Chemical 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 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

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

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

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

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

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.

Chemical Equilibrium

Uploaded by

Copyright:

Available Formats

Chemical Equilibrium

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chemical Equilibrium

Uploaded by

Copyright:

Available Formats

20.110J / 2.772J / 5.

20.110/5.60 Fall 2005

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

What are pN , pH , and pNH

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)

Is this mixture in equilibrium?

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

20.110/5.60 Fall 2005

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

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

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

into pure products.

then the reaction will proceed spontaneously to form

then the backward reaction is spontaneous

20.110J / 2.772J / 5.601J

20.110/5.60 Fall 2005

the equilibrium constant

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

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

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

20.110J / 2.772J / 5.601J

20.110/5.60 Fall 2005

Lets take a = 1 mol and b = 2 mol

Using approximation method:

x 0.0044 mol (indeed << 1)

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

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

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

x = 0.0044 mol (same)

20.110J / 2.772J / 5.601J

20.110/5.60 Fall 2005

Effect of total pressure: example

Total # moles at Eq. =

where = x n is the fraction reacted

Le Chateliers Principle, for pressure:

20.110J / 2.772J / 5.601J

20.110/5.60 Fall 2005

K p = 2.3x 1012 at 298 K

Total # moles at Eq.

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

You might also like

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.