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4(g) 2 2(g)
O N NO 2
K mol
kJ
K mol
J
K mol
J
K mol
J
o
NO
o
O N
o
reactants
n
o
products
n
o
rxn
0.1758 - or 8 . 175
) 0 . 240 ( 2 ) 2 . 304 (
S 2 S
S n S n S
2(g) 4(g) 2
=
=
=
= A
Entropy, S
Example 2: Calculate AS
o
298
for the reaction
below. Use values in appendix K.
( ) ( ) ( ) g 2 g 2 g
NO O N NO 3 +
( ) ( ) ( )
( ) | |
K mol
kJ
K mol
J
K mol
J
0
NO
0
NO
0
O N
0
298
0.1724 - or 4 . 172
210.4 3 - 240.0 7 . 219
S 3 S S S
g g 2 g 2
=
+ =
+ = A
What is Spontaneity?
Spontaneous changes happen without any
continuing outside influences.
A spontaneous change has a natural direction (you have to
consider the conditions of the system).
Gibbs Free Energy
The change in the Gibbs Free Energy, AG, is a reliable
indicator of spontaneity of a physical process or
chemical reaction.
AG does not tell us how quickly the process occurs. It will
only tell if a reaction is spontaneous or non spontaneous
AG is the Energy released to the surroundings (after
the spontaneous process of the system) to do useful
work!
Gibbs Free Energy: Sign
Convention
+
Free
Energy
0
G < 0, spontaneous
UNSTABLE
G = 0, system equilibrium, STABLE
SYSTEM
G > 0, nonspontaneous
Free energy
released to
the
surroundings
Energy must be
applied from the
surroundings
Gibbs Free Energy and
Reversibility
If a process is spontaneous i.e. one with highly
negative G, it will IRREVERSIBLY proceed to
give-off energy (thats why its called FREE
ENERGY)
Consider rusting of iron (Fe)
O
2
+ 4 e
-
+ 2 H
2
O 4 OH
-
Fe Fe
2+
+ 2 e
4 Fe
2+
+ O
2
4 Fe
3+
+ 2 O
2
2e
-
+ O
2-
+ 2H
2
O 4OH
-
Fe
3+
+ 3 H
2
O Fe(OH)
3
+ 3 H
+
Fe(OH)
3
FeO(OH) + H
2
O
2FeO(OH) Fe
2
O
3
+ H
2
O
Gibbs Free Energy and
Reversibility
Free
Energy
kJ/mole
Reaction pathway
Fe
(s)
, O
2(g)
, H
2
O
(l)
Fe
2
O
3(s)
G
Surroundings receives free
energy
RUST FORMATION wastes important materials and ENERGY!
Gibbs Free Energy and
Reversibility
Once an egg is broken, you need a lot of
external energy to put it together again!
Not Spontaneous!
WORK!
Free Energy Change, AG,
and Spontaneity
Changes in free energy obey the same type of
relationship we have described for enthalpy,
AH, and entropy, AS, changes.
Standard states also in 25
o
C and 1 atm
Elements in their standard forms also has ZERO
free energy change of formation (G
f
o
= 0, also
H
+
(aq)
)
All other properties is similar to Enthalpy and
Internal energy
0
reactants
n
0
products
n
0
298
G n G n G A A = A
Calculation of Free Energy Change
Example: Calculate AG
o
298
for the decomposition of
CaCO
3(s)
.
) ( 2(g) 3(s)
CaO CO CaCO
s
+
mol
kJ
mol
kJ
o
CaCO f
o
O Ca f
o
CO f
o
rxn
4 . 130
)} 8 . 1128 ( )] 0 . 604 ( ) 4 . 394 {[(
] G [ ] G G [ G
(s)
3 ) ( 2(g)
+ =
+ =
A A + A = A
s
Calculation of Free Energy Change
Example: Calculate AG
o
298
for the oxidation of glucose,
C
6
H
12
O
6(s).
) ( 2 2(g) 2(g) 6(s) 12 6
O 6H 6CO 6O O H C
+ +
mol
kJ
mol
kJ
o
O f
o
H H C f
o
O H f
o
CO f
o
rxn
2 . 2881
)]} 0 ( 6 ) 0 . 909 [( )] 3 . 237 ( 6 ) 4 . 394 ( 6 {[
] G 6 G [ ] G 6 G 6 [ G
2(g)
(s)
6 12 6 ) ( 2 2(g)
=
+ + =
A + A A + A = A
Very Spontaneous! But why are we still
alive? We should have been liquefied! :B
Activation energy prevents many spontaneous reactions from
happening immediately.
Calculation of Free Energy Change
Free Energy Calculations
Consider the formation of ice
- spontaneous only at low temp ( 0
o
C), but is
an ordered process (entropy decreases)
Free Energy, Disorder, and Enthalpy
A A A G = H - T S (at constant T & P)
G = H TS
Because 0 AH 0 and 0 AS 0, there are
four possibilities for AG.
AH AS AG Reaction spontaneity
+ Spontaneous at all Ts.
Temp dependent Spont at low
Temp.
+ Temp dependent Spont at high Temp.
+ + NON Spont at all Ts.
Calculations at Equilibrium
Example: Use thermodynamic data to estimate the
normal boiling point of water.
S
H
T and S T H Thus
0. G process m equilibriu an is this Because
O H O H
(g) 2 ) ( 2
A
A
= A = A
= A
Calculations at Equilibrium
Assumptions
Enthalpy of Vaporization at 25
o
C is the same as Enthalpy
of Vaporization at the boiling point
Entropy of Vaporization at 25
o
C is the same as Entropy
of Vaporization at the boiling point
| |
assume H@BP H
H H H
H
H kJ@25 C
298
o
o
H O
o
H O
o
o
J
K
o o
2 (g) 2 ( )
A A
A A A
A
A
~
=
=
= +
l
2418 2858
44 0
. ( . )
.
( ) ( )
| |
K
kJ
K
J
0
rxn
K
J
0
rxn
0
O H
0
O H
0
rxn
0
rxn
0.1188 or 8 . 118 S
91 . 69 7 . 188 S
S S S
S BP @ S assume
2 g 2
= A
= A
= A
A ~ A
Calculations at Equilibrium
Calculations at Equilibrium
T =
H
S
H
S
.0 kJ
0.1188
K
370 K-273 K=97 C
o
o
kJ
K
o
A
A
A
A
~ = =
44
370
( )
% error =
370- 373 K
K
error
% error of less than 1%!!
373
100% 080% = .
Coupled Reactions
First step in utilizing glucose (in all organisms)
Non spontaneous
Coupled
Reaction
Spontaneous, yeah!