Different parameters to

define :-
spontaneity

-- payeal karmakar
&
Swarnali das
 SPONTANEOUS PROCESS

• WHAT IS SPONTANEOUS PROCESS?

SPONTANEOUS IS THE PROCESS

WHICH PROCEED ON ITS OWN
WITHOUT THE HELP OF ANY EXTERNAL
AGENGY.

• SPONTANEOUS PROCESS ARE

 SPONTANEITY:
IT THE POTENTIAL OF A
REACTION/PROCESS TO PROCEED
ON ITS OWN WITHOUT THE
ASSITANCE OF EXTERNAL AGENGY
 DIFFERENT
PARAMETERS TO
DEFINE SPONTANEITY
• ENTHALPY
• ENTROPY
• GIBBS FREE ENERGY
• HELMHOLTZ FREE ENERGY
 ROLE OF ENTHALPY
ENTHALPY

• ENTHALPY IS A MEASURE OF AMOUNT OF

ENERGY RELEASED OR ABSORBED DURING A
CHEMICAL REACTION.

• IT IS REPRESENTED BY ‘H’
 EXOTHERMIC REACTION
C (s) +2O2 (g) CO2 (g)
REACTANTS( Hf =0KJmol-1)

E
N
T
Hr = -393.5KJmol -1
H
A
L
P
PRODUCT ( Hf= -393.5KJmol-1)
Y
 ENDOTHERMIC REACTION:

• Ba(OH)2.8H2O+ 2NH4CL BaCL2.2H2O+2NH3

+ 8H2O
PRODUCT ( Hf
E
N = -3840KJmol-1 )
T
H
A
L
P ( Hr =133KJmol-1
REACTANT ( Hf = - 3973 KJmol-1 )
Y
 EXAMPLES OF SPONTANEOUS
REACTION
1. COMBUSTION OF METHANE:
CH4 (g) +2O2 (g) CO2 (g)+ 2H2O (g)
( Hr= -891 KJmol-1 )
2.KCl (s) + aq KCl (aq) , ( Hr =19 KJmol-1 )
3. H2O (s) H2O(l) ( Hr =6.0 KJmol-1 )
4.H2O(l) H2O(g) ( Hr = 44 KJmol-1 )
 • Hence we can conclude that reactions
either exothermic or endothermic can be
spontaneous.
• Therefore any enthalpy change in a particular
direction , positive or negative , cannot be the
only factor to decide if a chemical reaction
can be spontaneous or non- spontaneous.
 If we look at the all four chemical reaction
above,-----
 In (1.), there’s a generation of heat i.e. there
is significant increase in energy of the product
molecules of carbon dioxide and steam which
makes them move rapidly in all directions.

 in (2.) when potassium chloride dissolves ,

the regular arrangement of the crystal
structure is replaced by random distribution of
mobile ions,
  In (3.) when ice melts , the regular hydrogen
bonded structure of ice is replaced by less associated
fluid which is in water.

• In (4.), when water evaporates the

association of water molecules is replaced by
individual water vapour molecules moving
independently in vapour phase with much
higher
 In all the above reaction the
common factor is the transition of
the system from ordered
arrangement of particles to a less
ordered arrangement.
 ENTROPY
• THE DEGREE OF DISORDER OR RANDOMNESS
IN A SYSTEM IS MEASURED BY A PHYSICAL
QUANTITY CALLED ENTROPY.

• IT IS REPRESENTED BY ‘S’.
 EXAMPLES OF SPONTANEOUS
REACTION

Melting of Ice
• As we consider the melting of ice , when the ice melts
to water , we can observe that the ions are now free
to move , the ice moves to a state of disorder , hence
the entropy increases i.e. S > 0.
• Let us take another example:
• H2O (l) evaporation H2O (g)

• It is a spontaneous reaction.
• Here the entropy change is positive ,as water
goes from a ordered state of liquid to a
disordered state of vapour

S is positive
 When lime reacts with water , hydrated lime is
produced .
 It is a spontaneous reaction
 The entropy change S of the reaction is negative.
 This is because the solid and liquid reactants goes
from a more disordered state to a completely solid
phase product, which is more ordered.

CaO (s) + H2O (l) Ca(OH) 2 (s)

this is a example of spontaneous reaction with
negative change in entropy
 So clearly , a spontaneous reaction is
possible with both when entropy
change is positive and also when it is
negative

Therefore , a positive or
negative change in
entropy cannot predict if
reaction can be
spontaneous or not.
 Gibbs energy :
• Gibbs proposed that , both change in enthalpy of
a reaction and change in entropy of reaction
together decides if a reaction could be
spontaneous.
• Gibbs combined enthalpy change and entropy
change by the following equation---
G= H–T S
where , G = change in free Energy
H = change in enthalpy
S = change in entropy, T = temperature in Kelvin
• G is commonly called Gibbs energy .

• It can be defined as the maximum reversible

work that can be obtained from a particular
system .

• Gibbs proposed that all spontaneous physical

and chemical changes takes place in one
direction .
 A spontaneous reaction may involve increase or
decrease in enthalpy, and increase or decrease in
entropy but it will always involve a decrease in free
energy i.e. negative G .

• WHEN G IS NEGATIVE , THE REACTION

WOULD GO IN THE DIRECTION OF REACTANTS
FORMING PRODUCTS AND NOT IN THE
REVERSE DIRECTION .
 •When H is negative and S is positive, G will
be negative over all temperature.
• When H is negative and S is negative , G
will be negative at low temperature.
• When H is positive and S is negative , G will
not be negative at any at any temperature
.hence it would not be spontaneous.
• When H is positive and S is positive , G will
be negative at high temperatures.
 HELMHOLTZ FREE ENERGY
• IT CAN BE DEFINED AS THE USEFUL WORK
THAT CAN BE DONE BY A CLOSED SYSTEM.
• IT IS CALCULATED FOR SYSTEM UNDER
CONSTANT TEMPERATURE AND VOLUME.
• The concept was developed by Hermann von
Helmholtz.
• Helmholtz energy is represented by ‘A’.
 HELMHOLTZ ENERGY
• A= U–T S
where U = change in internal energy
S = change in entropy
T = absolute temperature
A chemical reaction is spontaneous when the
change in the Helmholtz free energy is
negative
 Difference between Gibbs and
Helmholtz free energy
Gibbs free energy HELMHOLTZ FREE ENERGY

Is negative
HELMHOLTZ FREE ENERGY IS NOT
PREFERED MUCH BECAUSE IT
CONSIDERS A CONSTANT VOLUME
CONDITION.
Thank u