Lecture 8 Summary

ASsys ASsurr
ASuniv
AHsys < 0
ASsys
ASsurr
ASuniv
AHsys < 0
ASsys
ASsurr
ASuniv
AHsys > 0
Spontaneous, exothermic
Spontaneous, exothermic
Spontaneous, endothermic
Lecture 9: Gibbs Free Energy G
Reading: Zumdahl 10.7, 10.9

Outline
Defining the Gibbs Free Energy (AG)
Calculating AG (several ways to)
Pictorial Representation of AG
Defining AG
Recall, the second law of thermodynamics:
AS
univ
= AS
total
= AS
sys
+ AS
surr
Also recall:
AS
surr =
-AH
sys
/T

Substituting,
AS
total
= AS
sys
+ AS
surr
-AH
sys
/T
TAS
total
= -TAS
sys
+

AH
sys

Multipling all by (-T) gives
We then define:
AG = -TAS
total
Substituting


AG = AH - TAS

AG = -TAS
sys
+

AH
sys
AG = The Gibbs Free Energy @const P
Giving finally
AG and Spontaneous Processes
Recall from the second law the conditions of spontaneity:
Three possibilities:
If AS
univ
> 0..process is spontaneous
If AS
univ
< 0..process is spontaneous in opposite
direction.
If AS
univ
= 0.equilibrium

In our derivation of AG, we divided by -T;
therefore, the direction of the inequality
relative to entropy is now reversed.
Three possibilities in terms of AS:
If AS
univ
> 0..process is spontaneous.
If AS
univ
< 0..process is spontaneous in opposite
direction.
If AS
univ
= 0. system is in equilibrium.

Three possibilities in terms of AG:
If AG < 0..process is spontaneous.
If AG > 0..process is spontaneous in opposite
direction.
If AG = 0.system is in equilibrium

Spontaneous Processes: temperature dependence
Note that AG is composed of both AH and AS terms
AG = AH - TAS
If AH < 0 and AS > 0.spontaneous at all T
A reaction is spontaneous if AG < 0. So,
If AH > 0 and AS < 0.not spontaneous at any T
If AH < 0 and AS < 0. becomes spontaneous at low T
If AH > 0 and AS > 0.becomes spontaneous at high T
Example: At what T is the following reaction
spontaneous?
Br
2
(l) Br
2
(g)
where AH = 30.91 kJ/mol, AS = 93.2 J/mol.K


AG = AH - TAS
Try 298 K just to see result at standard conditions
AG = AH - TAS
AG = 30.91 kJ/mol
- (298K)(93.2 J/mol.K)
AG = (30.91 27.78) kJ/mol
= 3.13 kJ/mol
> 0
Not spontaneous at 298 K
At what T then does the process become spontaneous?
AG = AH - TAS
T = AH/AS
T = (30.91 kJ/mol) /(93.2 J/mol.K)
= 0
Just like our previous calculation
T = 331.65 K
Calculating AG
In our previous example, we needed to determine
AH
rxn
and AS
rxn
separately to determine AG
rxn

But G is a state function; therefore, we can
use known AG to determine AG
rxn
using:

AG
rxn
= AG
prod.

AG
react.

Standard AG of Formation: AG
f

Like AH
f
and S, the standard Gibbs free
energy of formation AG
f
is defined as the
change in free energy that accompanies the
formation of 1 mole of that substance for its
constituent elements with all reactants and
products in their standard state.
As for AH
f
, AG
f
= 0 for an element in its standard
state:
Example: AG
f
(O
2
(g)) = 0
Example
Determine the AG
rxn
for the following:
C
2
H
4
(g) + H
2
O(l) C
2
H
5
OH(l)
Tabulated AG
f
from Appendix 4:
AG
f
(C
2
H
5
OH(l)) = -175 kJ/mol
AG
f
(C
2
H
4
(g)) = 68 kJ/mol
AG
f
(H
2
O (l)) = -237 kJ/mol
Using these values:
C
2
H
4
(g) + H
2
O(l) C
2
H
5
OH(l)
AG
rxn
= AG
f
(C
2
H
5
OH(l)) - AG
f
(C
2
H
4
(g))
AG
f
(H
2
O (l))

AG
rxn
= AG
prod.

AG
react.

AG
rxn
= -175 kJ - 68 kJ -(-237 kJ)
AG
rxn
= -6 kJ < 0 ; therefore, spontaneous
More AG Calculations
Similar to AH, one can use the AG for
various reactions to determine AG for the
reaction of interest (a Hess Law for AG)
Example:
C(s, diamond) + O
2
(g) CO
2
(g) AG = -397 kJ
C(s, graphite) + O
2
(g) CO
2
(g) AG = -394 kJ
C(s, diamond) + O
2
(g) CO
2
(g) AG = -397 kJ
C(s, graphite) + O
2
(g) CO
2
(g) AG = -394 kJ
CO
2
(g) C(s, graphite) + O
2
(g) AG = +394 kJ
C(s, diamond) C(s, graphite) AG = -3 kJ
AG
rxn
< 0..rxn is spontaneous
AG
rxn
Reaction Rate
Although AG
rxn
can be used to predict if a
reaction will be spontaneous as written, it
does not tell us how fast a reaction will
proceed.
Example:
C(s, diamond) + O
2
(g) CO
2
(g)
AG
rxn
= -397 kJ
But diamonds are forever.
<<0
AG
rxn
rate
Example Problem
Is the following reaction spontaneous under standard conditions?

4KClO
3
(s) 3KClO
4
(s) + KCl(s)
AH
f
(kJ/mol) S (J/mol.K)
KClO
3
(s) -397.7 143.1
KClO
4
(s) -432.8 151.0
KCl (s) -436.7 82.6
Example Problem Solution
Calulating AH
rxn


4KClO
3
(s) 3KClO
4
(s) + KCl(s)

AH
rxn
= 3AH
f
KClO
4
( )
+ AH
f
KCl
( )
4AH
f
KClO
3
( )
= 3(432.8kJ) + (436.7kJ) 4(397.7kJ)
= 144 kJ
Calulating AS
rxn


AS
rxn
= 3S KClO
4
( )
+ S KCl
( )
4S KClO
3
( )
= 3(151.0
J
K
) + (82.6
J
K
) 4(143.1
J
K
)
= 36.8
J
K
Example Problem Solution
Calulating AG
rxn


AG
rxn
= AH
rxn
TAS
rxn
= 144 kJ 298K
( )
38.6
J
K
( )
1kJ
1000 J
|
\

|
.
|
= 133kJ
AGrxn < 0 ;therefore, reaction is spontaneous.
Example Problem Continued
For what temperatures will this reaction be spontaneous?
Answer: For T in which AG
rxn
< 0.

AG
rxn
= AH
rxn
TAS
rxn
0 = AH
rxn
TAS
rxn
AH
rxn
AS
rxn
=
133kJ
38.6
J
K
( )
1kJ
1000J
|
\

|
.
|
= 3446K = T
Spontaneous as long as T < 3446 K.