20.110J / 2.772J / 5.

601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #9

page 1

Gibbs Free Energy, Multicomponent Systems,

Partial Molar Quantities, and the Chemical
Potential
Comments on

the special role of G(T,p):

If you know G(T,p), you know all other thermodynamic quantitites.

G
,
T p

p T

S =

V =

T p

H = G +TS

H = G T

U = H pV

U = G T

A = U TS

A =G p

S
C p =T

T p

G
G

p
T p
p T

p T

2G
C p = T
2
T p

We can get all the thermodynamic functions from G(T,p).

p-dependence of G(T,p)
From

for liquids, solids, and gases (ideal)

p T

V =

p2

G (T , p2 ) = G (T , p1 ) + Vdp
p1

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #9

Liquids and solids

V is small

G (T , p2 ) = G (T , p1 ) +V ( p2 p1 ) G (T , p1 )

page 2

G (T

Ideal gases
G (T , p2 ) = G (T , p1 ) +

p2

p1

p
RT
dp = G (T , p1 ) + RT ln 2
p
p1

Take p1 = p o = 1 bar
G (T , p ) = G o (T ) + RT ln

From

p
p0

T p

S =

or G (T , p ) = G o (T ) + RT ln p

(p in bar)

S (T , p ) = S o (T ) R ln p

Multicomponent systems, the chemical equilibrium, partial molar

quantitites.
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

G (T , p ,n1 ,n2 )

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #9

page 3

G
G
G
G
dG =
dT +
dp +
dn1 +
dn2

p T ,n ,n
n1 T , p ,n
n2 T , p ,n
T p ,n ,n

We define

 
2

 1
2

ni T , p ,nj i

 
1
2

as the chemical potential of species i

i (T , p , nj ) is an intensive variable

This gives a new set of fundamental equations for open systems

(mass can flow in and out, composition can change)
dG = SdT +Vdp + i dni
i

dH =TdS +Vdp + i dni

i

dU =TdS pdV + i dni

i

dA = SdT pdV + i dni

i

G
H
U
A
=
=
=

ni T , p ,nj i ni S , p ,nj i ni S ,V ,nj i ni T ,V ,nj i

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)

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #9

page 4

Consider moving an infinitesimal amount dn1 of component #1 from

phase a to phase b at constant T,p. Lets write the change in state.

dn1 (T , p ,phase a ) = dn1 (T , p ,phase b )
dG = S dT

+V dp + i dni = 1(b ) 1(a ) dn1

i

1(b ) < 1( a )

dG < 0

spontaneous conversion from (a) to (b)

1( a ) < 1(b )

dG > 0

spontaneous conversion from (b) to (a)

At equilibrium there cannot be any spontaneous processes, so

1( a ) = 1(b ) at equilibrium

e.g. liquid water and ice in equilibrium

ice
water

ice (T , p ) = water (T , p )

at coexistence equilibrium

For the cell in a salt water solution, water (cell ) (T , p ) > water (solution ) (T , p ) and
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

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #9

page 5

Partial molar quantities

i is the Gibbs free energy per mole of component i, i.e. the

partial molar Gibbs free energy

G
= i = Gi

ni T , p ,nj i

G = n1 1 + n2 2 + " + ni i = ni i = ni Gi
i

Lets prove this, using the fact that G is extensive.

G (T , p , n1 , n2 ) = G (T , p , n1 , n2 )
dG
(T , p , n1 , n2 ) = G (T , p ,n1 ,n2 )
d
G
G
( n1 )
( n2 )
+
=G

( n1 ) T , p ,n2 T , p ,n2 ( n2 ) T , p ,n1 T , p ,n1

 

n1

n2

is arbitrary, we can choose = 1

n1 1 + n2 2 = G

We can define other partial molar quantities similarly.

A
= Ai

n
i T , p ,nj i

A = n1A1 + n2A2 + " + ni Ai = ni Ai

i

partial molar Helmholtz free energy

note what is kept constant
H
= Hi

ni T , p ,n j i

not to be confused with

ni T ,V ,n

H = n1H1 + n2H2 + " + ni Hi = ni Hi

i

= i
j i

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #9

page 6

partial molar enthalpy

U
= Ui

ni T , p ,n j i

U = n1U1 + n2U2 + " + niUi = niUi

i

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
From

G (T , p ) = G o (T ) + RT ln

p
p0

(T , p ) = o (T ) + RT ln

Chemical potential in a mixture of ideal gases

onsider the equilibrium
pA + pB = ptot

mixed pure
A
A,B
p'A, p'B pA

Fixed Partition

At equilibrium

A ( mix ,T , ptot ) = A ( pure ,T , pA )

Also

pA ( pure ) = pA ( mix ) = ptot XA

Daltons Law

So

p
p0

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #9

page 7

A (mix ,T , ptot ) = A ( pure ,T , ptot XA )

p X
= Ao (T ) + RT ln tot A
p0
= Ao (T ) + RT ln

ptot
+ RT ln XA
p0

A ( pure ,T , ptot )

Note

A ( mix ,T , ptot ) = A ( pure ,T , ptot ) + RT ln XA

XA < 1

A (mix ,T , ptot ) < A ( pure ,T , ptot )

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!