Example 1
Example 2
Practice Exercise 1
Consider the combustion of propane:
C3H8(g) + 5O2(g) -------- 3CO2(g) + 4H2O ∆H = -2044kJ

Calculate ∆H in which 25.0g of water is released when propane is

burned in excess oxygen at constant pressure.
Practice Exercise 2
Ammonia reacts with oxygen according to the equation:
4NH3(g) + 5O2(g) -------- 4NO(g) + 6H2O ∆H = -906kJ

Calculate ∆H (in kJ) associated with the complete reaction of 155

g of NH3.
SPONTANEITY
ENTROPY
• The concept of entropy basically talks about the spontaneous changes that occur
in the everyday phenomenon or the tendency of the universe towards disorder.
ENTROPY
• Entropy is used to describe the behavior of a system in terms of thermodynamic properties
such as temperature, pressure, entropy, and heat capacity.
Properties of Entropy

 It is a thermodynamic function.

 It is a state function. It depends on the state of the system and not the path that is followed.

 It is represented by S but in the standard state, it is represented by S°.

 It’s SI unit is J/Kmol.

 It’s CGS unit is cal/Kmol.

 Entropy is an extensive property which means that it scales with the size or extent of a
system.
NOTE!!!
• The greater disorder will be seen in an isolated system, hence entropy also
increases. When chemical reactions take place if reactants break into more
number of products, entropy also gets increased.
• A system at higher temperatures has greater randomness than a system at a lower
temperature. From these examples, it is clear that entropy increases with a
decrease in regularity.

Entropy order: gas>liquid>solids

ENTROPY CHANGES AND
CALCULATIONS
NOTE:
• If ∆Stotal is positive, the process is spontaneous.
• If ∆Stotal is negative, the process is non-spontaneous.
• If ∆Stotal is zero, the process is at equilibrium.
What causes entropy?

Several factors affect the amount of entropy in a system. If you increase

temperature, you increase entropy.
• More energy put into a system excites the molecules and the amount of random
activity.
• As the gas expands in a system, entropy increases.
Example 3
Example 4
Example 5
Calculate the entropy of the surroundings for the following two reactions at
constant temperature and pressure,
a.) C2H8(g) + 5 O2(g) → 3 CO2(g) + 4H2O(g) ΔH = -2045 kJ
b.) H2O(l) → H2O(g) ΔH = +44 kJ
Practice Exercise 3
Determine if the entropy change will be positive or negative for the following
reactions:
A) (NH4)2Cr2O7(s) → Cr2O3(s) + 4 H2O(l) + CO2(g)
B) 2 H2(g) + O2(g) → 2 H2O(g)
C) PCl5 → PCl3 + Cl2(g)
ANSWERS:
A. (NH4)2Cr2O7(s) → Cr2O3(s) + 4 H2O(l) + CO2(g)
The reactant side contains only one mole where the product side has six moles produced. The was
also a gas produced. The change in entropy will be positive.

B. 2 H2(g) + O2(g) → 2 H2O(g)

There are 3 moles on the reactant side and only 2 on the product side. The change in entropy will
be negative.

C. PCl5 → PCl3 + Cl2(g)

There are more moles on the product side than on the reactant side, therefore the change in
entropy will be positive.
What is Thermodynamics?
The branch which deals with the movement of energy from one form to the other
and the relation between heat and temperature with energy and work done
In other terms we can define thermodynamics as the science stream that deals with
the study of the combined effects of heat and work on the changes of state of
matter confined by the laws of thermodynamics.
Define Chemical Thermodynamics
• Chemical thermodynamics is the study of relation between work, heat and
chemical reactions or with the physical changes of the state which are confined to
the laws of thermodynamics.

• Some general terms like heat, energy, and work were done are often used in
thermodynamics.
First Law of Thermodynamics
Rudolf Clausius and William Thomson (Kelvin) stated the First Law – which
preserves total energy –
First law of thermodynamics: When energy moves into or out of a system, the
system’s internal energy changes in accordance with the law of conservation of
mass.
.
“Energy can neither be created nor destroyed, it can only be transformed from one
form to another.”
∆U (universe) = ∆U (system) + ∆U (surr) = 0
Second Law of Thermodynamics
Rudolf Clausius and William Thomson (Kelvin) stated the Second Law of
Thermodynamics around 1850.
Initially, the Second Law was conceived in terms of the fact that heat does not flow
from a cooler body to a hotter one naturally.
Second law of thermodynamics: The state of the entropy of the entire universe, as
an isolated system, will always increase over time.

“The entropy of the universe increases in a spontaneous process and remains

unchanged in an equilibrium process.”
Second Law of Thermodynamics

In order to express the spontaneity of a reaction more directly, we introduce another

thermodynamic function called Gibbs† free energy (G), or simply fre energy.
GIBB’S FREE ENERGY
Gibbs free energy is equal to the enthalpy of the system minus the product of the
temperature and entropy. The equation is given as:

Gibbs free energy is a state function hence it doesn’t depend on the path. So change
in Gibbs free energy is equal to the change in enthalpy minus the product of
temperature and entropy change of the system.
GIBB’S FREE ENERGY
If the reaction is carried out under constant temperature{ΔT=O}
GIBB’S FREE ENERGY
Example 6
Example 7
Practice Exercise 4
Third Law of Thermodynamics
• The third law of thermodynamics states that the entropy of a perfect crystal at a
temperature of zero Kelvin (absolute zero) is equal to zero.
• At a temperature of zero Kelvin, the following phenomena can be observed in a
closed system:
• The system does not contain any heat.
• All the atoms and molecules in the system are at their lowest energy points.
• Therefore, a system at absolute zero has only one accessible microstate – it’s
ground state. As per the third law of thermodynamics, the entropy of such a
system is exactly zero.
Third Law of Thermodynamics
Zeroth Law of Thermodynamics
• When a body ‘A’ is in thermal equilibrium with another body ‘b’, and also
separately in thermal equilibrium with a body ‘C’, then body ‘B’ and ‘C’ will also be
in thermal equilibrium with each other. This statement defines the zeroth law of
thermodynamics. The law is based on temperature measurement.
UNIT II ENERGY AND
MATTER
PART III: ENTHALPY, ENTROPY, SPONTANEITY, GIBBS FREE ENERGY &
LAWS OF THERMODYNAMICS