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 #11

page 1

Equilibrium in Solution
The chemical potential for molecules in solution is given by a formula
that is very similar to that for ideal gases:
A (T , p , cA ) = Ao (T , p ) + RT ln cA = Ao (T , p ) + RT ln [A ]

The precise definition of the standard chemical potential Ao (T , p ) is

now more complicated; it is defined at a given pH, salt concentration,
etc, all solution properties that need to be defined in advance. We
will not go through those and take it as a given that the standard
state is appropriately defined.
Given a standard chemical potential Ao (T , p ) , then the analysis that
we did for the ideal gas follows straight through and we find for a
solution process

A A(g, T, p) + B B(g, T, p) = C C(g, T, p) + D D(g, T, p)

that following the ideal gas analysis in our previous lecture
[C ]C [D ]D
G ( ) = C C (T ) + D D (T ) A A (T ) + B B (T ) + RT ln
[A ] A [B ] B

and the equilibrium constant K comes out through

o
Grxn
= RT ln K ,

Where K = Qeq

K = e G

RT

[C ] [D ] at equilibrium as before, and where the

=

[A ] [B ]
C

concentrations Q are equilibrium concentrations.

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 #11

page 2

Temperature dependence of K (or Kp)

ln K (T ) =

G o

RT

d ln K
d G o G o
1 d G o
=

dT
dT RT RT 2 RT dT

But at fixed pressure and/or solutions properties (p = 1 bar, pH

constant, etc..)
d G o G o
=

dT
T 1 bar,pH constant, etc...

and from fundamental equation

G
dG = SdT +Vdp
= S
T p

o
o
1
d ln K H (T ) T S (T )
=
+
S o (T
2
dT
RT
RT

d ln K (T ) H o (T
=
dT
RT 2

G o
o

= S (T
T

T2

H o (T

)dT

Integrating:

ln K (T2 ) = ln K (T1 ) +

At constant p:

H o (T ) = H o (T1 ) + C p (T T1 )

T1

T2

ln K (T2 ) = ln K (T1 ) +

T1

RT

H o (T1 ) + C p (T T1 )

RT 2

dT

Over small T ranges, C p (T T1 ) can be assumed small and H o

independent of T.

H o 1 1
H o T2 T1
ln K (T2 ) ln K (T1 ) +
= ln K (T1 ) +

R T1 T2
R TT
1 2

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

If

Lecture #11

H o (T ) < 0

(Exothermic)

page 3

T2 >T1 means K p (T2 ) < K p (T1 )

The equilibrium shifts toward reactants

If

H o (T ) > 0

(Endothermic)

T2 >T1 means K p (T2 ) > K p (T1 )

The equilibrium shifts toward products

This is Le Chateliers principle for Temperature

Example: The Haber process

N2(g, T, p) + 3/2 H2(g, T, p) = NH3(g, T, p)
o
Hrxn
(298 K ) = 46.21 kJ/mol
o
Grxn
(298 K ) = 16.74 kJ/mol

Kp =

pNH

pH3 2 pN1 2
2

=p

XNH

XH3 2XN1 2
2

=e

16,740 J/mol

(8.314 J/K-mol)(298 K )

= 860

For p = 1 bar this is pretty good, lots of product. However, the

reaction at room T is slow (this is kinetics, not thermodynamics).
Raising T to 800 K can speed it up. But since H o (T ) < 0 (exothermic),
Le Chatelier tells us that the equilibrium will shift toward the
reactants.
Indeed:
What to do?

K p ( 800 K ) = 0.007

Note above

KX = p K p

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 #11

page 4

Again use Le Chatelier, but with pressure! If we increase p, Eq.

shifts toward products.

Run reaction at high T and high p

For p = 1 bar, T = 800 K, Kp = 0.007

KX =

XNH

XH3 2XN1 2
2

But at p = 100 bar,

= (1 ) K p = 0.007

much better!

K X = (100 ) K p = 0.7

Heterogeneous Equilibria

If a product or reactant is a solid or liquid, it will not appear in the

ratio of partial ps for Kp or in the concentrations if the equilibrium is
in solution. However, it must be used in G.
Why?

Take

A A(s) + B B(g) = C C(l) + D D(g)

The solid and liquid are not mixed they are pure states.
G = C C ( s, pure, p ) + D D ( g, mix, p ) A A ( l , pure, p ) + B B ( g, mix, p )

And for (l) or (s)

C ( pure, p ) o ( pure )

G = C Co + D Do A Ao B Bo + RT ln

(no p-dependence)

pDD
= G o + RT lnQ
B
pB

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 #11

pDD
B
pB Eq .

No A or C involved.

Kp =

But we still have

and

page 5

o
Grxn
= C Co + D Do A Ao B Bo

ln K p =

o
Grxn

RT

e.g. the decomposition of limestone

CaCO3 (s) = CaO (s) + CO2 (g)

T = 25C

Calculate equilibrium vapor pressure at room T and elevated T.

Data at 25C:
Substance
CaCO3 (s)
CaO (s)
CO2 (g)
o (kJ/mol)
-1128.8
-604.0
-394.36
Hfo (kJ/mol)
-1206.9
-635.09
-393.51
At equilibrium,

G = ( CaO, s ) + ( CO2 , g) ( CaCO3 , s )

= o ( CaO, s ) + o ( CO2 , g) + RT ln pCO2 o ( CaCO3 , s )
= G o + RT ln K p

where K p = pCO2 (at eq.)

The equilibrium constant includes only the gas, but G o includes

the solids too.
G o (kJ/mol) = -604.0 394.4 (-1128.8) = 130.4 kJ/mol
H o (kJ/mol) = -635.1 393.5 (-1206.9) = 178.3 kJ/mol

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 #11

page 6

Equilibrium pressure:
ln K p =

G o

RT

130, 400 J/mol

= 52.50
(8.314 J/K-mol) (298.15 K )

K p = 1.43x 10 23 bar

Nothing there at room T !

Try 1100 K:

H o 1
1

R 1100 K 298 K
178, 300 J/mol 1
1
= 52.50

= 0.17
8.314 J/K-mol 1100 K 298 K
(1100 K ) 0.84 bar

ln pCO2 (1100 K ) ln pCO2 (298 K ) +

pCO

Theres probably some change in Hfo over such a wide T range,

but clearly the equilibrium shifts dramatically.