SPONTANEITY AND EQUILIBRIUM

Prepared By: Muhammad Haris Hassan

Roll # 180301012
 WHAT IS A SPONTANEOUS PROCESS?
• A spontaneous process is a process which occurs without
any intervention nor does it require help from an external
agent for completion.
• For a process to be spontaneous, the change in total entropy
should be positive. This is the basic requirements for the
process to be spontaneous.
THERMODYNAMIC SQUARE
• dH = TdS + VdP
• dG = VdP – SdT
• dA = -PdV – SdT
• dU = TdS – PdV
1 𝑃
• dS = dU + 𝑑𝑉 (formed by rearranging
𝑇 𝑇
4th eq)
1 𝑉
• dS = dH + 𝑑𝑃 (formed by rearranging
𝑇 𝑇
1st eq)
SPONTANEITY CRITERIA
• 𝑑𝑈 𝑆,𝑉 <0
• 𝑑𝐻 𝑆,𝑃 <0
• 𝑑𝐴 𝑇,𝑉 <0
• 𝑑𝐺 𝑇,𝑃 <0
• 𝑑𝑆 𝑈,𝑉 >0
• 𝑑𝑆 𝐻,𝑃 >0
Under Under
constant constant
Temperature Temperature
and Volume and
Pressure

Under Under
constant constant
Entropy and Entropy and
Pressure Volume
Under constant
internal energy
and volume or
Under constant
enthalpy and
pressure
WHAT IS EQUILIBRIUM?
• In thermodynamics, equilibrium is a state where
there is absence of any macroscopic change of
energy or movement of matter either between
systems or in a system itself.
• In simpler words it means that a balance occurs.
EQUILIBRIUM
Now for example, lets consider
• 𝑑𝑈 𝑆,𝑉 =0 dH = TdS + VdP ,
to achieve equilibrium, dS and dP should
• 𝑑𝐻 𝑆,𝑃 =0 be equal to zero. This implies that there
• 𝑑𝐴 =0 shouldn’t be any change in either
𝑇,𝑉
entropy or pressure, and when that
• 𝑑𝐺 𝑇,𝑃 =0 happens, the difference in enthalpy will
also be zero, and only then the system
• 𝑑𝑆 𝑈,𝑉 =0 will be in equilibrium. This corresponds
• 𝑑𝑆 𝐻,𝑃 =0 to the theoretical definition of equilibrium
which defines as a state of balance.
WHICH CRITERIA IS THE MOST FEASIBLE?
The criteria involving entropy is
• 𝑑𝑈 𝑆,𝑉 <0
discarded right away because, for a
• 𝑑𝐻 𝑆,𝑃 <0 reaction to be spontaneous,
𝑑𝑆 𝑇𝑜𝑡𝑎𝑙 > 0, but this not only
• 𝑑𝐴 𝑇,𝑉 <0 includes the entropy of the system but
• 𝑑𝐺 𝑇,𝑃 <0 also the surrounding entropy.
Considering the fact that calculating
• 𝑑𝑆 𝑈,𝑉 >0 both system’s and surrounding’s
• 𝑑𝑆 >0 entropy is not feasible, this option is
𝐻,𝑃
discarded.
• As far as the criterion related to the energies are concerned,
the most practical is the one involving Gibbs free energy.
Keeping temperature constant is a pretty simple task
provided we have the right equipment, coupled with the fact
that most processes undergo in atmospheric pressure, if
the Gibbs free energy decreases, the reaction is
spontaneous.

• Similar logic for the Helmholtz’s free energy which comes in

second for being the most practical; keeping volume and
temperature constant, if the Helmholtz free energy
decreases, it is a spontaneous process.
THANK YOU