Entropy and

Free Energy
A reaction that does occur under the given set of conditions is called a
spontaneous reaction. If a reaction does not occur under specified
conditions, it is said to be nonspontaneous.
ENTROPY (S)
- is a measure of the randomness or disorder of a system.
- the greater the dispersal, the greater the entropy.
- The entropy change of a system, Δ𝑺system, can be quantified using two
approaches. The first approach is defined by Ludwig Boltzmann. In
1868 Boltzmann showed that the entropy of a system is related to the
natural log of the number of microstates (W):
S= klnW
where:
S = entropy
k = Boltzmann constant (1.38x10-23 J/K)
ln = natural logarithm
W = microstates
The entropy change for the process, ΔS, is:
ΔS = Sf-Si

From the equation above, we can write:

ΔS = klnWf – klnWi
𝑊𝑓
= kln 𝑊
𝑖
* What can we conclude from this equation?
The second approach to quantify the entropy change of
the system is the one by Rudolph Clausius, one of the
two persons who extended the work of Carnot.
𝑞𝑟𝑒𝑣
ΔSsystem =
𝑇

where: qrev – is heat transferred in a reversible process

T - constant Kelvin temperature
THE SECOND LAW OF THERMODYNAMICS
- is a physical law based on universal experience
concerning heat and energy interconversions.
One simple statement of the law is that heat
always moves from hotter objects to colder
objects, unless energy is supplied to reverse
the direction of heat flow.
- entropy increases in any spontaneous
process
Example 1
The melting of an ice cube in your palm is an irreversible process since
the temperature of the system (the ice cube) and the immediate
surroundings (your hand) is different. The melting requires 6.01 × 103
J/mol of heat. Calculate the entropy change of the system, surroundings
and universe.
Using equation 4 and taking T of the system as 0℃ (273 K), we can solve
the entropy change of the system as follows:
Given: T = 0℃
= 0 + 273 = 273 K
𝑞𝑟𝑒𝑣
Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 ≥ 𝑇
𝑞𝑟𝑒𝑣
Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚= 𝑇
Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚=(1 𝑚𝑜𝑙)(6.01 𝑥 103𝐽/𝑚𝑜𝑙)
273
Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = 22.0 J/K
For the entropy change of the surrounding, we use the same equation
but this time we will use the temperature of your hand and the heat it
lost. We assume that the temperature of your hand is the same as the
normal body temperature, 37. 0℃ (310 K).
Because the heat lost by your hand is the heat gained by the ice, the
heat lost by your hand is equal in magnitude to the heat gained by the
ice but has opposite sign, −6.01 × 103 J/mol. So the entropy change of
the surroundings is:
𝑞
Δ𝑆surroundings = 𝑇𝑟𝑒𝑣
Δ𝑆surroundings =(1 𝑚𝑜𝑙)(6.01 𝑥 103𝐽/𝑚𝑜𝑙)
310 K
Δ𝑆𝑠urroundings = 19.4 J/K
The universe is composed of the system and the surroundings. Therefore,
the entropy change of the universe is the sum of the entropy change of
the system and the surroundings.
Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒= Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚+ Δ𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠
Thus, the entropy change of the universe is:

Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒= [22.0+(-19.4)]
K
= 2.6 J/K

In summary,
Reversible process Δ𝑺universe = Δ𝑺system + Δ𝑺surroundings = 0
Irreversible process Δ𝑺universe = Δ𝑺system + Δ𝑺surroundings > 0
Gibbs Free Energy

➢ also known as the Gibbs function, Gibbs energy, or free

enthalpy, is a quantity that is used to measure the
maximum amount of work done in a thermodynamic system
when the temperature and pressure are kept constant.
➢ it is denoted by the symbol ‘G’.
➢ its value is usually expressed in Joules or Kilojoules.
➢ it can be defined as the maximum amount of work that can
be extracted from a closed system.
➢ This property was determined by American scientist Josiah
Willard Gibbs in the year 1876