Chapter 4

Chemical Equilibrium

Equilibrium applies to the extent of a reaction, the

concentration of product that has appeared after an
unlimited time, or once no further change occurs.
Guldberg
&
Waage,
1862

At equilibrium:

rateforward = ratereverse

A system at equilibrium is dynamic on the molecular

level; no further net change is observed because
changes in one direction are balanced by changes in
the other.
2

N2O4 2NO2

colourless

brown

At equilibrium, the product and reactant concentrations are

constant. K =[NO2]eq/[N2O4]eq

The range of equilibrium constants

small K
Magnitude of K is an
indication
of how far a reaction
proceeds toward
product at a given
temperature.

large K
intermediate
K

Chemical Potential
Change in the Gibbs free energy with respect to amount
at constant temperature and pressure.
Pi

wG

wni T ,P ,n j z i

Intensive variable

For systems with > 1 component, chemical potential does

not equal the change in free energy of the pure material
because each component interacts with the other, which
affects the total energy of the system.

Chemical potential for 1 component system

G

For pure substances, chemical potential = change in Gibbs

energy as the amount of material changes.
In chemical reactions: species, number of moles, phase
change.
H2(g) + Cl2(g) = 2HCl(g)
2H2(g) + O2(g) = 2H2O(l)
In considering equilibrium, need to consider these
changes.
6

Multi-component system
Broader definition for dG
dG

wG
wG
wG
wG




dT
dP
dn
dn2

wn1 T ,P ,n
wn2 T ,P ,n
wT P ,n1 ,n2
wP T ,n1 ,n2

2

 
 


1
S

dG

dG

P1

P2

wG
wG
wG

dT
dP

dni

wT P ,ni
wP T ,ni
i wni T,P,n j (j z i)
-SdT  VdP  i dni
i

Fundamental equation of chemical thermodynamics

7

Fundamental equations for open

systems
dG

 SdT  VdP  i dni

i

dH

TdS  VdP  i dni

i

dU

TdS  PdV  i dni

i

dA

-SdT  PdV  i dni

i

Pi = Gibbs free energy per mole of component i or the

partial molar Gibbs free energy
Pi

wG

wni T ,P ,n j zi

n1 P1  n2 P2
G

Gi

n1 P1  n2 P2  ...  ni Pi

ni P i G i
i

Chemical potential of a
substance is the slope
of the total Gibbs
energy of a mixture wrt
the amount of the
substance

10

1. Liquid water and ice in equilibrium

P ice (T , P )

P water (T , P )

2. Cell placed in hypotonic solution

water(cell )(T,P)  water(solu tion)(T,P)

11

PA (mix, T,P) < PA (pure, T,P) ?

Chemical potential of a pure (1-component) ideal gas
o

G(T , P ) G (T )  RT ln

P
P(T ,P )
o
P

P (T )  RT ln

P
Po

Chemical potential of a mixture of ideal gases

At equilibrium,
mixed A,
B
'
' P
PP
PBtot
A APB

pure A
PA

Membrane permeable
only to A

PA ( pure )

PA' ( mix )

P A ( mix ,T , Ptot )

Ptot X A

Daltons law

P A ( pure,T , PA )
P A ( pure,T , X APtot )

P Ao ( pure,T )  RT ln

X APtot
Po

P Ao ( pure,T )  RT ln Ptot  RT ln X A


P A ( pure ,T ,Ptot )

12

P A ( mix ,T , Ptot )

P A ( pure ,T , Ptot )  RT ln X A

? P A ( mix ,T , Ptot )  P A ( pure ,T , Ptot )

XA < 1

The chemical potential of A in the mixture is always less

than the chemical potential of A when pure, at the same
total pressure.
Entropy of A in mixture higher than when A is pure.

13

Extent of reaction
Dynamic equilibrium in which both reactants and products
are present but have no further tendency to undergo net
change.
Equilibrium composition corresponds to minimum G.
Extent of reaction (moles) : [

ni  ni ,o

Xi

where ni is the number of moles at t and vi is the

stoichiometric coefficient of the ith chemical species in the
reaction; +ve for products and ve for reactants.
ni = ni,o + vi
dni = vi d

14

Gibbs Energy Minimum

A+BC+D
A + B GAo  GBo
o
'Grxn

Reactants (and
products)
isolated from
other.

C + D GCo  GDo

Mixed reactants ;
mixed reactants
and products.
15

If Greaction < 0 forward reaction is spontaneous.

If Greaction > 0, reverse reaction is spontaneous.
If Greaction = 0, reaction is at equilibrium.

16

Ideal gas equilibria

Consider a general gas-phase reaction: A (g, T, P) B(g,T, P)
'r G PB  P A
o = standard chemical potential,
where

Pi

Pio

Pi
 RT ln o
P

Assume perfect gas behavior,

of the pure gas at 1 bar.

Partial pressure Pi = XiP

PA
PB
o
r G
 RT ln o )  ( P A  RT ln o )
P
P
Reaction
quotient
PB
o
P
r G o  RT ln
r G o  RT ln Q
PA
o
P
PB
where Q
PA
( PBo

17

Q: reaction quotient; 0 when PB = 0 to infinity when PA = 0.

'r G

'r G o  RT ln Q

Standard reaction Gibbs energy, rGo, is the difference in

the standard molar Gibbs energies of reactants and
products at 1 bar.

'r G

o
GB

o
 GA

PBo  P Ao

At equilibrium, rG = 0
o

0 r G  RT ln Qeq
Rename Qeq = Kp
r G o
ln K P

RT ln K P


r G o
RT

Kp does not depend on

pressure and is a function of T
only. Dimensionless number.

Kp

PB

PA equilibrium
18

Q - The Reaction Quotient

At any time, t, the system can be sampled to determine
the amounts of reactants and products present. A ratio
of products to reactants, calculated in the same manner
as K tells us whether the system has come to
equilibrium (Q = K) or whether the reaction has to
proceed further from reactants to products (Q < K) or in
the reverse direction from products to reactants (Q > K).
Q = [products]/[reactants]

More products make Q

larger, more reactants
makes Q smaller
19

Reaction direction and the relative sizes of

Q and K.

Reaction
Progress

reactants

products

Reaction
Progress

Equilibrium:
no net
change

reactants

products

20

Consider a general gas-phase reaction at T and P:

DA + EB JC + dD

'r G JPC  GPD  DP A  EP B

r G

J ( PCo  RT ln

PC
PD
PA
PB
o
o
o
)

G
(
P

RT
ln
)

D
(
P

RT
ln
)

E
(
P

RT
ln
)
D
A
B
o
o
o
o
P
P
P
P
J

PC PD
o o
P P
r Go  RT ln
D
E
PA PB
o o
P P

KP

PCJ PDG
D

D, E, J, G stoichiometric numbers

PA PB

where r Go

JuCo  GuDo  Du Ao  EuBo

All Pi values are divided by 1 bar, so Kp

is unitless
21

K in terms of mole fractions

J

PC PD

Po Po

KP
D
E
PA PB
o o
P P

where 'X J  G  ( D

KX

 'X

KP

X c P X D P G
o o
P P

E
D
X AP X B P
o o
P P
E)

P
o
P

'X

X cJ X DG

XD X E
A B

P 'X K X

Kx depends on the total pressure.

Unitless since P divided by 1 bar.

22

Comparing Q and K to Determine Reaction

Direction
PROBLEM:
For the reaction
N2O4(g)

2NO2(g), Kc = 0.21 at 1000C.

At a point during the reaction, [N2O4] = 0.12M

and [NO2] = 0.55M. Is the reaction at
equilibrium? If not, in which direction is it
progressing?

23

Solution

Qc =

[NO2]2
[N2O4]

(0.55)2
(0.12)

= 2.5

Qc is > Kc, therefore the reaction is not at equilibrium

and will proceed from right to left, from products to
reactants, until Qc = Kc.

24

Example problem
6H 2
18.0mol

P4

2.0 mol

4PH 3
1.0 mol

Reacted: H2 12 moles
8.0 mol ) P4 2 moles
Formed: PH3 8 moles

If all P4 reacts to form products,

(12.0 mol
For H 2 ,[

0.0 mol

For P4 , [
For PH 3 , [

No matter which species is used, same extent of reaction.

25

Initial and Equilibrium Concentration Ratios for the

N2O4-NO2 System at 200oC (473 K)
Ratio(Q)

Ratio(K)

Initial

[NO2]2

[N2O4] [NO2]

[N2O4]

0.1000

0.0000

0.0000

3.57x10-3

0.193

10.4

0.0000

0.1000

9.24x10-4

9.83x10-3

10.4

0.0500

0.0500

0.0500

2.04x10-3

0.146

10.4

0.0750

0.0250

0.00833

2.75x10-3

0.170

10.5

Experiment

Equilibrium
[N2O4]eq [NO2]eq

[NO2]eq2
[N2O4]eq

The individual equilibrium concentrations are different in each

case but the ratio of the equilibrium concentrations is constant.
26

The change in Q during the N2O4-NO2 reaction

K is a special value
of Q that occurs
when the reactant
and product terms
have their
equilibrium values.

27

Example
H2(g) + CO2(g) = H2O(g) + CO (g)
Initial no.
of moles
No.of moles
at equil.

H2(g)
a

CO2(g)
b

a-x

b x

T = 298 K, P = 1 bar
H2O(g)
0
x

CO(g)
0
x

Total number of moles at equilibrium = (a x) + (b x) + 2x

=a+b
Mole
fraction
'fGo (kJ/mol)

ax
ab

bx
ab

-394.36

x
ab

-228.57

x
ab

-137.17

28

Q for an overall reaction

If an overall reaction is the sum of two or more
reactions, the overall reaction quotient (or equilibrium
constant) is the product of the reaction quotients (or
equilibrium constants) for the steps:
Qoverall = Q1 x Q2 x Q3 x
Koverall = K1 x K2 x K3 x

29

Writing the Reaction Quotient for an Overall Reaction

Understanding reactions involving N2 and O2, the most
abundant gases in air, is essential for solving problems
dealing with atmospheric pollution. Here is a reaction
sequence between N2 and O2 to form nitrogen dioxide, a
toxic pollutant that contributes to photochemical smog.
(1) N2(g) + O2(g)
(2) 2NO(g) + O2(g)

2NO(g)
2NO2(g)

Kc1 = 4.3 x 10-25

Kc2 = 6.4 x 109

(a) Show that the Qc for the overall reaction sequence

is the same as the product of the Qcs of the individual
reactions.
(b) Calculate the Kc for the overall reaction.
30

SOLUTION:
(a)

(1) N2(g) + O2(g)

(2) 2NO(g) + O2(g)
N2(g) + 2O2(g)
Qc =

[NO2]2
[N2][O2]2

Qc1x Qc2 =
(b)

2
[NO]
2NO(g)
Qc1 =
[N2][O2]
2NO2(g)
Qc2 = [NO2]2
2NO2(g)
[NO]2[O2]

[NO]2
[NO2]2
[N2][O2] [NO]2[O2]

[NO2]2
[N2] [O2] 2

Kc = Kc1 x Kc2 = (4.3 x 10-25) x (6.4 x 109) = 2.8 x 10-15

31

Q for a forward and reverse reaction

2SO2( g)
Qc ( fwd)

O2( g)

2SO3( g)

[SO3 ]2
[SO2 ]2 [O2 ]

Reverse reaction
2SO3( g)
Qc ( r )

2SO2( g)

[SO2 ]2 [O2 ]
[SO3 ]2

O2( g)

A reaction quotient
(or equilibrium
constant) for a
forward reaction
is the reciprocal of
the reaction quotient
(or equilibrium
constant) for the
reverse reaction.

Qc ( fwd)

Kc(fwd) = 261, Kc(rev) = 1/261 = 3.83 x 10-3

32

Q for a reaction with coefficients

multiplied by a common factor
1

O 2( g )
2
[SO3 ]
[SO 2 ][O2 ]1/ 2

SO 2( g)
Q'c ( fwd)
Q'c ( fwd)

SO3( g)
Kc(fwd) = K1/2c(fwd) = (261)1/2 = 16.2

[SO3 ]

[SO ]2 [O ]
2
2

Q1c/( 2fwd)

n(aA  bB cC  dD)
Q' Q

[C] [D]

[ A ]a [B]b

and

1/ 2

A particular K has meaning

only in relation to a
particular balanced
equation.

K' K n
33

Determining the Equilibrium Constant for an Equation

Multiplied by a Common Factor
PROBLEM: For the ammonia formation reaction
N2(g) + 3H2(g)

2NH3(g)

the equilibrium constant, Kc, is 2.4x10-3 at 1000 K. If we

change the coefficients of the equation, which well call the
reference (ref) equation, what are the values of Kc for the
following balanced equations?
(a) 1/3N2(g) + H2(g)
(b) NH3(g)

2/3NH3(g)

1/2N2(g) + 3/2H2(g)
34

SOLUTION:
(a) The reference equation is multiplied by 1/3, so Kc(ref) will
be to the 1/3 power.
Kc = [Kc(ref)]1/3 = (2.4x10-3)1/3 = 0.13
(b) The reference equation is reversed and halved, so Kc(ref)
is to the -1/2 power.
Kc = [Kc(ref)]-1/2 = (2.4x10-3)-1/2 = 20.

35

Equilibrium Constant in Concentration Units

Relation between Kc and Kp
PV

nRT
n
so P
RT
V

KP

PCJ PDG

PADPBE

cRT

[C] J [D]G
J  G D E


RT
[ A ]D [B]E

[C] J [D]G
X


RT
[ A ]D [B]E

Kp = Kc(RT)Q
Note: Q only for gas = 'ngas

36

Converting Between Kc and Kp

A chemical engineer injects limestone (CaCO3) into the hot
flue gas of a coal-burning power plant to form lime (CaO),
which scrubs SO2 from the gas and forms gypsum. Find Kc
for the following reaction, if CO2 pressure is in atmospheres.
CaCO3(s)

CaO(s) + CO2(g)

Kp = 2.1x10-4 atm (at 1000 K)R = 0.0821 L*atm/mol*K.

37

Example problem: the Gibbs energies of formation of

NO2(g) and N2O4(g) are 51.30 and 102 kJ/mol, respectively
(standard state: 1 bar and 25 qC). Assume ideal behavior
and calculate for the reaction N2O4 2NO2, Kp (standard
state: 1 bar) and Kc (standard state: 1 mol/dm3)

38

Calculating Kc from Concentration Data

PROBLEM:
In order to study hydrogen halide decomposition, a
researcher fills an evacuated 2.00-L flask with 0.200mol
of HI gas and allows the reaction to proceed at 4530C.
2HI(g)

H2(g) + I2(g)

At equilibrium, [HI] = 0.078M. Calculate Kc.

39

Solution
[HI] =

0.200 mol

= 0.100 M

2.00 L
Let x be the amount of [H2] at equilibrium. Then x will
also be the concentration of [I2] and the change in of [HI]
will be the original concentration minus the stoichiometric
amount that reacted, 2x, or 0.078M.

40

concentration (M)

2HI(g)

initial

0.100

0.100 - 2x

equilibrium

[HI] = 0.078 = 0.100 - 2x

[H2] [I2]
[HI]2

I2(g)
0

+ x

+ x

x = 0.011M

[0.011][0.011]
=

-2x

change

Qc =

H2(g)

= 0.020 = Kc

(0.078)2
41

Calculating Equilibrium Concentration with

Simplifying Assumptions
PROBLEM:

Phosgene is a potent chemical warfare agent that

is now outlawed by international agreement. It
decomposes by the reaction
COCl2(g)

CO(g) + Cl2(g)

Kc = 8.3x10-4 (at 3600C)

Calculate [CO], [Cl2], and [COCl2] when the following
amounts of phosgene decompose and reach equilibrium in a
10.0-L flask.
(a) 5.00 mol COCl2

(b) 0.100 mol COCl2

42

SOLUTION:

(a) 5.00 mol/10.0 L = 0.500M

(b) 0.100 mol/10.0 L = 0.0100M

Let x = [CO]eq = [Cl2]eq and 0.500-x and 0.0100-x = [COCl2]eq, respectively, for
(a) and (b).
[CO][Cl2]
Kc =
[COCl2]
(x) (x)
(a) Kc = 8.3x10-4 =
(0.500-x)
assume x is << 0.500 so that we can drop x in the denominator
8.3x10-4

(x) (x)
(0.500)

4.15x10-4 = x2

x 2.0 x 10-2
(0.500 - x) = 4.8x10-2

CHECK: 0.020/0.500 = 0.04 or 4% percent error

[CO] = [Cl2] = x = 2 x 10-2 M
[COCl2] = 0.500 M x = 0.480 M

43

(b)

Kc = 8.3x10-4 =

(x) (x)
(0.010 - x)

Dropping the -x will give a value for x = 2.9x10-3M. (0.010 - x) 0.0071M

CHECK: 0.0029/0.010 = 0.29 or 29% percent error
Using the quadratic formula produces x = 2.5x10-3 and 0.0100-x = 7.5x10-3M
[CO] = [Cl2] = x = 2.5 x 10-3 M
[CoCl2] = 1.00 x 10-2 M x = 7.5 x 10-3 M

44

Units of the Equilibrium Constant

An equilibrium constant expressed in terms of activities
or fugacities is called a thermodynamic equilibrium
constant. Dimensionless (divided by unit quantity: 1 bar,
1 M, 1 mol kg-1). Denoted by superscript zero.
Practical equilibrium constant has units which depend
on the reaction.
A B Z
Kc

[ Z]
dm3mol 1
[ A ][B]
45

Deviations from Ideal Behavior

Ideal behavior

P
o
Gm
 RT ln o
P
P
' r G ' r Go  RT ln B
PA

Gm

'r G

' r Go  RT ln

CB
CA

Real gases: attract each other weakly at large distances

(corresponding to low pressures) and repel strongly when closer
(at high pressures).
Gilbert Newton Lewis (1875 1946): fugacity (f)
Fugacity is the pressure adjusted for lack of ideality.
46

Real gas:

Gm

o
Gm

f
 RT ln o
f

The ratio of the fugacity of a substance in any state to

the fugacity in the standard state is known as the
activity, a.
Since the fugacity in the standard state = 1 bar, the
fugacity of a gas is numerically equal to its activity.
Therefore,

Gm

o
Gm
 RT ln(a)

47

Molar Gibbs energy of a real gas.

48

Fugacities of N2 gas at 0 C
P (atm)

Fugacity
(atm)

0.99955

10

9.956

50

49.06

100

97.03

150

145.1

200

194.4

300

301.7

400

424.8

600

743.4

800

1196

1000

1839
49

Equilibrium in Nonideal Systems

For gases, use fugacity or activity of the species
instead. If the pressures are low enough then use
pressures instead.
fgas
a gas
Po
r Go RT ln K oa
where Koa is the dimensionless equilibrium constant in
terms of activities.

K oa

aCJ aDG

D
E
a a
A B eq
50

Chemical Equilibrium in Solution

Define chemical potential for molecules in solutions as
Pi= Poi + RT ln ai
activity ai = Ji.xi where Ji is the activity coefficient, xi is
the mole fraction.
aA + bB cC + dD
Expressing the equilibrium constant in terms of activities,
Ka

aCc aDd
aAa aBb

J Cc J Dd
a b
J AJ B

xCc xDd
a b
x A xB

For uncharged species in solution, behaviour close to ideal,

so K can be expressed in concentrations, mole fractions,
molalities.
Number of moles
of solute in 1 kg of 51
For ions, activities must be used.
solvent

Le Chateliers Principle
When a chemical system at equilibrium is subjected
to a stress, the system will return to equilibrium by
shifting to reduce the stress.
If the concentration increases, the system reacts to
consume some of it.
If the concentration decreases, the system reacts to
produce some of it.

52

Effect of a change in concentration

PCl3(g)

Cl2(g)

PCl5(g)

The equilibrium shifts to the right

if a reactant is added or a product
is removed.
The equilibrium shifts to the left
if a reactant is removed or a product
is added.
At 523 K,
Qc

[PCl5 ]
[PCl3 ][Cl2 ]

24.0

Kc

The effect of added Cl2 on the PCl3-Cl2PCl5 system.

53

The Effect of Added Cl2 on the PCl3-Cl2-PCl5 System

Concentration (M)
Original equilibrium

PCl3(g)
0.200

Change
New equilibrium

Cl2(g)
0.125

PCl5(g)
0.600

+0.075

Disturbance
New initial

0.200

0.200

0.600

-x

-x

+x

0.200 - x

0.200 - x

0.600 + x
(0.637)*

*Experimentally determined value.

0.037

54

At equilibrium,

K c ( original )
K c (new )

0.600
24.0
(0.200 )(0.125 )
0.637
24.0
(0.163 )(0.163 )

At a given temperature, Kc does not change with a change in

concentration.

55

Predicting the Effect of a Change in Concentration on

the Equilibrium Position
PROBLEM:

To improve air quality and obtain a useful product, chemists often

remove sulfur from coal and natural gas by treating the fuel
contaminant hydrogen sulfide with O2;
2H2S(g) + O2(g)

2S(s) + 2H2O(g)

What happens to
(a) [H2O] if O2 is added?

(b) [H2S] if O2 is added?

(c) [O2] if H2S is removed?

(d) [H2S] if sulfur is added?

56

Solution

2H2S(g) + O2(g)

2S(s) + 2H2O(g)

[H2O]2

Q=

[H2S]2[O2]
(a) When O2 is added,

(b) When O2 is added,

(c) When H2S is removed,

(d)

57

Effect of a change in pressure

Changing the concentration of a gaseous component.
Adding an inert gas no effect on the equilibrium
position because the volume and moles of the reactant
and product gases do not change.
Changing the volume of the reaction vessel large
shift in the equilibrium.
Halve the volume, pressure doubles. Q
PCl3(g) + Cl2(g) PCl5(g)
If pressure doubles, Qc < K

[PCl5 ]
[PCl3 ][Cl2 ]
58

The effect of pressure (volume) on an

equilibrium system.

lower P
(higher
V)
more
moles of
gas

higher
P
(lower
V)
fewer
moles of
gas

59

Predicting the Effect of a Change in Volume (Pressure)

on the Equilibrium Position
PROBLEM:
How would you change the volume of each of the following
reactions to increase the yield of the products ?
(a) CaCO3(s)

CaO(s) + CO2(g)

CO2 is the only gas present. To increase its yield, we

should increase the volume (decrease the pressure).
(b) S(s) + 3F2(g)
SF6(g)
There are more moles of gaseous reactants than products,
so we should decrease the volume (increase the pressure)
to shift the reaction to the right.
60

Solution
(c) Cl2(g) + I2(g)

2ICl(g)

There are an equal number of moles of gases on both

sides of the reaction, therefore a change in volume will
have no effect.

61

Example: effect of total pressure

N2O4(g) = 2 NO2(g)
How does pressure affect this reaction ?
Initial no. of moles n
0
Moles at equil.
n x
2x
nx
2x
Xi at equil.
nx

fraction reacted, D
moles reacted
moles initially

nx

62

Effect of a Change in Temperature

Only temperature changes can alter K.
Consider heat as a product or a reactant.
In an exothermic reaction, heat is a product.
In an endothermic reaction, heat is a reactant.
A temperature rise will increase Kc for a system with
a positive 'H0rxn.
A temperature rise will decrease Kc for a system
with a negative 'H0rxn.

63

Predicting the Effect of a Change in Temperature

on the Equilibrium Position
How does an increase in temperature affect the
concentration of the underlined substance and Kc for the
following reactions?
(a) CaO(s) + H2O(l)
CaO(s) + H2O(l)

Ca(OH)2(aq) 'H0 = -82kJ

Ca(OH)2(aq) + heat

64

Solutions
(b) CaCO3(s)
CaCO3(s) + heat

(c) SO2(g)
SO2(g) + heat

CaO(s) + CO2(g)

'H0 = 78kJ

CaO(s) + CO2(g)

S(s) + O2(g)

'H0 = 297kJ

S(s) + O2(g)

65

Vant Hoff Equation : the effect of T on K

ln K (T )

d ln K
'G o


RT
dT

d
dT

'G o


RT

'G o
1 d'G o

2
RT
RT dT

At P = 1 bar, constant pH etc,

d'G o
dT

w'G

wT P

1bar ,pHcons tan t ,etc ..

From fundamental equation, dG = -SdT + VdP

w'G o
wG
o

S

'
S
(T )

wT P
wT P

d ln K
dT
d ln K
dT

'H o (T )  T'S o (T ) 1
o

'
S
(T )
2
RT
RT
'H o (T )
vant Hoff equation
2
RT

66

For a finite temperature change, integrate

T2

ln K (T2 )

'H o (T )
ln K (T1 ) 
dT
2
RT
T1

At constant pressure, 'H o (T)

'H o (T1 )  'C p (T - T1 )

'H o (T1 )  'C p (T - T1 )

lnK(T2 ) lnK(T1 ) 
dT
2
RT
T1
T2

For small T ranges, assume 'Cp(T-T1) small and 'Ho

independent of T.

'H o
ln K (T2 ) | ln K (T1 ) 
R

1 1

T2 T1

'H o
ln K (T2 ) | ln K (T1 ) 
R

1 1

T2 T1

If 'Ho(T) < 0, (exothermic), T2 > T1, ?K(T2) < K(T1).

Equilbrium shifts towards reactants
If 'Ho(T) > 0, (endothermic), T2 > T1, ?K(T2) > K(T1).
Equilibrium shifts towards products.
Le Chateliers principle for temperature.

Determining Equilibrium Parameters from Molecular Species

PROBLEM:

For the reaction X(g) + Y2(g)

XY(g) + Y(g) 'H>0
the following molecular scenes depict different reaction
mixtures. (X = green, Y = purple)

(a) If Kc = 2 at the temperature of the reaction, which

scene represents the mixture at equilibrium?
The equilibrium constant, K, is [XY][Y]
[X][Y2]
scene 1:
scene 2:
scene 3:

69

Determining Equilibrium Parameters from Molecular Species

(b) Will the reaction mixtures in the other two scenes

proceed toward reactant or toward products to reach
equilibrium ?
Scene 1
Scene 3

70

Determining Equilibrium Parameters from Molecular Species

(c) For the mixture at equilibrium, how will a rise in

temperature affect [Y2]?

71

Haber Process for the Synthesis of

Ammonia
N2(g) + 3H2(g)
T (K)

200.
300.
400.
500.
600.
700.
800.

2 NH3(g)

'Horxn = -91.8 kJ

Kc

7.17 x 1015
2.69 x 108
3.94 x 104
1.72 x 102
4.53 x 100
2.96 x 10-1
3.96 x 10-2

To maximize NH3
yield,
1. Decrease [NH3]
2. Increase pressure
3. Decrease temperature

72

Percent yield of ammonia vs. temperature (0C)

at five different operating pressures.

73

Key stages in the Haber process for

synthesizing ammonia.

Lack of Effect of a Catalyst

A catalyst shortens the time it takes to reach equilibrium
but it has no effect on the equilibrium position.
74
74

Heterogeneous equilibrium
XAA(s) + XBB(g) = XCC(l) + XDD(g)
The solid and liquid are in their pure states, not mixed.
'G XC PC ( l , pure, P )  XD PD ( g , mix , P ) 

>X A P A ( s , pure,P )  XB PB ( g , mix ,P )@

But P(pure,P) = Po(pure)

no P dependence
PDXD
o
o
o
o
'G XC PC  XD PD  X A P A  XB PB  RT ln XB




PB
o
'G

'G

XD
P
'G o  RT ln DXB
PB

At equilibrium, K p
No A or C involved.

PDXD
PBXB

Reaction quotient for a heterogeneous system

solids do not
change their
concentrations

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

[CaO][CO2 ]
[CaCO3 ]

K 'c

[CaO] and [CaCO3 ] are constants, ? incorporate them into K 'c

[CO2 ] K c
Define the activities of pure solids and liquids as unity.

76

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

CaCO3(s)

CaO (s)

CO2 (g)

Po (kJ mol-1)

-1128.8

-604.0

-394.36

'fHo (kJ mol-1)

-1206.9

-635.09

-393.51

At equilibrium,
'G P ( CaO , s )  P ( CO2 , g )  P ( CaCO3 , s )
P o ( CaO , s )  P o ( CO2 , g )  RT ln PCO  P o ( CaCO3 , s )
2

'G o  RT ln K P

where K p P CO at equlibrium
2

77

At 1100 K,

Solubility product
AgCl(s) Ag+(aq) + Cl- (aq)

[ Ag ][Cl ]
[ AgCl]

K 'c

[ Ag ][Cl ] Ksp

79