Equilibria Constant Expressions for Related Reactions

Consider the equilibrium involving nitrogen, hydrogen and ammonia

For 1 mol NH3 production

Kc2 = ?

Will the value of equilibrium constant, Kc2 for the 1 mol NH3 production be
same the value of Kc1 . To relate Kc1 and Kc2, the equilibrium constant expression
for each equation will be:

And
It shows that Kc1 is the square of Kc2; Kc1 = (Kc2)2
So,

Whenever the stoichiometric coefficients of a balanced equation are multiplied

by some factor, the equilibrium constant for the new equation (K c2 in this case) is
the old equilibrium constant (Kc1) raised to the power of the multiplication
factor.
What is the value of Kc3 for the decomposition of NH3

It is clear that Kc3 is the reciprocal of Kc1 i.e. Kc3 = 1/Kc1 = 1/3.5 x 108) = 2.9 x
10-9. The equilibrium constant for a reaction and that for its reverse are the
Reciprocal of one another.
If a reaction has a very large equilibrium constant, the reverse reaction will have
a very small one.
If a reaction is strongly product-favoured then its reverse is strongly
Reactant-favoured.
In case of NH3 the forward reaction has a large equilibrium constant (3.5 x 10 8)
so is reverse reaction, decomposition of ammonia has a small equilibrium
constant (2.9 x 10-9)
Practice Problem:
The balanced equation for conversion of oxygen to ozone has a very small value
of Kc.
(a) What is the value of Kc if the equation is written as:

(b) What is the value of Kc for the conversion of ozone to oxygen?

Equilibrium Constant for a Reaction That Combines Two or More
Other Reactions

If two chemical equations can be combined to give a third, the equilibrium

constant for the combined reaction can be obtained from the equilibrium
constants for the two original reactions.
e.g. Air pollution is produced when nitrogen monoxide forms from nitrogen and
oxygen and then combines with additional oxygen to form nitrogen dioxide.

The sum of these equations is:

If two chemical equations can be summed to give a third, the equilibrium
constant for the overall equation equals to the product of the two
equilibrium constants for the equations that were summed.
This is the significant tool to obtain equilibrium constants without having to
measure them experimentally.
Practice Problem:
Given these equilibrium reactions and constants:

Calculate the equilibrium constant for the following reaction:

Strategy: comparing the given equations with target equation to see how much
given equations needs to be change.
The target equation has SO2 on the left, so equation 1 needs to be inverse or
taking reciprocal of equation 1. The target equation has SO3 on the right, no
need of change but multiply each coefficient by 2 or squaring equation 2.
Once done then we can multiply their equilibrium constants.

Reasonable Check: Equation 1 has very large equilibrium constant, so it’s

inverse is quite small.
Practice Problem:
When carbon dioxide dissolves in water it reacts to produce carbonic acid,
H2CO3(aq), which can ionize in two steps.

Calculate the equilibrium constant for the following reaction.

The Meaning of the Equilibrium Constant:
The equilibrium constant value tells you how far a reaction will proceed when
the equilibrium time is achieved. Also, it helps to calculate how much product
will be present at equilibrium. There are three important cases to consider:
Case 1. Kc >>1: Reaction is strongly product-favourd; equilibrium
concentrations of product are much greater than equilibrium concentrations of
reactants.
Example:

The very large Kc value tells us that if 1 mol each of NO and O 3 are mixed in a
flask at 25 C and allowed to come to equilibrium, [NO 2]O2] >> [NO][O3].
Case 2. Kc << 1: Reaction is strongly reactant-favourd; equilibrium
concentrations of reactants are much greater than equilibrium concentrations of
product.
Example:

This means that [O3]2 << ]O2]3 and if O2 is placed in a flask at 25 C, very little O3
will be found when equilibrium is achieved.
Case 3. Kc ≈ 1: Equilibrium mixture contains significant concentrations of
reactants and products; calculations are needed to determine equilibrium
concentrations.
Example:
 Using Equilibrium Constants
As equilibrium constant have numeric values, they can be used to predict
Quantitatively in which direction reaction will proceed and extent of reaction
Predicting the direction of a Reaction
 50 mmol NO2(g) and 100 mmol N2O4(g) at room temperature-10L vessel
 Is the system at equilibrium? If not, in which direction it will react to achieve
equilibrium.
 Reaction quotient, Q: same mathematical form as Kc but is a ration of actual
concentrations in mixture, instead of equilibrium concentrations.
 If Q is equal to Kc, then the reaction is at equilibrium. The concentrations will
not change.
 if Q is less than Kc, then the concentration of products are not as large as they
they would be at equilibrium. The reaction will proceed from left to right to
increase the product concentration until they reach their equilibrium values.
 If Q is greater than Kc, then the product concentrations are higher than they
would be at equilibrium. The reaction will proceed from right to left,
increasing reactant concentrations until equilibrium is achieved.
 Problem Example:
Consider the following equilibrium, which is used industrially to generate H 2 gas

If 1 mol CH4, 1 mol H2O, 0.5 mol CO and 2 mol H2 are mixed in 10 L vessel at
Room temperature, will the concentration of H2O be greater or less than 0.10
mol/L when equilibrium is reached?
Strategy: calculate initial conc. of each gas and then Q. Compare Q
with Kc.
Units are defined by equilibrium constant expression, leave them out.

Here, Q << Kc, forward reaction will occur, reaction of CH4 with H2O will form
CO and H2 until equilibrium is established.
The initial conc.H2O was 0.10 mol/L; when H2O react with CH4, the H2O
Concentration decreases.
Practice Problem: consider the following equilibrium

The equilibrium conc. are [SO2] = 0.102, [O2] = 0.0132 and [SO3] = 0.184.
Suddenly, the conc. of SO2 is doubled. Calculate Q and show, that the forward
Reaction would take place.
 Calculating Equilibrium Concentrations:

To see how much product is formed and how much reactants remain when
Equilibrium is reached. Considering the following reaction.

Suppose place 4 mol O2 and large excess of S in an empty 1 L flask and allow the
the system to reach equilibrium. We can calculate the quantity of O 2 left and the
quantity of SO2 formed at equilibrium.
S8 is solid and does not appear in the equilibrium constant expression.
We know the initial conc. of reactants and products but do not know how many
moles per liter of O2 are consumed during the reaction.
 Mole ration is: (1 mol SO2)/(1 mol O2), x mol/L SO2 is formed when x mol/L
O2 is consumed.
 The equilibrium conc. of SO2 is: (0 mol/L plus x mol/L), putting these values
into equilibrium constant expression, we get:

Solving for x:
 The equilibrium conc. of SO2 is x = 4 mol/L and that of O2 is 4 – x mol/L or
0 mol/L which means, all the O2 has been converted to SO2.
 Very large Kc value (4.2 x 1052) implies that all reactant converted to products.
 The reaction is strongly product favoured.
Practice Problem: consider synthesis of H2 from CO and steam

Suppose you place 0.0025 mol/L CO and 0.0025 mol/L H 2O into a container and
heat the mixture. What is conc. of each of the four substances at equilibrium?
Strategy: ratios are: 1:1, equal # of moles are consumed, generating tabulated data
The conc. of products are both equal to 1.9 x 10 -3 mol/L while the conc. of
Reactants are equal to (0.0025 – x ) = 6 x 10-4 mol/L

Reasonable Check: Substituting values in equilibrium constant expression:

Shifting a Chemical Equilibrium Le Chatelier’s Principle
Suppose you’re environmental engineer, biologist, geologist etc:
 You want to measure H3O+ in a lake. Hydronium ion is involved in many
different equilibrium reactions in a lake.
 How can you predict the influence of changing conditions? e.g.
 What happens if there is large increase in acid rain?
 Or if Lime(Calcium Oxide) a strong base is added to the lake?
These questions can be answered qualitatively using Le Chatelier’s Principles.
By definition; If a system is at equilibrium and the conditions are changed
So that it is no longer at equilibrium, the system will react to reach a new
Equilibrium in a way that partially counteracts the change.
Shifting of an equilibrium:
Changing Concentrations of Reactants or Product

If conc. of reactant or product change in equilibrium constant expression, the

System is no longer at equilibrium, it means, Q have different value than Kc.
 If conc. of reactant is increased, the system will react in the forward direction
 If conc. of reactant is decreased, the system will react in the reverse direction
 If conc. of product is increased, the system will react in the reverse direction.
 If conc. of product is decreased, the system will react in the forward direction.
To see why this happens, consider the following equilibrium reaction

2 mmol of cis-2-butene is placed in 1 L container. The forward reaction will occur as the
Initial conc. of product is 0. The forward reaction will be faster than reverse reaction until
The conc. of trans-2-butene reaches to 1.5. If you suddenly half the conc. of reactants,
the reverse reaction will occur without affecting reverse rate as conc. of product has not
changed.
Effect of changing concentration: enzyme catalyzed chemical equilibria-increase
the conc. of essential substance.
Industrial processes: maximize the yield of product
In Nature: formation of limestone, stalactites and stalagmites in caves, crust of
Limestone slowly develops in a tea kettle when you boil hard water.
Both these examples involve CaCO3. Lime is CaCO3 present in underground
deposits.
If ground water is saturated with CO2, results in bed of limestone below the surface of earth,
and forward reaction will occur till equilibrium is reached.
The groundwater contains ions like Ca2+ and Mg2+ results in hard water.
In all equilibria, reverse reaction occurs in addition to the forward reaction.
Mixing of CaCl2 and NaHCO3 (salts of Ca2+ and HCO3- ions) results in CO2 and CaCO3
formation. All the Ca2+ and HCO3- ions will convert into CO2 solid CaCO3 and water
Reaction of CaCl2(aq) with NaHCO3(aq)
Changing Volume or Pressure in Gaseous Equilibria
The pressure in a gaseous equilibrium by changing the volume of the container.
Tripling the pressure on the equilibrium.
Reducing the volume of the container to 1/3 of its original value at constant T.
Decreasing the volume, increases the pressure of N2O4 and NO2 to 3 times
their equilibrium values. As [NO2] is squared in the equilibrium constant but
[N2O4] is not, tripling both conc. Increases the numerator of Q by 3 2 = 9 but
Increase the denominator by 3.

Q is greater than Kc under the new conditions, the reaction should proceed in
Reverse direction (reactant formation)
Le Chatelier’s Principle: decreasing the pressure, which can happen if the total
Number of gas phase molecules decreases.
In case of N2O4/NO2 equilibrium, the reverse reaction should occur because
One N2O4 molecule is produced for every two NO2 molecules that react. A shift
to the left reduces the number of gas phase molecules and hence the pressure.
Changing Temperature
With change in T, change the equilibrium constants values and system will form
a new equilibria.
e.g. consider endothermic gas phase reaction of N2 and O2 to give NO

for endothermic reaction, an increase in temperature always increase Kc, the

Reaction will become more product-favoured at higher T.
for exothermic reaction, an increase in temperature always decrease Kc, the
Reaction will become less product-favoured at higher T.