Are you sure?
This action might not be possible to undo. Are you sure you want to continue?
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.
This action might not be possible to undo. Are you sure you want to continue?
Use one of your book credits to continue reading from where you left off, or restart the preview.