EQUILIBRIUM

When non reversible chemical reactions proceed to completion, the concentration of the
reactants gradually decrease, until there is NO limiting reactant remaining.
Most chemical reactions, however, do not proceed to completion, even if the mixture is
allowed to react over a long period of time. If there is sufficient energy available, products
will collide to form activated complexes, which will then recombine to form reactants.
Therefore, a reverse reaction occurs.
During the course of a reversible chemical reaction, the concentration of products and
reactants will change, and ultimately reach a value that remains constant. At the instant that
the individual concentrations are no longer changing, the system is in equilibrium.
Consider the reversible system initially consisting of reactants only.

If reactants have sufficient energy when they collide, products will be formed.
The initial rate of conversion of reactants to products (the forward reaction) is high, due to
the presence of large numbers of reactant molecules which frequently collide.
As the reaction proceeds, the concentration of reactant(s) decreases.

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As the reactant concentration decreases, the rate of the forward reaction will decrease
(fewer reactant numbers result in less frequent collisions and hence fewer successful
collisions).
At the same time, the concentration of products increases.
As the product concentration increases, the rate of the reverse reaction will increase
(greater product numbers will result in more frequent collisions and hence more successful
collisions).
The rate of the forward reaction continues to decrease and the rate of the reverse reaction
continues to increase until they become equal i.e. there is no net reaction occurring. At
this point, the concentrations of the reactants and products are constant, and the system is
in equilibrium.
Forward Reaction
Reactants

Products

Reverse/Back Reaction
Equilibrium is a dynamic state in which the rates of the forward and reverse
reactions are equal i.e. The rate at which the product is being produced is balanced
by the rate at which the reactant is being consumed.
Note:
If the rate of the forward reaction (Rf) is not equal to the rate of the reverse/back reaction
(Rb), the system is NOT in equilibrium.
Net forward reactions:
If the rate of the forward reaction (Rf) is greater than the rate of the reverse/back reaction
(Rb), an overall or net forward reaction is occurring. Products are being formed at the
expense of reactants.
If the rate of the forward reaction (Rf) is less than the rate of the reverse/back reaction (Rb),
an overall or net back reaction is occurring. Reactants are being formed at the expense of
products.

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IMPORTANT POINTS REGARDING

SYSTEMS AT EQUILIBRIUM

If a reversible reacting system is not at equilibrium, it must eventually attain equilibrium.

When equilibrium has been reached, the forward and reverse (back) reactions continue
to occur and at equal rates i.e. the system does NOT stop.

At equilibrium, individual reactant and product concentrations remain constant

i.e. individual concentrations do not change (unless the system is removed from
equilibrium). This does NOT imply that the reactant and product concentrations are
EQUAL in value.

The equilibrium mixture contains every reactant and product.

The speed at which a system reaches equilibrium varies from reaction to reaction.
Some reactions will reach equilibrium in a matter of seconds. For some reactions, it
takes many years to reach a steady state.

As the products are able to recombine to produce reactants, the amount of product
produced in equilibrium systems will always be less than the amount calculated using
standard stoichiometric manipulations.

Not all chemical reactions will reach equilibrium. For example, equilibrium is unlikely to
be attained in open systems.

Equilibrium can be approached from either direction via the forward or reverse (back)
reaction.

When a system is at equilibrium:

The temperature of the system will remain constant.

In gaseous systems, the temperature, volume and pressure will be constant.
There will be no observable colour changes.
The reaction is incomplete.
The amounts and concentrations of reactants and products do not change.

It appears to the observer that the reaction has stopped, but this is an illusion.
There is no net reaction occurring, but both reactions continue to take place at exactly
the same rate.

Equilibrium can be recognised by measuring:

Conductivity
pH
Pressure
Temperature

When a system is in equilibrium, it exists in a state of maximum stability.

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THE EQUILIBRIUM CONSTANT

The extent to which a chemical reaction proceeds is described by the Equilibrium Constant
( K eq or K or Kc ).
The equilibrium constant also indirectly describes:

The ratio of products to reactants at equilibrium.

The proportion (or percentage) of reactants that will be converted to products.

The equilibrium constant is an experimentally deduced relationship which describes the

relative concentrations of products to reactants when the system has reached equilibrium.
The general rule for calculating the equilibrium constant is called the equilibrium law and is
described mathematically as follows:
Given aA + bB

cC + dD , then the equilibrium constant is K eq =

d
[C ]ceq [ D]eq
a
[ A]eq
[ B]beq

i.e. The Equilibrium Constant is calculated by substituting the concentrations of each

chemical species when the system is in equilibrium into the above expression.
Note:

The equilibrium constant is reported for the forward reaction at a particular

temperature.

The Keq value for a particular reaction is temperature dependant. If the temperature of
the system is changed, the Keq will also change. Changes to other parameters like
concentration or dilution do not change Keq.

Different chemical reactions have different equilibrium constants.

The equilibrium law expression refers to the equation as written ( K is equation

related).
For example: Given that A + B

C , K = 10 i.e. K =

[C ] = 10
[ A][ B ]

If the mole ratios are doubled, the K value will also change.

[C ]
K=
2
2
[ A] [ B ]
2

2 A + 2B

2C ,

[C ]
=
= 102 = 100
[ A][ B ]

Whatever the change in the mole ratios, raise K to that value.

If the reaction is written in reverse, the value of K for this reaction will be the reciprocal
of the forward reaction.

K reverse =

1
K forward

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When the system is not in equilibrium the value of

[C ] c [ D ] d
is referred to as the
[ A] a [ B ]b

concentration fraction or reaction quotient (Q).

Regarding equilibrium constants for reactions involving gases:

We can use the concentrations of gaseous substances to calculate equilibrium
constants, however, it is often more convenient to use partial pressures.
The partial pressure of a gas is directly proportional to the amount present in mole,
which is a measure of concentration.
i.e. Using PV = nRT ,

P=

n
RT = cRT
V

Therefore, given aA( g ) + bB( g )

cC( g ) + dD( g ) , the expression for the equilibrium

constant may be written as K eq =

P c

pCeqc pDeqd
pAeqa pBeqb

To determine the units for the equilibrium constant:

Substitute the unit M (molar) into each concentration in the fraction. Then simplify
units by applying the appropriate index laws.

Important Notes:

As the [ H 2 O( l ) ] in aqueous solutions is constant ( 55.5 M ) , we omit [ H 2 O( l ) ] when

calculating the units of the corresponding equilibrium constant.
For example: CH 3 COOH ( aq ) + H 2 O ( l ) CH 3 COO ( aq ) + H 3O + ( aq )

K eq =

[CH 3COO ] [ H 3O + ]
M
[CH 3COOH ][ H 2O]

M M

Units =

As the [solid ] in gaseous and aqueous systems is constant, we omit [solid ] when
calculating the units of the corresponding equilibrium constant.
For example: C ( s ) + H 2 O ( g ) CO( g ) + H 2 ( g )

K=

[CO ][ H 2 ]
M
[ H 2O][C ]

M M

Units =

Include H 2O( l ) and solids in equilibrium law expressions, but ignore these species
when determining the corresponding equilibrium constants and their units.
If asked for Ka or K w , DO NOT include H 2O( l ) .

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QUESTION 13
Write balanced equations for the reactions with the following equilibrium laws:
2

(a)

H 2( g ) CO( g )
K=
CH 3OH ( g )

(b)

H 2 S( g )
K=
2
S2( g ) H 2( g )

QUESTION 14
Consider the reaction: 2 A( s ) + 3B( l )

C( aq ) + 4 D( aq )

Which of the following is the correct expression for the equilibrium constant?

[ A] [ B ]
4
[C ][ D ]

[C ][ D ]

[C ][ 4 D ]
[ 2 A][3B ]

[C ][ D ]
[ A][ B ]

Solution

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THE SIGNIFICANCE OF K
The equilibrium constant provides us with valuable information regarding the composition of
a reaction mixture, and whether it consists mainly of reactants or products when the system
is at equilibrium.
Informally, the equilibrium constant represents the proportion of the system that is in the
product phase i.e. the percentage conversion of reactants to products.

A large K eq ( K > 10 4 ) indicates that there are more products than reactants at
equilibrium.

A small K eq ( K < 10 4 ) indicates that there are less products than reactants at
equilibrium.

A medium K eq ( 10 4 to 10 4 ) indicates that there are significant amounts of reactants

and products at equilibrium.

For values of K eq between 10 4 and 10 4 , the concentration of products increases as

the value of K eq increases.

Note:

The equilibrium constant can never be equal to zero as all reactions in equilibrium
systems proceed to some extent, even if negligibly.

The equilibrium constant does NOT provide an indication of the rate of a reaction.
A high K eq value DOES NOT imply a fast reaction rate.

Catalysts do not change the position of the equilibrium but will allow the system to
reach equilibrium more quickly.

The equilibrium constant has NO bearing on the spontenaity of a reaction. A high K eq

value does not indicate that a reaction is spontaneous.

The extent of a chemical reaction may also be described in terms of the position of
equilibrium.

If a reaction favours the formation of products, we say that the position of equilibrium
lies to the right.

If a reaction favours the formation of reactants, we say that the position of equilibrium
lies to the left.
Reactants Products
Left

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QUESTION 15
Consider the following reactions:
A

I (aq ) + I 2(l )

Cu(2aq+ ) + 4 NH 3( aq )

K = 7.1102

I 3( aq )

Cu [ ( NH 3 ) 4 ]( aq )
2+

K = 1.4 1013

Answer the following questions by choosing one of the options below.

A
B
C

Reaction A
Reaction B
Answer cannot be determined from the given information

(a)

Identify the reaction which is most complete.

(b)

Which reaction will display the fastest reaction rate?

(c)

Which reaction has the smallest activation energy barrier?

(d)

Which reaction is spontaneous?

QUESTION 16
The equilibrium constant for the reaction below at 25o C is 1.7 1010 M 2 .

AgCl ( s ) Ag (+aq ) + Cl (aq )

Which of the following answers represents the equilibrium constant at 50o C ?
A

2 1.7 1010 M 2

1
1.7 1010 M 2
2

(1.7 10 )

K cannot be determined

10 2

M 2

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QUESTION 17
The graphs below illustrate the changes in the reactant and product concentrations in a
catalysed and uncatalysed reaction system, If the other reaction conditions are
identical,which set of curves (solid lines or broken lines), best represents the uncatalysed
system?

Solution

THE CONCENTRATION FRACTION/REACTION QUOTIENT

When the system is not in equilibrium the expression

[C ] c [ D ] d
is referred to as the
[ A] a [ B ]b

concentration fraction or reaction quotient (Q).

The concentration fraction provides a wealth of information, and is frequently used
to determine:

If a system is in equilibrium.
When the Concentration Fraction is equal to the Equilibrium Constant, the system is in
equilibrium.

How far a system is from attaining equilibrium.

The smaller the difference between the concentration fraction and the equilibrium
constant, the closer the system is to a state of equilibrium.

The direction in which equilibrium is being approached.

When Q < Keq the system is said to be approaching equilibrium via a net forward
reaction. The concentration of the products will increase and the reactant
concentrations will decrease, until the values of Q and Keq become equal.
When Q > Keq , equilibrium will be approached via a net back reaction. The
concentration of the products will decrease and the reactant concentrations will
increase, until the values of Q and Keq become equal.

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CALCULATIONS INVOLVING SYSTEMS

AT EQUILIBRIUM
METHOD:
Step 1: Write an expression for the equilibrium constant.
Step 2: Substitute the equilibrium concentrations and/or equilibrium constant into the
equilibrium expression.
Step 3: Solve for the required value.
WATCH OUTS:
(a)

Have I been given data in terms of mole or concentration?

If you are given information in terms of mole, do not forget to convert data to
concentrations before you substitute values into the equilibrium law.

(b)

Is the given data at equilibrium, or have initial concentrations been supplied?

You must only substitute concentrations at equilibrium into the equilibrium expression
(otherwise, a concentration fraction will be obtained). Never substitute initial
concentrations.
If initial concentrations or number of mole are given, use the mole ratios in the
balanced chemical equation to determine how much of each substance is reacting. Use
this information to then determine how much of each species is present at equilibrium.

(c)

Have there been any changes in temperature?

If a temperature change occurs - you cannot use the previous equilibrium constant. If
new concentrations are not given or a new equilibrium constant is not supplied, you will
be unable to calculate an answer.

ADDITIONAL POINTS:

Do not forget to include the appropriate units. Note that at times, there are no units!!!

If asked to determine whether a system is in equilibrium, calculate the concentration

fraction for the system. If this value is equal to the equilibrium constant, then the
system is in equilibrium.

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QUESTION 17
Calculate the equilibrium constant for the reaction 2 H 2( g ) + O2( g )

2 H 2O( g )

if the equilibrium concentrations are as follows:

[ H 2 ] = 0.30 M , [O2 ] = 0.30 M , [ H 2O] = 1.8 102 M

Solution

Kc =

[ H 2O( g ) ]2
[ H 2( g ) ]2 [O2( g ) ]

(1.8 102 ) 2
= 0.012 M 1
2
0.30 0.30

QUESTION 18
The formation of nitrosyl chloride from nitric oxide was investigated at a particular
temperature.

2 NO( g ) + O2( g )

2 NOCl( g )

The pressures if gases at equilibrium were pNO = 0.22 atm , pO2 = 0.11 atm and

pNOCl = 0.32 atm . Calculate the equilibrium constant, K p , for the reaction.
Solution

( pNOCl )
Kp =
2
( pNO ) ( pCl
2

(0.32) 2
= 19 atm 1
2
(0.22) (0.11)

QUESTION 19
Consider the reaction: A + 3B

2C + D .

Analysis of an equilibrium mixture in a 2.0 L container shows that 2.0 mol of A, 0.50 mol of
B and 3.0 mol of D are present. If the equilibrium constant of the reaction is 0.024 M 1 ,
calculate the amount of C, in mol, in the equilibrium mixture.
Solution

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QUESTION 20
The following reaction was allowed to reach equilibrium: U + V xW .
When the system is at equilibrium, the concentration of each species present is

[U ] = 0.3M
[V ] = 0.4 M
[W ] = 0.5M
If the value of K is 1.04 for the given temperature of this experiment, then the value of x is
A
B
C
D

1
2
3
4

Solution

QUESTION 21
Given the equilibrium: A2 ( g ) + 4C( g ) 2 AC2( g )
It follows that, for the reaction AC2 ( g )

K1 = 4.8

1
A2( g ) + 2C( g )
2

K2 = X .

X would be:
A

1
4.8

2 .4

1
2.4

1
4 .8

Solution

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QUESTION 22
Some hydrogen and nitrogen are placed in a 1.0 dm3 flask at 500o C . A reaction occurs and
ammonia is formed. At equilibrium , p ( N 2 ) = 50 atm , p ( H 2 ) = 150 atm and

K = 2.65 106 atm 2 .

(a)

Write an expression for the equilibrium constant for this reaction.

(b)

Calculate the partial pressure of ammonia.

(c)

The experiment was repeated at the same temperature and the partial pressures of the
gases were found to be p ( N 2 ) = 1.85 atm , p ( H 2 ) = 5.35 atm and p ( NH 3 ) = 1.75 atm
(i)

Show that the system is not in equilibrium.

(ii) In which direction is equilibrium approaching? Via a net back or forward reaction?

(d)

State the equilibrium constant for the reaction 2 NH 3( g )

3H 2( g ) + N 2( g ) at 500o C

in a 2.0 dm3 flask.

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EQUILIBRIUM CALCULATIONS BASED ON INITIAL

MOLE/CONCENTRATIONS
If initial concentrations or number of mole are given, we must first determine the amounts
present at equilibrium before calculating equilibrium constants.

METHOD:
Step 1: Determine the initial number of mole of each species.
If the initial number of mole of product is not given, assume that its amount is
equal to zero.
Step 2: Calculate the amount in mole of each species at equilibrium.
Use the mole ratios in the balanced chemical equation, together with the given
data to determine the number of mole being transferred during the reaction.
Then use common sense to determine whether to add or subtract the number of
mole being transferred to/from the initial number of mole.
Step 3: Calculate the concentrations at equilibrium.
Step 4: Calculate the equilibrium constant.
Problems of this nature are best resolved using the table below:
Reactants

Products

Mole Ratio
Initial Number of Mole
Change in Mole
Final Mole at Eq
Concentration at Eq

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QUESTION 23
One of the steps in the production of sulfuric acid is the oxidation of sulfur dioxide ( SO2 ).
The reactants form an equilibrium with the product, sulfur trioxide ( SO3 ), according to the
equation: 2 SO 2 ( g ) + O 2 ( g ) 2 SO 3( g ) .

2.000 mole of SO2 , 2.000 mole of O2 were placed in 10.00 L vessel and allowed to reach
equilibrium. When equilibrium was established, 0.150 mole of SO2 remained.
Calculate the value of the equilibrium constant at this temperature.
Solution

SO3

SO2

O2

2.000

2.000

Change in Mole

2.000 - 0.150
= 1.850

1.850

1.850

Final Mole at Eq

0.150

2.000 - 0.925
= 1.075

1.850

Mole Ratio
Initial Number
of Mole

Concentration
at Eq

K eq =

[ SO3 ]2
=
[ SO2 ]2 [O2 ]

C=

0.150
= 0.0150M 1.075
C=
= 0.1075M
10
10

2
0

C=

1.850
= 0.1850 M
10

(0.1850) 2
= 1.41103 M 1
(0.0150) 2 (0.1075)

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QUESTION 24
Fe 3+ ions react with SCN ions according to the equation: Fe(3aq+ ) + SCN (aq ) Fe( SCN ) (2aq+ ) .
+
If 0.060 mole of Fe 3+ and 0.13 mole of SCN and 0.10 mole of Fe( SCN ) (2aq
) are initially

added to 500 ml of water and at equilibrium, 0.16 mole of SCN are present, calculate a
value for the equilibrium constant.
Solution

Mole Ratio

Initial Number of Mole

Change in Mole

Final Mole at Eq

Concentration at Eq

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QUESTION 25
For the reaction 2 HI ( g ) H 2 ( g ) + I 2 ( g ) , 4.00 mole of HI ( g ) was allowed to react in a 2.0 L
vessel at a constant temperature. When equilibrium had been attained, it was found that
25% of the HI molecules had dissociated. Calculate the equilibrium constant for the
reaction.
2 HI ( g ) H 2( g ) + I 2( g )
Solution

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FORCED CHANGES TO EQUILIBRIUM SYSTEMS

If a system is removed from equilibrium by an external change, it has been experimentally
determined that the concentration of reactants and products will change until a new
equilibrium position is established. In effect, the system will oppose the change which was
made to it. This idea is referred to as Le Chateliers Principle.
If an equilibrium system is subjected to an external change the system will
adjust itself to partially oppose the effect of the change
The new equilibrium position may be attained by favouring a net forward or reverse
reaction. The direction of the net reaction will simply depend upon which reaction (the
forward or back reaction) will oppose the change which was introduced.
Factors that will cause changes to equilibrium systems include:

Concentration changes at constant temperature and volume.

Volume changes at constant pressure and temperature.
Temperature changes.

The effects of an external change on a system may be determined using a number of

different approaches, including:

Le Chateliers Principle
The Concentration Fraction
Rate/Time and Concentration/Time graphs.

The safest (and most fool proof) method is by analysing the corresponding Rate/Time and
Concentration/Time graphs.

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IMPORTANT NOTES
Unless otherwise specified or implied, always assume that when a change is introduced,
that the temperature of the system remains constant.
Read questions carefully to determine whether changes in amounts or concentrations or
positions of equilibrium are required.
When equilibrium is re-established:

The value of K will remain unchanged unless a temperature change has occurred.
The proportions of reactants and products alter in such a way as to keep the ratio in the
K expression unchanged.

The concentrations of the reactants and products will be different from that in the initial
equilibrium system.

The rate of the forward reaction will be equal to the rate of the reverse reaction, but
both reaction rates will be different from the previous equilibrium system.
If the imposed change increases the concentration of particles, final reaction rates of
both the forward and back reaction will increase.
If the imposed change decreases the concentration of particles, final reaction rates of
both the forward and back reaction will be lower than in the previous equilibrium
system.

QUESTION 26
According to Le Chateliers principle, when disrupted by a change at constant temperature,
an equilibrium system
A
B
C
D

Will restore original conditions.

Will not reach equilibrium again.
Will reach a new equilibrium position but with a different value for K .
Will reach a new equilibrium position with the same value of K .

Solution

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