Lecture 7

Gibbs free energy

= − = −

Changes at constant p, more common in chemical reactions

Criterion for spontaneous change , ≤0

Chemical reactions are spontaneous in the direction of

decreasing Gibbs energy

Spontaneous endothermic reaction, >0

>0

Even then, < 0 if the reaction is spontaneous

 Gibbs free energy
= −

= + −

= + + ( )− −

For Isothermal change,

= + + −

For Reversible change, = , =

= +
,
=− + + +
: additional
,
non-expansion work

= , +
 Gibbs free energy

= , +

At constant p, = ,

Change in Gibbs free energy is the maximum non-expansion work!

∆ = ,

Q. How much will be the minimum amount of glucose consumed by

a man weighing 70 kg to climb a vertical wall of 3 m ?

Molar mass of glucose = 180 g mol-1

∆ ° = −2808 !" #$% &' , ∆ ° = 259.13 "- &' #$% &' .

 Combining 1st and 2nd Laws
= +

For reversible change in a closed system that does no additional work,

= −

But dU is a state variable, so,

= .

= − Fundamental equation

∝ ∝−

⇒ ( , )
 Maxwell relation
( , )

1 1
= + = −
1 1
also
2 3

1 1
⇒ = =−
1
and
1 2 3

U is a state function so dU is an Exact differential

1 1
∴ =− A Maxwell relation
1 3
1 2

Applying same logic for the other state functions H, G and A, we get
the other Fundamental equations and Maxwell relations
 The Fundamental equation of Chemical
Thermodynamics

= −

1 1
Also, = +
1 1

1 1
⇒ = and =−
1 1

1
=− > 0, for all substances, so decreases as increases
1

1
= > 0, for all substances, so increases as increases
1 (for constant and composition)
 Chemical Potential

=− +

This is true for a pure substance or for a mixture, whose composition

remains constant throughout.

But it does depend on the composition. Lets say, we have a mixture of

two components,

= ( , , 5' , 56 )

1 1 1 1
= + + 5' + 56
1 ,78 ,79
1 ,78 ,79
15' , ,79
156 , ,78

Generally,
1 1 1
= + +; 5.
1 ,7:
1 ,7:
15. , ,7<
.
 Chemical Potential

1 1 1
= + +; 5.
1 ,7:
1 ,7:
15. , ,7<
.

=− + + ; = . 5.
.

1
= =.
15. , ,7<

=. is the chemical potential of the ith species

If , and all the 5>? @ are kept constant, while 5. amount of the ith species
is added, then the change in Gibbs free energy is =. .
 Chemical Potential

1
= =.
15. , ,7<

is extensive, 5. is extensive, so =. is intensive

AB has the same value everywhere within a system at equilibrium

Let us transfer 5. amount of i

=.C =.D
from A to B

A B C = =.C (− 5. )

D
= =.D ( 5. )
 Chemical Potential
Total change in Gibbs free energy of the system,

= C + D = =.C − 5. + =.D ( 5. )

= (=.D − =.C ) 5.

If =.D > =.C , then, > 0; Nonspontaneous process

If =.C > =.D , then, < 0; Spontaneous process

Substance i flows from area of high chemical potential to area of low

chemical potential.

All flow stops when =.C = =.D , and, = 0; and the system is in equilibrium!!

=. is hence called “Chemical Potential”.

It is a measure of escaping tendency. If =. is high at a point in the system,

substance wants to escape from there.
 Chemical Potential

For a mixture, = ; = . 5. For a pure substance, ==5

.

Molar Gibbs free energy ⇒= = = ̅= F

5
Now, =− + += 5

At constant and 5, =

F( )= +G
°
F F
H

For an ideal gas, F = °

F + I ln
L

At constant , the pressure,

= = =° + I ln gives the measure of potential
of a gas ( L = 1 MN#)
Gas flows from areas of high pressure to low pressure, till pressure is
uniform throughout: mechanical equilibrium !
 Chemical Potential

H2 H2
O9
H2

N2
N2 H2 N2

O9 + P9

O9 has to be uniform throughout at equilibrium !

=O9 is also uniform throughout at equilibrium

=O9 QRS = =O9 (mixture)

=°O9 + I ln O9 = =O9 (mixture)

=. mixture = =°. + I ln . . is partial pressure

of [ in a mixture

=°. = chemical potential of pure gas [ at and °

 Chemical Potential

=. mixture = =°. + I ln .

e. = mole fraction
. = e.
of i in a mixture
= total pressure
=. mixture = =°. + I ln + I ln e.

=. mixture = =.( f ) , +I ln e.

=.( f ) , = chemical potential of gas [ at temperature and pressure

same as that of the total pressure of the mixture, .

Now, e. ≤ 1, so, =. mixture ≤ =.( f ) ,

This means the gas will always flow from the pure chamber (an area of
high potential) to the mixture (area of low chemical potential).
 Gibbs energy of mixing

,
, , 5' , , 56 , , 5g , , 5g
h = 5' + 56 + 5g

' 6 g

.7.i. j =; . = ; =°. 5. k.7 j = ; = . 5.

. . .

∆ F.l = ; =. 5. − ; =°. 5.
. .

∆ F.l = ; 5. (=. − =°. ) = ; 5. I ln e.

. .
5. = e. 5
∆ F.l = 5I ; e. ln e.
.
 Gibbs energy of mixing

∆ F.l = 5I ; e. ln e.
.

For a pure substance, e. = 1, hence, ∆ F.l =0

For a mixture of two substances, if e' = e, then e6 = 1 − e

∆ F.l = 5I e ln e + 1 − e ln 1 − e

Now, e < 1 ∆ F.l <0

Ideal binary mixture
n
Spontaneous process!!
∆ F.l
5I
∆ F.l = −5I ; e. ln e.
.

∆ F.l >0 n m n. p o
 Chemical equilibrium
, constant

Is a chemical reaction Spontaneous?

= ; = . 5.
.

Let ξ be the advancement of the reaction

5. = 5. ° + ν. ξ
5. = ν. ξ

= ; =. ν. ξ
.
1
= ; ν. =.
1ξ , .

Rate of increase of Gibbs free energy with the advancement of the reaction
 Chemical equilibrium
1
= ; ν. =. Rate of increase of Gibbs free energy
1ξ ,
with the advancement of the reaction
.
1
If <0 the reaction is spontaneous
1ξ ,

1
If >0 the reaction proceeds in backward direction
1ξ ,

1
If =0 has minimum value, the reaction is in equilibrium
1ξ ,

1
=0 ⇒ ; ν. =. =0
1ξ , , s . , , s
by definition
1
or ∆ = ; ν. =. =∆
1ξ ,
.
 Chemical Equilibrium ∆ = ; ν. =.
.

At equilibrium ∆ =0

Forward reaction spontaneous,

∆ < 0 Exergonic (work producing) ∆ <0
e.g. carbohydrate oxidation ∆ >0

∆ >0
Backward reaction spontaneous,
Endergonic (work consuming) ∆ =0
e.g. electrolysis of water
Extent of the reaction ξ

For reaction of an ideal mixture of gases

v:
∆ = ; ν. =. = ; ν. (=°. + I ln .) = ; ν. =°. + I ln t t =u .
.
. . .

∆ = ∆ ° + I ln t

At equilibrium ∆ ° = −I ln - where - = u .
v:
equilibrium constant
.