Introduction
Equilibrium is the most important characteristic property of reversible
reactions. These reactions for which the forward reaction occurs to a much
greater extent are considered to be unidirectional in nature and whenever the
rate of forward reaction is equal to rate of backward reaction, equilibrium is
attained, not to forget that equilibrium exists only in closed system.
It is the state of system at which temperature, pressure, volume and
composition have fixed value and does not vary with time. Chemical
Reactions can be divided into two categories:
1. Irreversible Reactions: The reactions which proceed to completion and
the products fail to recombine to give back reactants. For example
AgNO3 + NaCl ⟶ AgCl + NaNO3
2. Reversible Reactions: The reactions which never go to completion and
products recombine to give back reactants. For example
PCl5(g) ⇌ PCl3(g) + Cl2(g)
N2(g) + 3H2(g) ⇌ 2NH3(g)
Physical Equilibrium
We know that solid, liquid and gas are the three states of substance.
Therefore, three types of physical equilibrium are possible. These are
Solid(s) ⇌ liquid (l)
Liquid(l) ⇌ gas(g)
Solid(s) ⇌ gas(g)
Here the sign double half arrows ( ⇌ ) pointing in the opposite directions is
both for the reversible change as well as for the equilibrium state.
1. Solid(s) – liquid(l) equilibrium: At equilibrium two processes takes place
at the same rate i.e.,
Ice(s) ⇌ water(l)
H2O(s) ⇌ H2O(l)
At equilibrium,
Rate of melting of ice = Rate of freezing of water
The temperature at which the solid and liquid states of a pure substance are
in equilibrium at the atmospheric pressure is called the normal freezing point
or melting point of that substance.
2. Liquid(l) – gas(g) equilibrium:
H2O(l) ⇌ H2O(g)
In such type of equilibrium,
Rate of vaporisation of water = Rate of condensation of water vapour
3. Solid(s) – gas(g) equilibrium: Such type of equilibrium is attained in case
of volatile solids.
Example : If solid iodine is placed in a closed vessel, violet vapours starts
appearing in the vessel. The intensity of violet vapour increases with time and
ultimately it becomes constant.
I2(s) ⇌ I2(g)
In this equilibrium,
Rate of sublimation = Rate of condensation
Read also: Redox Reactions Class 11 Notes Chemistry Chapter 8
Solids in liquids:
Suppose sugar is added continuously into a fixed volume of water at room
temperature and stirred thoroughly with a glass rod. First the sugar will keep
on dissolving but then a stage will come when no more sugar dissolves.
Instead it settles down at the bottom. The solution is now said to be saturated
and in a state of equilibrium. In this state
Rate of dissolution = Rate of precipitation
Sugar(s) ⇌ Sugar (in solution)
The amount of the solid in grams that dissolves in 100 g of the solvent to form
a saturated solution at a particular temperature is called the solubility of that
solid in the given solvent at that temperature.
Gases in liquids
Such type of equilibrium is present in soda water bottle in which CO2 gas is
dissolved in water under high pressure. There is a state of dynamic
equilibrium between the CO2 present in the solution and the vapours of the
gas above the liquid surface at a given temperature.
CO2(g) ⇌ CO2(aq)
Henry’s law
It states that, The mass of gas that dissolved in a given mass of a solvent at
any temperature is proportional to the pressure of the gas above the surface
of the solvent.
m∝p
m = kp
where k is Henry’s constant and its value depends upon the nature of the gas,
nature of liquid and temperature.
General Characteristics of Physical Equilibrium
1. Equilibrium is possible only in a closed system at a given temperature.
2. Both the opposing processes occur at the same rate and there is a
dynamic but stable condition.
3. All measurable properties of the system remain constant.
4. When equilibrium is attained for a physical process, it is characterised
by constant value of one of its parameters at a given temperature.
5. The magnitude of such quantities at any stage indicates the extent to
which the physical process has proceeded before reaching equilibrium.
Read also: System of Particles and Rotational Motion Class 11
Physics Notes Chapter 7
Chemical Equilibrium
Every reversible reaction consists of one pair of reaction, one is forward and
other is backward reaction. At one stage during reversible reactions, forward
and backward reaction proceed at the same time with the same rate, the
reaction is then said to be in equilibrium. If the opposing processes involve
chemical reactions, the equilibrium is called Chemical equilibrium.
(i). Law of Chemical Equilibrium
This law states that the rate of an elementary reaction is proportional to the
product of the concentration of the reactants. At a constant temperature, the
rate of a chemical reaction is directly proportional to the product of the molar
concentrations of the reactants each raised to a power equal to the
corresponding stoichiometric coefficients as represented by the balanced
chemical equation. Let us consider the reaction,
A+B⇌C+D
rf = Kf[A][B]
rb = Kb[C][D]
At equilibrium rf = rb.
Kf[A][B] = Kb[C][D]
Kc=KfKb=[C][D][A][B]��=����=[�][�][�][�]
Kc is called the equilibrium constant, [ ] ⟶ denotes active masses.
For a general reversible reaction
aA + bB ⇌ cC+ dD
Kc=[C]c[D]d[A]a[B]b��=[�]�[�]�[�]�[�]�
(ii). Equilibrium constant of reverse reaction
Equilibrium constant for the reverse reaction is the inverse of the equilibrium
constant for the reaction in the forward direction.
K'c=1Kc�′�=1��
Read also: Conceptual Questions for Class 11 Physics Chapter 7
System of Particles and Rotational Motion
(iii). Relation between Kp and Kc
For a general reversible reaction
aA + bB ⇌ cC+ dD
Kc=[CC]c[CD]d[CA]a[CB]b��=[��]�[��]�[��]�[��]� .....(1)
Kp=[PC]c[PD]d[PA]a[PB]b��=[��]�[��]�[��]�[��]�
Kp=[CC]c×[RT]c.[CD]d×[RT]d[CA]a×[RT]a.
[CB]b×[RT]b��=[��]�×[��]�.[��]�×[��]�[��]�×[��]�.
[��]�×[��]�
Kp=[CC]c[CD]d(RT)c+d[CA]a[CB]b(RT)a+b��=[��]�[��]�(��)�+�[
��]�[��]�(��)�+�
From eq. (1),
Kp=Kc(RT)(c+d)−(a+b)��=��(��)(�+�)-(�+�)
Kp=Kc(RT)Δn��=��(��)Δ�
Where, Δn = difference of stoichiometric coefficients of gaseous products and
reactants.
(iv). Characteristics of Equilibrium
1. At the state of equilibrium, certain available properties like pressure,
concentration and density becomes constant.
2. Chemical equilibrium can be established from either side.
3. A catalyst can cause the state of equilibrium to be reached faster, but
does not alter the state of equilibrium.
4. Chemical equilibrium is dynamic in nature.
5. Any change in external stress (Pressure, temperature or concentration)
causes disturbance in equilibrium state. The state of equilibrium being
stable, is again reached by some adjustment.
6. If temperature is changed, a new equilibrium is achieved with a new
value for relative concentration of products and reactants.
7. If temperature is kept constant, pressure and concentration of
reactants / products is altered, system shifts in forward or backward
direction in order to nullify the alteration (stress).
(v). Factors Affecting Equilibria
1. Change in Concentration: When the concentration of any of the reactants
or products in an equilibrium reaction is altered, the equilibrium mixture’s
composition changes in order to minimize the effect of the concentration
change.
2. Change in Temperature: According to Le-Chatelier’s principle if the
temperature of an equilibrium system is increased, the equilibrium will move in
the direction of the added heat.
3. Change in Pressure: The pressure has no effect on the equilibrium if the
number of moles of gaseous reactants and products does not change. The
change in pressure in both liquids and solids can be neglected in
heterogeneous chemical equilibrium.
3. Change in Volume: When the volume of a gaseous mixture at equilibrium
is increased, the equilibrium moves in the direction of a larger number of
gaseous molecules.
4. Effect of a Catalyst: The equilibrium is unaffected by the catalyst. This is
due to the fact that the catalyst favours both forward and backward reactions
equally.
Homogeneous Equilibria
When in an equilibrium reaction, all the reactants and the products are
present in the same phase (i.e., gaseous or liquid) it is called
a homogeneous equilibrium. For example,
N2(g) + 3H2(g) ⇌ 2NH3(g)
Heterogeneous Equilibria
When in an equilibrium reaction, the reactants and the products are present in
two or more than two phases, it is called a heterogeneous equilibrium.
The equilibrium between water vapour and liquid water in a closed container
is an example of heterogeneous equilibrium.
H2O(l) ⇌ H2O(g)
Le Chatelier's Principle
It states that if a stress is applied to a system in equilibrium, the equilibrium for
the time being gets disturbed. As a result system moves in a direction which
tends to relieve the external stress and finally a new equilibrium is attained.
Ionic Equilibrium
(i). Electrolyte
Electrolytes are the substances which conduct electricity in molten state or in
solution. Example HCl, NaCl, KCl, CH3COOH etc.
(ii). Arrhenius theory of Electrolytic dissociation
When an electrolyte is dissolved in a solvent it spontaneously dissociates into
oppositely charged particles called ions, to a considerable extent. Electrolytic
ionization or dissociation gives ions and unionized molecules in solution. For
neutrality, the total charge on cations is equal to the total charge on the
anions.
(iii). Degree of Dissociation (α)
It is the fraction of one mole of the electrolyte that has dissociated under the
given conditions. The value of α depends on temperature, dilution of
electrolyte, nature of electrolyte and solvent.
α = No. of ionized moles / Total mo. moles
(iv). Ostwald's Law of Dilution
According to this law, "The degree of ionization (or dissociation) of any weak
electrolyte is inversely proportional to the square root of concentration."
α=√KCα=��
Where, K = proportionality constant
Concepts of Acids and Bases
(i). Arrhenius Concept
Acid: Any substance when dissolved in water, increases the concentration of
H+. e.g., HCl, H2SO4, HNO3 etc.
Base: Any substance when dissolved in water, increases the concentration of
OH-. e.g., NaOH, KOH etc.
(ii). Bronsted - Lowry Concept
Acid: Species (Molecule or ion) that donates a proton to another species.
Base: Species (Molecule or ion) that accepts a proton from another species.
HCl(Acid) + NH3(Base) ⟶ NH+4 + Cl-
(iii). Lewis acids and bases
According to Lewis concept of acids and bases, a Lewis acid is an electron
pair acceptor and a Lewis base is an electron pair donor.
Lewis acids: H+, Ag+, Fe2+, AlCl3, BF3, BCl3, BeCl2 etc.
Lewis Bases: Cl-, CN-, OH-, X-, NH-2, SH- etc.
An acid base reaction is the sharing of an electron pair with an acid by a base.
This process is simply defined as coordination or neutralisation.
1. A strong acid is an acid that ionizes completely in water.
HCl(aq) + H2O (l) ⟶ H3O+ (aq) + Cl-(aq)
2. A weak acid is an acid that is only partially ionized in water.
CH3COOH(aq) + H2O(l) ⇌ CH2COO-(aq) + H3O+(aq)
3. A strong base is a base that ionizes completely in water.
KOH(aq) ⟶ K+(aq) + OH-(aq)
4. A weak base is a base which is partially ionized in water.
NH3(aq) + H2O(l) ⇌ NH+4(aq) + OH–(aq)
The pH Scale
pH of solution may be defined as negative logarithm of hydronium ion
concentration.
pH = –log[H3O+]
pH=log1[H3O+]��=log1[�3�+]
The pH range at 25°C is taken as 0 to 14.
pH = 7 Neutral
pH > 7 Basic
pH < 7 Acidic
Common Ion Effect
The suppression in the dissociation of a weak electrolyte by the addition of a
strong electrolyte having a common ion is called common ion effect.
For example: Ionisation of acetic acid (CH3COOH) and effect of addition of a
small amount of acetate ion
CH3COOH(aq) ⟶ CH3COO-(aq) + H+(aq)
CH3COONa(aq) ⟶ CH3COO-(aq) + Na+(aq)
Buffer Solution
A buffer solution is that solution which resists any change in its pH value on
addition of small amount of acid or base. Although the pH of buffer changes
on doing so, but the change in pH value will be less than the expected
change. There are three types of buffer solution.
1. Acidic Buffer
This consists of solution of a weak acid and its salt with strong base. Example;
CH3COOH and CH3COONa.
2. Basic Buffer
This consists of solution of weak base and its salt with strong acid. e.g.,
NH4OH and NH4Cl
3. Salt Buffer
It is a solution of salt which itself can act as a buffer. Such a salt is the salt of
weak acid and weak base. For example,
CH3COONH4 ⇌ NH4+ + CH3COO-
When an acid is added, it reacts with CH3COO- to produce CH3COOH and
when a base is added, it react with NH4+ to produce NH4OH.
Buffer Capacity
It is the number of moles of acid or base required by one litre of a buffer
solution for changing its pH by one unit.
Buffer Capacity = No. of moles of acid or base adder per litre / Change in pH
Solubility and Solubility Product
The number of moles of solute in one litre of a saturated solution (mole / L) is
defined as solubility. Let us calculate solubility of salt AgCl.
AgCl ⇌ Ag+ + Cl-
Ksp = [Ag+][Cl-]
Ksp is called solubility product.
In pure water,
Ksp = [Ag+][Cl-]
Ksp = S2 { ∵ S = [Ag+] = [Cl-] }
S=√Ksp�=���
Summary
1. Equilibrium : It represents the state of a process in which the
properties like temperature, pressure, concentration of the system do
not show any change with the passage of time.
2. Physical equilibrium : It is a state of equilibrium in which the two
opposing processes involve changes in physical state only.
3. Chemical equilibrium : It is a state of equilibrium in which the two
opposing processes involve change of chemical species.
4. Reversible reaction : A reversible reaction is one which proceeds in
both the forward and backward directions.
5. Law of mass action : This law states that at constant temperature, the
rate of chemical reaction is directly proportional to the product of molar
concentrations of the reacting substances.
6. Equilibrium constant (K): It is the ratio of the product of the molar
concentrations of the substances formed to that of the reacting
substances raised to the powers equal to their stoichiometric
coefficients in the chemical equation at a particular temperature.
7. Henry’s law : The mass of a gas dissolved in a given mass of a solvent
at any temperature is directly proportional to the pressure of the gas
above the solvent.
8. Le Chatelier’s Principle : When a system in dynamic equilibrium is
subjected to a stress such as a change in concentration, pressure or
temperature, the equilibrium shifts in a direction that opposes or
reduces the stress.
9. Strong electrolytes : Electrolytes which are ionized almost completely
in aqueous solution under similar conditions of concentration and
temperature are called strong electrolytes.
10. Weak electrolytes : Electrolytes which are poorly ionized in aqueous
solution under similar conditions of concentration and temperature are
called weak electrolytes.
11. Solubility product : It is the product of concentration of ions in a
saturated solution of a sparingly soluble salt at a given temperature.
12. Arrhenius acid-base concept : According to Arrhenious, an acid is a
substance which gives hydrogen ions and base is a substance which
gives hydroxyl ions in aqueous solutions.
13. Bronsted-Lowry acid-base concept : According to this concept, an
acid is a proton donor and base is a proton acceptor.
14. Lewis acid-bases concept : According to this concept, an acid is an
electron pair acceptor and base is an electron pair donor.
15. pH value : pH value of a solution is the negative logarithm of the
hydrogen ion concentration (in moles per litre) present in it. Thus pH = -
log[H+]
16. Irreversible reaction : If a reaction cannot take place in the reverse
direction i.e., the products formed do not react to give back the
reactants under the same conditions is called an irreversible reaction.
17. Homogeneous equilibria : When in an equilibrium reaction, all the
reactants and the products are present in the same phase (i.e., gaseous
or liquid), it is called a homogeneous equilibrium.
18. Heterogeneous equilibrium : When in an equilibrium reaction, the
reactants and the products are present in two or more than two phases,
it is called a heterogeneous equilibrium.
19. Buffer solution : It is defined as a solution which resists in its pH value
even when small amounts of the acid or the base are added to it.
20. Conjugate base : A base formed by the loss of proton by an acid is
called conjugate base of the acid.
21. Conjugate acid : An acid formed by the gain of a proton by the base is
called conjugate acid of the base.
