Chemistry& 163

General Chemistry 3
Chapter 13: Fundamental Equilibrium Concepts

13.1 Chemical Equilibria

13.2 Equilibrium Constants

13.3 Shifting Equilibria: Le Châtelier’s Principle

13.4 Equilibrium Calculations

16.4 Free Energy

Chapter 13: Fundamental Equilibrium Concepts

13.1 Chemical Equilibria

Chemical kinetics describes how fast a product is produced.

Reactants → Products

Speed of reaction? = kinetics problem

Chemical equilibrium properties describe how much product can

be produced.

Reactants → Products

How much product made? = equilibrium problem

Previously, we have used stoichiometry calculations to
determine the amounts of products.

A  B
moles of A = moles of B

In these problems we are assuming the reverse reaction is not

occurring.
As we saw when discussing reaction rates sometimes the
reverse reaction is significant:

(1) A + B → C (fast and reversible) Rate1 = k1[A][B]

(2)C → D (slow) Rate2 = k2[C]
Overall: A + B → D

In this case the 1st step and its reverse are occurring at equal
rates:
A + B → C (fast) Rate1 = k1[A][B]
C → A+ B (slow) Rate-1 = k-1[C]

Rate1 = Rate-1 = k-1[C] = k1[A][B]

A system where the forward and reverse reaction are occurring
at the same rate is described as being at equilibrium.

A + B C
When a system is at equilibrium the amounts of products and
reactants is constant.

Previously we had used the idea of a full car park to

visualize this idea

“The vapor pressure of liquid is the

partial pressure of a liquid when it is in
equilibrium with its vapor”
Chapter 13: Fundamental Equilibrium Concepts

13.1 Chemical Equilibria

When a system has obtained a state of dynamic equilibrium the
rate of the forward reaction equals the rate of the reverse reaction.
From this time on if no change is made to the system the amounts
of products and reactants will remain unchanged.
Chapter 13: Fundamental Equilibrium Concepts

13.2 Equilibrium Constants

Some reactions achieve equilibrium after nearly all reactants
have been converted to products.

H2O + CO H2 + CO2

In this kind of system we say the equilibrium “lies to the right”

Some reactions achieve equilibrium when nearly all reactants
are unreacted.

H2 + I2 2HI

Equilibrium

In this kind of system we say the equilibrium “lies to the left”

For a reversible reaction it is observed that:

“at constant temperature the same equilibrium state is achieved

regardless of the initial amounts of reactants and products”

This is referred to as the “Law of Mass Action”

What is meant by the same equilibrium state?

For example consider the reaction:

H2O + CO H2 + CO2

The data for experiment 1 and 2 indicates that it doesn’t matter

what direction the reaction runs in we arrive at the same
equilibrium concentrations.
For the reaction:
aA + bB cC + dD

We can write the concentration equilibrium constant Kc:

[C ]c [ D] d
Kc  The exponents in this equation are
[ A] a [ B]b the stoichiometric coefficients.

Where [x] is equal to the concentration (molL-1) of x divided by

the standard state concentration of 1 molL-1
For a gaseous reaction:
aA + bB cC + dD

We can write the equilibrium constant in terms of pressure Kp:

( PC ) c ( PD ) d
Kp  Equilibrium constants are unit-less
( PA ) a ( PB ) b

Where Px is equal to the partial pressure (atm) of x divided by

the standard state pressure of 1 atm
An alternative statement of the Law of mass action is:

“at constant temperature the same equilibrium constant (K) is

observed regardless of the initial amounts of reactants and
products”

What does a large value of K indicate ?

What does a small value of K indicate?
Example: Use the data below to calculate Kc for each experiment.

2NO2 N2O4

[N 2 O4 ] (0.00139)
Experiment 1 : K c  2
 2
 4.70
[ NO2 ] (0.0172)
(0.00280)
Experiment 2 : K c   4.70
(0.0244) 2
(0.00452)
Experiment 3 : K c  2
 4.70
(0.0310)
(0.00452)
Experiment 4 : K c   4.70
(0.0310) 2
In most cases:

Kc  K p

However, if you know one you can calculate the other. Consider
the reaction:

2NO(g) + O2(g) 2NO2(g)

In this reaction 3 moles of gas reacts to produce 2 moles of gas.

ngas  moles of gaseous product - moles of gaseous reactant  2 - 3  - 1

For this reaction:
2NO(g) + O2(g) 2NO2(g)

Kc is given by:
[NO2 ] 2
Kc 
[NO] 2 [O2 ]

The concentration of gas in terms of pressure can be found be

re-arranging the ideal gas law.
PV  nRT
P n
  concentration
RT V
We can now rewrite Kc in terms of pressure:
2NO(g) + O2(g) 2NO2(g)

[NO 2 ] 2
Kc 
[NO] 2 [O2 ]
as :
Px
[x] 
RT
we can write :
2
 PNO2 
 
 RT  P  RT 
2 2
Kc   2 
NO2
   K p  ( RT )
 PNO   PO2 
2
PNO PO2 RT 
3

   

 RT   RT 

K c ( RT ) 1  K p
The relationship between Kc and Kp is:
n gas
K p  K c  ( RT )

Example: Calculate Kp for the following

CO(g) + Cl2(g) COCl2(g) Kc = 3.9 x 10-2 at 1000. K

n gas  1  2  1
n gas
K p  K c ( RT )  3.9  10  2  (0.0821 1000) 1  4.8  10  4
Your turn!

Calculate Kp for the following

S2(g) + C(s) CS2 Kc = 28.5 at 500. K

H2(g) + I2(g) 2HI(g) Kc = 49 at 730. K

Kp = 6.9 x 10-1

Kp = 49

Note: if Δngas = 0 then Kc = Kp

Consider the following reaction:
[ N 2 O4 ]
Kc 
2NO2 N 2 O4 [ NO2 ] 2

If we wrote the reverse reaction:

N2O4 2NO2

Then Kc would be:

[ NO2 ] 2
Kc 
[ N 2 O4 ]

In general terms:
1
K reverse 
K forward
Example: Given:

CO(g) + Cl2(g) COCl2(g) Kc = 3.9 x 10-2 at 1000. K

What is Kc for the following at 1000. K?

COCl2(g) CO(g) + Cl2(g)

1 1
K c ,reverse   2
 26
K c , forward (3.9  10 )
Consider the following reaction:
[ N 2O4 ]
Kc 
2NO2 N 2 O4 [ NO2 ]2

If we multiply the reaction x 4:

8NO2 4N2O4

Then Kc for this new reaction would be:

4
[ N 2O4 ]4
 [ N 2O4 ] 
K 'c  8
 K c  2 

[ NO2 ]  [ NO2 ] 
In general terms:

For the reaction:

aA + bB cC + dD

[C ]c [ D]d
Kc 
[ A]a [ B ]b

For n-times the reaction:

n(aA + bB cC + dD)

n
 [C ] [ D]
c d

K c '   a b

 [ A] [ B ] 
If we have a multi-step reaction:

aA + bB cC + dD [C ]c [ D]d
Step 1: K c ,1 
[ A]a [ B ]b

cC + dD eE + fF [ E ]e [ F ] f
Step 2: Kc,2 
[C ]c [ D]d

What is Kc for the overall reaction?

[ E ]e [ F ] f
aA + bB eE + fF K c ,overall 
[ A]a [ B ]b
For a series of equilibrium reactions:
aA + bB cC + dD eE + fF

The overall Kc is given by the product of the Kc values for the

steps:

c
[C ] [ D] d
[ E ]e [ F ] f
K c ,1  1st step Kc,2  2nd step
[ A]a [ B ]b [C ]c [ D]d

[C ]c [ D]d [ E ]e [ F ] f [ E ]e [ F ] f
K c ,overall   
a b c
[ A] [ B ] [C ] [ D] d
[ A]a [ B ]b Overall
Example: At 1000 K, the value of Kc of the following reaction is 1.5 x 106

(1) N2O4 2NO2

At 1000 K, the value of Kc of(2)

theNfollowing 2NO2 -10
2 + 2O2reaction is 1.4 x 10

N2 + 2O2 N2O4
Calculate the Kc value of :

(1) N2 + 2O2 2NO2 K c ,1  1.4  1010

1 7
(2) 2NO2 N2O4 Kc,2   6 . 7  10
1.5  106

N2 + 2O2 N2O4 K overall  K c ,1  K c , 2

1
 1.4  1010   9 . 3  10 17

1.5  106
For a reaction not yet at equilibrium we may calculate the
reaction quotient, Q.
e.g.
[ H 2 ][CO2 ]
H2O(g) + CO(g) H2(g) + CO2(g) Qc 
[ H 2 O][CO ]

A reaction will spontaneously move in the direction that leads to

Q = K.
If we measure the concentration of reactants and products and
calculate Q and compare with K we can determine which way the
reaction will “move” to obtain equilibrium

Reactants  Products Products  Reactants

No net change

Kc Qc
Qc Kc
Qc Kc

Q c < Kc Q c = Kc Q c > Kc
Example: The value of Kc for the following reaction:
2NO2 N2O4

is 4.7 at 373 K. Is a mixture of two gases in which [NO 2] = 0.025 mol/L and [N2O4] =
0.0014 mol/L at equilibrium? If not in which direction will the reaction proceed?

0.0014
Q 2
 2.24
0.025
QK

The reaction will proceed in the direction of the products (to the right).
Most chemical equilibria are heterogeneous, that is the
products and reactants are in more than one phase:

NaCl(aq) + AgNO3(aq) NaNO3(aq) + AgCl(s)

What is the concentration of AgCl(s)? does it ever change?

The concentrations of pure solids are constant at a given

temperature.
Consider the equilibria:

Sucrose(aq) + H2O(l) Fructose(aq) + Glucose(aq)

What is the concentration of H2O(l)? does it ever change?

The concentrations of pure liquids are constant at a given

temperature.
We are only interested in concentrations that change as we move
towards equilibrium.

Terms for pure liquids and pure solids are not included in our
expressions for Q and K.

e.g.

[ NaNO3 ]
Kc 
[ NaCl ][ AgNO3 ]
Chapter 13: Fundamental Equilibrium Concepts

13.2 Equilibrium Constants

If we define the equilibrium constant for a reversible reaction as
below:

( PC ) c ( PD ) d
Kp 
( PA ) a ( PB ) b

a reversible reaction will arrive at equilibrium concentrations such

that the value of the equilibrium constant is always the same.
n gas
Kc and Kp are related by the formula: K p  K c ( RT )
Chapter 13: Fundamental Equilibrium Concepts

13.2 Equilibrium Constants

When the direction of a reaction is reversed the value of Kreverse is
1
K reverse 
given by: K forward

When a reaction is multiplied by a factor “n” the value of K ’ is

given by:
K ' K n

When a reaction is composed of multiple steps the value of K is

given by the product of the K values for the individual steps:
K overall  K1  K 2  K 3 ....
Chapter 13: Fundamental Equilibrium Concepts

13.2 Equilibrium Constants

A system not at equilibrium (Q ≠ K) will spontaneously move in the
direction to bring it to equilibrium. If Q < K then reactants will be
converted into products until equilibrium is achieved. If Q > K then
products will be converted into reactants until equilibrium is
achieved.
Chapter 13: Fundamental Equilibrium Concepts

13.2 Equilibrium Constants

As the concentrations of pure solids and pure liquids are
constants they are not included in the expressions for Q and K.
Chapter 13: Fundamental Equilibrium Concepts

13.3 Shifting Equilibria: Le Châtelier’s Principle

Le Châtelier’s principle states:

“When a change is made to a chemical system at equilibrium

the system will spontaneously return to the equilibrium
position”

Henry Louis Le Châtelier

1850 - 1936
 “When a change is made to a chemical system at equilibrium
the system will spontaneously return to the equilibrium
position”

What do we mean by a “change”?

Any physical or chemical change that results in Q ≠ K

What do we mean by a “chemical system at equilibrium”?

We mean Q = K for the system

 “When a change is made to a chemical system at equilibrium
the system will spontaneously return to the equilibrium
position”

What do we mean by “spontaneously return to the

equilibrium position”?

We mean that without intervention the system will adjust so

Q=K
Consider the following equilibrium system:

CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

Qc for this system is:

[CS 2 ][ H 2 ] 4
Qc 
[CH 4 ][ H 2 S ] 2

When the system is at equilibrium Qc = Kc

Will Qc get bigger or smaller if we add additional CH4?

 CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

[CS 2 ][ H 2 ] 4
Qc 
[CH 4 ][ H 2 S ] 2

Initially, Qc = Kc

Increasing the [CH4] results in the denominator of the

expression for Qc getting bigger and Qc becoming smaller.

i.e. after addition of CH4, Qc < Kc

 CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

[CS 2 ][ H 2 ] 4
Qc 
[CH 4 ][ H 2 S ] 2

Initially, Qc = Kc After addition of CH4, Qc < Kc

Le Châteliers principle tells us the system will adjust so that

Qc = Kc again.

So how can we make Qc bigger?

 CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

[CS 2 ][ H 2 ] 4
Qc 
[CH 4 ][ H 2 S ] 2

Initially, Qc = Kc. After addition of CH4, Qc < Kc

So how can we make Qc bigger?

By making the numerator in Qc smaller (consuming reactants)

and making the denominator bigger (producing products).
 CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

The net result of adding CH4 to this system was the formation of
more products.

“the equilibrium moved to the right”

Adding reactants always results in the equilibrium moving to the

right.

Similarly, removing products will also result in the equilibrium

moving to the right.
Increase concentration Increase concentration
of reactants equilibrium of products equilibrium
moves to right moves to left

CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

Decrease concentration Decrease concentration

of reactants equilibrium of products equilibrium
moves to left moves to right
The famous “donkey cart” picture takes on new meaning when we think
in terms of equilibria.
Changes in pressure may influence equilibrium systems that
contain gaseous components.

2NO2 N2O4

PN 2O4
Qp 
( PNO2 ) 2

Changes in pressure may occur in one of three ways:

• Changing the amount of one of the components

• Changing the volume of the reaction vessel

• Adding an inert gas into the system

We have already discussed how the system will respond to changing
the amount of one of the components

2NO2 N2O4

What the affect of changing the volume of the reaction vessel will
have is less obvious.

Recall: 1
P and Pα n
V
Consider the system:
2NO2(g) N2O4(g)

If the system is at equilibrium when:

PNO2  X and PN 2O4  Y
then :
PN 2O4 Y
Kp   2
P 
NO2
2
X

What is the affect of halving the container volume?

Initially:
PN 2O4 Y
2NO2(g) N2O4(g) Kp   2
P 
NO2
2
X
PNO2  X PN 2O4  Y

If we half the volume we will double the partial pressure of each

gas:

2Y 2Y
2NO2(g) N2O4(g) Qp  
2 X 2 4X 2
PNO2  2 X PN 2O4  2Y

2Y 2
Qp  2
 K p  0.5 K p
4X 4
Initially:
PN 2O4
Kp 
2NO2(g) N2O4(g) P 
NO2
2

Reducing container volume by half:

2NO2(g) N2O4(g) Q p  0.5  K p

Qp is now < Kp

How will the system respond?

By producing more products

How changes in volume affect gaseous equilibria are best
understood by considering how amount and pressure are
related:
nα P

Consider the following equilibria:

2NO2(g) N2O4(g)
2 moles of gas 1 mole of gas

Reducing container volume results in an increase in pressure:

If the system moves to the right the number of moles of gas and
the pressure will reduce.

2NO2(g) N2O4(g)
2 moles of gas 1 mole of gas

Equilibrium shifts to right

This will bring the system back in to equilibrium

Example: How will the following system respond to a reduction in
volume?

3 moles of gas 5 moles of gas

A reduction in volume will increase the pressure. The system will

spontaneously adjust to decrease the pressure. The equilibrium
will move to the left.
Example: How will the following system respond to an increase in
volume?
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(g)

9 moles of gas 10 moles of gas

An increase in volume will decrease the pressure. The system will

spontaneously adjust to increase the pressure. The equilibrium will
move to the right.
Qp is determined only by the partial pressure of each reactant
and product.
CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

 
PCS 2 PH 2
4

Qp 
PCH 4 P 
H2S
2

Adding an inert gas will increase the total pressure but will not
change any of the partial pressures.

Will adding an inert gas cause the equilibrium position to

shift? Adding an inert gas does not affect the equilibria
Temperature changes result in a change in the value of K.

For an exothermic process:

A + B C + Heat

Typically, increasing T decreases K favoring reactants (and vice

versa)

For an endothermic process:

A + B + Heat C

Typically, increasing T increases K favoring products (and vice

versa)
Catalysts increase the rate of the forward and reverse reactions
to an equal extent.

Catalysts decrease the time it takes for a system to reach

equilibrium they do not affect the position of equilibrium.
Chapter 13: Fundamental Equilibrium Concepts

13.3 Shifting Equilibria: Le Châtelier’s Principle

If a system at equilibrium is perturbed the system will adjust to
bring it back into equilibrium. This perturbation may include:
– Changes in concentration
– Changes in partial pressure

Changing the temperature of a system changes K, typically. If we

consider heat as a reactant/product we can predict the effect of a
temperature change.
Catalysts do not affect the position of the equilibrium.
Chapter 13: Fundamental Equilibrium Concepts

13.4 Equilibrium Calculations

In complex equilibrium problems concentrations of some
species may not be known.

In order to solve these kinds of problems we should first construct

the reaction table (ICE table):

Pressure (atm) CO2(g) + C(solid) 2CO(g)

Initial - - -
Change - - -
Equilibrium - - -
Example: Solid graphite that has been heated to 1080K is reacted with CO2 at an initial
pressure of 0.458 atm.
CO2(g) + C(solid) 2CO(g)

The system is allowed to come to equilibrium at which time the total pressure is 0.757
atm. What is Kp?

Pressure (atm) CO2(g) + C(solid) 2CO(g)

Initial 0.458 - 0
Change -x - +2x
Equilibrium (0.458 – x) - +2x

Ptotal  PCO2  PCO

0.757  (0.458  x)  2 x
0.757  0.458  x Now we update our reaction table
x  0.757  0.458  0.299
 Pressure (atm) CO2(g) + C(solid) 2CO(g)
Initial 0.458 - 0
Change -0.299 - +(2 x 0.299)
Equilibrium 0.159 - 0.598

PCO2  0.458  0.299  0.159

PCO  2  0.299  0.598
PCO 2 0.598 2
Kp    2.25
PCO2 0.159
Often we know the equilibrium constant and initial concentrations and wish to determine the equilibrium concentrations:

Example: for the reaction shown below at 900K Kc = 1.56 if CO and H2O are combined in the same vessel to give initial

concentrations of 2.0 M and 1.00 M, respectively. What are the equilibrium concentrations of CO and H2O?

CO(g) + H2O(g) CO2(g) + H2(g)

Begin by writing the reaction table:

Conc (M) CO(g) + H2O(g) CO2(g) + H2(g)

Initial 2.0 1.0 0 0

Change -x -x +x +x
Equilibriu 2-x 1-x x x
m
[CO2 ][ H 2 ] x2 x2
Kc    2  1.56
[CO ][ H 2O ] (2  x )(1 x ) x  3 x  2
1.56  ( x 2  3 x  2)  x 2
1.56 x 2  4.68 x  3.12  x 2  0
0.56 x 2  4.68 x  3.12  0

This is a quadratic equation which we can solve using the

quadratic formula.
A quadratic equation has the form:

ax2 + bx + c = 0

In our equation:
0.56 x 2  4.68 x  3.12  0

a = 0.56

b = -4.68

c = 3.12

We can solve for x using the quadratic formula:

 b  b 2  4ac 4.68   4.68 2  4  (0.56  3.12 ) 4.68  3.86

x  
2a 2  0.56 1.12
x  7.6M or 0.73M
 Conc (M) CO(g) + H2O(g) CO2(g) + H2(g)

Initial 2.0 1.0 0 0

Change -x -x +x +x
Equilibriu 2-x 1-x x x
m
Considering our reaction table only one of these answers makes sense:

x = 0.73 M

Conc (M) CO(g) + H2O(g) CO2(g) + H2(g)

Initial 2.0 1.0 0 0

Change -0.73 -0.73 +0.73 +0.73
Equilibriu 1.27 0.27 0.73 0.73
m
Sometimes we need to calculate Q first so we know which
direction the change will occur.

Example: The value of Kc for the reaction:

N2O4 2NO2

is 0.21 at 373 K. If a reaction vessel initially contains 0.030 M NO2

and 0.030 M N2O4, what are the concentrations of the two gases
at equilibrium?
 Conc (M) N2O4 2NO2
Initial 0.030 0.030
Change ? ?
Equilibriu ? ?
m
(0.030) 2
Qc   0.030  K c
0.030

Change will be to produce more products

Conc (M) N2O4 2NO2

Initial 0.030 0.030
Change -x +2x
Equilibriu 0.030-x 0.030+2x
m
 Conc (M) N2O4 2NO2
Initial 0.030 0.030
Change -x +2x
Equilibriu 0.030-x 0.030+2x
m

(0.030  2x) 2
Kc   0.21
(0.030  x)
0.21  (0.030  x)  (0.030  2x) 2
6.3  10 3  0.21x  9.00  10 4  4x 2  0.060x
(9.00  10 4  6.3  10 3 )  0.060x  0.21x  4x 2  0
4x 2  0.270x  5.4  10 3  0
3
 b  b 2  4ac  0.270  (0.270)  4  4  ( 5.4  10 )
2
x   -0.084 or 0.016
2a 2a
Updating our ICE table gives:

Conc (M) N2O4 2NO2

Initial 0.030 0.030
Change -0.016 +2x
Equilibriu 0.014 0.062
m
Chapter 13: Fundamental Equilibrium Concepts

13.4 Equilibrium Calculations

Given initial concentrations and an equilibrium constant it is
possible to establish a reaction (ICE) table to ease the
determination of the equilibrium concentrations of the reactants
and products.
Chapter 13: Fundamental Equilibrium Concepts
16.4 Free Energy
We have already seen that if ΔG is < 0 a reaction will proceed spontaneously to the
right.

CH4(g) + O2(g) → CO2(g) + 2H2O(g) ΔG < 0

2H2O(g) + CO2(g) → CH4(g) + O2(g) ΔG > 0

Is there another way of predicting if a reaction will proceed spontaneously?

If Q < K the reaction proceeds spontaneously to the right

If Q > K the reaction proceeds spontaneously to the left
A reaction will proceed spontaneously until ΔG = 0 (no net
movement either to products or reactants)

Alternatively we can say,

A reaction will proceed spontaneously until Q = K

i.e. When ΔG = O the system is at equilibrium

Q and ΔG are both measures of how far a system is from

equilibrium.
We find that the relationship between ΔG and Q is:

ΔG  ΔG   RTlnQ

Where ΔGo is the change in free energy under standard

conditions:

Recall, ΔGo can be calculated using the tables in Appendix 4 and

the following formula:

ΔG o  
products
nG oformation   nG
reactants
o
formation
When the system is at equilibrium:
ΔG  0
and
QK

If we substitute these values into our expression for ΔG:

ΔG  ΔG   RTlnQ
0  ΔG   RTlnK
Rearranging :
ΔG    RTlnK
Example: Use the following data to calculate Kp for the reaction at 298 K:

N2(g) + 2O2(g) 2NO2(g)

N2(g) + O2(g) 2NO(g) Go = 173.2 kJ

2NO(g) + O2(g) 2NO2(g) Go = -69.7 kJ

N2(g) + O2(g) 2NO(g) Go = 173.2 kJ

2NO(g) + O2(g) 2NO2(g) Go = -69.7 kJ

N2(g) + 2O2(g) 2NO2(g) Go = 173 + (-69.7) = 103.3 kJ

ΔG    RTlnK
ΔG  103.3  10 3
lnK     41.69
RT 8.314  298
K  e  41.69  7.81  10 19
We have noted qualitatively that K is dependent on temperature.

e.g.

Co(H2O)62+(aq) + 4Cl-(aq) + Heat CoCl42-(aq) + 6H2O(l)

Pink Blue

The value of K is clearly dependent on T. Is there a quantitative

relationship between T and K?
In Chemistry II we learnt that ΔHo, ΔSo, ΔGo and T are related by:

ΔG   ΔH   TS 

We can express ΔGo in terms of K:

e.g. we can express ΔG  in terms of K :

ΔG    RTlnK
substituting into above :
- RTlnK  ΔH   TS 
Rearranging :
H   1  S 
lnK    
R T  R
A plot of lnK versus 1/T will be linear with slope = -ΔHo/R and
intercept = ΔSo/R
H   1  S

lnK    
R T  R

ΔS  (Note: We are assuming ΔH

intercept  and ΔS vary little with temp.)
R

H 
slope  
R
To simplify calculations we can write this expression in a “two-point
form”

 K1  H  1 1
ln      
 K2  R  T1 T2 

This formula is known as the “van’t Hoff equation”

Note the similarity to the two-point form of the Arrhenius equation

and the Clausius-Clapeyron equation.
The Clausius-Clapeyron equation is a special case of the van’t
Hoff relationship:
A(l) A(g) Hvap

Kp = PA


 K1  ΔH 1 1
ln      
 K2  R  T1 T2 

for a liquid in equilibrium with its vapor

K p  Pvap
H  H vap

 P1  ΔH vap 1 1
ln      
 P2  R  T1 T2 
Example: At 600 K for the following reaction KC = 1.7 x 108 :

2SO2(g) + O2(g) 2SO3(g)

An engineer places 0.0040 mol of SO2(g) and 0.0028 mol O2(g) in a 1.0 L container and raises the

temperature to 1000 K. At equilibrium 0.0020 mol of SO3(g) is present. Calculate ΔHrxn.

(mol/l) 2SO2(g) + O2(g) 2SO3(g)

I 0.0040 0.0028 0
C -2x -x +2x
E 0.0020 0.0028 - x 2x

0.0040  2 x  0.0020

x
0.0040  0.0020  0.0010
2
 (mol/l) 2SO2(g) + O2(g) 2SO3(g)
I 0.0040 0.0028 0
C -2x -x +2x
E 0.0020 0.0018 0.0020

[SO3 ] 2 (0.0020)2
Kc  2
 2
 556 at 1000K
[SO2 ] [O2 ] (0.0020) (0.0018)

K  ΔH 1 1
ln 1      
 K2  R  T1 T2 

 K1   1.7  10 8 
 Rln   8.314  ln 
 K 2   ΔH   556   1.58  10 5 J  158 kJ
1 1  1 1 
     
T
 1 T2   600 1000 

Exothermic process (heat is a product) makes sense as T is raised that K became smaller
Chapter 13: Fundamental Equilibrium Concepts
16.4 Free Energy
ΔG and Q are both measures of the spontaneity of a chemical
process. They are related via the formula:

ΔG  ΔG   RTlnQ

Once a system has reached equilibrium the observed K may be

used to determine the ΔGo via the formula:

ΔG    RTlnK
Chapter 13: Fundamental Equilibrium Concepts
16.4 Free Energy
The dependence of K on temperature is described by:
H   1  S

ln K    
R T  R

Thus, a plot of lnK versus 1/T will be linear with slope = -ΔH/R and
intercept ΔS/R.

The van’t Hoff equation is a convenient rearrangement of this

expression:
 K1  H  1 1
ln      
 K2  R  T1 T2 