Thermodynamics

Chapter 20
Thermodynamics
Prediction of whether change will occur
No indication of timeframe

Spontaneous:
occurs without external intervention

Nonspontaneous:
requires outside push
16_343
E
n
e
r
g
y
Reaction progress
Reactants
Products
Domain of kinetics
(the reaction pathway)
Domain of
thermodynamics
(the initial and
final states)
Entropy and Spontaneity
Driving force for a spontaneous change is an
increase in entropy of the universe

Entropy, S: measure of disorder

Spontaneous change implies:
more order less order
fewer ways of arranging particles more
Second Law of Thermodynamics
In any spontaneous change, there is always an
increase in entropy of the universe.



Units: J
K
0 S S S
surr sys univ
> + =
Entropy
1877 Ludwig Boltzmann:


k = Boltzmann constant, R/N
A

W = no. of possible arrangements

Third Law of Thermodynamics:
The entropy of a perfect crystal at 0 K is zero.

W ln k S=
Positional Entropy
Why does a gas expand into a vacuum?



Expanded state has highest positional probability
of states available.

solution gas or liquid, solid, pure
gas liquid solid
S S
S S S
<
<< <
Other factors in entropy
Size:
increase in S with increasing size (mass)

Molecular complexity:
increase in S with increasing complexity

Generally effect of physical state >> complexity
Reactions
For a spontaneous reaction:



NaOH
(s)
+ CO
2(g)
Na
2
CO
3(s)
+ H
2
O
(l)

S
0
64.45 213.7 139 69.94 J/K

Is the reaction spontaneous as written?
0 S n S n S
0
r r
0
p p
0
rxn
> =

Spontaneity and S
Spontaneous: AS
univ
> 0
Nonspontaneous: AS
univ
< 0
At equilibrium: AS
univ
= 0



AS
sys
can be positive if AS
surr
increases enough
surr sys univ
S S S + =
16_03T
Table 16.3 Interplay of ASsys and ASsurr in Determining the Sign of ASuniv
Signs of Entropy Changes
Process Spontaneous?
+ + Yes
No (reaction will occur
in opposite direction)
+ ? Yes, if AS
sys
has a
larger magnitude
than AS
surr

+ ? Yes, if AS
surr
has a
larger magnitude
than AS
sys
AS
sys
AS
surr
AS
univ
+
Surroundings and S
univ

Surroundings add or remove heat
Exothermic:
Aq
sys
< 0
Aq
surr
> 0 so AS
surr
> 0

Endothermic:
Aq
sys
> 0
Aq
surr
< 0 so AS
surr
< 0
AS
surr
and AS
sys

AS
surr
:

AS
surr
- Aq
sys

AS
surr
1/T




At constant pressure:
T
q
S
sys
surr
=
T
H
S
sys
surr
A
=
The Math
Given:

@constant P:

Multiply by
T:

Result:
sys sys sys
sys sys univ
sys
sys univ
surr sys univ
T H G
T H T
T
H
S S
S S S
S
S S
=
=
=
+ =
0 S implies 0 G
univ
> <
Reactions and AG
AG
0
: Standard Free Energy
Reactants in standard states are
converted to products in standard states

=
0
r r
0
p p
0
rxn
G n G n G
Gibbs Free Energy
Overall criterion for spontaneity


from the standpoint of the system

A process at constant temp. and pressure is
spontaneous in the direction AG decreases

S T - H G A A =
AG = AH - TAS
AH AS AG
Spontaneous?
Good: AH < 0 Good: AS > 0 Good: AG < 0 Good: AG < 0
- + -
At all
temperatures
- - ?
At low
temperatures
+ + ?
At high
temperatures
+ - +
Not at any
temperature
Summary
AG < 0 Spontaneous as written

AG > 0 Not spontaneous as written
Reverse process spontaneous

AG = 0 At equilibrium
A Closer Look
TAS:
energy not avail. for doing work
AG:
E avail. as heat E not avail. for work
max. work available (constant T and P)

Amount of work actually obtained depends on path
S T - H G A A =
AG and Work
AG
Spontaneous max. work obtainable
Nonspontaneous min. work required

Work and path-dependence
w
max
(w
min
) process performed reversibly
theoretical
w
actual
< w
max
performed irreversibly
real world
Reversible vs. Irreversible Processes
Reversible:
The universe is exactly the same as it was before
the cyclic process.

Irreversible:
The universe is different after the cyclic process.

All real processes are irreversible.
Some work is changed to heat.
Free Energy and Pressure
Q: reaction quotient from mass action law
RTlnQ G G
0
+ A =
Free Energy and Equilibrium
K: equilibrium constant
At
equilibrium: AG = 0
K = Q
RTlnK G
0
=
RT
G

e
0

K

=
16_354
0
Fraction of A reacted
0.5 1.0
G
Equilibrium
occurs here
0
Fraction of A reacted
0.5 1.0
G
Equilibrium
occurs here
0
Fraction of A reacted
0.5 1.0
Equilibrium
occurs here
(a) (b) (c)
G
A B
AG and Extent of Reaction
A B
AG
0
B
< AG
0
A

Spontaneous
C D
AG
0
D
> AG
0
C

Nonspontaneous
Temperature Dependence of K
Plot lnK vs. 1/T
slope = -AH
0
/R intercept = AS
0
/R

*assumes AH
0
, AS
0
relatively T independent
0 0 0
S T - H RTlnK G A A = =
b mx y
R
S

T
1
R
H
lnK
RT
G

0 0 0
+ =
A
+
|
.
|

\
|
A
= =