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Spontaneity: Decrease in The Enthalpy A Criterion For Spontaneity ?

1. Spontaneous processes are irreversible and involve an increase in entropy of the universe, though not all processes with decreasing enthalpy are spontaneous. 2. Entropy is a measure of disorder, and spontaneous processes favor the direction of increasing disorder and entropy. 3. The Gibbs free energy change (ΔG) of a process determines its spontaneity at constant pressure and temperature, with negative ΔG corresponding to spontaneity.

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Prakhar Gupta
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365 views11 pages

Spontaneity: Decrease in The Enthalpy A Criterion For Spontaneity ?

1. Spontaneous processes are irreversible and involve an increase in entropy of the universe, though not all processes with decreasing enthalpy are spontaneous. 2. Entropy is a measure of disorder, and spontaneous processes favor the direction of increasing disorder and entropy. 3. The Gibbs free energy change (ΔG) of a process determines its spontaneity at constant pressure and temperature, with negative ΔG corresponding to spontaneity.

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Prakhar Gupta
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© © All Rights Reserved
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Spontaneity

 A spontaneous process is an irreversible process and may only be


reversed by an external agency.
 Decrease in the enthalpy a criterion for spontaneity ? :
Decrease in the enthalpy may be a contributory factor for
spontaneity but it is not true for all the cases.
 A spontaneous reaction may be a fast one but not may be the
function of the first one….
 Any two gases can combine to form a product but the rate of
spontaneity differs from equation to equation.
Enthalpy diagrams for exothermic reactions
and endothermic reactions
ENTROPY AND SPONTANIETY
 We introduce another thermodynamic function here called, entropy
(S).higher the isolation, higher the entropy.
 The change in entropy accompanying a chemical reaction, may be estimated
qualitatively taking some structures in mind.
 A crystalline solid will have the lowest entropy, whereas the gaseous state
will have the highest entropy.
 Entropy, like any other thermodynamic function includes internal energy(U),
enthalpy (H) is a state function and ∆S independent of its path.
 Whenever heat is added to a system its molecular lotions increase causing
randomness in the system. Thus this heat (q) has a randomising effect.
 Thus, the temperature is the measure of the average chaotic motion of
particles in a system.
Mathematical representation
 Heat added to a system at lower temperature causes greater
randomness than when the same quantity of heat is added to it at
higher temperature , therefore entropy change is inversely proportional
to temperature and therefore:-
∆S=
The total entropy change ( )for the system and surroundings of a
spontaneous process is given by:-

= +

when a system is in equilibrium , the entropy is maximum, and the


change in entropy ∆S=0
 We can say that entropy for a spontaneous process increases till it
reaches its maximum and at equilibrium the change in entropy is
0. since entropy is a state property, we can calculate the entropy
as a reversible process by the following formula:-

We will find that both for reversible and irreversible expansion for
an ideal gas , under isothermal conditions ∆U=0,but +
is not equal to zero .therefore ∆U does not
discriminate between reversible and irreversible process whereas
∆S does.
Gibbs energy and spontaneity
*

 We know that nor increase nor a decrease in the entropy of a


substance can determine the spontaneity of the process, for this
we determine a new thermodynamic function called gibbs(G).
G=H-TS
Gibbs is an extensive property and a state function, therefore the
change in the Gibbs energy for a system is defined as follows :-
= - -
Therefore, simply we can write this equation as :-
∆G= ∆H-T∆S
 Thus, gibbs energy change = enthalpy change-temperature x
entropy change and is therfore referred to gibbs equation.
 Gibbs energy’s SI unit is joules (J)
 If the system is in thermal equilibrium with the surroundings ,
then the temperature of the surroundings is the same as that of
the system. Also increase in enthalpy of the surroundings is equal
to decrease in the enthalpy of the system.
 Therfore entropy change (in surrounding)is equal to :-

T T
Therefore:
=
 Rearranging the above equation we get :-

 For a spontaneous process , >0


Therefore >0
-( )>0
Therefore we can also write : -∆G>0
or,
∆G = ∆H-T∆S < 0
∆G is the net energy available to do useful work and thus is
measure to do useful work and thus a measure of ‘free energy’.
 ∆G gives a criteria for spontaneity at constant pressure and
temperature.
(a) if ∆G is negative (<0) the process is spontaneous.
(b) if ∆G is positive (>0) the process is non spontaneous.
If a reaction has positive enthalpy change and positive entropy
change, it can be spontaneous when T∆S is large enough to
outweigh ∆H.This can happen in 2 ways:-
(a) The positive entropy change of the system can be small in
which T can be large.
(b) The positive entropy change of the system can be large in
which case, T can be small.
(T refers to temperature)
Gibbs energy change and equilibrium
 The criteria for an equilibrium reaction is :-
A+ B ⇋ C +D
Hence, G = 0
Gibbs energy for a reaction in which all reactant and products are
in standard state, GO=0 is related to the equilibrium constant of
the reaction as follows :
0 = GO+ RT In K
or GO = -RT In K
Therefore GO = -2.303 RT log K
 In case of endothermic reactions heat evolved will be large and
positive whereas in case of exothermic reactions the heat evolved
will be small and negative.
 Therefore depending upon the temperature and other factors like
internal energy entropy change, and rate of kinetic diffusion the
entropy change is determined.
 It is possible to estimate the value of ∆GOfrom the measurement
of ∆HO and ∆SOand then calculate the value of K at any
temperature for economic yields of the products.
 If K is measured directly in the laboratory and value of ∆GOat
any other temperature can be calculated
THE END

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