Lecture 8 Summary

AS°sys AS°surr
AS°univ
AH°sys < 0
AS°sys
AS°surr
AS°univ
AH°sys < 0
AS°sys
AS°surr
AS°univ
AH°sys > 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
AG°rxn < 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.

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