CHEM0020 - Chemistry II

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3.0 CHEMICAL EQUILIBRIUM

3.1 Introduction

Water will evaporate when heated up in open air. In the other hand what will
happen to the water molecules if we place the water in a closed container?

The same process occurs where the molecules will be evaporated but the released
molecules will be trapped in the container.

The molecules in gas form will move around the space in container and collide
with other molecules of water. The collision will change back the water vapor to
liquid.

When the exchange between water vapor and water in the form of liquid is the
same, then the reaction is considered to be at equilibrium.

When the matter changes from liquid to gas, it is called evaporation process.
When the gas forms liquid it is named condensation process.

Terms and conditions for equilibrium process:

1. The equilibrium only occurs in a closed container where no substance can be added or
released during the process.

2. Equilibrium is reached when there is no further changes.

In equilibrium quantitative matters can change: for instance the concentration of

substance, the density or pressure of substance can change during the equilibrium
process. While the qualitative character of the substance never change in the
process. For example, the quality of water or ethanol used is still same.

3. Equilibrium is reached in two ways either from the left to right of an equation or vice
versa.

4. Equilibrium is reached when the rate of reaction for both ways is equal.

5. The equilibrium equation can be written as followed:

Water Water vapor

H2O (l) H2O (g)

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3.2 Equilibrium constant. Kc

Consider the following equation:

aA + bB cC + dD

The equilibrium constant for this equation is

Kc = [C]c[D]d
[A]a[B]b

Example 1:
Calculate the equilibrium constant for this reaction, if at 445oC the concentration at
equilibrium is 0.2M of hydrogen gas, 0.2M iodine vapor and 1.6M hydrogen iodide.

H2 + I2 2HI

Kc = [HI]2
[H2][ I2]

= [1.6]2 = 64
[0.2][0.2]

Unit of the Kc = [HI]2 = M2 = no unit

[H2][ I2] MxM

Example 2:
Calculate the equilibrium constant for this reaction, if 0.335 moles of PCl5, 0.04 moles
PCl3 and 0.94 moles Cl2 is mixed in 1.5 L container.

PCl5 (g) PCl3 (g) + Cl2 (g)

Kc = [PCl3][Cl2]
[PCl5]

= [0.04 mole/ 1.5 L][ 0.94 mole/ 1.5 L ]

[0.335 mole/ 1.5 L ]

= 0.0759 M

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Exercise:
1. For system CS2 (g) + 3O2 (g) CO2 (g) + 2SO2 (g) , Calculate the
equilibrium constant, Kc if the concentration of CS2 = 2.35, O2 = 1.45, CO2 = 2.21 and
SO2 = 4.20 in mol dm-3 unit.

2. A mixture at equilibrium contains 1.5 moles of hydrogen gas, 1.8 moles of fluorine gas
and 0.5 moles of hydrogen fluoride in a container with volume of 4 dm3. Calculate the Kc
for this reaction.
H2 (g) + F2 (g) 2HF (g)

Equilibrium constant in the term of partial pressure

Generally the equilibrium constant is stated in concentration unit, Kc. But for
gaseous samples it can be easily stated in partial pressure quantity.

From the ideal gas equation, PV = nRT,

P = n · RT
V

= [gas] · RT with [gas] in the unit of mol dm-3

At constant temperature, the pressure is directly proportional to concentration, p

[gas].

Thus the equilibrium constant for the following reaction can be written as below:

H2 (g) + I2 (g) 2HI (g)

Kp = P2HI
PH2 · PI2

Example 3:
At a constant temperature, a mixture reaches equilibrium. The ozone has partial pressure
of 0.123 atm while oxygen has partial pressure of 1.148 atm. Calculate the equilibrium
constant for this reaction. 3O2 (g) 2O3 (g).

Kp = P2O3 = (0.123)2 = 0.010 atm-1

P3O2 (1.148)3

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Exercise:
The equilibrium constant, Kp for the decomposition of phosphorus pentachloride to
phosphorus trichloride and chlorine gas is found to be at 1.05. If the equilibrium partial
pressures of PCl5 and PCl3 are 0.875 atm and 0.463 atm, respectively, what is the
equilibrium partial pressure of Cl2?

PCl5 (g) PCl3 (g) + Cl2 (g)

3.3 Heterogeneous equilibrium

Heterogeneous equilibrium is found in a reversible reaction involving reactants

and products that are in different phases.

For example, when calcium carbonate is heated in a closed vessel, the following
equilibrium is obtained:

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

We have solids and gas present in the equilibrium reaction. We usually write the
equilibrium constant as

Kc = [CaO] [CO2]
[CaCO3]

However the concentration of solids does not depend on the quantity of the
substances present. For this reason the term [CaCO3] and [CaO] are themselves
constant and can be considered having the value of 1.

So the equilibrium constant becomes

Kc = 1 · [CO2] = [CO2]
1

Exercise:
Write the equilibrium constant expression Kc and Kp if applicable, for each of the
following heterogeneous system.

a) N2O4 (g) 2NO2 (g)

b) NH4Cl (s) NH3 (g) + HCl (g)
c) Mg (s) + 2HCl (g) MgCl2 (s) + H2 (g)
d) P4 (s) + 6Cl2 (g) 4PCl3 (l)
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3.4 What does the equilibrium constant tell us?

In general the equilibrium constant helps us to predict the direction in which a

reaction mixture will proceed to achieve equilibrium and to calculate the
concentrations of reactants and products once equilibrium has been reached.

Predicting the direction of a reaction:

The equilibrium constant, Kc for the reaction:

H2 + I2 2HI, is 54.3 at 430oC. Suppose that in a certain experiment we
place 0.243 mol of H2, 0.146 mol of I2 and 1.98 mol of HI in a 1 L container at 430oC.
Will the experiment form more H2 and I2 or more HI?

Inserting the starting concentration in the equilibrium expression,

[HI]2 (1.98)2
Qc = = = 111
[H2] . [I2] (0.243) . (0.146)

- the calculated value is greater than Kc, so this system is not at equilibrium.

- We get higher value because the [product] is higher, consequently the HI

will react to form more H2 and I2.

- Reaction proceeds to left to reach equilibrium.

To determine in which direction the reaction will proceed to achieve equilibrium, we

compare the values of Qc and Kc.

3 possible cases to determine direction: 5

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Condition Explanation
Qc < Kc The ratio of concentration of products to
reactants is too small. To reach
equilibrium, reactants must be converted
to products. The system proceeds from
left to right to reach equilibrium.
Qc = Kc The system is at equilibrium.

Qc > Kc The ratio of concentration of products to

reactants is too large. To reach
equilibrium, products must be converted
to reactants. The system proceeds from
right to left to reach equilibrium.

Example 4:
At the start of a reaction, there are 0.249 mol N2, 0.0321 mol H2 and 6.42 x 10-4 mol NH3
in a 3.5 L reaction vessel at 375oC. If the equilibrium constant, Kc for the reaction is 1.2
at this temperature, decide whether the system is at equilibrium. If it is not, predict which
way the reaction will proceed.

N2 (g) + 3H2 (g) 2NH3 (g)

Answer:
[N2] = 0.249/3.5 = 0.071 mol L-1

[H2] = 0.0321/3.5 = 9.17 x 10-3 mol L-1

[NH3] = 6.42 x 10-4 /3.5 = 1.83 x 10-4 mol L-1

[NH3 ]2 (1.83 x 10-4 )2

Qc = = = 0.611
[N2] . [H2]3 (0.0711) . (9.17 x 10-3)3

Qc < Kc, the system is not at equilibrium.

The reactants must be converted to products, so the reaction will proceed

from left to right.

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Exercise:
The equilibrium constant, Kc for the formation of nitrosyl chloride, an orange-yellow
compound, from nitric oxide and chlorine gas: 2NO (g) + Cl2 (g) 2NOCl (g) is
6.5 x 104 at 35oC. In a certain experiment, 2.0 x 10-2 mol of NO, 8.3 x 10-3 mol of Cl2 and
6.8 mol of NOCl are mixed in a 2L flask. In which direction will the system proceed to
reach equilibrium?

3.5 Calculating equilibrium concentration.

If we know the equilibrium constant for a reaction, we can calculate the

concentrations in the equilibrium mixture.

Depending on the information given, the calculation may be straightforward or

complex. In most common cases only the initial concentration of reactant will be
given.

Example 5:
The chemical equilibrium below has Kc of 24.0 at 200oC.

cis-stilbene trans-stilbene

Suppose that only cis-stilbene is initially present at a concentration of 0.850 mol/L. How
do we calculate the concentrations of cis-stilbene and trans-stilbene?

Answer: cis-stilbene trans-stilbene

Initial (M) : 0.850 0

Changes (M) : -x +x

At Equilibrium : 0.850 – x +x
(M)

Kc = [trans-stilbene]
[cis-stilbene]

24 = x
0.850 – x

x = 0.816 M
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So the equilibrium concentrations are

[Cis-stilbene] = 0.850 – 0.816

= 0.034 M

[trans-stilbene] = 0.816 M

Example 6:
A mixture of 0.50 mol H2 and 0.50 mol I2 was placed in a 1 L stainless steel flask at
430oC. The equilibrium constant for this reaction, H2 (g) + I2 (g) 2HI (g) is 54.3.
Calculate the concentrations of H2, I2 and HI at equilibrium.

Answer:

Step 1:
- The stoichiometry of the reaction is 1 mol of H2 reacting with 1mol of I2
to yield 2 mol HI.
- Let x be the depletion in concentration (mol/L) of H2 and I2 at equilibrium.
- It follows that the equilibrium concentration of HI must be 2x.
- The amount of substance used as initial is 0.5 H2 and 0.5 I2.

- We can summarize the changes in concentration as below:

H2 + I2 2HI
Initial (M) : 0.50 0.5 0.0
Change (M) : -x -x +2x
Equilibrium (M) : 0.5-x 0.5-x 2x

Step 2: The equilibrium constant is given by

Kc = [HI]2
[H2][ I2]

Substituting with the values given, we get

54.3 = (2x)2
(0.5-x)(0.5-x)

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After solving the problem, we will get a quadratic equation in the form of
ax2 + bx + c = 0. The solution for x value can be calculated using

x = -b ± b2 – 4ac
2a

x = 0.393 M

Step 3: at equilibrium, the concentrations are

[H2] = (0.5 –0.393) = 0.107M

[I2] = (0.5 –0.393) = 0.107M
[HI] = 2 x 0.393 = 0.786M

3.6 Factors that affect chemical equilibrium

Chemical equilibrium represents a balance between forward and reverse reactions.

Changes in experimental conditions may disturb the balance and shift the
equilibrium position either to left or right.

For example when we say the equilibrium position shifts to right, we mean that
the net equation is now from left to right.

Variables that can be controlled experimentally are concentration, pressure,

volume and temperature.

Le Chatelier’s rule helps us to predict the direction in

which equilibrium will move when a change in
concentration, pressure, volume and temperature occurs. Le
Chatelier’s rule states that if external changes
(concentration, pressure, volume and temperature) are
applied to a system at equilibrium, the system adjusts to
reach a new equilibrium level.

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3.6.1 Changes in concentration

Consider this reaction: Iron (III) thiocyanate [Fe(SCN)3] dissolves readily in

water to give a red solution. The reaction equation is as below.

FeSCN2+ (aq) Fe3+ (aq) + SCN – (aq)

red pale yellow colorless

Adding the concentration of SCN – ions, the equilibrium shifts from right to left.

FeSCN2+ (aq) Fe3+ (aq) + SCN – (aq)

Adding Fe3+ ions, it would shift the equilibrium from right to left.

FeSCN2+ (aq) Fe3+ (aq) + SCN – (aq)

Adding the concentration of iron(III) thiocyanate, FeSCN2+ ions, the equilibrium

shifts from left to right.

FeSCN2+ (aq) Fe3+ (aq) + SCN – (aq)

Increasing the concentration of products shifts the

equilibrium to the left, and increasing the concentration
of the reactant shifts the equilibrium to the right.

3.6.2 Changes in volume and pressure

Changes of pressure do not affect liquid and solid, as they are virtually
incompressible.

Gases are greatly affected by changes in pressure.

According to Le Chatelier’s rule, if pressure is added, the equilibrium will move

in the direction which gives less pressure.

Pressure is proportional to number of molecules in a constant volume in a

reaction.

Thus we can conclude that with increasing pressure (increasing the number of
molecules), the equilibrium will move from direction which has bigger
number of molecules to the direction with less number of molecules. 10
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Reducing the pressure (or the number of molecules), the equilibrium will
move from direction, which has less molecules to the direction with bigger
number of molecules.

Example 7:

N2O4 2 NO2

i) increase pressure : 2 moles to 1 mole

N2O4 2 NO2 (shifts to left)

ii) reduce pressure: 1 mole to 2 moles

N2O4 2 NO2 (shifts to right)

3.6.3 Changes in temperature

Le Chatelier states that when the temperature is increased, the equilibrium

will move to the direction that absorbs heat.

In chemical reaction, there are exothermic and endothermic processes.

Exothermic process releases heat to the surrounding.

- The H has negative sign.

- The main process towards right is releasing heat.
- The backward process will absorb heat.
- When the temperature is increased the equilibrium will shift to left where
it absorbs heat.

Endothermic process absorbs heat from the surrounding.

- The H has positive sign.

- The main process towards the right that is absorbing heat.
- The backward process will release heat.
- When the temperature is increased the equilibrium will shift to right where
it absorbs heat.

Add temperature: equilibrium moves toward the direction that

absorbs heat 11
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Reduce temperature: equilibrium moves towards the direction that

release heat.

Example 8:

Consider the following reaction.

6CO2 (g) + 6H2O (l) C6H12O6 (s) + 6O2 (g) H = + 2816 kJ

Based from the energy changes, this system is an endothermic process (from left
to right).
Increase in temperature, the system shifts to right.
Decrease in temperature, it shifts to left.

Example 9:

Consider the following reaction.

N2 (g) + 3H2 (g) 2NH3 (g) H = - 92.38 kJ

Based from the energy changes, this system is an exothermic process (from right
to left).
Increase in temperature, the system shifts to left.
Decrease in temperature, it shifts to right.

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