CHEMICAL POTENTIAL AND

GIBBS DISTRIBUTION

Chemical Equilibrium

Remember that T was the property, two system share when they
are in thermal equilibrium (flow of energy).

The Chemical Potential ( , V , N ) governs the flow of particles

(diffusive contact) between the systems, just as the temperature
governs the flow of energy.
We will show that if of the two system is different, particles will flow
from the system with higher 1 to the system with lower 2 , until

1 = 2

Consider 1 + 2 as shown in the figure:

dN1

dN2

negative

positive

System 1

System 2
, V1, N1

Reservoir

, V2, N2

Energy exchange

We have shown earlier that for a system S in thermal equilibrium with

reservoir , the Helmholtz free energy F is minimum compatible with

, V , N and other constraints.

This is also true for S1 + S2 (here N = N1 + N2 = constant).

F = F1 + F2 = U1 + U 2 ( 1 + 2 )
Since N is constant,

dN = 0 = dN1 + dN 2
dN1 = dN 2
At the minimum,

F1
F2

dN 2 = 0
dF = 0 =
dN1 +

N1
N 2
Also V1 ,V2 hold constant.

is a minimum.

 F1 F2

dN1 = 0

N1 N 2

()

F1 F2
=
= j ( , V j , N j ) (condition for equilibrium).

N1 N 2
The chemical potential is defined as

:= ( , V , N )
N ,V
If 1 > 2 we see from () that dF < 0 when dN < 0 Particles flow
from the system with larger to the system with lower

Since Particles are not divisible, the strict definition of is in terms of

a difference (as opposed to derivative)

( , V , N ) F ( ,V , N ) F ( ,V , N 1)
If several chemical species are present , each has its own chemical
potential

F
j =
N
j

,V , N1, N 2 ,...

Example: Chemical Potential of the Ideal

Gas
Remember: The free energy of the monatomic ideal gas is

F = ln Z
or
Z1N
F = [ N log Z1 log N !] = log

N
!

V
1
where Z1 = 3 = nQV , nQ = 3 (Quantum concentration)
DB
DB
and DB = 22 M

Use

N!
F ( N ) F ( N 1) = ( N N + 1) log Z1 log

(
N

1
)!

= [ log Z1 log N ] = log( N )

Z1
or = log n

, where n = N .
nQ
V

depends on concentration, not on N or V separately.

Increases as n increases! This is what one would expect intuitively.

Using Ideal gas law p = n we can write

= log( p nQ ).

Internal and Total Chemical Potential

Consider the two systems of charged particles. A potential step
between them can be established by applying a voltage.
S2
S1

2 ,

1 ,

Initially 2 > 1 , yielding (initial) = 2 1

Now apply V to S1 such that

qV = q(V2 V1 ) = (initial)
If F2 is fixed, the potential step rises F1 by

N1 (initial)

(increase in potential energy)

For diffusive equilibrium we need

1 (final) = 1 (initial) + [ 2 (initial) 1 (initial)] = 2 (initial) = 2 (final)

( initial )

The barrier qV brings S1 and S2 into diffusive equilibrium.

Note: The chemical potential

potential energy.

The difference in is equal to a potential barrier that will bring two

systems into equilibrium.

When external potentials are present

= tot = ext + int

int :Internal chemical potential, defined as

if no external

potential is present.
The equilibrium condition

2 = 1 can than be written as

tot = 0
ext = int .

Example: Variation of barometric pressure

with altitude.
System (2)

Place the zero of the potential energy

at ground level, then the potential
energy per molecule at height h is
Mgh, where M is the particle mass

and g the gravitational acceleration.

The internal chemical potential of
the particles is given by

n
int = log n ,
Q

ext = Mgh.

System (1)

A model of the variation of atmospheric

pressure with altitude.

The total chemical potential is

(h) = log n(h) n + Mgh

Q

In equilibrium, the chemical potential must be every where identical:

log n(h) n + Mgh = log n(0) n

Q
Q

n(h) = n(0) exp Mgh

For an ideal gas p = n

p (h) = p (0) exp Mgh = p(0) exp h ,

hc
where
hc =
.
Mg
This is barometric pressure equation.

Barometric pressure equation gives us dependence of the pressure on

altitude in an isothermal atmosphere of a single chemical species.
At the characteristic height hc = Mg the atmospheric pressure
decreases by the fraction e

0.37 .To estimate the characteristic

height, consider an isothermal atmosphere composed of nitrogen

molecules with a molecular weight of 28.
24
Mass of an N2 molecule is 48 10 gm. .

14

k
T
is
4
.
0

10
erg.
B
At temperature 290K the value of

With g = 980cms-2, the characteristic height is then 8.5km.

Batteries
One of the most vivid examples of chemical potentials and potential steps
is the electrochemical battery. In the lead-acid battery the negative
electrode consists of metallic lead, Pb, and the positive electrode is a
layer of reddish-brown lead oxide, PbO2, on a Pb substrate. The
electrodes are immersed in diluted sulfuric acid, H2SO4, which is partially
ionized into H+ ions SO4-- ions. It is the ion that matter.

(-) electrode

(+) electrode

Pb

PbO2

SO4--

2e-

Pb

2H+ + H2SO4

2e-

Convert to PbSO4
2H2O

The lead-acid battery consists of a Pb and a PbO2 electrode immersed in

partially ionized H2SO4. One SO4 ion converts one Pb atom into PbSO4 + 2e-;
two H+ ions plus one un-ionized H2SO4 molecule convert one PbO2
molecule into PbSO4 + 2H2O, consuming two electrons.

In the discharge process both the metallic Pb of the negative electrode

and the PbO2 of the positive electrode are converted to lead sulfate,
PbSO4.
Discharge Process:
Negative electrode:

Pb + SO 4 PbSO 4 + 2e ;
Positive electrode:

PbO 2 + 2H + + H 2SO 4 + 2e PbSO 4 + 2H 2 O.

( a)
( b)

Because of () the negative electrode acts as a sink for SO4-- ions,

keeping the internal chemical potential (SO4-- ) of the sulfate ions at the
surface of the negative electrode lower than inside the electrolyte.

(-) electrode

(+) electrode
(H+)

(SO4--)

- 2eV-

(SO4--)

(H+)

+ eV+

The electrochemical potentials for SO4-- and H+ before the development of

internal potential barriers that stop the diffusion and the chemical reaction.

Because of (b) the positive electrode acts as a sink for H+ ions, keeping
the internal chemical potential (H+) of the hydrogen ions lower at the
surface of the positive electrode than inside the electrolyte. The chemical
potential gradients drive the ions towards the electrodes, and they drive
the electrical currents during the discharge process.
(-) electrode

(+) electrode

(x)

+ V+

- V-

The electrostatic potential (x) after the formation of the barrier.

If battery terminals are not connected, a electrical potential (x) develops

until they equalize the chemical potential steps. Diffusion stops when:
at - electrode

-2q V- = (SO42-)

at + electrode

+q V+ = (H+).

The two potentials V- and V+ are called half-cell potentials.

The total electrostatic potential difference developed across one full cell of
the battery, as required to stop the diffusion reaction, is
V = V+ - V- = 2.0 volt.
This is the open-circuit voltage or EMF (electromotive force) of the battery.
There is a small electron current through the electrolyte, however it is
negligible! Otherwise a battery would discharge quickly. Electrons

An alternative way to calculate the chemical potential.

Now the number of quantum states has to depend on the number of
particles

d =
dU +
dV +
dN
U V , N
V U , N
N U ,V
Assume isotropic process dV = 0, select d , dU , dN in such a way
that d = 0, call these values ( ) , ( U ) , ( N ) respectively then

d = 0

when

( ) = ( U ) + ( N ) ,
U N
N U
After division by ( N ) ,
( ) = ( U ) + .

( N ) U N ( N ) N U

=

+

U N N ,V N U ,V
N ,V

=
+

,V
,V

U ,V
By the original definition of chemical potential

U
F

+

( , V , N )

,V
,V

U ,V

and on comparison with above equation

=
.
N U ,V

Thermodynamic identity
We can generalize the statement of the thermodynamic identity to
include systems in which the number of particles is allowed to change.

d =
dU
+
dV
+

dU
U V , N
V U , N
N U ,V



1

d = dU + pdV dN
or

dU =
d

Thermal heat

pdV

Mechanical work

dN

Chemical work

Grand Canonical Ensemble and

Grand Potential

Canonical Ensemble

Grand Canonical Ensemble

Volume is fixed

Volume is fixed

Can exchange energy with

reservoir

Can additionally exchange

particles with reservoir

Concept of thermal equilibrium

Concept of chemical/diffusive
equilibrium

Definition of temperature

Definition of chemical potential

(energy fluctuates)

(particle number fluctuates)

Boltzmann factor

Gibbs factor

Canonical partition function

Gibbs sum
(Grand Canonical partition function)

Free energy

Grand potential

Gibbs Factor
System

Reservoir

What is the probability of

finding the system in a
microstate S with some

U,V,N
State S

U tot U
Vtot V
N tot N

given values of U and

N?
Exchange energy and particles

U and N fluctuate, V is fixed

Derivation follows exactly along the lines of the canonical case. The
probability is proportional to the multiplicity!

P( SU , N )

g (reservoir + system)

no bounbary effects

g (reservoir ).

g ( system)

system is in fixed microstate

= g (reservoir ).1
= g r (U tot U , N tot N )
= exp{ r (U tot U , N tot N )}

r
r

= exp r (U tot , N tot )

U
N
Taylor
U
U

tot
tot
1

= exp r (U tot , N tot ) U + N

= constant . exp (U N )

Hence: The probability of finding the system in a particular state S, in

which it has energy U and particle number N is proportional to the
Gibbs factor
P(SU,N)

(U N ) .
exp

In order to get an equality, and not just a proportionality, we need to

find the normalization factor. It is called the Gibbs sum or grand
canonical partition function:

- ( H N ( SN ) N )
Z ( , V , ) := exp

N =0 S N

So that we have

exp (U N )

P ( SU , N ) =
Z ( , V , )

The logarithm of Z is again a thermodynamic potential:

( ,V , ) := ln Z ( ,V , )
It is called Grand Potential.

Relation of the grand potential with other

thermodynamic potential:

exp

) = Z = exp ( H ( S
N

SN

) N )

= g N (U ) exp (U N )

N U
= exp( (U , N ) ) exp (U N )

N,U
= exp (U N )

N ,U

For large systems only the largest term in the sum will contribute
significantly

exp minU N

N ,U
large system

Taking the logarithm, we find

min{U N }
N ,U

= min{ F N }.
N

Example: What is the average number of particles in

our system
Consider

N = N P ( S N )
N =0 S N

N exp ( H ( S ) N )

N =0 S N

( H N ( S N ) N )
exp

N =0 S N

( H N ( S N ) N )

exp

N =0 S N

( H N ( S N ) N )
exp

N =0 S N


Z ( , V , )

=
=
ln Z ( , V , )
Z ( , V , )

Also

( ln Z ( ,V , ) ) = ( ,V , )

N =

1 Z
Z

exp

Z = N exp s ,

N S

since

=


1

N =

log Z .