Chapter two Chemical Equilibrium

Types of Equilibrium

Dynamic Equilibrium Chemical Equilibrium

Ionic Equilibrium

The equilibrium system: [Dynamic equilibrium]

- It is a stationary system apparently but in reality, it is dynamic.
 Example:
- If a closed vessel containing water is heated, 2 opposite processes
occur which are: Vaporization & Condensation
Vaporization
Water (liquid) Water (vapour)
Condensation

(1) (2) (3)

e of vaporization is greater than rate ofRate
condensation
of condensation
Reaching equilibrium
increases between vaporization and condens

- Vaporization continues until vapour pressure = saturated water

vapour pressure, where:

- Saturated water vapour pressure:

43
Chapter two Chemical Equilibrium

- At equilibrium: number of water molecules which vaporize = number of

water molecules which condense.
 Vapour pressure:
It is the pressure of water vapour found in air at certain temperature.
 It is the maximum pressure of water vapour that can be found in air at
certain temperature.
- Conclusion:

Reaching the equilibrium state does not mean that the change from one
state to another stops but means that the change from one state to
another is continuous in two directions with the same rate and at the
same time.
Chemical Reactions
Type of Irreversible reaction Reversible reaction
reaction (Complete reaction) (Incomplete reaction)
Definition - Reaction, which goes in one - Reaction, which occurs in
: direction only & products do not two directions, (Forward
react once more with each other & backward) both
to reform the reactants under the reactants and products
condition of the reaction. are continuously found in
A+B→C+D the reaction. (products
recombine again)
A+BC+D
Examples NaCl + AgNO3 → NaNO3 + AgCl  CH3COOH + C2H5OH
:

Mg + 2HCl → MgCl2 + H2↑
CH3COOC2H5 + H2O
HCl + Na2O NaCl + H2O

 Give reasons:
 The reaction of NaCl with AgNO3 is a complete reaction.
- Because the products cannot recombine with each other to form
the reactants as one of the products escape from the system.
[AgCl (Solid ppt)] [NaCl + AgNO3 → NaNO3 + AgCl]
 The reaction of Mg with HCl is an irreversible reaction.

44
Chapter two Chemical Equilibrium

- Because the products cannot recombine with each other to form

the reactants as one of the products escape from the system.
[gas evolves which is H2] [Mg + 2HCl → MgCl2 + H2↑]

 When a blue litmus paper is put in the solution produced

from the reaction between acetic acid & ethyl alcohol, it
changes to red although the products are neutral.
- Because this is a reversible reaction which continues in both
directions with the same rate, thus both reactants and products
are found in the solution and since the acetic acid has an acidic
effect, the blue litmus paper changes to red.
CH3COOH + C2H5OH  CH3COOC2H5 + H2O
Acid Neutral Neutral Neutral

 Chemical Equilibrium:
It is a dynamic system takes place when the rate of forward reaction
equals the rate of backward reaction.

Remember:
Chemical equilibrium occurs only in reversible reactions.
At equilibrium: the concentrations of the reactants and products are
not changed: the equilibrium position remains unchanged since all
reactants and products are still found in the system, (no gas evolves, no
precipitate is deposited) and the reaction conditions such as
temperature and pressure are not changed.
Equilibrium state may be reached rapidly or slowly according to the
factors affecting the rate of chemical reaction.

Rate of chemical reaction:

- It is the rate of change in the concentration of reactant or product
per unit time.

45
Chapter two Chemical Equilibrium

- During the complete reaction, the concentration of the reactants

decrease and the concentration of the products increase.

Factors affecting Chemical Equilibrium:

1- Concentration 2- Temperature 3- Pressure

Le Chatelier Principle:

“The Changes in any of the conditions of a chemical equilibrium

such as concentration, pressure or temperature will shift the
equilibrium in the direction which will oppose this change.”

46
Chapter two Chemical Equilibrium

1- Concentration:
Increasing the concentration of the reactants shifts the equilibrium forward
& vice versa.

Ex (1): CH3CO OH + H OC2H5 CH3COOC2H5 +

Acetic acid Ethyl acetate ester
H2 O Ethanol

 If the concentration of the acid or the alcohol increases, the

equilibrium will shift forward.
 If the concentration of the ester or water increases, the equilibrium will
shift backward.
 Adding conc. Sulphuric acid (H2SO4) will absorb water shifting the
equilibrium forward.

Ex (2): FeCl3 + 3NH4SCN ⇌ Fe(SCN)3 + 3NH4Cl

 If excess of FeCl3 is added, the red colour of the solution increases,
which indicates the formation of excess of iron (III) thiocyanate.

Ex (3): BiCl3 + H2O ⇌ BiOCl + 2HCl

Bismuth chloride White colour
 If excess of water is added, the white colour increases.
 If excess of HCl is added the white colour decreases or disappears.

2- Temperature:
Types of chemical reactions

Exothermic reactions
Endothermic reactions

A- Exothermic reactions: [ ]
 Example (1):

47
Chapter two Chemical Equilibrium

N2 + 3H2 ⇌ 2NH3 + heat

Or N2 + 3H2 – heat ⇌ 2NH3
Or N2 + 3H2 ⇌ 2NH3 [∆H = -ve]
 At equilibrium: The reaction is an exothermic reaction.
 Decreasing the temperature: the equilibrium will shift forward.
 Increasing the temperature: The equilibrium will shift backward.

Remember:
 In industry: "Haber & Busch method":
N2 + 3H2 2NH3 + heat
 Heating (500 oC & iron as a catalyst) are used because:
1- Cooling increases the yield of ammonia but the reaction will slow
down.
2- To reach to the activation energy of nitrogen.

48
Chapter two Chemical Equilibrium

 Example (2):

2NO2 NO 2 4
Nitrogen
+
tetra oxide
heat
Nitrogen dioxide colourless
Reddish brown

 On cooling a flask containing nitrogen dioxide, the reddish brown

colour of the gas will gradually decrease until it disappears
completely.
 While if the flask is removed from this cooling mixture and returned
to room temperature, the reddish brown colour starts to reappear
gradually.
 Conclusion:
- If an exothermic reaction at equilibrium cooled, the
reaction goes in the forward direction in order to liberate
heat.
- The rate of the reaction is directly proportional to any rise
in temperature.
Give reasons:

49
Chapter two Chemical Equilibrium

- On putting NO2 in an ice mixture, decolourization takes

place, while at room temperature , its colour return.
- At equilibrium, NO2 & N2O4 are formed in the reaction. Decreasing
temperature, the equilibrium will shift forward with formation of N2O4
Increasing temperature, the equilibrium will shift backward with the
formation of NO2.

- 2NOdioxide
Nitrogen 2 N2O4 + heat
Reddish brown Nitrogen tetra oxide
colourless

B- Endothermic reactions: [ ]
 Example:
N2 + O2 + heat ⇌ 2NO
Or N2 + O2 ⇌ 2NO – heat
Or N2 + O2 ⇌ 2NO [∆H = +ve]
 Decreasing the temperature: the equilibrium will shift backward.
 Increasing the temperature: The equilibrium will shift forward.
Remember:
 If the reaction is neither exothermic nor endothermic, raising
temperature only causes equilibrium to be reached faster without
shifting its position.

3-Pressure: [In case of gases]

a- If the number of moles of reactants and products is equal.
N2 + O2 + heat  2NO
2 moles 2 moles

Change in pressure does not affect the equilibrium state.

b- If the number of moles of reactants & products is not equal.

50
Chapter two Chemical Equilibrium

 At high pressure:
The equilibrium shifts in the direction that decreases the number of moles.
 At low pressure:
The equilibrium shifts in the direction that increases the number of
moles.

 Example (1):

N2 + 3H2 2NH3 + heat

2 moles
4 moles
 Example (2):

2SO3 2SO2 + O2
2 moles 3 moles

 Remember:

 Big number of moles Small number of moles

 Small number of moles Big number of moles

 There is no effect for pressure except in a gaseous reaction.
 The volume of the solid or the liquid is neglected when it is
compared to gas volumes.

Remember:
 Some reactions end in a very short time.
Ex: AgNO3 + NaCl  NaNO3 + AgCl

 Some reactions are slow.

Ex: Oil + NaOH  Soap + glycerol

 Some reactions are very slow.

Ex: Rusting of iron.

51
Chapter two Chemical Equilibrium

Nat

1)Nature of the reactants:

a. Type of bonding in the reactants:
i. Ionic compounds:
- They have a very high rate of reaction. [i.e. they undergo very fast
reactions]
Because they can easily change to ions. (Ions of the reactants
combine with each other instantly)
Ex: NaCl + AgNO3 → NaNO3 + AgCl

ii. Covalent compounds:

- They have very slow rate of reaction. [i.e. they undergo slow
reactions]
Ex: organic reactions (esterification)

b. Surface area exposed to the reaction:

- As the surface area of the reactant increase, the rate of the reaction
increases. (S.A α rate of the reaction)
Ex: The reaction of zinc powder with hydrochloric acid is faster than
the reaction of a zinc block with hydrochloric acid even if the zinc in
both reactions has the same mass.

52
Chapter two Chemical Equilibrium

Remember:
 The rate of the reaction increases for soluble ionic compounds
whenever the surface area of the reactant increases.

2)Concentration of the reactants:

The larger the number of the reacting molecules (higher concentration),

the greater the chance of collision per unit time, thus the rate of
reaction increases.

 Remember:
 In the reactions involving gases, the chemical reaction happens when
the molecules of gas collide with each other (are in continuous
motion in all directions).
 The rate of the reaction is directly proportional to the concentration
of the reactants.

Law of mass action: [Waage and Goldberg]

“At a constant temperature, the rate of chemical reaction is
directly proportional to the product of multiplication of the
reactant concentrations; each is raised to the power of the
number of molecules or ions in the balanced chemical equation.”

 Example:

FeCl3 + 3NH4SCN r1 Fe (SCN)3 + 3NH4Cl

Ammonium thiocyanide
Iron III chloride r2 IronBlood
thiocyanide
colorless Red
Pale yellow

53
Chapter two Chemical Equilibrium

 On adding an excess amount of FeCl3, the forward reaction takes place &
so the red colour of the solution increases.
 While on adding an excess amount of NH4Cl, the backward reaction
takes place & so the red colour of the solution decreases.
 When the rate of backward reaction (r2) equals the rate of the forward
reaction (r1) then the reaction will be in equilibrium state.

r1 [FeCl3] [NH4SCN]3

r1= k1 [FeCl3] [NH4SCN]3
r2 [Fe(SCN)3] [NH4Cl] 3
r2= k2 [Fe(SCN)3] [NH4Cl] 3

Where:
-The brackets [ ] represents the concentration in mole/liter.
-k1 , k2 are the rate constant for the forward and backward
reactions.
 At equilibrium:
r1 = r2
k1 [FeCl3] [NH4SCN]3 = k2 [Fe(SCN)3] [NH4Cl]3

- The product of is a constant value referred to as Kc which known as

equilibrium constant of the reaction.

 Example 1:
Calculate the equilibrium constant of the following reaction:
I2 + H2 → 2 HI

54
Chapter two Chemical Equilibrium

Where, the concentration of iodine = 0.221 mole/liter

The concentration of hydrogen = 0.221 mole/liter
The concentration of hydrogen iodide = 1.563 mole/liter
Solution:

 Example 2:
Substance (A) reacts with substance (B), to form (C) & (D). If the quantities of
substances at equilibrium by unit mole is 2, 2, 0.6 & 0.6 mole. Calculate the
equilibrium constant for this reaction if the volume of the reaction is 2 liters.
Solution:
A + B ⇌C + D
Number of moles: 2 2 0.6 0.6

Concentration =

Concentration =
1 1 0.3 0.3

Kc = Kc = = 0.9
 Remember:
 If K < 1 , this means that [C]P < [C]R which means that the
c

backward reaction is faster than the forward reaction.

Ex:
AgCl(S) Ag+(aq) + Cl –(aq)
Kc = [Ag+] [Cl - ] = 1.7 X 10 -10
►The value of Kc indicates the insolubility of AgCl in water.
►If Kc > 1 , this indicates that [C]R < [C]P which means that the
reaction proceeds almost to its end. This means that the forward
reaction is the predominant reaction.
Ex:
H2 (g) + Cl2 (g) 2HCl (g)

55
Chapter two Chemical Equilibrium

K c = 4.4 X 10 32

► If Kc = 1, this means that [C]P = [C]R therefore an equilibrium state

is reached.
► Concentration of water, solid substances, and precipitates should
not appear in the equilibrium constant equation; because their
concentrations remain constant whatever their quantities.
► The concentration of water or solvent is considered as a constant
because it is not varied in the reaction.

3) Temperature of the reaction:

 Collision theory:
"The theory assumes that: to have a chemical reaction,
molecules of the reactants must collide with each other."
(Rate of the chemical reaction α Temperature)

 Give reasons:
 Only molecules of very high velocity can react.
- Because their kinetic energy is high enough to break the bonds
within the molecules so that the chemical reaction can take place.
Therefore, the molecule must have a minimum amount of energy to
react during collision.

 Remember:
 Activation Energy:
- It is the minimum amount (quantity) of energy that must be gained by
the molecule to react at collision.
 Activated molecule:

56
Chapter two Chemical Equilibrium

- It is the molecule which has kinetic energy that equals or exceeds

the activation energy.
The rate of the reaction is directly proportional to any rise in
temperature. [The rate of chemical reaction is double
(approximately) if the temperature is raised by 10 oC]
Activation energy in the absence of catalyst is greater than the
activation energy in the presence of catalyst.

 Applications:
 Give reasons:
 In summer, food spoils quickly if it is left in the air.
- Due to the rise in temperature, which speeds up the decomposition
reaction in food.
 Pressure cookers (Presto) are used in cooking.
- To obtain a high temperature to speed the reactions required for
cooking food in short time.

► Experiment to illustrate the effect of temperature on a

reaction at equilibrium:
Cooling
2NO2 N2O4 + Heat
Reddish brown Heating Colourless

57
Chapter two Chemical Equilibrium

 On cooling a flask containing nitrogen dioxide, the reddish brown

colour of the gas will gradually decrease until it disappears completely.
 While if the flask is removed from this cooling mixture and returned to
room temperature, the reddish brown colour starts to reappear
gradually.
 Conclusion:
- If an exothermic reaction at equilibrium cooled, the reaction
goes in the forward direction in order to liberate heat.
- The rate of the reaction is directly proportional to any rise in
temperature.

4) Pressure:

Remember:
 In the solution, we express the concentration of a substance by using
the term Molarity, & the degree of concentration is expressed by
putting the substances in between these brackets [ ].
 If the reactants & products are in the gaseous state, their
concentration is expressed by using the partial pressure.

►Example:
N2 + 3H2 2NH3 = -92KJ
High pressure Low pressure

4 molecules 2 molecules
 In the previous reaction, 4 molecules react to form 2 molecules i.e. the
formation of ammonia is accompanied by decrease in the number of
molecules & consequently a decrease in the volume.
 By increasing the pressure, the rate of the formation of ammonia
increases.
 By increasing the pressure on a gaseous reaction at equilibrium, a shift in
the direction of reducing the pressure (or in the direction in which the
volume is less) takes place.
 The pressure constant Kp indicates the concentration of the substances
which can be expressed by partial pressure.

58
Chapter two Chemical Equilibrium

 The pressure constant can be expressed also in molar concentration.

►Example:
Calculate the pressure constant Kp of the following reaction:

N2(g)+2O2(g) 2NO2(g)
Where NO2=2 atmospheric pressure, O2=1 atmospheric pressure,
N2=2 atomic pressure.
 Solution:

- Therefore the pressure constant = 20

5) Catalysts:

Definitions:
 They are the substances that cause a change in the rate of the
chemical reaction without itself being changed.

 They are the chemical substances that accelerate the rate of the
reaction without affecting the reactants, the product or itself.

 The catalyst decreases the activation energy required for the reaction
as it accelerate the forward and backward reactions.
 Catalysts are used in industry instead of heating as heating is very
expensive & results in an increase in the cost of the products due to the
additional cost of the fuel used for heating.
 Catalysts are used in more than 90% of the industrial processes such as
petrochemical industries and food.

59
Chapter two Chemical Equilibrium

 Catalysts are also used in catalytic converters utilities in modern cars

to convert the gaseous combustion products which causes air pollution
into safe products.

 Catalysts are metals, metal oxides or compounds.

 Enzymes:
- They are high molecular weight proteins produced in living cells.
- Enzymes act as catalysts for many biological and industrial
processes.
 The rate of the reaction increases in the presence of a catalyst.

Graph S. p.10 (opp.)

6) Light:

Some chemical reactions are affected by light.

60
Chapter two Chemical Equilibrium

 Photosynthesis process is affected with light as chlorophyll in plants

absorbs light and form carbohydrates in the presence of carbon dioxide
and water.
Photographic films contain silver bromide in a gelatinous layer, when light
falls on the film, silver ion accept electrons from bromide ions and are
converted into silver metal; bromine is absorbed in the gelatinous layer.
-The increase in light intensity is associated with an increase in the
amount of silver formed. Ag+ + e - → Ag

Ionic Equilibrium
 It is the equilibrium between the molecules of a weak electrolyte &
its ions.
Applications of the law of mass action in ionic equilibrium
►Electrolytic Solutions:
 Classification of electrolytic solutions according to ionization in water:
Non-electrolytic substances Electrolytic substances
- These are the substances which -These are substances which ionize when dissolved in water.
do not ionize when dissolved in -They conduct electricity.
water. -They are divided in to 2 types:
- They do not conduct electricity.
- Ex: covalent compounds [such as: Strong electrolytes Weak electrolytes
sugar & starch] - They undergo complete - They undergo incomplete
ionization. ionization.
- All unionized molecules - They ionize partially.
are changed in to ions.
- Ex: strong acids, strong
alkalis & salts. - Ex: weak acids & weak alkalis.
 HCl → H+ + Cl-  CH3COOH  CH3COO- + H+
 H2SO4 → 2H++ SO4-2  NH4OH  NH4+ + OH-
 NaCl → Na+ + Cl-  H2CO3  2H+ + CO3-2
 NaOH → Na+ + OH-

 Remember:
 Ionic compounds:

61
Chapter two Chemical Equilibrium

- They are the compounds whose +ve & -ve ions are attracted to each
other by electrostatic attraction forces.
- They are substances which when dissolved in water +ve & -ve ions
are liberated from their crystal structure & their solutions conduct
electricity.
 Covalent compounds:
- They are the compounds in which the bonds between their atoms
are covalent.
Ex: HCl & pure ethanoic acid
- Both HCl & pure ethanoic acid are ionized in water but with
different degrees:
 Hydrogen chloride gas is ionized in nearly 100 %.
 Ethanoic acid undergoes ionization at much less extent.

 Experiment (1):
1. Test the electrical conductivity of
pure ethanoic acid, and of hydrogen
chloride gas dissolved in benzene.
2. The lamp will not light in both
cases, which indicates that neither
of the two liquids contains ions,
which conduct the electric current.

 Experiment (2):
1 1
1. Dissolve 10 mole of HCl gas in one liter of water & 10 mole of pure acetic
acid in water to make 2 solutions of equal concentration of acids.
2. Test the electrical conductivity of each solution.
3. In case of HCl, the lamp gives a strong illumination, while it gives
a faint illumination with acetic acid.
4. This indicates that the first solution contains a large number of ions,
while the second does not.

62
Chapter two Chemical Equilibrium

 Experiment (3):
1. Test the action of dilution over HCl and CH3COOH solution and its effect
on the conductivity of electric current (strength of illumination of the
lamp).
2. Dilute each to 0.01molar then test the electrical conductivity.
3. Dilute each to 0.001molar then test it again.
4. The illumination of the lamp is not affected in case of the dilution of
hydrochloric acid, but illumination increases in case of the dilution of
acetic acid.
 Conclusion:
 Covalent compounds such as dry hydrogen chloride and pure
ethanoic acid ionize in water.
 Ionization of hydrogen chloride is complete but that of ethanoic
acid is very limited.
 Therefore, the acidic solution of HCl is a good conductor of
electricity, where as ethanoic acid solution is a bad conductor.
 Also the extent of ionization of hydrochloric acid is not affected by
dilution.
 But the extent of ionization of ethanoic acid increases by dilution
indicating the presence of more ionized molecules of the acid.
HCl → H+ + Cl–
CH3COOH H+ + CH3COO –

Hydroxonium ion:
 Give reasons:
 On ionization of acids in aqueous solutions, no free hydrogen
ions (protons) are found.
- Because the hydrogen is attracted to the lone pair of electrons on
the oxygen atom by a coordinate bond forming the hydroxonium
ion (or hydrated proton).
[HCl + H2O → H3O + + Cl – ]

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Chapter two Chemical Equilibrium

 Definitions:
 Ionization:
- A process in which unionized molecules are changed into ions.

 Complete Ionization: (Irreversible reaction)

- A process in which all unionized molecules are changed into ions.
(Occurs in strong electrolytes)

 Incomplete (weak) Ionization: (Reversible reaction)

- A process in which a small ratio of unionized molecules are
changed into ions. (Occurs in weak electrolytes)

 Ionic equilibrium:
- Equilibrium arising between the molecules of weak electrolyte
and the ions resulting from it.
Weak electrolyte  Dissociated ions
AB  A + + B-

Remember:
 The law of mass action can be applied only in the case of solution
of weak electrolytes.
 Strong electrolytes do not contain undissociated molecules since
they are completely ionized.
 Dilution by water increases the ionization of weak electrolyte.
 Dilution with water has no effect on ionization of strong
electrolyte.
Ostwald law
 Ostwald managed to find the relation between the extent of
ionization – alpha (α) and concentration (C) in mole/liter

64
Chapter two Chemical Equilibrium

 A monoprotic weak acid (HA) dissociates in water according to the

equation: 1 mole  mole +  mole
Where: = degree of ionization
HA H+ + A –
1 mole -- --
1-α α α

- By applying the law of mass action:

Where: [H+] [A-] [HA] = the concentrations of the produced ions and
the undissociated acid molecules at the equilibrium state.
Ka = the ionization or dissociation constant of the acid.

- When one mole of the weak acid (HA) dissolves in (V) litre of the
solution, then at equilibrium.

- If the number of the dissociated moles is α mole, then the

number of undissociated mole from HA= (1-) and the
number of moles of H+ and A- produced =  mole
HA H+ + A –
 
- After dissociation number of moles:  

- Therefore the concentration of the substance (mole/litre) at

equilibrium is: HA H+ + A –

Conc. of Conc.
Concentration of H+ of A-
undissociated ions

- By substitution in the equation of mass action given:

65
Chapter two Chemical Equilibrium

 Ostwald's Law for dilution:

- It is the relation between degree of ionization and the degree of
dilution.
- This relation is known as Ostwald's Law for dilution which
illustrate the quantitative relationship between the degree of
ionization ( and dilution.
Remember:

The degree of dilution is directly proportional with the degree of
ionization.
 At a constant temperature, the degree of ionization () increases by
dilution. ( so the Ka value remains constant)
 The ionization of the weak acid increases when its dilution increases.
(concentration decrease)
 In case of weak electrolytes, the degree of ionization () is small
enough and can be neglected.
- Consequently the value (1-) is considered approximately one
HA H+ + A –
Very low value that
could be neglected

Very weak  Ka . V =  2
electrolyte
- Therefore, the volume (V) is directly proportional with  2

- Since the concentration of weak acid mole/liter

- Therefore, 2 is inversely proportional with concentration.

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Chapter two Chemical Equilibrium

-This means that increasing dilution (decreasing concentration)

causes an increase in dissociation degree and vice versa .

 Example 1:
Calculate the concentration of hydrogen ion in 0.1 molar hydrocyanic
acid (HCN) solution at 25oC, providing that the equilibrium constant
of the acid Ka=7.2X10-10

 Solution:

HCN + H2O H3O+ + CN –

Applying Ostwald Law:
Ka =  2 X C
7.2 X 10-10 =  2 X 0.1

∴ The concentration of hydrogen ion = 8.5 X 10 -5X 0.1

= 8.5 X 10 -5 X 0.1 = 8.5 X 10 6 mole / litre

 Example 2:
Arrange the following acids in an ascending order according to their
strength if the ionization constants of the acids are:
Hydrofluoric acid (HF) → Ka = 6.7 x 10-4
Hydrocyanic acid (HCN) → Ka = 7.2 x 10-10
Nitrous acid (HNO2) → Ka = 5.1 x 10-4

 Solution:
As the ionization constant of the acid increases, the concentration of H+
increases & the strength of the acid also increase.
HCN < HNO2 < HF

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Chapter two Chemical Equilibrium

Remember:
A monoprotic weak acid (HA) Degree of ionization
A diprotic weak acid is (H2 A)
 Number of
moles dissociated

Concentration of
ions in 1 liter

Calculation of hydroxonium ion concentration of weak acids:

 When a weak acid such as acetic acid with a concentration (c) dissociate
in water according to the equation
CH3COOH + H2O CH3COO - + H3O+
[1-
 The dissociation constant for such reaction

∴ [H3O+] = [ CH3COO -]

∴ The equilibrium constant is:

 Since the acid is weak, the amount dissociated () is small and can
be neglected so (C-) = (C)

Concentration of H3O+ for strong monoprotic acid as HCl

= Concentration of original acid

 Example:

68
Chapter two Chemical Equilibrium

Calculate the hydrogen ion concentration in 0.1 molar acetic acid

solution at 25oC, provided that the equilibrium constant of the acid is
1.8 X 10 -5.
 Solution:

Calculation of the concentration of hydroxyl ion of weak

bases:
Weak bases: partially dissociated bases in aqueous solutions.
The concentration of hydroxyl ion can be calculated in a similar way to that
used for hydroxonium ion.

 Example:
NH3 + H2O NH4+ + OH –

This equation reveals that one mole of both NH4+ and OH- ions is formed.

 Since the dissociation constant of ammonia is small, a small portion of

ammonia dissociates and at equilibrium , the concentration of the
remaining ammonia [NH3] equals the original concentration of ammonia
(Cb).

Concentration of OH- for strong monohydroxy base as NaOH

= Concentration of original base
 Example 1:
 Calculate the equilibrium constant for ammonium hydroxide, if the
concentration of hydroxyl ion (degree of dissociation [α]) = 1.342 x 10-3
molar in a solution 0.1 molar.

69
Chapter two Chemical Equilibrium

 Solution:
NH3 + H2O  NH4+ + OH-

Kb = = 1.8 x 10-5
Concentration of [NH4+] = concentration of [OH-]

Kb =
Ammonia is a weak base & the dissociation constant is small, a small
portion of ammonia is dissociated.
At equilibrium, the concentration of the remaining ammonia equals
the original concentration of ammonia (Cb)

Kb =

[OH-] =

 Example 2:
Calculate the equilibrium constant for ammonium hydroxide, if the
concentration of hydroxyl ion (degree of dissociation [α]) = 1.342x10-3 molar
in a solution 0.1 molar.
 Solution:
NH3 + H2O  NH4+ + OH-

Kb = = = =18x10-6
 Ionization of water:
 Pure water is a very poor conductor of electricity, but some conductivity
is detected. (Water is a poor electrolyte).

2H2O H3O + + OH – H2O H + + OH –

 The equilibrium constant is expressed by the relation:

Product of the concentration of products = 10 -14

70
 Chapter two Chemical Equilibrium

Concentration of reactants

 It is clear from the equilibrium constant that a very small number of

water molecules ionize.
 The number of unionized water molecules can be considered as constant
value [H2O]. Therefore:
Kw [H2O] = [H +] [OH – ]=10 -14
Where, Kw [H2O] has a constant value.
 This product is called the ionic product of water (Kw)
Kw = [H +] [OH – ] = 10 –14

 Give reasons:
 Water is neutral. [water has no effect on litmus]
- Because the concentration of H + ions (which is responsible for the acidic
properties) = the concentration of OH – ions (which is responsible for the
basic properties).
- {Kw = [10 –7][10 –7
] = 10 –14 }

 Ionic product of water: (Kw)

-It is the resultant of multiplying the concentration of hydrogen [H +] times
that of hydroxyl ion [OH – ]. It equals 10 –14 mole/liter.
- If the concentration of hydrogen ion increases, the concentration of the
hydroxyl ion will decrease with the same amount.
 The hydrogen exponent: (pH value)
 Definition:
- It is the negative logarithm of hydrogen ion concentration:
pH = - log [H+] pH = - log [H3O+]

Or:
- The value, which measures the acidity or the alkalinity of the
solution. (by positive value ranging from zero to 14)

71
Chapter two Chemical Equilibrium

 This is a way for expressing the degree of acidity or alkalinity for

aqueous solution.
Kw = [H+] [OH-] = 10-14
Using – log for the previous equation;
-log Kw = - log [H+] – log [OH-] = - log 10 -14

 Since p means (- log), so by substitution;

pH Kw = pH + pOH = 14
pH Kw = 7 + 7 = 14

Remember:
 Acidic solution pH < 7
 Neutral solution pH = 7
 Basic solution pH > 7

►pH scale:

Zero 7 14
Acidity increase neutral Alkalinity increase

Hydrolysis of salt solution:

 Hydrolysis:
-It is the reaction between salt and water to produce acid and base.

 Neutralization:
-It is the reaction between acid and base to produce salt and water.

 Examples for some electrolytes:

Weak electrolyte Strong electrolyte
- NH4OH - HCl
- NH4NO3 - KCl
- CH3COOH - NaCl
- H2CO3 - HNO3
- H2SO4

72
Chapter two Chemical Equilibrium

- KOH
- NaOH

 Effect of salt solutions on litmus:

Salt produced from the reaction of Effect of the salt on litmus
Strong Acid + Strong base Neutral
Weak Acid + Weak base Neutral
Strong Acid + Weak base Acidic
Weak Acid + Strong base Basic

 Experiment:
1. Place 4 different salt solutions in 4 test tubes.
2. Test each solution in a tube with litmus paper.
Experiment Observation Conclusion
1. Action of Na2CO3 solution Turns litmus blue. Alkaline solution
2. Action of NH4Cl solution Turns litmus red. Acidic solution
3. Action of CH3COONH4 No action on litmus Neutral solution
4. Action of NaCl solution No action on litmus Neutral solution

 Give reasons:
 Sodium carbonate [Na2CO3] solution has an alkaline effect on
litmus.

- Because:
1- Sodium carbonate [Na2CO3] is a salt from a weak acid & strong
base.
2- It is hydrolyzed as follows:
2H2O 2H + + 2OH –
Na2CO3 CO3 –2 + 2Na+
Na2CO3 + 2H2O H2CO3 + 2Na+ + 2OH –

73
Chapter two Chemical Equilibrium

 In the previous reaction H 2CO3 , Na+ and OH –

ions are
formed.

NaOH is not formed H2CO3 is formed

- Because it is a strong - Due to the reaction between
electrolyte, which is hydrogen ions (formed from
completely ionized. ionization of water) and
carbonate ions. (H2CO3 is a
weak electrolyte)

 According to Le Chatlier's principle, other water molecules ionize to

compensate the decrease in hydrogen ions. Therefore, the OH- ion
concentration increase and the solution becomes basic PH > 7.

 Give reasons:
 Ammonium chloride [NH4Cl] solution has an acidic effect on
litmus.

- Because:
1- Ammonium chloride [NH4Cl] is a salt from a strong acid & weak
base.
2- It is hydrolyzed as follows:

H2O H + + OH –
NH4Cl Cl – + NH4 +
NH4Cl + H2O H + + Cl – + NH4OH

HCl is not formed NH4OH is formed

- Because it is a strong - Due to the reaction between
electrolyte, which is hydrogen ions (formed from
completely ionized & can ionization of water) and
not recombine again. chloride ions. (NH4OH is a
weak electrolyte)

74
Chapter two Chemical Equilibrium

- According to Le Chatlier's principle, other water molecules ionize to

compensate the decrease in hydroxyl ions. Therefore, the hydrogen
ion concentration increases and the solution becomes acidic PH < 7.

 Give reasons:
 Ammonium acetate [CH3COONH4] solution has a neutral effect
on litmus.
- Because:
- 1- Ammonium acetate [CH3COONH4] is a salt from a weak acid &
weak base.
- 2- It is hydrolyzed as follows:
H2O H + + OH –

CH3COONH4 CH3COO – + NH4 +

CH3COONH4 + H2O CH3COOH + NH4OH

- Both CH3COOH & NH4OH are formed, as they are weak electrolytes.

- The concentration of the hydrogen ions formed from ionization of the

weak acid (CH3COOH) is very small & equals the concentration of
hydroxyl ions formed by the ionization of the weak alkali.

- Thus the solution is neutral PH = 7.

 Sodium chloride [NaCl] solution has a neutral effect on

litmus.
- Because:
1- Sodium chloride [NaCl] is a salt from a strong acid & strong base.
2- It is hydrolyzed as follows:
H2O H + + OH –

NaCl Cl – + Na +
Solid(aq.) (aq.)
75
Chapter two Chemical Equilibrium

NaCl + H2O H + + OH – + Na + + Cl –
 Both HCl & NaOH are strong electrolytes, which are completely
ionized.
 Thus H+ ions and OH – ions resulting from the ionization of water
remains as they are, thus the solution of NaCl is neutral PH = 7.
Solubility product:
 When a solute is added to a certain quantity of suitable solvent, at
specific temperature, the solute dissolves.
 If further solute is added , it also dissolves but this dissolution process
does not proceed to endless.
 We reach to a state where the solution is saturated with the solute and
the solution becomes unable to dissolve more solute in its constant
volume and temperature.
 Any solute added at this stage will precipitate in the solution.
 A dynamic equilibrium state between the solid substance (solute) and
solution (solvent) is established, where the rate of dissolution equals the
rate of precipitation and the concentration of the solution remains
constant
 In this case the law of mass action can be applied:
- The dissolution of the sparingly soluble lead bromide in water is given
by relation:
PbBr2(aq)  Pb2+(aq) + 2Br—(aq)
- Therefore, the equilibrium constant is given by the relation:

- Since that, the solid PbBr2 concentration remains almost constant

76
Chapter two Chemical Equilibrium

Ksp=[Pb2+][Br--]2
Where, Ksp is known as solubility product constant.

Remember:
 Solubility product for any sparingly soluble ionic compound is
the product of multiplication of the concentration (expressed as
mole/litre) of its ions, raised to the power of the number of ions,
which exist in equilibrium with its saturated solution.

 Example:
-5
If the degree of solubility of AgCl is 10 mole/litre. Calculate the
solubility product of AgCl
 Solution:
AgCl(S)  Ag+(aq) + Cl—(aq)
Ksp=[Ag+][Cl--]
Ksp=10 -5 X 10 -5 = 10 -10
 Remember:
 = [C] , When volume = 1liter.
 IF volume 1, means number of mole.
 ( ) cannot to be ignored If its percentage is more
than 10 %.
 Concentration of ions = no. of ions X degree of
solubility

77
Chapter two Chemical Equilibrium

Answered problems

 Example 1:
At 4000C , 2HI → H2 + I2 . The [HI] = 0.22 mole/liter
[H2] = 0.001 , [I2] = 0.023 . Calculate the equilibrium constant.
 Solution:
2HI  H2 + I2

KC = = = 4.75 X 10-4

 Example 2:
Calculate the equilibrium constant with Haber’s method if the
pressure of ammonia = 1.5 atmospheric pressure & the pressure of
hydrogen & nitrogen is double the pressure of ammonia for each.
 Solution:
N2+ 3H2  2NH3

KC = = = =0.02777

 Example 3:
Organic acid its degree of ionization 5% & its concentration is 0.19.
Calculate ionization constant or equilibrium constant.
 Solution:
Ka = C X 2
Ka =0.19X (0.05)2 = 4.75X10-4
Ka = 4.75 X10-4

 Example 4:
Calculate the [H+] in the solution of 0.1 molar of HCN at 250C.
(KC =7.2X10-10). ► N.B:
 Solution:  = [C] , When volume = 1liter.
HCN  H+ + CN –
IF volume 1,
means number of mole.

78
Chapter two Chemical Equilibrium

Ka =

KC =
[H+]2 = 7.2X10-10 X 0.1 =7.2 X10-11
 [H+] =√ 7.2 X 10−11 = 8.485 X 10-6
 Another solution:
HCN  H+ + CN –
(1- ) = 1/10
Ka = C X 2
7.2 X 10-10 = 0.1X 2

2
=
2
=7.2 X 10-9
= √ 7.2 X 10−9 =8.485 X10-5

Concentration:

C= = 8.4X10-6 ,where; Volume= (O.1 = 1/10)

 Example 5:
Calculate the concentration of the acid. Its degree of ionization is
3.72 , Ka = 6.86 X 10-5
 Solution:
2
Ka = C X
-5 2
= C X (3.72) [C] =
6.86 X10

 Example 6:

79
Chapter two Chemical Equilibrium

A weak acid of Ka =1.8 X10-5 ,if the concentration of this acid in 3

solutions is 0.1 , 0.2 , 0.3 . Compare between the degrees of
ionization of the acid & give conclusion.
 Solution:
2
Ka =C ×

= 1.8 × 10 – 5 = 0.1 × 2
, 2
= = 1.8 × 10 –4

–3
= = 1.34 × 10 molar
2
Ka = C ×

–5 2 2 –5
= 1.8 × 10 = 0.2 × , = = 9 × 10
-3
= = 9.4 × 10 molar
2
Ka = C ×

= = 1.8 × 10 – 5 = 0.2× 2
, 2
= = 6×10 –5

= = 7.74 ×10 -3 molar

- Conclusion:
 As concentration decreases , degree of ionization increases.
 As concentration increases , degree of ionization decreases.
 Example 7:
If the degree of ionization of monoprotic acid = 33% in 0.2 molar
solution. Calculate ionization constant. ►N.B:
 Solution:  (Alpha) cannot to be
ignored If it’s percentage
is
Ka= more than 10 %.

-4
Ka= = = 3.2 × 10

80
Chapter two Chemical Equilibrium

 Example 8:
Calculate the pH value of solution its concentration of [OH] is 9X10 -
11
.
 Solution:
pH = - log [H +]
pOH = log [O H]
pOH = - log [9 × 10 -11] = 10.04
pH + pOH = 14
pH = 14 – 10.04 = 3.96
 Example 9:
Calculate the pOH value of acid its concentration is 3X10 -3.
 Solution:
pH = - log [H +]
pH = - log [3 × 10 -3] = 2.5228
pH + pOH = 14
pOH = 14 – 2.5228 = 11.4772

IV- Notes:
►Le Chatelier Principle:
►Concentration:

.‫الناحية التى أزود فيها يسير التفاعل عكسها‬ .1

 Pressure:
** ‫عند زيادة الضغط‬
‫التفاعل يمشى ناحية‬
‫ الـ‬molecules ‫األقل‬
volume ‫دى‬XXX‫و عن‬XXX‫ ل‬
Pressure ‫الزم أحولها‬
5 → 3 By increasing the
‫ فمعنى‬
Decrease = pressure
increase the volume
* ‫ يعتمد على عدد الـ‬molecules
81 in volume decreases
in Pressure
Chapter two Chemical Equilibrium

 Temperature:
* ‫ لو التفاعل‬Endothermic H = + ve
‫ بأضع الحرارة مع الـ‬/ ‫ بييمتص حرارة‬Reactants
Heat + A + B C+D

* ‫ لو التفاعل‬Exothermic H = - ve
‫ بأضع الحرارة مع الـ‬/ ‫بيطلع حرارة‬ Product
A+B C + D + Heat

► In the following reaction, what happen when?

H2 + CO2 H2O + CO ΔH = -30
1- Increase the concentration of CO → The reaction shift backward.
2- Increase the concentration of CO2 → The reaction shift forward.
3- Decrease the concentration of H2 →The reaction shift backward.
4- Increase the temperature → The reaction shift backward.
5- Cooling → The reaction shift forward.
6- Increase the Pressure → No effect. Because 2 = 2

Mg/Na Hydrolysis
Basic
Ca/Ba/K

Cl / Br
* ‫ االثنين معًا مثل‬NaCl ‫ يصبح الـ‬solution (Neutral)
SO4 / PO4 Acid
NO3 / I

82
Chapter two Chemical Equilibrium

Questions on Chapter Seven

I- Give reason:
1)Reaction of hydrochloric acid with magnesium is a complete one while that
of ethyl alcohol & acetic acid is a reversible one.
2)Increasing the pressure leads to increasing the amount of ammonia gas
when prepared from nitrogen & hydrogen.
3)The rate of a chemical reaction increases by increasing the surface area of
reactants.
4)Aqueous solution of sodium carbonate has an alkaline effect on litmus.
5)In the following 2 reactions:
(a) 2NO2  2NO + O2
(b) H2 + I2  2HI
Why in the first reaction the equilibrium state is affected by the change of
the pressure, while in the second one the equilibrium state is not affected by
the change of the pressure.
6)The catalytic factor does not affect the equilibrium state in a reversible
reaction.
7)pH value of pure water = 7.
8)Addition of hydrochloric acid (HCl) to hydrogen sulphide (H2S) leads to
decreasing in sulphide ion (S2-) concentration in the solution.
9)Hydrogen chloride solution conduct the electricity with a higher degree
than the acetic acid solution whatever they have the same concentration.
10) The rate of a chemical reaction increases by increasing the
temperature.
11) Butagas cylinders should not be heated from outside.
12) Covalent compounds react slower than ionic ones.
13) The rate of a chemical reaction increases by increasing the
concentration of reactants.
14) It is preferable to use catalysts than heating to increase the rate of
slow reactions.
15) The color of nitrogen dioxide is removed by cooling while the color
returns back when left in the air.
16) Aqueous solution of ammonium sulphate turns litmus red.
17) Equilibrium state is a dynamic process but not a stationary one.

83
Chapter two Chemical Equilibrium

II- Write down the scientific term:

1)They are solutions which are non-ionized in water & do not conduct the
electric current.
2)At constant temperature, the degree of dissociation (α) increases by
increasing the dilution while the value of dissociation (ionization) constant
does not change.
3) It is a decomposition of the salt when it dissolves in water to form positive
& negative ions which the salt is derived from them.
4)It is the negative logarithm of hydrogen ion concentration.
5)The product of multiplying the concentration of the hydrogen ion (H+) &
hydroxyl ion (OH-) produced from the ionization of water & equals 10-14
mole / liter at 25 oC.
6)A state of equilibrium arising between molecules of a weak electrolyte &
ions resulting from it.
7)Some molecules are changed in to ions, it happens in weak electrolyte.
8)All molecules are changed in to ions, it happens in strong electrolyte.
9)A substance that increases the rate of the reaction without itself being
changed in mass or chemical properties.
10)Changes in any of the conditions of a chemical equilibrium such as
concentration, pressure or temperature will shift the equilibrium in the
direction which will oppose the change.
11)They are solutions which ionize in water & conduct electricity.
12)The minimum amount of energy that must be gained by a molecule to
react at collision.
13)At constant temperature, the rate of the chemical reaction is directly
proportional to the product of reactant concentration.
14)The rate of change in the concentration of reactants per unit time.
15)The multiplication of the concentration of the ions of partial soluble
compound in water estimated by mole / liter which are found in
equilibrium state with its saturated solution.
16)A dynamic state reached when the rate of forward reaction equals the
rate of backward reaction when the concentration of both the reactants &
products are constant & under the same condition of pressure &
temperature.
17)The pressure of water vapor in air at a certain temperature.

84
Chapter two Chemical Equilibrium

18)Reactions proceed in both directions forward & backward since both

reactants & products are constant & under the same condition of
temperature & pressure.
19)The maximum water vapor pressure of water at a certain temperature.
20)The equilibrium system is apparently stationary but in reality it is
dynamic.
21)Reactions proceed in one direction only because the products can not
recombine to form the reactants under the same reaction conditions.

III- Explain the following:

1)Practical experiment shows that the rate of chemical reaction depends on
the surface area of reactants.
2)Water is a weak electrolyte - find its ionic dissociation equation concluding
its equilibrium constant with applying the law of mass action.
3)Activation energy, how does it lead to increasing the rate of chemical
reaction.
4)Ionization & its types with examples.
5)The functions of catalysts in the chemical reaction.

IV- Show by practical experiment each of the following:

1)The effect of increasing reactant surface area on the reaction rate.
2)Dynamic equilibrium state.
3)The effect of concentration on the rate of the reaction.
4)The effect of temperature on an equilibrium reaction.

V- Miscellaneous questions:
1- In which of the following reactions do you expect that percentage of
dissociation increases with decreasing the temperature:
a) NH3 + heat  1/2 N2 + 3/2 H2
b) HI  1/2 H2 + 1/2 I2 + heat
c) H2O + heat  H2 + 1/2 O2
2- In which of the following reactions do you expect that percentage of
dissociation increases with increasing the temperature, giving reason:
a) NO  1/2 N2 + 1/2 O2 + heat
b) N2O4  N2 + 2O2 + heat
c) SO3 + heat  SO2 + 1/2 O2

85
Chapter two Chemical Equilibrium

3- Show by practical experiment that increasing the dilution of a solution

leads to increasing the degree of ionization of weak electrolytes.

4- What are the types of the chemical reactions? Define each of them –
then mention the type of the following chemical reactions, giving reason:
a) 2HCl + Na2CO3 → 2NaCl + H2O + CO2
b) BaCL2 + Na2SO4 → 2NaCl + BaSO4
c) Na2CO3 + K2SO4 → K2CO3 + Na2SO4

5- Arrange the following solutions in ascending order according to its

value of hydrogen exponent knowing that they have the same
concentration:
a) NH4Cl – NaCl – HCl – Na2CO3
b) NaOH – K2SO4 – NH4OH – HCl

6- Mention Le Chatelier's principle then show how this principle is deduced

from preparation of Ammonia in industry.

7- In the following equilibrium chemical reaction:

FeCl3 + 3NH4SCN  Fe(SCN)3 + 3NH4Cl
Red blood color
 What is happen on the concentration of Fe(SCN)3 when we add:
a)An excess amount of ammonium thiocyanate.
b)An excess amount of ammonium chloride.
8- Find the equilibrium constant for the chemical reaction:
FeCl3 +3NH4SCN  Fe(SCN)3 +3NH4Cl
9- Explain why the equilibrium state arises when ammonium sulphate is
hydrolyzed in water.
10- Show the effect of the following factors on the equilibrium of the
following reactions:
a) Adding 0.1 gm of silver: Fe2+(aq) + Ag+(aq) → Fe3+(aq) + Ag(s)
b) Adding copper sulphate solution: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

86
Chapter two Chemical Equilibrium

11- In the following equilibrium reaction:

H2 (g) + CO2(g) → H2O(g) + CO(g) ∆ H = 41 Kj
 Explain what happens when:
a) Increasing pressure
b) Addition of water
c) Addition of carbon dioxide
d) Increasing the temperature
e) Decreasing the vessel size
12- The following reaction is an exothermic reaction:
ZnO(s) + CO(g) → CO2(g) + Zn(s)
(a) Rewrite the equation using ∆ H symbol.
(b) Show the effect of each of the following on the equilibrium of the
reaction which happens in a compressor: (a) Adding CO gas
(b) Adding a piece of zinc
(c) Adding a catalyst (d) Increasing
the temperature
VI- Problems:
1) If the degree of solubility of silver chromate Ag2CrO4 at 32 oC is 7.5 x 10-6
mole / liter. Calculate its Ksp value.
2) Calculate the degree of solubility of barium chromate BaCrO4 given that
the solubility product of barium chromate is 2.3 x10-10.
3) Calculate the hydrogen exponent for a solution with hydrogen ion
concentration equals 4.6 x 10-5 then deduce the hydroxyl exponent of this
solution.
4) Calculate the hydrogen exponent & the hydroxyl exponent for the
following solutions:
a) Sodium hydroxide solution 0.1 molar.
b) Hydrochloric acid solution 0.00001 molar
c) A solution its hydrogen ion concentration equal 3.5 x 10-4 molar
5) The following reaction has 2 values of equilibrium constant at two
different temperatures as follows:
a) At 350 oC H2 + I2 → 2HI Kc = 67
o
b) At 448 C H2 + I2 → 2HI Kc = 50
Are the forward reactions exothermic or endothermic?

87
Chapter two Chemical Equilibrium

6) The following reaction has 2 values of equilibrium constant at two

different temperatures as follows:
At 350 oC N2 + 3H2 → 2NH3 Kc = 1 x 10-2
At 448 oC N2 + 3H2 → 2NH3 Kc = 1.6 x 10-1
Are the forward reactions exothermic or endothermic?

7) Calculate the degree of solubility of silver chloride in one liter of water, if

its solubility product equal 1.78 x 10-10
8) If the degree of solubility of calcium carbonate in water is 0.22
mole/[Link] the solubility product value.
9) Calculate the degree of solubility of barium sulphate [BaSO4] given that,
its solubility product equal 1.6 x 10-5
10) A solution its hydroxyl exponent is 9.8. Find the hydrogen exponent of
this solution.
11) A solution its hydrogen exponent is 5.3. Find the hydroxyl exponent of
this solution.
12) Calculate the degree of ionization in solution of acetic acid 0.02 molar
given that [Ka] of this acid equals 1.85 x 10-5 mole / liter.
13) An organic acid of one proton, its ionization degree is 8% at 19 oC in
solution its concentration 0.023 molar. Calculate the equilibrium constant of
this acid.
14) Arrange the following acids in order of their increasing its strength –
given that; the ionization constant of them are:
a) Ka of carbonic acid = 4.52 x 10-7 mole / liter
b) Ka of hydrofluoric acid = 7.2 x 10-4 mole / liter
c) Ka of formic acid = 1.77 x 10-4 mole / liter
15) At 25 oC the dissociation degree of weak organic acid of one proton is
25% in solution its concentration 0.3 mole / liter. Calculate the ionization
constant of this acid.
16) If the ionization constant of an organic acid of one proton is 2.56 x 10-2 &
the degree of ionization of this acid in its solution is 0.32% .Calculate the
concentration of the solution by mole / liter.

88
Chapter two Chemical Equilibrium

17) In the following equilibrium reaction: PCl3 + Cl2 → PCl5 Kc = 1.15 If

the concentrations of PCl3 , Cl2 respectively are 0.16 – 3.1 mole / liter
respectively. Calculate the concentration of phosphorus penta chloride.
18) Calculate the value of equilibrium constant for the decomposition of
N2O4 to NO2 given that the concentrations for each of them respectively by
mole / liter are: 0.8164 – 0.3672.

19) In the following equilibrium reaction:

CO + H2O → CO2 + H2
If the concentrations for each of them respectively by mole / liter are 0.2 –
2.8 – 0.7 – 0.8.
Calculate the value of equilibrium constant & show the direction of the
reaction.
20) Calculate the value of equilibrium constant for the following reaction:
PCl5 → PCl3 + Cl2
Knowing that the concentrations of phosphorus penta chloride, phosphorus
trichloride & chlorine respectively are 2 mole/ liter, 4.2 mole / liter, 1.5 mole
/ liter.

21) From practical experiments of the following reaction:

AB → A + B
It was possible to obtain the data, which are present in the following table
by mole / liter.
Experiment Concentration (A) Concentration Concentration
(B) (AB)
1 0.6 1.7 1.2
2 2.52 0.3 0.9
3 0.668 2 1.6
Suppose that these results were achieved by the law of mass action, What
is the value of equilibrium constant for this reaction?

22) The following reactions are at equilibrium state:

(a) SO2(g) + 1/2O2(g) → SO3(g) Kc 1 = 2.2

89
Chapter two Chemical Equilibrium

(b) NO2(g) → NO(g) + 1/2O2(g) Kc 2 = 4

1- Write the equilibrium constant for each reaction
2- Calculate the equilibrium constant Kc 3 of the reaction:
SO2(g) + NO2(g) → SO3(g) + NO(g)

Evaluation guide questions

A- Choose from the column (B) what is suitable for column

(A):-
(A) (B)
1) The vapour pressure a) Is apparently a stationary state but in
2) The rate of chemical reality it is dynamic.
reaction b) All unionized molecules are changed into
3) Kp ions, which happens in strong
4) The equilibrium state electrolytes.
5) Complete ionization c) Is a way of expressing the degree of
6) pH value acidity & alkalinity for aqueous solution.
7) Activated molecules d) Is the equilibrium constant expressed by
8) Activation energy the partial pressure of gases.
9) Ionic product of water e) Is the pressure due to water vapour in air
at a certain temperature.
f) Is the change in concentration of
reactants per unit time.
g) Are those molecules which have kinetic
energy that equals or exceeds the
activation energy.
h) Is the product of multiplication of the
concentration (expressed as mole/liter) of
its ions, which exist in equilibrium with
its saturated solution.
i) Is the minimum amount of energy that
must be gained by a molecule to react at
collision.
j) Is the resultant of multiplying the
concentration of hydrogen ion times that
of hydroxyl ion & it equals 10-14

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Chapter two Chemical Equilibrium

mole/liter.

B- Choose the correct answer:-

1. 3During the reversible reaction, the graph between the concentration & time
indicates …..
a) The concentration of the reactants decreases until it is completely
consumed
b) The concentration of the products increases & the concentration of
the reactants until they reach the equilibrium
c) The concentration of both the reactants & the products increase until
they reach equilibrium
d) There is no change in the concentration of both of the reactants & the
products since the beginning of the reaction
2. Some reactions occur instantaneously such as ……….
a) The reaction of acetic acid & ethanol to produce ethyl acetate ester &
water
b) Insertion of a strip of magnesium metal in hydrochloric acid solution
c) The reaction of silver nitrate solution & sodium chloride solution
d) b & c
3. Some reactions are slow such as ……….
a) The reaction of AgNO3 solution with NaCl solution
b) The reaction of oil & NaOH to produce soap & glycerol
c) Insertion of a strip of magnesium metal in hydrochloric acid solution
d) The reaction of NaOH solution with hydrochloric acid solution
4. If the value of the equilibrium constant is less than one, this means that
………..
a) The reaction is reversible
b) The concentration of the products are less than the concentration of
the reactants
c) The reaction is complete & instantaneous
d) a & b
5. If the value of the equilibrium constant is high, this means that ………….
a) The reaction proceeds almost to its end
b) The concentration of the reactants is larger than the concentration of
the products
c) The concentration of the products is larger than the concentration of
the reactants
d) a & c
6. The increase of temperature increases the rate of the reaction as it ………….

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Chapter two Chemical Equilibrium

a) Increases the proportion of activated molecules

b) The kinetic energy of the activated molecules is high enough to break
the bonds within the molecules
c) Supply the energy needed for endothermic reactions
d) All the previous

7. The increase of pressure increases the rate of the reactions which are
characterized by ………
a) Both the reactants & products of the reaction are in the gas phase
b) The reaction is accompanied by a reduction in the volume of the
produced gas
c) The reaction is reversible
d) All the previous
8. The catalyst is a substance that …………..
a) Increases the rate of the slow chemical reactions
b) Save much of the heat energy needed to enhance the reaction
c) Does not affect the position of equilibrium
d) All the previous
9. Strong electrolytic solutions are characterized by ………….
a) Contain completely ionized substances
b) The dissolved substances are ionized instantaneously & conducts the
electric current
c) The dissolved substances ionize slowly & are bad conductors of the
electric current
d) a & b
10. The solution of hydrogen chloride gas in benzene ……………
a) Contains ions & illuminates the lamp which is connected to 2 poles
dipped in the solution
b) Does not contain ions & does not illuminate the lamp
c) The chemical bond between the hydrogen atom & chlorine atom in
gaseous HCl is ionic
d) a & c
11. The solution of pure acetic acid in water …………….
a) Contains ions & illuminate the lamp which is connected to 2 poles
dipped in the solution
b) Does not contain ions & does not illuminate the lamp
c) Contain ions that increase in number on dilution with water
d) a & c
12. …………… is acidic solution.

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Chapter two Chemical Equilibrium

a) Pure water b) Sea water c) Vinegar d) Ammonia solution

13. …………… is alkaline solution.
a) Pure water b) Magnesia emulsion c) NaOH solution d) b & c

14. the ionization constants, Ka of sulphurous acid H2SO3, hydrofluoric acid HF,
acetic acid CH3COOH & carbonic acid H2CO3 are 1.7x10-2, 6.7x10-4, 1.8x10-5
& 4.4x10-7 respectively. The strength of these weak acids can thus be
arranged as follows …….
a) Sulphurous > hydrofluoric > acetic > carbonic
b) Carbonic > acetic > hydrofluoric > sulphurous
c) Carbonic > hydrofluoric > sulphurous > acetic
d) Hydrofluoric > acetic > sulphurous > carbonic

15. …………… is neutral solution.

a) Pure water b) Sea water c) Orange juice d) Hydrochloric acid
16. Solution of sodium carbonate in water …………….
a) Turns litmus paper red b) Turns litmus blue
c) Has an alkaline effect on litmus d) b & c
17. Solution of sodium chloride in water …………….
a) Turns litmus paper red b) Turns litmus blue
c) Has a neutral effect on litmus d) b & c

18. Hydrolysis of salt solutions …………….

a) Is the reverse reaction of neutralization
b) Occurs when salts are derived from a weak acid & a strong base or
the reverse
c) Occurs for salts derived from a strong acid & a strong base
d) All the previous
19. Given the following reaction at equilibrium: CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)
, An increase in the concentration of O2(g) at constant temperature &
pressure will result in …
a) An increase in the concentration of CH4(g)
b) An increase in the concentration of CO2(g)
c) A decrease in the concentration of CO2(g)
d) A decrease in the concentration of H2O(g)

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Chapter two Chemical Equilibrium

[Link] pH value represents a solution with the lowest OH- ion

concentration?
a) 1 b) 7 c) 10 d) 14
+ - -14
[Link]: Kw = [H ][OH ] = 1x10 at 298 K.
What is the concentration of H+ ion in pure water at 298 K?
a) 1x10-7 mol/liter b) 1x107 mol/liter
c) 1x10-14 mol/liter d) 1x1014 mol/liter
[Link] compound is an electrolyte?
a) C6H12O6, glucose solution b) C6H6, benzene
c) CH3OH, methanol d) CH3COOH, acetic acid

23. The following figure shows a bottle containing ammonia gas dissolved in
water.
NH3 gas
Aqueous NH3
a) Adding excess of water b) Adding excess of ammonia gas
c) Cooling the bottle contents d) Covering the bottle opening
24. The ionization constants (Ka) of four weak acids are shown below. Which Ka
represents the weakest of these acids?
a) Ka = 1.0x10-5 b) Ka = 1.0x10-4
c) Ka = 7.1x10 -3
d) Ka = 1.7x10-2

25. Given the system at equilibrium: AgCl(s)  Ag+(aq) + Cl-(aq) , When 0.1 M HCl is
added to the system, the equilibrium will shift to the …………..
a) Right & the conc. of Ag+(aq) will decrease
b) Right & the concentration of Ag+(aq) will increase
c) Left & the concentration of Ag+(aq) will decrease
d) Left & the concentration of Ag+(aq) will increase
26. Given the following reaction at equilibrium: N2(g) + 3H2(g)  2NH3 (g) + heat ,
Which change would shift the equilibrium to the right?
a) Increase of temperature
b) Increase of the pressure
c) Decrease of the nitrogen gas concentration
d) Decrease of the hydrogen gas concentrations

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Chapter two Chemical Equilibrium

C- Write the scientific reasons for each of the following:-

1. The reaction between acetic acid & ethanol is considered as reversible
reaction.
2. Pressure pans are used in cooking foods.
3. The rate of chemical reaction increases on adding hydrochloric acid to iron
filings while decreases on adding hydrochloric acid to the same mass of iron
but in the form of a block.
4. No free hydrogen ion is present in an aqueous solution of strong acids.
5. The law of mass action cannot be applied in the case of strong electrolyte
solutions.
6. The law of mass action can be applied in the case of weak electrolyte
solutions.
7. Water has neutral effect on litmus.
8. The ionic product of water equals 10-14 mole/liter.
9. Iron III chloride solution has an acidic effect on litmus.
10. Sodium carbonate solution has an alkaline effect on litmus.
11. Sodium chloride solution has a neutral effect on litmus.
12. The amount of ammonia prepared from the reaction between nitrogen &
hydrogen increases as the pressure increases.

D- By using balanced chemical equations explain what happens

in each of the following cases:-
1. Addition of excess iron III chloride solution to ammonium thiocyanate
solution.
2. Putting a closed flask filled with reddish brown nitrogen dioxide gas in
cooling mixture.
E- Answer the following:-
1. An equilibrium constant expression is only valid if the reaction is balanced.
Balance the following equation, and then write the equilibrium constant
expression for the balanced equation.
HCl + O2  Cl2 + H2O

2. A value of Keq should include proper units such as mole/liter or liter/mole so

that further calculations using Keq will have the correct units. Calculate the
value of the equilibrium constant for the following reversible reaction. N 2(g) +
3H2(g)  2NH3(g)

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Chapter two Chemical Equilibrium

The concentrations of the equilibrants (reactants & products) at

equilibrium at 400 oC are as follows: N2(g) = 1.2 mole/liter , H2(g) = 0.80
mole/liter , NH3(g) = 0.28 mole/liter

3. Write the equilibrium constant expression for the following reversible

reaction:
CuO(s) + H2(g)  Cu(s) + H2O(g) [Note that H2O is a vapour that behaves as
a gas not a liquid in this reaction]

4. A forward endothermic reaction can be written to show heat as a

requirement on the reactant side. The following forward reaction is
endothermic. Which equation is correctly written?
a)Heat + CaCO3(s)  CaO(s) + CO2(g)
b) CaCO3(s)  CaO(s) + CO2(g) + heat
5. In the previous question, if the temperature is raised, indicate whether
the concentration of the following reactant & products increases or
decreases.
a) CaCO3 b) CaO c) CO 2
6. In the following reaction: PCl5(g)  PCl3(g) + Cl2(g)
a. how many moles of gas are on the reactant side of this reaction?
b. How many moles of gas are on the product side of the reaction?
c. Which side of the reaction would be favoured by an increase in
pressure?
d. Which side of the reaction would be favoured by a decrease in
pressure?

7. For the following reversible reaction, increasing the pressure will favour
which side of the reaction? H2(g) + I2(g)  2HI(g)

8. The reversible reaction below is presently at equilibrium:

2CO(g) + O2(g)  2CO2(g) + heat, In order to increase the concentration of the
produced
CO2 gas, indicate whether you would increase or decrease the following
conditions:
a) pressure b) temperature c) concentration of O 2
gas

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Chapter two Chemical Equilibrium

9. Write the equilibrium constant expression for the solubility product of the
very slightly soluble salt AgBr. AgBr(s)  Ag+(aq) + Br-(aq)
10. The solubility product equation represents the dynamic equilibrium
between a solid & its dissociated ions in a saturated solution. Bi 2S3(s)  2Bi3+
(aq) + 3S (aq)
2-

Write the solubility product expression for the saturated aqueous solution of
Bi2S3.
11. Solid barium sulphate is shaken in contact with pure water at 25 oC for
several days. Each day a sample is withdrawn & analyzed for its barium
concentration. After several days, the value of [Ba2+] was constant, indicating
that the equilibrium:
BaSO4(s)  Ba2+(aq) + SO42-(aq) has been reached. The concentration of Ba2+ is:
1.04x10-5 mole/liter. Calculate Ksp for BaSO4
F- Solve the following problems:-
1) Find the pH value of the following solutions, their [H +] are:
a) 10-5 b) 10-12 c) 10-7
And indicate whether each of these solutions is acidic, alkaline or
neutral.
2) The following equation indicates the ionization of acetic acid, a weak
acid, its concentration C = 0.5 M in its aqueous solution.
CH3COOH(aq) + H2O(l)  H3O+(Aq) + CH3COO-(Aq)
(1-α) C αC αC
α is the degree of ionization of the acid – if the ionization constant of the
acid, Ka = 1.8x10-5, Find:
a) the degree of ionization of the acid
b) the concentration of the hydroxonium ion in the acid solution
c) the pH of the acid solution

3) The following equation indicates the ionization of a weak base,

ammonium hydroxide, its concentration C= 0.1 M.
NH4OH(aq)  NH4+(Aq) + OH-(Aq)
(1-α) C αC αC
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Chapter two Chemical Equilibrium

α is the degree of ionization of the acid – if the ionization constant of

the acid, Kb = 1.6x10-5, Find:
a) the degree of ionization of the base
b) the concentration of the hydroxyl ion in the alkaline solution
c) the pOH of the acid solution
d) the pH of the acid solution
4) The degree of solubility of aluminium hydroxide is 10-6 mole/liter.
Calculate the solubility product of Al(OH)3.

5) Calculate the equilibrium constant Kp for the reaction:

N2(g) + 3H2(g)  2NH3(g), H=-92 KJ , the pressure of the gases are: 2.3
atmosphere for N2, 7.1 atmosphere for H2 & 0.6 atmosphere for NH3.
Comment on the value of Kp & how could the product of the reaction be
increased? & why?

6) The Ksp for CaF2 is 3.9x10-11. What is the solubility of CaF2 in water in
grams per liter
7) The equilibrium constant expression for the reversible reaction:

H2(g) + I2(g)  2HI(g), is Keq =

At 458 oC, the equilibrium mixture consists of:
[HI] = 1.5x10-2 mole/liter, [H2] = 4.6x10-3 mole/liter, [I2] = 1.0x10-3
mole/liter
a)Calculate the value of K at 458 C.
eq
o

b) If you were to repeat the previous reaction using three times as

much starting materials (H2 & I2) but kept the temperature at
458oC. What would be the value of Keq?
c) After determining the equilibrium constant of a reaction
experimentally, it is used for predicting the amount of products at
equilibrium or the amount of reactants needed for another
preparation of the same reaction at the same temperature.
Determine [HI], the concentration of hydrogen iodide at

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Chapter two Chemical Equilibrium

equilibrium if: [H2] = 1.24x10-2 mole/liter, [I2] = 2.46x10-2

mole/liter
d) Using the value of Keq determined from part (a) & noting that
the reaction was also carried at 458 oC
General Secondary certificate examinations

 Write down the scientific term:

1) The minimum amount of energy that must be gained by a molecule to
react at collision. [1st
session 2005 - 2009]
2) Molecules which have kinetic energy that equals or exceeds the activation
energy.
[2nd session
2006]
3) The change in the concentration of reactants per unit time. [2nd
session 2007]

 Compare between:
1) Chemical equilibrium & ionic equilibrium. [2nd session 2005 – 1st
session 2006]
2) Reversible reaction & irreversible reaction.[2nd session 2008 – 1st
session 2009]
 Choose the correct answer:
 One of the following salt solutions turns litmus blue: [1st
session 2008]
a) Potassium sulphate b) Ammonium acetate
c) Iron III nitrate d) Sodium acetate

 Explain the role of each of the following:

 Le Chatlier in explaining the scientific bases. [1st
session 2008]

 What’s meant by?

99
Chapter two Chemical Equilibrium

 Ionic equilibrium [2nd session

2008]

 Give reason:
 The ionic product of water Kw = [10-7][10-7] = 10-14. [2nd
session 2006]

 Explain the effect of the concentration of the reactants on the

rate of the chemical reaction. [1st session
2007]
 What are the factors affecting the rate of chemical reaction?
[2nd session 2008]
 Problems:
1) The following reaction has reached the equilibrium state:
H2(g) + CO2(g)  H2O(g) + CO(g), H=41.1 KJ , What is the action of each of
the following changes on the concentration of hydrogen gas? [1st
session 2005]
a- Adding excess of carbon dioxide.
b- raising the temperature.
2) Calculate the equilibrium constant (Keq) of the reaction:
N2(g) + 2O2(g)  2NO2(g)
Provided that the atmospheric pressures are 2, 1 & 0.2 for the gases
NO2, O2, N2 respectively.
[2nd session 2006]
3) In the reaction: PCl5(g)  PCl3(g) + Cl2(g) , What is the number of moles of
the reactant gas? Which side of the equation (products or reactants) will
increase by increasing the pressure?
[1st session 2007]
4) Calculate the solubility product of silver chloride (AgCl),
if the degree of solubility is 10-5 mole/liter. [2nd
session 2007]
Calculate the degree of dissociation in 0.1 molar hydrocyanic acid (HCN)
solution at 25 oC. Providing that the equilibrium constant of the acid Ka=
7.2x10-10 [1st session 2008]
5) If the equilibrium constant for the following reaction is 15.75 [2nd
session 2008]

100
Chapter two Chemical Equilibrium

Cl2 + PCl3  PCl5

And the concentrations of chlorine & phosphorus trichloride were 0.3 &
0.84 mole/liter respectively. Calculate the concentration of phosphorus
pentachloride.
6) Calculate the concentration of hydroxonium ions (H3O+) in a 0.2 molar
solution of acetic acid at 25oC given that the equilibrium constant of the
acid is 1.8x10-5. [1st session 2009]

101