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Chemical Equilibrium

CHAPTER 9:
CHEMICAL EQUILIBRIUM (REVERSIBLE REACTIONS)

9.1 Introduction
Some reactions can occur from either direction. This means that products can either be
converted to reactants or reactants converted products. Such reactions are called reversible.
Definition: A reversible reaction is a reaction in which the products of the reaction can react
or decompose to form the initial reactants under suitable conditions.
When reversible reactions occur in a closed system, they gradually attain a state of dynamic
equilibrium with time. A reversible reaction is not necessary a reaction in dynamic equilibrium
unless it takes place in a closed system with both the forward and backward reactions occur at
the same rate. Dynamic means continues to occur without stopping. Equilibrium in this context
means the concentrations or partial pressures of reactants and products remain constant with
time due to forward and backward reaction occurring at the same rate. The sign “⇌” in a
chemical reaction indicates that the reaction is reversible or in equilibrium. Chemical reactions
such as W + X ⇌ Y + Z, with the sign “⇌” between the reactants and the products are called
reversible reactions or equilibrium reactions.
Definition: A dynamic chemical equilibrium is a state in a reversible reaction in a closed
system where the concentrations of the reactants and the products are constant as a result of
equal rate of forward and the reverse reactions.
Thus characteristics of dynamic equilibrium are:
- Both the reactants and the products are present in the system at any given moment
- The equilibrium can be attained beginning with only products or reactants in a closed
system at a given condition.
- At equilibrium, all measurable or observable properties of the system such as
concentrations, partial pressures, colour intensity, temperature etc remain constant.
- The rate of forward reaction is equal to the rate of the reverse reaction.
- If the forward reaction is exothermic, then the backward reaction will be endothermic
and vice versa.
- At equilibrium, concentration or partial pressures of reactants and products remain
constant but not necessary the same under a given condition like temperature, catalyst.
- Catalyst has no effect on equilibrium position.
- Equilibrium is indefinite unless an external factor disturbs it.
The following conditions are necessary for a system to attain chemical equilibrium:
- The system must be closed
- The chemical reaction must be reversible.
Examples of reversible reactions that attain equilibrium in a closed system
CaCO3(s) ⇌ CaO(s) + CO2(g), 2SO2(g) + O2(g) ⇌ 2SO3(g), N2(g) + 3H2(g) ⇌ 2NH3(g).
Definition: An equilibrium mixture is the mixture of constant amounts of reactants and
products in a system which is in a state of dynamic equilibrium.
The concentrations or partial pressures of reactants and products remain constant at
equilibrium because the rate of the forward reaction is equal to the rate of the backward
reaction. For a chemical reaction such as R(g) ⇌ P(g) or R(aq) ⇌ P(aq), at equilibrium, the
amounts of reactant (R) and product (P) may be the same as illustrated in Fig 9.1a or
different as illustrated in Fig 9.1b and Fig 9.1c below.
concentration

concentration

concentration

P P R
R R P

t time t time t time

Fig 9.1a Fig 9.1b Fig 9.1c

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Chemical Equilibrium

In each of the graphs above, equilibrium is attained at time “t”. When → is used between
reactants and products, it implies that the reverse reaction is not possible or rarely achieved
e.g. H+(aq) + OH– (aq) → H2O(l).
Equilibrium mixture is also called equilibrium composition.

Determining when a reaction reaches equilibrium

Some characteristic properties of a system such as colour intensity, pressure, pH, electrical
conductivity may be observed with time to notice when the reaction in a closed container attains
equilibrium. The system attains a state of dynamic equilibrium when the chosen property becomes
constant with time.
Property Why property is suitable to know when equilibrium is attained
Concentration Concentration of reactant or product can easily be measured using
a titration set up.
Possible sources of errors in this method and example:
-Opening the closed system to extra a sample of the mixture could
allow exchange of material between the system and the
surroundings.
-A reactant or product whose concentration is not of interest may
also react with the titrant.
Pressure Number of moles of gaseous reactants and products are not equal
so that pressure change of the systems can be measured using a
manometer
Electrical conductance Number of moles of aqueous ions of reactants and aqueous ions of
products are not equal so that change in electrical conductance of
reaction mixture can easily be measured using a conductivity meter
pH Change in pH of the reaction mixtures can easily be measured
using a pH meter.
Colour One reactant or product is coloured so that change in colour
intensity of reaction mixture can be monitored using a colorimeter.
Act:
(a) For each reaction in a closed system, state brief how it can be monitored to know when
the reaction attains a state of dynamic equilibrium.
(i) H2(g) + I2(g) ⇌ 2HI(g). The purple colour intensity of iodine vapour will gradually
decreases with time and become constant when equilibrium is attained.
(ii) CaO(s) + CO2(g) ⇌ CaCO3(s). The pressure of the system will gradually decrease with
time and become constant when equilibrium is attained.
(iii) CH3COOH(l) + C2H5OH(l) ⇌ CH3COOC2H5(l) + H2O(l).
- The pH of the reaction mixture will increase with time and remain constant when
equilibrium has been attained.
- After a reasonable time intervals, extract about 25cm3 samples of the mixture and
titrate against NaOH(aq) using phenolphthalein indicator. This process is repeated
for some time until three end points of titration remain constant at different time
intervals indicating that the equilibrium has been attained.
(iv) IO3–(aq) + 5I–(aq) + 6H+(aq) ⇌ 3I2(aq) + 3H2O(l). The electrical conductivity of the
reaction mixture will decrease with time and remain constant when equilibrium
has been attained.
(b)
Radioisotopes can be used to show that dynamic equilibrium exists. In the esterification
reaction above, if water with oxygen-18 (18O) is added to the system, after sometime,
ethanoic acid with oxygen-18 will be detected using Geiger Muller tube or charged particle counter .

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Chemical Equilibrium

9.2 The Equilibrium Law and Equilibrium Constant

The following rules are applied when writing and using equilibrium constants (Kc or Kp)
expressions.
- Kc applies to reactions which can involve any state of matter. Kp only applies to a
reaction that contains at least a gaseous species. Only species in the same states of
matter can appear in an equilibrium constant expression.
- Species on the right (products) on the right side of the equilibrium sign (⇌) appear as
the numerator (on top) and species on the left (reactants) of the equilibrium sign (⇌)
appear as the denominator (under) of the equilibrium expression
- The power to which the concentration or partial pressure of each species is raised in the
equilibrium expression is equal to the coefficient (mole ratio) of the species in the
stoichiometric balanced equilibrium reaction
- Pure solids and/or pure liquids or solvents do not appear in the equilibrium expression
for heterogeneous equilibrium involving aqueous species or gases.
- Water as a product or reactant does not appear in a equilibrium expression for a
reaction in aqueous medium since it is the solvent.
- For a net equilibrium reaction obtained by summing two or more equilibrium reactions,
Kcnet = Kc1 x Kc2 x Kc3 ……… OR Kpnet = Kp1 x Kp2 x Kp3 ………
- The equilibrium constant of the backward reaction is simply the reciprocal of the
equilibrium constant of the forward reaction i.e. Kcb = 1/Kcf at constant temperature.

Kc for the forward reaction H2(g) + I2(g) ⇌ 2HI(g) is and for the

backward reaction 2HI(g) ⇌ H2(g) + I2(g) is . Thus .

For a homogeneous equilibrium reaction: aW + bH ⇌ cY + dZ, the equilibrium constant

(Kc) in terms of molar concentration (Kc) and in terms of partial pressures (Kp) are given
below by the equilibrium law.

and respectively.

Where [Y]eq is the concentration of product ‘Y’ at equilibrium, (PY)eq is the partial pressure
of product ‘Y’ at equilibrium, ‘a’, ‘b’, ‘c’ and ‘d’ are the number of moles of ‘W’, ‘H’, ‘Y’
and ‘Z’ respectively in the stoichiometric balance equation. For the Kc expression, ‘W’, ‘H’,
‘Y’ and ‘Z’ are either all gases or all in their aqueous forms. For the Kp expression, ‘W’,
‘H’, ‘Y’ and ‘Z’ can only be all gaseous since Kp only applies to a species in the gaseous
state.
Law: The equilibrium law states that for a reversible reaction at equilibrium, the product
of the molar concentrations of the products raised to their stoichiometric coefficients
divided by the product of molar concentrations of the reactants raised to their
stoichiometric coefficients in a balanced equation is a constant at constant temperature.

Units of equilibrium constant

The units of equilibrium constant are not unique and depend on the stoichiometric balanced
equation and states of the substances in equilibrium. Concentration of substances in
equilibrium is usually expressed in moldm-3. The units of Kp will also depend on the units of
the partial pressure. Consider the Kc expression below:

, units of Kc = = (moldm-3)c + d - a - b.

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Chemical Equilibrium

Consider the Kp expression below:

, units of Kp = = (atm)c + d - a - b, if partial pressures are in

atmospheres (atms).

Importance of equilibrium constant (Kp or Kc):

- To find equilibrium concentrations
- To find the measurement of extent of reaction. Higher Kc or Kp value means complete
reaction easy to achieve. An equilibrium constant of about 1000 is an indication of a
complete reaction while an equilibrium constant of about 0.001 is an indication of almost
no reaction.
- Stability of products. The higher the Kc or Kp, the more stable the product. For the reactions
N2(g) + O2(g) ⇌ 2NO(g), Kc = 6.5 x 10-16 and N2(g) + 2O2(g) ⇌ 2NO2(g), Kc = 8.7 x 10-10
moldm-3. NO2 is a more stable product than NO. Thus 2NO(g) + O2(g) ⇌ 2NO2(g) is easily
achieved than 2NO2(g) ⇌ 2NO(g) + O2(g).
Act01:
For each of the following equilibrium reactions, write down an expression for the
equilibrium constant Kc and/or Kp. Also determine the units of the equilibrium constant
considering pressure in atmospheres (atm) or pascals (Pa) or Nm-2.
(a) CH3COOH(l) + CH3CH2OH(l) ⇌ CH3COOCH2CH3(l) + H2O(l).
(b) CH3COOH(aq) + CH3CH2OH(aq) ⇌ CH3COOCH2CH3(aq) + H2O(l).
(c) 3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) + 4H2(g),
(d) CaCO3(s) ⇌ CaO(s) + CO2(g).
(e) CO(g) + H2O(g) ⇌ CO2(g) + H2(g),
(f) CaO(s) + CO2(g) ⇌ CaCO3(s).
(g) Cu2+(aq) + Zn(s) ⇌ Zn2+(aq) + Cu(s).
(h) Cr2O72-(aq) + 6Fe2+(aq) + 14H+(aq) ⇌ 2Cr3+(aq) + 6Fe3+(aq) + 7H2O(l).
(i) 2H2S(g) + SO2(g) ⇌ 3S(s) + 2H2O(l)
As a short-coming or limitation of the equilibrium constant, it does not indicate rate of the
reaction. Kc for the reaction 2H2(g) + O2(g) ⇌ 2H2O(g) is 9.1 x 1080 mol-1dm6 at 25°C but the
reaction does not occur spontaneously at room temperature.

Characteristics features of equilibrium constant (Kp or Kc):

- The equilibrium constant only applies to a system at equilibrium
- Equilibrium constant is constant only if temperature is constant.
 For an exothermic reaction, increasing the temperature decreases the value of Kp or K c. The
equilibrium shifts in the endothermic or backward direction to remove the added heat .
 For endothermic reactions, increasing the temperature increases the value of Kp or K c. The
equilibrium shifts in the endothermic or forward direction to remove the added heat.
- The numerical value of equilibrium constant is not affected by any changes in
concentration, pressure of either reactants or products or presence of a catalyst
- A larger equilibrium constant indicates that equilibrium position lies to the right i.e. a
greater proportion of products to reactants while small equilibrium constant indicates
that a equilibrium position lies to the left i.e. greater proportion of reactants to products.
- If an equilibrium reaction is multiplied by a factor ‘n’, then the equilibrium constant of
the resulting reaction will be raised to the factor ‘n’. Thus Kc or Kp for a given

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Chemical Equilibrium

equilibrium reaction at a given temperature can only have different values if

stoichiometric coefficients of the reaction are changed.
-
Act02:
(a) Assuming that the equilibrium constant Kp for the reaction: N2(g) + 3H2(g) ⇌ 2NH3(g) is
64 atm–2 at 40°C. Deduce a value and units of Kp for each equilibrium reaction below at
40°C.
(i) 2N2(g) + 6H2(g) ⇌ 4NH3(g).
(ii) ½N2(g) + 3/2H2(g) ⇌ NH3(g).
(b) The equilibrium constant Kc for the reaction X + Y ⇌ Z varies with temperature as
shown on the table below.
Temperature/ºC 25 300 400
Kc 4.26 x 108 1.02 x 10–5 8.00 x 10–7
Do you expect the reaction to be endothermic or exothermic? Explain.
(c)
Necessary conditions for the equilibrium constant for a given reaction to remain constant:
- The temperature of the system must not change
- Stoichiometric coefficient of species in the equilibrium reaction must not change
Mole percent of a substance = (mole fraction substance) x (100) .
Partial pressure of gas ‘G’ = (mole fraction of ‘G’) x (total pressure) of system i.e. pG = XGPT .
Where pG = partial pressure of gas ‘G’ in the system, XG = mole fraction of gas ‘G’ in the
system and PT = total pressure of the system.

The following steps should be applied to calculate Kc or Kp.

Steps to calculate Kc
1 From the balanced equilibrium reaction, write 1 From the balanced equilibrium reaction, write
down the expression for Kc.
2 Deduce the number of moles of each species
present at equilibrium.
3 Calculate the concentration of each species
present in the Kc expression.
4 Substitute the respective concentrations of each
species into Kc expression to obtain Kc value.
5 Substitute moldm-3 into Kc expression to obtain
units of Kc.
Steps to calculate Kp
down the expression for Kp.
2 Deduce the number of moles of each species
present at equilibrium.
3 Calculate the mole fraction of each species present
at equilibrium.
4 Calculate the partial pressure of each species
present in the Kp expression.
5 Substitute the respective partial pressure of each
species into Kp expression to obtain Kp value.

Examples on Kc and Kp:

Most problems on Kc or Kp can be solved using the ICE table where I = initial amount, C = change
and E = equilibrium amount. Any equilibrium reaction of the form:
aW + bH ⇌ cY + dZ, with ‘a’ and ‘b’ moles of ‘W’ and ‘H’ respectively placed in the system
and a degree of dissociation ‘α’ at equilibrium, will have the ICE table below.
aW + bH ⇌ cY dZ
I a b 0 0
C – aα – bα +cα +dα
E a – aα b – bα +cα +dα

1. (a) 1 mole of HI(g) is allowed to dissociate in a 1dm3 vessel at 440°C. Only 0.78 mol of
HI(g) were left at equilibrium. What is the equilibrium constant of this reaction at 440°C?
(b) if 2 mol of H2(g) and 1 mol of I2(g) are mixed together in a 1dm3 vessel at 440°C,
how may moles of HI(g), H2(g) and I2(g) will be present at equilibrium at 440°C?
(c) 1.2mol of I2(g) and 1.5mol of H2(g) are mixed in a 1dm3 closed system. After some time, the
equilibrium amount of HI(g) is found to be 1.6mol. Calculate Kc and state with an
explanation whether the equilibrium reaction was actually attained at 440°C or not.

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Chemical Equilibrium

Solution:
(a)
2HI(g) ⇌ H2(g) + I2(g)
I 1 0 0
C – 0.22 +0.11 +0.11
E 0.78 +0.11 +0.11

= 0.02.

(b) let the amount dissociated be ‘x’

H2(g) + I2(g) ⇌ 2HI(g)
I 2 1 0
C -x -x +2x
E 2-x 1-x +2x

= 50. =>

4x2 = 50(2 - 3x + x2) => 4x2 = 100 - 150x + 50x2 => 46x2 - 150x + 100 = 0.

For any equation of the form: ax2 + bx + c = 0,

=> => x = 2.33 or 0.93.

It should be recalled that x cannot be 2.33 because equilibrium concentrations calculated using
2.33 will be negative values which are physically meaningless. So x can only be 0.93.
Thus moles of each species at equilibrium is given by:
H2(g) = 2 – 0.93 = 1.07mol, I2(g) = 1 – 0.93 = 0.07mol, H2(g) = 2(0.93) = 1.86mol.
(c) 2x = 1.6, so x = 0.8, (1.5-x) = 0.7 and (1.2-x) = 0.4

= 9.14. The equilibrium reaction was not attained at

440°C since Kc = 9.14 is different from Kc = 50 at 440°C.

2. (a) Using partial pressures, show that for a gaseous reaction of the type: XY(g) ⇌ X(g) + Y(g) at
constant temperature, the pressure at which XY(g) is exactly ¼ dissociated is numerically
equal to 15 times the value of equilibrium constant (Kp).
(b) What is the fraction of dissociation for the reaction XY(g) ⇌ X(g) + Y(g), at a given temperature
if the total pressure at equilibrium is eight (8) times the equilibrium constant (Kp).
3. Some equilibrium reactions (Equilibrium I and Equilibrium II) with their respective equilibrium
constants at a given temperature (T°C) are given below.
Equilibrium reaction I: N2(g) + 2O2(g) ⇌ 2NO2(g), KcI = 3 x 10-17 mol-1dm3.
Equilibrium reaction II: 2SO2(g) + O2(g) ⇌ 2SO3(g), KcII = 8 x 1025 mol-1dm3.
Calculate the equilibrium constant (Kc) at the at the same temperature (T°C) for the reaction:
4SO3(g) + N2(g) ⇌ 2NO2(g) + 4SO2(g).
Solution:
(a) Multiply equilibrium II by 2, reverse it and add to equilibrium I.
4SO2(g) + 2O2(g) ⇌ 4SO3(g), K’c = (KcII)2 = (8 x 1025mol-1dm3)2.
=> K’c = 6.4 x 1051mol-2dm6.

Reverse equilibrium II and add to equilibrium I.

4SO2(g) + 2O2(g) ⇌ 4SO3(g), K’’c = = 1.56 x 10-52 mol2dm-6.

N2(g) + 2O2(g) ⇌ 2NO2(g), KcI = 3 x 10-17 mol-1dm3.

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4SO3(g) + N2(g) ⇌ 2NO2(g) + 4SO2(g). Kc = (K’’c x KcI).

 Kc = (1.56 x 10-52 mol2dm-6)(3 x 10-17 mol-1dm3) = 4.68 x 10-69 moldm-3.
Exercises on Kc:
1. 2mol of N2(g) and 3mol of H2(g) are mixed in a 2dm3 closed system. After some time, the
equilibrium amount of N2(g) in the equilibrium reaction: N2(g) + 3H2(g) ⇌ 2NH3(g) is found to be
1.6 mol . Calculate Kc. Ans = 0.274mol-2dm6.
2.
Relationship between Kp and Kc
The ideal gas equation; PV = nRT permits a number of relationships for gaseous systems to be
worked out based on the assumption that the gases in the system behave like ideal gases. If
temperature and pressure are kept constant, then the volume of the gas will be proportional to the
number of moles of the gas in the system (v α n). This is Avogadro’s law on gases. Consequently,
percentage by volume of a gas in a system is the same as its mole percentage (mole fraction
expressed in percentage). Thus 15% by volume of gas X in a system of gases means mole fraction of
gas X in the system is 0.15.
This relationship between Kp and Kc only exists for an equilibrium reaction that contains at least a
gaseous species. The relationship is derived using the ideal gas equation PV = nRT. Taking the
reaction: N2(g) + 3H2(g) ⇌ 2NH3(g) into consideration,

and . From the ideal gas equation,

partial pressure, . But = concentration, => = [NH3(g)]RT. Substituting the

partial pressure of each species into the Kp expression gives

. => = Kc(RT)-2.

Thus for any homogeneous gaseous reaction of the form: aW + bH ⇌ cY + dZ,

Kp = Kc(RT)(c + d – a – b) where R = universal gas constant and T = temperature in kelvins. In general,
Kp = Kc(RT)∆n where ∆n = (total number of moles of gaseous products) – (total number of moles of
gaseous reactants).
Definition: The partial pressure of a gas is the pressure that a gas would exert if it alone occupied
the available volume of the container.
Definition: The mole fraction of a substance is the number of moles of that substance in the system
divided by the total number of moles in the system.
Worked example:
The equilibrium constant Kc for the reaction: N2(g) + 3H2(g) ⇌ 2NH3(g) at 25°C is 4 x 108 mol-
2
dm6. Calculate Kp for the above reaction at 25°C. Gas constant
R = 0.08205 atmdm-3mol-1K-1.
Solution:
Kp = Kc(RT)-2, => Kp = (4 x 108)(0.08205 x 298)-2 = 6.69 x 105 atm.

Exercises on Kp:
1. At equilibrium, the reaction: 2XY(g) ⇌ X2(g) + Y2(g) has a total pressure ‘PT’ at 50°C. Show that the
equilibrium constant (Kp) for the reaction at 50°C is 1/81 if degree of dissociation is 4/11.
2. At equilibrium, the reaction: 2XY(g) ⇌ X2(g) + Y2(g) has a total pressure ‘PT’ at 50°C.
Show that for the degree of dissociation ‘δ’, the equilibrium constant (Kp) for the equilibrium
reaction is independent of the total pressure (PT).
3. 1.0 mole of PCl5 vapour was heated to 500K in a sealed vessel. The equilibrium mixture, at a
pressure of 6.2 atm, contained 0.6 moles of chlorine. Calculate the value of K p and give the units
for Kp. The equation for the reaction: PCl5(g) ⇌ PCl3(g) + Cl2(g). Ans; Kp = 3.5atm.

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Chemical Equilibrium

4. At a certain temperature, and a total pressure of 0.95 atm, bromine vapour contains 45% by
volume of bromine atoms at equilibrium. The equilibrium equation is Br 2(g) ⇌ 2Br(g).
(a) Calculate Kp for the equilibrium
(b) At what total pressure (without temperature change) would the percentage (%) by volume of
bromine atoms be reduced to 30%?
(a) Since % by volume gives mole fraction, => PBr(g) = 0.45(0.95) = 0.43atm, PBr2(g) = 0.55(0.95)
= 0.52atm. => Kp = (0.43atm)2/0.52atm = 0.36 atm. Ans; (a) Kp = 0.36 atm.
(b) Let the total pressure = PT. Thus pBr(g) = 0.3(PT) = 0. 3PT, PBr2(g) = 0.7(PT) = 0.7 PT. => Kp =
(0.3 PT)2/0.7 PT = 0.36 atm. => 0.13 PT = 0.36atm, => PT = 0.36/0.13 = 2.77 atm. (b) PT = 2.77
atm
Exercises on Kp and Kc:
1. Some equilibrium reactions (Eqm I, Eqm II and Eqm III) with their respective equilibrium
constants at a given temperature (T°C) are given below.
Eqm reaction I: N2(g) + O2(g) ⇌ 2NO(g), KcI = 5.0 x 10-31.
Eqm reaction II: 2NOCl(g) ⇌ 2NO(g) + Cl2(g), KcII = 4.7 x 10-4 moldm-3.
Eqm reaction III: N2(g) + 3H2(g) ⇌ 2NH3(g), KcIII = 9.1 x 105mol-2dm6.
(a) Calculate the equilibrium constant (Kc) at the at the same temperature (T°C) for the
reaction: 2NH3(g) + O2(g) + Cl2(g) ⇌ 2NOCl(g) + 3H2(g).
(b) Why are the units of equilibrium constant not given for the equilibrium reaction I?
(c) Suggest the Kp value for the equilibrium reaction I if temperature of the system is
maintained at (T°C). State a reason for the value of Kp suggested.
2.
Answers:
1. (a) Ans, Kc = 1.2 x 10-33moldm-3.
(b) Number of moles of gaseous products equal to number of moles of gaseous reactants.
(c) Kp = 5.0 x 10-31 since number of moles of gaseous products equal to number of moles of
gaseous reactants.

9.3 Experimental determination of equilibrium constant

- Several tubes are set up with different starting concentrations of reactants
- The content of the tubes are allowed to reach equilibrium at the same temperature
- The concentration of one or more of the species is determined at equilibrium and can be used to
obtain the concentration of the other species in the system.
Differences between equilibrium constant and rate constant.
Equilibrium constant Rate constant
It is a ratio of the concentration of products to It is a constant of proportionality relating rate of
concentration of reactants raised to their a reaction to the concentration of the reactants at
respective stoichiometric coefficients in the constant temperature.
balanced equilibrium equation at constant
temperature.
It describes a reaction that does not change with It describes a reaction that changes with time
time
Its expression usually requires concentrations of Its expression may require only the
reactants and products. concentrations of reactants.
Stoichiometric coefficients used directly to Experimental data used to write expression and
write expression not stoichiometric coefficients
9.4 Types of Equilibrium
Two main types of chemical equilibrium exist i.e. homogeneous equilibrium and heterogeneous
equilibrium.
(a) Homogeneous equilibrium:
This is a type of equilibrium in which all the species in the equilibrium reaction are in the same
phase e.g. N2(g) + 3H2(g) ⇌ 2NH3(g).
(b) Heterogeneous equilibrium:

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Chemical Equilibrium

This is a type of equilibrium in which all the species in the equilibrium reaction are not in the
same phase e.g. 3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) + 4H2(g).
9.5 Le Chatelier’s Principle and Factors Affecting Equilibrium
A stress or constrain (concentration, pressure and temperature) on a reaction at equilibrium causes a
change on the equilibrium position but not on the equilibrium constant. Temperature is the only
stress or constrain that affects both the equilibrium position and the equilibrium constant.
The effect of each stress can be explained using Le Chatelier’s principle.
Principle: Le Chatelier’s principle states that when a system at equilibrium is subjected to a
constrain, the system responds in a way that counteracts or opposes the constraint.

Definition: An Equilibrium position is the relative amounts of products to reactants present in an

equilibrium mixture.
Important notes about equilibrium position:
- Equilibrium position is said to shift to the right when the amount of products is increasing while
the amount of reactants is decreasing.
- Equilibrium position is said to shift to the left when the amount of reactants is increasing while
the amount of products is decreasing.
Act03:
(a) Explain the meaning of the following.
(i) Equilibrium position lies to the right. A relative high proportion of products than reactants.
(ii) Equilibrium position shifts to the right. Forward reaction occurring faster than reverse
reaction due to added stress.
(b)
Factors affecting the position of chemical equilibrium
Le Chatelier’s principle is applied in order to explain the effect of change in pressure, concentration
or temperature on a system at equilibrium.
(a) Change in concentration:
If reactants are added, the equilibrium position will shift to the right by consuming the added
reactants in order to oppose the change and restore equilibrium. If products are removed, the
equilibrium position will shift to the right to replace the products removed in order to oppose the
change and restore equilibrium.
(b) Change in pressure:
This factor only affects reaction systems in which the number of moles of gaseous reactants is
different from the number of moles of gaseous products. If the pressure is increased, equilibrium
position shifts to the side of the reaction with fewer moles of gaseous molecules in order to
oppose the change and restore equilibrium. If the pressure is decreased, the equilibrium position
will shift to the side of the reaction with more moles gaseous molecules in order to oppose the
change and restore equilibrium.
(c) Change in temperature:
If the temperature is increased, the equilibrium position will shift to the endothermic direction
(direction that absorbs heat) in order to remove heat added in order to oppose the change and
restore equilibrium. If the temperature is decreased, the equilibrium will shift to the exothermic
direction (direction that generates heat) in order to replace heat removed in order to oppose the
change and restore equilibrium.
(d) Adding a catalyst:
Adding a catalyst to a reaction in a state of dynamic
EaF unatalysed path
equilibrium has no effect on the position of equilibrium. This
Potential energy

∆Ea
is because a catalyst increases the rates of the forward and
EaR backward reactions equally. The activation energies of both
catalysed the forward and backward reactions are reduced by the same
path magnitude in the presence of a catalyst. A catalyst can only
reduce the time taken for a reaction to reach equilibrium but
Reaction path has no effect on a reaction already at equilibrium.
EaF = activation energy for forward reaction, EaR = activation energy for backward (reverse)
reaction, ∆Ea = Change (decrease) in activation energy in the presence of a catalyst.
Act03:

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
 Page 10 of 11
Chemical Equilibrium

(a) The equation for the industrial manufacture of ammonia (Haber process) is given below.
N2(g) + 3H2(g) ⇌ 2NH3(g); ΔH = -92 kJmol-1.
What will be the effect on the position of equilibrium and yield of ammonia if the following changes
are applied to the system? Explain.
(i) Temperature of the system is increased. The equilibrium position will shift to the left
(endothermic direction) to remove heat added since the forward reaction is exothermic. In this
case, yield of ammonia reduced.
(ii) The pressure of the system is decreased. The equilibrium position will shift to the left since the
total number of moles of gaseous reactants is more the total number of moles of gaseous
products. In this case, yield of ammonia reduced
(iii) Concentration of nitrogen gas is increased by pumping more nitrogen into the system. The
equilibrium position will shift to the right so as to consume the added amount of nitrogen for
equilibrium to be restored. In this case, yield of ammonia increased.
(iv) Concentration of ammonia gas is increased by pumping more ammonia into the system. The
equilibrium position will shift to the left so as to consume the added amount of ammonia for
equilibrium to be restored. In this case, yield of ammonia reduced.
(v) Concentration of hydrogen gas is decreased. The equilibrium position will shift to the left so as
to replace the amount of hydrogen removed for equilibrium to be restored. In this case, yield
of ammonia reduced.
(vi) Concentration of ammonia gas is decreased by liquefying the ammonia and tapping off from the
system. The equilibrium position will shift to the right so as to replace the amount of
ammonia removed for equilibrium to be restored. In this case, yield of ammonia increased.
(vii) Iron catalyst is added to the system. No effect on the equilibrium position since the catalyst
speeds up rate of forward and the reverse reaction equally.
(b) Suggest possible changes in the industry to improve on the yield of ammonia. Frequently remove
the ammonia formed, increase concentration of reactants, decrease temperature of the system.
(c) The equation for the equilibrium reaction between iodine vapour and hydrogen at 440ºC is given
below.
I2(g) + H2(g) ⇌ 2HI(g); ΔH = -10.4 kJmol-1.
What will be the effect on the position of equilibrium if:
(i) The pressure of the system is increased? No effect on the equilibrium position since the total
number of moles of gaseous products is equal to the total number of moles of gaseous
reactants.
(ii) The pressure of the system is increased? The equilibrium position will shift to the right
(exothermic direction) to replace the heat removed since the forward reaction is exothermic.
(d) The equation for the equilibrium reaction between iron and steam is given below.
3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) + 4H2(g),
What will be the effect on the position of equilibrium if the pressure of the system is increased? No
effect on the equilibrium position since the total number of moles of gaseous products is equal to
the total number of moles of gaseous reactants.
The table below give examples of stress on an equilibrium position and equilibrium constant.
Effect on equilibrium
Change Type of change (stress) Effect on equilibrium position
constant
Add reactant or remove
Moves to right No effect
product
Concentration
Add product or remove
Moves to left No effect
reactant
Increase pressure or Moves towards side with fewer gas
No effect
Pressure decrease volume moles
(or volume) Decrease pressure or Moves towards side with more gas
No effect
increase volume moles
Moves in endothermic direction Increases (if H = +ve)
Increase temperature
(right if H = +ve, left if H = -ve) Decreases (if H = -ve)
Temperature
Moves in exothermic direction Decreases (if H = +ve)
Decrease temperature
(left if H = +ve, right if H = -ve) Increases (if H = -ve)

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
 Page 11 of 11
Chemical Equilibrium

Catalyst Add or remove catalyst No effect No effect

*Catalyst is not a stress here because its presence or absence does not affect the position of
equilibrium.

9.8 Practice Exercises and Examination Questions

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N