Lecture 6 Free Energy

James Chou
BCMP201 Spring 2008
Equilibrium = A system reaching a state of
maximum entropy.

Equilibrium = All microstates are equally
probable.


S = k
B
ln!

A quick review of the last lecture
I. Principle of Maximum Entropy
E1
E2
Not in Equilibrium Equilibrium
Picture from hyperphysics.phy-astr.gsu.edu
T = A measure of the tendency of an object to spontaneously give up energy to its
surroundings.

T = dE dS
( )
N,V
II. Temperature
III. The Boltzmann & Gibbs Distribution.


p E
a
( )
= A! exp
"E
a
k
B
T
#
$
%
&
'
(


When a small system is in thermal equilibrium with the large surrounding, the
probability distribution of the energy state of the small system follows the Boltzmann
distribution and is dependent only on the T of the surrounding.
Where does the energy for doing work come from?
The concept of chemical potential
Todays lecture outline
Chemical equilibrium, how !G governs the direction
of a chemical reaction
Free Energy, !G
Work
Work can be harnessed from a system in the process of going from non-equilibrium to
equilibrium. At equilibrium, the system can no longer do work.
A B

W = F ! dr
A
B
"
Sign convention: Work done on the system is positive
Work done by the system is negative.
Some commonly used units: 1 N m = 1 Joule = 10
7
erg = 0.239 cal.
At the single molecule level, k
B
T is commonly used because 1 k
B
T ! 4 pN nm.
In thermodynamics, work typically
involves volume change.

W = ! F" dr
A
B
#
= ! P" A dr
A
B
#


W = ! P" dV
V1
V 2
#
Ideal Gas
F
int
dr
F
op
Example:
A mole of ideal gas initially has a pressure of 2
atm, and then expands at a constant temperature
of 300 K against the atmosphere pressure (1 atm)
until equilibrium is reached. How much work is
done by the system?
Ideal Gas
F
int
dr
F
op
Heat Block 300 K

W = P
op
V
2
!V
1
( )
=1247 J
Ideal Gas
F
int
dr
P = 1 atm
Heat Block 300 K
Irreversible

P
op
=1 atm


W = P
op
! dV
V1
V 2
"
= nRT
dV
V
= nRTln
V
2
V
1 V1
V 2
"
= (8.314 J mol
-1
K
-1
) (300 K) ln 2
=1728 J
Ideal Gas
F
int
dr
Heat Block 300 K
Reversible

P
int
= P
op
P
V
A
B
A reversible process has well-
defined path.
T1
T2
Heat (Q) is amount of energy transferred between different objects. An isolated body does
not have heat.
What is heat?
368 K
298 K
What is the relation between heat and temperature?

T =
dE
dS
!
"
#
$
%
&
N,V
T is defined at constant V. So T is not related
to work. In this definition, replace dE with Q.
Q = T!S
Heat
Ideal Gas
F
int
dr
F
op
Heat Block 300 K
Energy of one mole of ideal gas:

E =
3
2
RT
.
Since T = const,

!E = 0.
Problem: For biological systems at constant T,

!E is a poor indicator of the work done by
or done to the systems.
But

W = ! P
op
" dV
V1
V 2
#
= !1728 J
.
The thermodynamic relation for internal energy E
!E = Q+W= T!S " P!V
Ideal Gas
F
int
dr
F
op
Heat Block 300 K

!S = k
B
ln V
2
N
( )
" k
B
ln V
1
N
( )
= Rln
V
2
V
1
= Rln
P
1
P
2

= 8.314 J mol
-1
K
-1
( )
ln2 = 5.76 J K
-1
!G = !E + ! PV ( ) " T!S
= " 300 K ( ) 5.76 J K
-1
( )
= "1728 J
Now how about

!G = ! E + PV
( )
" T!S
?
0 0
Introducing the definition of free energy G
Surrounding, B
a
For the surrounding B,

!E
B
= Q
B
+W
B
= T!S
B
" P!V
B
.

!E = !E
B
+ !E
a
= 0 " !E
B
= #!E
a
,

T!S
B
= #!E
a
+ P!V
B
Principle of maximum entropy:

T!S
tot
= T!S
B
+ T!S
a
= "!E
a
+ P!V
B
+ T!S
a
# 0.

!V
B
= "!V
a

!E
a
+ P!V
a
"T!S
a
# 0
!G
a
G of the system, a, in equilibrium with the universe decreases as
S of the universe increases
Surrounding, B
a
A
B
Not equilibrium
Equilibrium
Useful Work
A small system a is in thermal contact with a large surrounding B. B will stay in its original
equilibrium because a is too small to affect it. Define the Gibbs Free Energy of a (G
a
) to be


G
a
= E + PV !TS ( )
a
.

a will move to a new equilibrium to minimize G
a
and during the process, useful work can be
obtained.
Normally, for biological systems, T and P of the surrounding are constant, and hence

!G
a
= !E
a
+ P!V
a
"T!S
a
# 0
represents the maximum useful work can be extracted from a.
The four thermodynamic quantities and their relations to useful work
Internal Energy:

E

!E = Q+W
expansion
+W
useful
= TdS " PdV +W
useful
At constant S and V,

W
useful
= !E
.
Enthalpy:

H = E + PV

!H = !E + P!V +V!P = T!S +V!P +W
useful
At constant S and P,

W
useful
= !H
.
Helmholtz free energy:

F = E !TS

"F = "E !T"S ! S"T = !P"V ! S"T +W
useful
At constant T and V,

W
useful
= "F
.
Gibbs free energy:

G = E + PV !TS

"G = "E + P"V +V"P !T"S ! S"T =V"P ! S"T +W
useful
At constant T and P,

W
useful
= "G
.
The concept of chemical potential

G = E + PV !TS

E
kin
+ N
1
!
1
+ N
2
!
2
1 2
G is a function of both E and N
i
, at constant T and P.


G E, N
1
, N
2
( )
= E + PV !TS, E = E
kin
+ N
1
"
1
+ N
2
"
2
Define chemical potential of specie i to be

i
=
dG
dN
i
T,P,N
j
, i! j

T =
dE
dS
N,V
Remember what is temperature?
T describes the tendency of a system to give up energy. T depends
on kinetic energy of molecules.
describes the tendency of a molecular specie to chemically react.
depends on both concentration and internal energy of the
molecule.
What is the chemical potential
1
in the 2-component ideal gas?

1
=
dG
dN
1
=
dE
dN
1
!T
dS
dN
1
="
1
!T
dS
dN
1


G E, N
1
, N
2
( )
= E + PV !TS, E = E
kin
+ N
1
"
1
+ N
2
"
2
?


S = k
B
ln
2!
3N / 2
3N /2 "1
( )
!
#
$
%
&
'
( 2m)
kin
( )
3N / 2
V
N
1
N!
2!!
( )
"3N 1
2
*
+
,
,
-
.
/
/
Dont worry about this

3
2
k
B
T


T
dS
dN
1
=
3
2
k
B
Tln
mk
B
T
2!!
2
"
#
$
%
&
'
( k
B
Tln
N
1
V
"
#
$
%
&
'
Concetration, C
1

1
=!
1
+ k
B
TlnC
1
"
3
2
k
B
Tln
mk
B
T
2#!
2
Define the standard chemical potential

1
0
=!
1
"
3
2
k
B
Tln
mk
B
T
2#!
2
C
1
0
( )
3/ 2
We obtain

1
= k
B
Tln
C
1
C
1
0
!
"
#
$
%
&
+
1
0
Also true for aqueous solution
For gas, C
0
= 1 mole / 22 L.
For solutes in aqueous solution, C
0
= 1 mole / L = 1 M.
For solvent, C
0
= the molarity of the pure solvent
e.g. C
0
of H
2
O is 55.5 M.
The Concept of Chemical Equilibrium
1 2


!G =
dG
dN
1
"
#
$
%
&
'
dN
1
+
dG
dN
2
"
#
$
%
&
'
dN
2
, dN
1
= (dN
2

= !
dG
dN
1
"
#
$
%
&
'
dN
2
+
dG
dN
2
"
#
$
%
&
'
dN
2
At equilibrium,


!G = 0 "
2
=
1
" chemical equilibrium

!G
dN
2
=
2
"
1
The difference in chemical potential is the available chemical
energy to do work per unit of molecule.


A+ B ! AB
At chemical equilibrium,

i
= Nk
B
T ln C
i
C
i
0
( )
+
i
0
= RT ln C
i
C
i
0
( )
+
i
0

AB
!
A
+
B
( )
= 0

AB
0
!
A
0
!
B
0
RT
+ ln
C
AB
/ C
AB
0
C
A
/ C
A
0
( )
C
B
/ C
B
0
( )
"
#
$
$
%
&
'
'
= 0
When does a chemical reaction stop?
Define equilibrium constant K
eq
K
eq
= exp
!"G
0
RT
#
$
%
&
'
(
=
C
AB
/ C
AB
0
C
A
/ C
A
0
( )
C
B
/ C
B
0
( )

!G
0
1 M
K
eq
= exp
!"G
0
RT
#
$
%
&
'
(
=
C
AB
C
A
C
B

pK ! "log
10
K
eq

AB
0
!
A
0
!
B
0
RT
+ ln
C
AB
/ C
AB
0
C
A
/ C
A
0
( )
C
B
/ C
B
0
( )
"
#
$
$
%
&
'
'
= 0
The equilibrium constant
!G = !G
0
+ RT ln
C
2
C
1
0


!G
0
fixed
( )

!G

RT ln
C
2
C
1

!G
0
= "RT lnK
eq
The general equation for !G at any point of the reaction
1 2
!G
0
can be determined if equilibrium C
i
's are known.
!G
0
can also be calculated from standard free energy
of formation !G
f
0
.

!G
0
= !G
f , ADP
0
+ !G
f , Pi
0
" !G
f , ATP
0
" !G
f , H2O
0
= "30.3 kJ/mol
ATP + H2O ! ADP + P
i
!G = !G
0
+ RT ln
C
ADP
C
ADP
0
( )
C
P
C
P
0
( )
C
ATP
C
ADP
0
( )
C
H2O
C
H2O
0
( )
1 mM 55.5 M 0.1 mM 1 mM typical cellular concentration
An example of cellular chemical potential
ATP + H2O ! ADP + P
i
"G
0
= #30.3 kJ/mol
!G = !G
0
+ RT ln
C
ADP
C
ADP
0
( )
C
P
C
P
0
( )
C
ATP
C
ADP
0
( )
C
H2O
C
H2O
0
( )

= !30.3+ 2.748 ln
1.0 "10
!3
( )
1.0 "10
!4
( )
1.0 "10
!3
= !53.1 kJ / mol
1 mM 55.5 M 0.1 mM 1 mM typical cellular concentration
Living organisms constantly perturb G away from its minimum
so that there is free energy to do work.
Entropic Force
Force in Mechanics
In classical mechanics, potential energy U of an object can be defined in terms of the work
required to move the object from A to B with no net change in kinetic energy.
A
B

F ! dL
A
B
"
= # dU
A
B
"
= # U
B
#U
A
( )

F = !
dU
dL
Entropic Force
Similarly, in the case of isothermal compression of ideal gas from V
A
to V
B
, the total kinetic
energy stays the same, but the free energy G changes.
Ideal Gas
dL
F
T Reservoir

F ! dL
A
B
"
= # dG
V
A
V
B
"

!G = "T!S = "k
B
NT
V
B
V
A
#
$
%
&
'
(

F = !
dG
dL
What is the entropic force exerted on the wall by an ideal gas at constant T?
F
T Reservoir
dL
L

F = !
dG
dL

G = E + PV !TS

F = !
dE
dL
!
d PV
( )
dL
+ T
dS
dL
0

S = k
B
ln!= k
B
ln E
kin
3N / 2
" V
N
( )
+ const

= k
B
ln E
kin
3N / 2
( )
+ k
B
ln V
N
( )
+ const

dS = k
B
N
V
dV = k
B
N
L
dL

F = T
dS
dL
= k
B
NT
L

PV = Nk
B
T
F
H2O
movable semi-permeable wall
solute
Since the volume of water roughly stays the
same, the entropy of water does not change.
However, the solutes still want to maximize
entropy by expansion, just like an ideal gas.


F = k
B
NT
L
,
F
A
=
N
V
k
B
T
vant Hoff equation
concentration

P
osmotic
= Ck
B
T
Osmotic force is similar to the expansion force of an ideal gas
Take home messages
In a chemical reaction

A !B, the difference between
A
and
B
is amount of
chemical energy available to do work per unit of molecule. At chemical
equilibrium,

A
=
B
, or G = 0.
The chemical potential of molecular specie i in a mixture is defined as
It is the tendency of that molecular specie to chemically react, which
depends on both its concentration and internal energy of the molecule.

i
=
dG
dN
i
T,P,N
j
, i! j
For a small system a in thermal contact with a large surrounding B, maximizing
entropy is equivalent to minimizing the Gibbs free energy.

G
a
= E
a
+ PV
a
! TS
a


During the process of a going from non-equilibrium to equilibrium at constant T
and P, the maximum useful work that can be transduced is

"G
a
.