1

2011 Imam Siswanto Kimia Fisika I

KIMIA FISIKA I
Free Enery and Equilibrium
2
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
All changes in nature are due to the tendency on the part of system to
reach a condition of maximum stability commensurate with the state of
each system, i.e., equilibrium. Once equilibrium has been reached, the
propensity toward further change disappears and we say that the system
is stable. As long as a system is away from equilibrium it will experience a
tendency to reach that state, and the tendency will be greater the greater
the distance from equilibrium.


3
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
Work results only when the tendency of systems to attain
equilibrium is harnessed in some way. From a system in equilibrium no work
can be obtained, but a system on the way to equilibrium may be made to
yield useful work. The amount of work that can be recovered from any
system undergoing a change depends both on the nature of the change and
the manner in which the system is harnessed. However, for each particular
process there is a maximum amount of work the system can possibly do,
and this maximum work may be taken as a measure of the tendency of the
system in question to undergo change.

4
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
A system undergoing change can perform maximum work only
when the change is carried out reversibly. If the process is not completely
reversible, the amount of work obtainable is always below the maximum, the
difference appearing as heat. The driving force behind the change is still,
however, the maximum work difference between the final and initial states,
for this difference still represents the highest possible quantity of energy that
tends to appear in utilizable form as a result of the process. Whether it does
appear or not depends entirely on the manner in which the process is
conducted, and in no way affect the conclusion that the maximum work a
process may perform, if conducted properly is the true measure of the driving
tendency behind the process.
5
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
The Helmholtz Free Energy
The Helmholtz free energy of any system, A, is defined as
A=E TS
Where E and S are, respectively, the internal energy and entropy of a system.
Since E, T, and S depend only on the state of the system, A must also be a state
function.


Under isothermal condition, when T
2
= T
1
= T, this equation reduces to
A= E T S
Since under isothermal condition T S = q
r
, we have
A = E q
r

= - w
m


A is sometimes called the maximum work content of a system.






6
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
The Helmholtz Free Energy
For any pure substance A is most conveniently expressed in terms of T and V
as the independent variables.




Now, if we completely differentiate the equation A = E TS we get
dA = dE SdT TdS
= dE SdT dq
r

Since TdS = dq
r
.
But dq
r
= dE + PdV, hence

dA = dE SdT dE PdV

= S dT PdV







V T
A A
dA dT dV
T V
c c
| | | |
= +
| |
c c
\ . \ .
7
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
The Helmholtz Free Energy
Previously we have



Comparing this equation with
dA = S dT PdV

we see that

and
V T
A A
dA dT dV
T V
c c
| | | |
= +
| |
c c
\ . \ .
V
A
S
T
c
| |
=
|
c
\ .
T
A
P
V
c
| |
=
|
c
\ .
8
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
The Helmholtz Free Energy
An alternative equation for variation of A with T : Differentiation of the quantity
A/T with respect to T at constant V,








But A + TS = E, therefore
2
( / )
V
V
A
T A
A T T
T T
c
| |

|
c c
( \ .
=
(
c

2
A TS
T
+
=
2
( / )
V
A T E
T T
c
(
=
(
c

9
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
AA for Reactions
For any reaction such as
aA + bB + = cC + dD +

AA is given by the sum of the As for the products minus a similar sum for the
reactants :
AA = (cA
C
+ dA
D
+ . . . ) (aA
A
+ bA
B
+ . . . )

The variation of AA with temperature at constant volume :
( )
... ...
C D A B
V V V V V
A A A A A
c d a b
T T T T T
( ( c c A c c c
| | ( | | | | | |
= + + + +
| | | | ( (
(
c c c c c
\ . \ . \ . \ .

[ ...] [ ...]
C D A B
cS dS aS bS =
S = A
10
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
AA for Reactions
We have A= E T S, and if we insert equation into the
equation we get :



An alternative expression for variation of AA with T


( )
V
A
S
T
c A
(
= A
(
c

( )
V
A
A E T
T
c A
(
A = A +
(
c

( )
2
/
V
A T
E
T T
c A (
A
=
(
c

11
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
The Gibbs Free Energy
The Gibbs free energy of any system, G, is defined as
G=H TS

Where the temperature is constant :
AG = AH - TAS

An alternative way :
G = A + PV

An similar to that for A :

=




12
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
An alternative expression for dependence of G on T follows from
differentiation of the quantity G/T with respect to T at constant P, namely :

(

2


Example :
The Gibbs Free Energy
13
First Energy and Equilibrium
2011 Imam Siswanto Kimia Fisika I
For constant temperature :

=
Then
=
2
1


=

1

For solids and liquids
= (
2

1
)
The Gibbs Free Energy Calculation