5.

60 Spring 2008 Lecture #14 page 1

Multicomponent Systems, Partial Molar Quantities,
and the Chemical Potential
So far weve worked with fundamental equations for a closed (no
mass change) system with no composition change.
dU TdS pdV dA SdT = = pdV
dH =TdS +Vdp dG = SdT +Vdp
How does this change if we allow the composition of the system to
change? Like in a chemical reaction or a biochemical process?
Consider Gibbs free energy of a 2-component system ( , ,
1
,
2
) G T p n n
dG =
|

\
c
c
T
G
|
|
.
, ,
dT +
|

\
c
c
G
p
|
|
.
dp +
|

\
c
c
G
n
1
|
|
.
dn
1
+
|

\
c
c
n
G |
|
dn
2
p n n 2 .
1 2 , ,
1 2
, ,
2
T p n , ,
1

T n n T p n

S
V
1

2
We define
i

| cG
|
|
as the chemical potential of species i
\
cn
i .
T p n , ,
j =i
(
, ,
j
)
is an intensive variable
i
T p n
This gives a new set of fundamental equations for open systems
(mass can flow in and out, composition can change)
dG = SdT +Vdp +

i
dn
i
i
dH =TdS +Vdp +

i
dn
i
i
dU TdS pdV +

i i
= dn
i
dA = SdT pdV +

i
dn
i
i
5.60 Spring 2008 Lecture #14 page 2
| cG | | cH | | cU | | cA |

i
=
|
=
|
=
|
=
|
S p n , T V n ,
\
cn
i .
T p n , ,
j =i
\
cn
i .
, ,
j =i
\
cn
i .
S V n ,
j =i
\
cn
i .
,
j =i
At equilibrium, the chemical potential of a species is the same
everywhere in the system
Lets show this in a system that has one component and two parts,
(for example a solid and a liquid phase, or for the case of a cell
placed in salt water, the water in the cell versus the water out of
the cell in the salt water)
Consider moving an infinitesimal amount dn
1
of component #1 from
phase a to phase b at constant T,p. Lets write the change in state.
(
, , phase a
)
= dn T p
(
, , phase b
)
dn T p
1 1
a
dG =

1
( ) b

1
( )
(

dn
1
a

1
( ) b
<
1
( )
dG < 0 spontaneous conversion from (a) to (b)
b

1
( ) a
<
1
( )
dG > 0 spontaneous conversion from (b) to (a)
At equilibrium there cannot be any spontaneous processes, so
b

1
( ) a
=
1
( )
at equilibrium
e.g. liquid water and ice in equilibrium
water
ice

ice
( , ) =
water
( , ) T p T p
at coexistence equilibrium

5.60 Spring 2008 Lecture #14 page 3
water cell
T p
(
, and For the cell in a salt water solution,
( )
, >
water solution )
T p ( ) ( )
the cell dies as the water flows from the cell to the solution (this is
what we call osmotic pressure)
The chemical potential and its downhill drive to equilibrium will be
the guiding principle for our study of phase transitions, chemical
reactions, and biochemical processes
Partial molar quantities

i
is the Gibbs free energy per mole of component i, i.e. the
partial molar Gibbs free energy
| cG
|
=
i
= G
i
\ .
cn
i
T p n
=
, ,
j i
G = n +n + +n = n n G
1 1 2 2 i i i i
=
i i
i i
Lets prove this, using the fact that G is extensive.
G T p ( , , n
1
, n
2
) = ( , ,
1
,
2
) G T p n n
( , ,
1
, n ) ( , ,
1
,
dG
T p n
2
= G T p n n
2
)
d
|
cG
| | c( ) n
1
| |
cG
| | c(n
2
) |
|
|
|
+
|
|
|
= G
c n
.
c
.
n
c n
2
c
.
, ,n \
( )
1 \
T p , , \
( )
. \
T p T p n
2
, ,
1

1
, ,
2

T p n

n
1
n
2
n
1 1
+n
2

2
= G


__________________________________________________
5.60 Spring 2008 Lecture #14 page 4
We can define other partial molar quantities similarly.
| cA |

c
|
= A
i
A = n A +n A ++n A = n A
1 1 2 2 i i i i
i
\
n
i .
, ,
j i
T p n
=
partial molar Helmholtz free energy
note what is kept constant not to be confused with

|
c
c
n
A
|
|
=
i
\ i .
T V n
=
, ,
j i
| cH |

cn
|
= H
i
H = n H + n H + + n H = n H
1 1 2 2 i i i i
i
\ i .
T p n
=
, ,
j i
partial molar enthalpy
| cU |

cn
i
|
, ,
j i
=U
i
U = nU + n U + + nU =
i 1 1 2 2 i i
nU
i
i
\ .
T p n
=
partial molar energy
Lets compare of a pure ideal gas to in a mixture of ideal gases.
Chemical potential in a pure (1-component) ideal gas
o o
From (
,
)
= G ( ) + RT ln
p

(
,
)
= T +
p
G T p T T p ( ) RT ln
p
0
p
0
Chemical potential in a mixture of ideal gases
Consider the equilibrium
p
A
' + p
B
' = p
tot
mixed
A,B
pure
A
p
A
p'
A,
p'
B
Fixed Partition
\
At equilibrium mix T p , , = pure T p
A
(
tot
)
A
( , ,
A
)
5.60 Spring 2008 Lecture #14 page 5
Also p
A
( pure ) = p
A
'
(mix ) = p
tot
X
A
Daltons Law
So

A
(mix T p , ,
tot
) =
A
(pure T p
tot
X
A
) , ,

A
( ) + RT

| p X
|
|
=
o
T ln
tot A
\
p
0 .
=
A
o
( ) T + RT ln
p
tot
+ RT ln X
A
p
0
( pure T p
tot
)
A
, ,

A
( , ,
tot
) =
A
( pure T p
tot
) + RT ln X
A
mix T p , ,
Note X
A
< 1
A
(mix T p ,
tot
) <
A
( ,
tot
) , , pure T p
The chemical potential of A in the mixture is always less than the
chemical potential of A when pure, at the same total pressure. This
is at heart a reflection about entropy, the chemical potential of A
in the mixture is less than if it were pure, under the same (T,p)
conditions, because of the underlying (but hidden in this case)
entropy change!