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 #10

page 1

Chemical Equilibrium
Ideal Gases
Question: What is the composition of a reacting mixture of ideal
gases?
e.g.

N2(g, T, p) + 3/2 H2(g, T, p) = NH3(g, T, p)

What are pN , pH , and pNH

2

at equilibrium?

Lets look at a more general case

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

The is are the stoichiometric coefficients.
Lets take a mixture of A, B, C, and D with partial pressures
pA = XA p , pB = XA p , pC = XC p , and pD = XD p

Is this mixture in equilibrium?

We can answer by finding G if we allow the reaction to proceed
further.
We know i (T , p ) for an ideal gas in a mixture
and we know that G = ni i
i

G ( ) = C C ( g,T , p ) + D D ( g,T , p ) A A ( g,T , p ) + B B ( g,T , 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 #10

page 2

where is an arbitrary small number that allows to let the reaction

proceed just a bit.
We know that

pi

1 bar implied

i ( g,T , p ) = io (T ) + RT ln pi

where io (T ) is the standard chemical potential of species i at 1 bar

and in a pure (not mixed) state.

p C p D
G ( ) = C Co (T ) + D Do (T ) A Ao (T ) + B Bo (T ) + RT ln C A D B
pA pB

G = G + RT lnQ

where

G = C Co (T ) + D Do (T ) A Ao (T ) + B Bo (T )

and

pCC pCD
Q = A B is the reaction quotient
pA pB

G is the standard change in free energy for taking pure reactants

into pure products.

o
o
o
G o = Grxn
= Hrxn
T Srxn

or

o
o
G o = Gform
( reactants )
( products ) Gform

If

G ( ) < 0

then the reaction will proceed spontaneously to form

more products

G ( ) > 0

then the backward reaction is spontaneous

G ( ) = 0

No spontaneous changes

Equilibrium

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 #10

page 3

o
= RT lnQeq
At Equilibrium G ( ) = 0 and this implies Grxn

Define

Qeq = K p

the equilibrium constant

D
C
pCC pCD
XC XC

p
=
A B = p KX
A B
p
p
X
X
A B eq
A B eq

Kp =

and thus

o
Grxn
= RT ln K p , K p = e G

RT

Note from this that K p (T ) is not a function of total pressure p.

It is KX = p K p which is KX ( p ,T ) .
Recall that all pi values are divided by 1 bar, so Kp and KX are
both unitless.
________________________________________________

T = 298 K
p =1 bar

Example: H2(g) + CO2(g) = H2O(g) + CO(g)

H2(g)

CO2(g)

H2O(g)

CO(g)

Initial #
of moles

# moles
at Eq.

a-x

b-x

Total # moles at Eq. = (a x) + (b x) + 2x = a + b

Mole fraction
at Eq.

a x
a +b

b x
a +b

a +b

a +b

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 #10

o
Gform
(kJ/mol)

o
rxn

and

= 28.6 kJ/mol

Kp =

pH O pCO
2

pH pCO
2

page 4

-396.6
Kp = e

XH OXCO
2

XH XCO
2

-228.6

28,600 kJ/mol

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

-137.2

= e 11.54 = 9.7 x 10 6

x2
=
( a x ) (b x )

Lets take a = 1 mol and b = 2 mol

We need to solve
A)

x2

(1 x )(2 x )

= 9.7 x 10 6

Using approximation method:

K << 1, so we expect x << 1 also.
Assume

1 x 1, 2 x 2

x2

(1 x )(2 x )

x2
2

= 9.7 x 10 6

x 0.0044 mol (indeed << 1)

B)

Exactly:

x2
= K p = 9.7 x 10 6
2
x 3x + 2

x 2 (1 9.7x 10 6 ) + 3x ( 9.7x 10 6 ) 2 ( 9.7x 10 6 ) = 0

x =

3 ( 9.7x 10 6 )
2 ( 9.7x 10 6 )

9 ( 9.7x 10 6 ) + 4 (1 9.7x 10 6 ) 2 ( 9.7x 10 6 )

2

2 (1 9.7x 10 6 )

The - sign gives a nonphysical result (negative x value)

Take the + sign only

x = 0.0044 mol (same)

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 #10

page 5

Effect of total pressure: example

N2O4(g) = 2 NO2(g)
Initial mol #

# at Eq.

n-x

2x

Xis at Eq.

n x
n +x

2x
n +x

Total # moles at Eq. =

n x + 2x = n + x

Kp =

2
pNO

pN O

2 4

Kp = p

2
p 2XNO

pXN O

2 4

4 2
1 2

where = x n is the fraction reacted

K
(1 ) 4 pp = 2
2

2x

4x 2
n + x

=p
=p 2
n x2
n x

n + x

Kp Kp

1 +
=
4p 4p

Kp
4p
1
=
2 =
Kp

4p
1 +
1 +

4p
Kp

4p
= 1 +

K p

1 2

If p increases, decreases

Le Chateliers Principle, for pressure:

An increase in pressure shifts the equilibrium so as to decrease the
total # of moles, reducing the volume.
In the example above, increasing p shifts the equilibrium toward the
reactants.
---------------

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 #10

page 6

Another example:
2 NO(g) + O2(g) = 2 NO2(g)
Initial mol #

# at Eq.

2-2x

1-x

2x

Xis at Eq.

2 (1 x )
3x

1x
3x

2x
3x

Kp =

2
pNO

2
pNO
pO

2
p 2XNO

2
p 2XNO
pXO

2
XNO

2
p XNO
XO

K p = 2.3x 1012 at 298 K

Total # moles at Eq.

= 2 2x + 1 x + 2x
=3-x

2
1 x (3 x )

(1 x )

K p >> 1 so we expect x 1 3 - x 2

Kp

p (1 x )3

or

(1 x )

pK p

2
x =1
pK p

13

In this case, if p then x as expected from Le Chateliers principle.