ENTROPY

CONCEPT OF
ENTROPY
WHAT IS ENTROPY
?Entropy (S), with the SI unit of joules per
Kelvin (J/K), is a thermodynamic quantity that
is a measure of how spread out or dispersed a
system’s energy is, among the different possible
ways that a system can contain energy.
 Entropy refers to the state of order/disorder of a system.

A change in order is a change in the number of ways of arranging the

particles. It is a key factor in determining the direction of a spontaneous
process.

more order less order

solid liquid gas

more order less order

crystal + liquid ions in solution

THE 2nd LAW OF
THERMODYNAMICS
The law states that:
“The entropy of the universe increases in a
spontaneous process and remains unchanged
in an equilibrium process.”
Because the universe is made up of the system and
the surroundings,
SYMBOLS:
(ΔSuniv) = the entropy change in the universe
(ΔSsys) = the entropy changes in the system
(ΔSsur) = the entropy changes in the surroundings
 CALCULATING THE STANDARD
ENTROPY OF THE REACTION ∆S°rxn
the standard entropy of reaction ΔS° rxn is
given by the difference in standard entropies
between the products and the reactants.

ΔS° rxn = = ΣnS° (products) − ΣmS° (reactants)

 1. ENTROPHY CHANGES IN THE
SYSTEM (ΔSsys)
The entrophy of the system or the entrophy of the
reaction ΔS° rxn is the difference in the standard
entropies between products and reactants.
Expressed in: J/K.mol
ΔS° rxn = = ΣnS° (products) − ΣmS° (reactants)
 2. Entropy Changes in the Surroundings
(Δssur)
For constant-pressure process the heat change is equal
to the enthalpy change of the system ΔHsys,. Then the
change in entropy of the surroundings ΔSsurr is
proportional to the -ΔHsys.
Expressed in: J/K.mol
The change in entropy for a given amount of heat absorbed also depends on
the temperature.

• If the temperature of the surroundings is high, the molecules are already

quite energetic. Therefore, the absorption of heat from an exothermic
process in the system will have relatively little impact on the motion of the
molecules and the resulting increase in entropy of the surroundings will be
small.
• However, if the temperature of the surroundings is low, then the addition of
the same amount of heat will cause a more drastic increase in molecular
motion and hence a larger increase in entropy.
 3. Entropy change in the universe
(ΔSuniv)
As stated earlier, the entrophy of the
universe is the sum of the entrophy changes
in the system and in the surroundings.
Expressed in: J/K.mol
ΔSuniv = ΔSsys + ΔSsur
What is Gibbs free energy?
How does it relate to the
spontaneity of a reaction?
 GIBBS FREE ENERGY, G
In thermodynamics, the Gibbs free
energy (or standard free energy) is a
thermodynamic potential that can be
used to calculate the maximum
reversible work that may be performed
by a thermodynamic system at a
constant temperature and pressure.

JOSIAH WILLARD
GIBBS
If the entropy of the universe increases then
the ΔG of the system will decrease. The
direction of spontaneous change is negative
ΔG for system. The ΔG tells us if a change
can occur for a chemical reaction.
 Methods to determine change in Gibbs Free
Energy (ΔG) • Determining ΔG using ΔH and ΔS
data.

The change in free energy (ΔG) of a

system for a constant-temperature
process is
ΔG = ΔH –TΔS
EXAMPLE 1:
Summary of conditions for spontaneity and equilibrium at
constant temperature and pressure in terms of ΔG
Factors affecting the sign of ΔG What!
combinations of enthalpy change (ΔH) and entropy
change (ΔS) can!happen?!
In order to predict the sign of ΔG according to the
equation: ΔG = ΔH- TΔS, we need to know both ΔH and
ΔS. Temperature may also influence the direction of the
spontaneous reaction. The four possible combinations
are shown below.
 How can we determine the
temperature that will cause a
reaction to occur?
Calcium oxide (CaO), also called quicklime is prepared by
decomposing limestone (CaCO3) in a kiln at high
temperature and the reaction proceeds as:
SOLUTION:
 SEATWORK:
Given: ΔH°= +177kJ and ΔS°=
+285J/K for the reaction
NH4Cl(s) —> NH3 (g) + HCl (g)
Find the ΔG° at 25 °C and ΔG at
500 °C.
How is Gibbs free energy change
determined if the standard free energy
of formation ΔGf° for the reactants and
products are available?
Calculating ΔG from Standard Free Energies

ΔGf° is the standard free energy of formation

at 25 °C and 1atm for 1 mol of compound
formed from its elements. The ΔGf° can be
used to get the ΔG of a reaction just like using
ΔHf° to get ΔH for reaction. The standard free
energy ΔG° of element in the standard state is
0
FORMULA:
Sample Problem :

Will this reaction occur at

298 K ?