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M.E.S INDIAN SCHOOL, DOHA - QATAR

Notes 2023-2024

Section: BOYS AND GIRLS Date : 04/11/2023

Class & Div. : XI (All divisions) Subject: CHEMISTRY
Lesson / Topic: Unit VII: EQUILIBRIUM
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Reversible reaction
Reaction in which products can combine to give back the reactants.
In this reaction both forward and backward reaction take place. It is represented by a double arrow.

Irreversible reaction
Reaction in which products do not give back the reactants. It is represented by a single arrow.
NaOH + HCl → NaCl + H2O
Characteristics of Equilibrium
1. At equilibrium, rate of forward reaction = rate of backward reaction ie equilibrium is dynamic in
nature.
2. Concentration of reactants and products remain constant at equilibrium.
3. Equilibrium is attained in a closed container. [In open vessel, matter will escape]
4. Catalyst does not affect the equilibrium. Consider the reaction, A + B → C+ D

The graph explains that after a certain time, the concentration of reactant
and product becomes constant, i.e system reaches equilibrium.

Q. Chemical equilibrium is dynamic in nature. Explain.

1. At equilibrium, rate of forward reaction = rate of backward reaction.
2. Concentration of reactants and products remain constant at equilibrium. Equilibrium Law or
Law of Chemical
Equilibrium Law or Equilibrium.
Law of Chemical Equilibrium.
It states that at a given temperature, the concentrations of the products divided by the concentrations of the
reactants, with each concentration term raised to the power equal to their stoichiometric coefficients (no. of
moles) in balanced equation has a constant value.

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Kc = [C]c[D]d
[A]a[B]b
Equilibrium constant (Kc)
It is the concentrations of the products divided by the concentrations of the reactants, with each concentration
term raised to power equal to their stoichiometric coefficients (no. of moles) in balanced equation.

Concentration quotient or reaction quotient (Q c =[product]/[reactant])

It is the concentration ratio at any stage of the reaction.
At equilibrium, Qc = Kc

Characteristics of equilibrium constant (K c)

1. Kc depends only on the equilibrium concentration of reactants and products.
2. It is independent of initial concentrations of the reactants and products.
3. Equilibrium constant is temperature dependent.
4. The equilibrium constant for the reverse reaction is equal to the inverse of the equilibrium constant
for the forward reaction .

, Kc = x

• , K′c = 1/ x
5. If a chemical equation is multiplied by a number, then power of equilibrium constant is equal to that
number.
H2 + I2 → 2 HI , Kc = x
2
• 2H2 + 2I2 → 4 HI , Kc = x
1/2
• 1/2H2 +1/ 2I2 → HI , Kc = x

Q. Explain why pure solid and liquid can be ignored while writing equilibrium constant expression? The
molar concentration of a pure solid or liquid is constant and is taken as unity.
Q. Write the equilibrium constant expression

1.
Kc = [CaO(s)][CO2(g)] Kc = [CO2(g)] or Kc = PCO2
[CaCO3(s)] Since [CaCO3(s)] and [CaO(s)] are both constant.
2.
Kc = [Ni(CO)4]
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[CO]4

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3.
Kc = [AgNO3]2
[HNO3]2

4
Kc = [NH3(g)]2

[N2(g)]. [H2(g)]3
Homogeneous equilibria
In a homogeneous system, all the reactants and products are in the same phase.

Eg:

Heterogeneous equilibria
In a heterogeneous system, the reactants and products are in the different phase.

Derive the relation between Kp and Kc

The ideal gas equation is
PV = nRT
⇒ P = (n/v) RT [n/V is concentration C in mol/L]
Where, P is the pressure , n is the no. of moles of the gas, V is the volume and T is the temperature.
P = CRT, [C is concentration, R= 0.0831 bar litre/mol K] Consider
a gaseous reaction

Kc = [C]c[D]d
[A]a[B]b
Kp = (PCc)(PDd)
(PAa)(PBb)
= [C]c [D]d (RT)c+d
[A]a [B]b (RT)a+b
= [C]c [D]d (RT)(c+d) – (a+b)
[A]a [B]b
Kp = [C]c [D]d(RT)Δn
[A]a [B]b
Kp = Kc (RT)Δn

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where Δn = (number of moles of gaseous products) – (number of moles of gaseous reactants)

Kc = equilibrium constant in terms of concentration of the reactants and products.
Kp = equilibrium constant in terms of partial pressure.
R = Universal gas constant(0.0831 bar litre/mol K)
Q. Write the relation between Kp and Kc
i) ; Δn = 2-(3+1)
Kp = Kc (RT)-2

ii) ; Δn 2-2 =0
Kp = Kc (RT)0 ; Kp = Kc

Application of equilibrium constant

• to predict the extent of a reaction.
• to predict the direction of the reaction, and
• to calculate equilibrium concentration
i. Predicting the Extent of a Reaction
• If Kc > 103, products predominate over reactants.
i.e., if Kc is very large, the reaction proceeds nearly to completion.
at 300K Kc = 4.0 x 1031.
• If Kc < 10-3, reactants predominate over products.
i.e., if Kc is very small, the reaction proceeds rarely. Consider the following examples:
, at 298 K Kc = 4.8 x 10-31.
• If Kc is in the range of 10-3 to 103, appreciable concentrations of both reactants and products are present.

, Kc = 57.0 at 700K.

ii. Predicting the Direction of the Reaction

The equilibrium constant helps to predict the direction of the reaction. For this purpose, we calculate Qc, and
by comparing the values of Qc and Kc, we can predict the direction of reaction.
• Qc > Kc, backward reaction.
• Qc < Kc, forward reaction.
• Qc = Kc, the reaction is at equilibrium.

iii.To calculate Equilibrium Concentrations o f reactant and product, if Kc value is known.

Q. The value of Kc for the reaction is 2 x 10-3. At a given time, the composition of
reaction mixture is [A] = [B] = [C] = 3 x 10-4 M. In which direction the reaction will proceed? Qc
= [B][C]
[A]2 as [A] = [B] = [C] = 3 x10-4M
Qc = (3 x 10-4) (3 x 10-4) = 1
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(3 x 10-4)2 as Qc > Kc so the reaction will proceed in the reverse direction.

Factors affecting equilibria

Le Chatelier’s principle
When a system in equilibrium is subjected to any change in factors like concentration, temperature, pressure,
the system will act in such a way to counteract (cancel) the effect of that change.
We will be talking about effect on equilibrium constant because of five type of changes
1. Effect of change in concentration of reactant or product
2. Effect of change in Pressure
3. Effect of change in Temperature
4. Effect of addition of catalyst
5. Effect of addition inert gas at constant volume
Note - Only change in temperature changes the value of equilibrium constant. Change in concentration or Pressure will disturb the equilibrium for
aF 061,Rev
while 01,dtd will
but the reaction 10 shift itself in such a way that the same equilibrium constant is achieved. Addition of catalyst won't even do that.
Effect of concentration change

• When concentration of reactant increases (reactant is added), the equilibrium shifts in the forward
direction(right).
• When concentration of reactant decreases (reactant is removed), the equilibrium shifts in the backward
direction(left)
• When concentration of product increases (product is added), the equilibrium shifts in the backward
direction(left)
• When concentration of product decreases (product is removed), the equilibrium shifts in the forward
direction(right)
Eg:

If H2 is added at equilibrium, then forward reaction will be favoured.

Addition of HI will favour the backward reaction.
Removal of HI will favour the forward reaction.
Removal of H2 will favour the backward reaction.

Effect of Pressure change.

• If pressure is increased, then the equilibrium shifts in the direction of lesser no. of moles of gas.
Eg:

Increase in pressure will favour forward reaction [lesser no. of moles]

• If pressure is decreased, then the equilibrium shifts in the direction of greater no. of moles of
gas.
Eg:

Decrease in pressure will favour forward reaction [greater no. of moles]

=
• If there is no change in no. of moles, pressure has no effect .

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Effect of change in temperature.

• Increase in temperature favours endothermic reaction [positive ∆H] i.e, when T increases
equilibrium shifts in the endothermic direction.
• Decrease in temperature favours exothermic reaction [negative ∆H] i.e, when T decreases
equilibrium shifts in the exothermic direction. Eg:
ΔH= – 92.38 kJ mol-1 is an exothermic process.
Increase in temperature favour endothermic reaction i.e. backward reaction, Kc decreases. Decrease
in temperature favour exothermic reaction i.e. forward reaction, Kc increases.

Remember
Change in equilibrium constant with temp depends upon the sign of ∆H for the reaction.
For endothermic reaction [positive ∆H], equilibrium constant increases with increase in temperature.
For exothermic reaction [negative ∆H], equilibrium constant decreases with increase in temperature. For
forward reaction, Kc ↑. For backward reaction, Kc↓

Effect of catalyst
• Catalyst does not affect the equilibrium .
• Catalyst increases the rate of reaction by lowering the activation energy for the forward and reverse
reaction by exactly the same amount.

Effect of Inert Gas Addition

• If an inert gas [such as argon is added which does not take part in the reaction] is added at constant
volume , the equilibrium remains undisturbed.
Reason: Partial pressures or the molar concentrations of the substance does not change with the addition of an
inert gas at constant volume. Exercises
1.The following concentrations were obtained for the formation of NH 3 from N2 and H2 at equilibrium
at 500K. [N2] = 1.5 x10-2M. [H2] = 3.0 x10-2 M and [NH3] = 1.2 x 10-2M. Calculate equilibrium constant.

Kc = [NH3(g)]2/[N2(g)][H2(g)]3= (1.2 x 10-2)2/(1.5×10-2)(3.0×10-2)3 = 0.106355

x 104 = 1.06 x 103

2.At equilibrium, the concentrations of N2=3.0 x10-3M, O2 = 4.2 x 10-3M and NO= 2.8 x10-3M in a sealed
vessel at 800K. What will be Kc for the reaction
Kc = [NO]2/[N2][O2] = (2.8 x 10-3)2/(3.0×10-3M)(4.2×10-3M) = 0.622

3.PCl5, PCl3 and Cl2 are at equilibrium at 500 K and having concentration 1.59M PCl 3, 1.59M Cl2 and
1.41 M PCl5. Calculate Kc for the reaction,
Kc = [PCl5][Cl2]/[PCl5] = (1.59)2/(1.41) = 1.79

4. the value of the equilibrium constant, Kc is 3.75 x 10-6 at 1069

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K. Calculate the Kp for the reaction at this temperature

Kp = Kc(RT)Δn Δn = (2+1) – 2 = 1
-6
Kp = 3.75 x 10 (0.0831 x 1069) = 0.033

5.The value of Kc for the reaction is 2 x 10-3. At a given time, the composition of
-4
reaction mixture is [A] = [B] = [C] = 3 x 10 M. In which direction the reaction will proceed?
Qc = [B][C]/ [A] as [A] = [B] = [C] = 3 x10 -4M
-4 -4 -4
Qc = (3 x 10 )(3 x 10 ) / (3 x 10 )2 = 1 as Qc > Kc so the reaction will proceed in the reverse direction.
6. What is Kc for the following equilibrium when the equilibrium concentration of each substance is:

[SO2]= 0.60M, [O2] = 0.82M and [SO3] = 1.90M ?

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7 . Write the expression for the equilibrium constant, Kc for each of the following reactions:

8.Find out the value of Kc for each of the following equilibria from the value of Kp:

9. 14

9. For the following equilibrium, K = 6.3 x 10^14 at 1000 K

What is Kc, for the reverse reaction?
10. Explain why pure liquids and solids can be ignored while writing the equilibrium constant expression ?
11. The equilibrium constant expression for a gas reaction is -

Write the balacned chemical equation for it.

12. Equilibrium constant, Kc for the reaction N2 + 3H2. <--> 2NH3 at 500 K is 0.061
At a particular time, the analysis shows that composition of the reaction mixture is 3.0 mol L -1 N2, 2.0 mol L1
H2 and 0.5 mol L-1 NH3. Is the reaction at equilibrium? If not in which direction does the reaction tend to
proceed to reach equilibrium?
13. Does the number of moles of reaction products increase, decrease or remain same when each of the
following equilibria is subjected to a decrease in pressure by increasing the volume?

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14. Which of the following reactions will get affected by increasing the pressure? Also, mention whether
change will cause the reaction to go into forward or backward direction.

15. Dihydrogen gas is obtained from natural gas by partial oxidation with steam as per following endothermic

reaction:
(a) Write as expression for Kp for the above reaction.

BLANK....

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(b) How will the values of Kp and composition of equilibrium mixture be affected by (i) increasing
the pressure (ii) increasing the temperature (iii) using a catalyst ?
16. Describe the effect of :
a) addition of H2 b) addition of CH3OH c) removal of CO d) removal of CH3OH on
the equilibrium of the reaction:
17. At 473 K, equilibrium constant Kc for decomposition of PCl5 is 8.3 x 10-3. If decomposition is depicted as

a) write an expression for Kc for the reaction.

b) what is the value of Kc for the reverse reaction at the same temperature ?
c) what would be the effect on Kc if (i) more PCl5 is added (ii) pressure is increased (iii) the temperature is
increased ?
18.Predict which of the following reaction will have appreciable concentration of reactants and products:

Ionic equilibrium

Ionic equilibrium: Equilibrium that involves ions in aqueous solution

Different concepts of ACIDS and BASES

• Arrhenius concept of acids and bases:

Acids − Substances that produce hydrogen ions or H3O+ in water.

Eg: HCl, HNO3,H2SO4

(Or)

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Bases − Substances that produce hydroxyl ions in water.

Eg: NaOH ,KOH

• The Bronsted-Lowry acids and bases:

Acids − substances that can donate a proton (hydrogen ion )H+ Eg: HCl, HNO3,H2SO4

Bases − substances that can accept a proton (hydrogen ion )H+ Eg: NH3, OH-

Conjugate acid-base pair:

Acid-base pair that differs only by one proton

Amphoteric substance
Substance which behave both as acid and base (or)

Substance which can donate and accept proton (H+)

Eg: H2O, HCO3-, HSO4- and NH3 can act both as Bronsted acids and bases.

Note: Conjugate acids should have one extra proton

Conjugate bases should have one proton less

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Q.The species: H2O, HCO3-, HSO4- and NH3 can act both as Bronsted acids and bases. For each case give the
corresponding conjugate acid and conjugate base.

Species Conjugate acid Conjugate base

H2O H3O+ OH−

H2CO3

H2SO4

NH3

• Lewis acids and bases:

Acids − species that accept an electron pair

Bases − species that donate an electron pair

o Examples of Lewis acids − AlCl3, BF3, BCl3 Co3+, Mg2+, H+ o

Examples of Lewis bases − H2O, NH3, OH−, F−

Q.What will be the conjugate bases for the following Brönsted acids:HF, H2SO4 and HCO3-? [Conjugate bases
should have one proton less]

Conjugate bases are: F-, HSO4- and CO32- respectively.

Q.Write the conjugate acids for the following Brönsted bases: NH2-, NH3 and HCOO- ?.

[Conjugate acid should have one extra proton]

Conjugate acids are: NH3, NH4+ and HCOOH respectively.

Q. Classify the following species into Lewis acids and Lewis bases and show how these act as such: (a) HO -
(b)F- (c) H+ (d) BCl3

HO- ,F- - Lewis base [electron pair donor].

H+, BCl3 - Lewis acid [electron pair acceptor].

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Readerback Questions:

7.35 What is meant by the conjugate acid-base pair? Find the conjugate acid/base for the following
species:HNO2, CN-, HClO4, F-, OH-, CO32-, and S2-

7.36 Which of the followings are Lewis acids? H2O, BF3, H+, and NH4+

7.37 What will be the conjugate bases for the Brönsted acids: HF, H2SO4 and HCO3-?

7.38 Write the conjugate acids for the following Brönsted bases: NH2-, NH3 and HCOO-.

7.39 The species: H2O, HCO3-, HSO4- and NH3 can act both as Brönsted acids and bases. For each case give the
corresponding conjugate acid and base.

7.40 Classify the following species into Lewis acids and Lewis bases and show how these act as Lewis
acid/base: (a) OH- (b) F- (c) H+ (d) BCl3 .
Self – Protolysis of water [Self – ionization of water]

Ionic product of water

Ionic product of water is defined as the product of molar concentration H+ and OH-

Kw = [H+] [OH−]

Where, Kw = Ionic product of water

• At 298 K, [H+] = [OH−] = 1.0 × 10−7 M

So, Kw = [H+] [OH−]
= ( 10−7 M x10−7 M )
Kw =10−14 M2

• The value of Kw depends upon temperature.

• Comparison between [H3O+] and [OH−]
o For acidic solution, [H 3O+] > [OH−]
o For neutral solution, [H3O+] = [OH−]
o For basic solution, [H3O+] < [OH−]
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The pH scale

pH of a solution is defined as the negative logarithm of hydrogen ion concentration.

pH= -log[H+]

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At 250 C [298K] pure water has hydrogen ion concentration = 10-7 M

Therefore pH of pure water is

Acidic solutions have pH < 7

Basic solutions have pH > 7

Neutral solutions have pH = 7.

Q. The concentration of hydrogen ion in a sample of soft drink is 3.8 x 10-3M. What is its pH

pH=-log[H+] = – log[3.8 x 10-3 ] = – {log[3.8] + log[10-3]}

= – {(0.58) + (- 3.0)} = – { – 2.42} = 2.42

Therefore, the pH of the soft drink is 2.42 and it can be inferred that it is acidic.
Readerback Questions.

7.41. The concentration of H+ ion in a sample of soft drink is 3.8 x 10-3 M. what is its pH?

7.42. The pH of a sample of vinegar is 3.76. Calculate the concentration of hydrogen ion.

7.48. Assuming complete dissociation, calculate the pH of the following solutions:

(a) 0.003 M HCl (b) 0.005 M NaOH (c) 0.002 M HBr (d) 0.002 M KOH

7.55. Calculate the hydrogen ion concentration in the following biological fluids whose pH are given below: (a)
Human muscle-fluid, 6.83 (b) Human stomach fluid, 1.2

(c) Human blood, 7.38 (d) Human saliva, 6.4.

7.56. The pH of milk, black coffee, tomato juice, lemon juice and egg white are 6.8, 5.0, 4.2, 2.2 and 7.8 resp.
Calculate corresponding hydrogen ion concentration in each.
Buffer Solution

The solutions which resist change in pH on dilution or with the addition of small amounts of acid or alkali
are called buffer solutions.
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Our blood is a buffer solution. It contains H2CO3 and salt of it (HCO3-). That is why even when acidic/basic substance
enters the blood stream, PH remains in between 7.35-7.45 and doesn't fluctuate much.

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Acidic Buffer- E.g., mixture of acetic acid (CH3COOH) and sodium acetate (CH3COONa)
Mixture of weak acid (CH3COOH) and a salt formed by that weak acid and strong base (NaOH)
Basic Buffer- E.g. mixture of ammonium hydroxide (NH4OH) and ammonium chloride (NH4Cl).
Mixture of weak base(NH4OH) and a salt formed by that weak base and strong acid (HCl)
Neutral Buffer- Ammonium acetate (NH 4Cl)
(NH4 CH3COO) Mixture of -
weak acid : acetic acid (CH3COOH) and weak base : Ammonium hydroxide(NH4OH)
Common Ion Effect

The suppression of dissociation of weak electrolyte by the addition of strong electrolyte having common
ion is called Common Ion Effect

• Dissociation of acetic acid is suppressed by the addition of HCl or CH3COONa

If any one of H+ ions or CH3COO− is added from an external source, then the equilibrium will shift in
the direction of the un-dissociated acetic acid (i.e., in the backward direction).

Solubility Product Constant( )

Solubility product is the product of concentration of ions of the sparingly soluble salt in a saturated
solution.

Relation between solubility product ( ) and solubility(S)

Solubility of salt, S = (Ksp / xx . y y)1 / x + y

Where x and y are the no. of ions formed in solution.

Greater the value, greater is the solubility of the salt.

Equilibrium constant,

BaSO4 is a pure solid, so = Constant

We can write,
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Where, K sp = Solubility product constant or Solubility product.

Q. Calculate the solubility of A 2X3 in pure water, assuming that neither kind of ion reacts with water. The
solubility product of A2X3, Ksp = 1.1 x 10-23.
Solution :
A2X3 → 2A3+ + 3X2-

S = (Ksp / xx . y y)1 / x + y = [ 1.1 x 10-23/ 22 x 33 ]1/2+3 = [1.1 x 10-23/ 4 x 27 ]1/5

=[ 1.1 x 10-23/ 108 ]1/5 = [1 x 10-25] 1/5 = 1.0 x 10-5 mol/L.

Q. The values of Ksp of two sparingly soluble salts Ni(OH)2 and AgCN are 2.0 x 10-15 and 6 x 10^(-17)

x 0-17 respectively. Which salt is more soluble? Explain.

S = [6 x 10-17/ 1x1]1/2 = 7.746 x 10-9

S = (Ksp / xx . y y)1 / x + y = [ 2 x 10-15/1x 2 2 ]1/1+2 = 7.938 x 10-6

Ni(OH)2 is more soluble than AgCN.

• Stronger the acid, larger is the value of Ka.

pKa = −log(Ka) pKb

=pKb = -log(kb)
−log (Kb)

Relation between Ka and Kb

Kw = Ka × Kb = 10−14 mol2 L−2 pKw

=Pkw
pKa=+Pka
pKb+=Pkb
14 = 14

Where Ka and Kb are ionization constant of acid and its conjugate base
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Factors Affecting Acid Strength

Acidic strength of HA increases down the group

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o Reason: Down the group, the size of A increases, so, the strength of the H - A
− A bond decreases ( bond break easily)

• Acid strength of HA increases from left to right across a period

• Reason: Across a period, electronegativity increases

Hydrolysis of Salts and the pH of their Solutions

- a reaction in which one of the ions from a salt reacts with water, forming either an acidic or basic solution

(i) salts of strong acid and strong base is neutral e.g.,NaCl : Hydrolysis of no ions take place : pH = 7
(ii) salts of weak acid and strong base is basic e.g., CH3COONa : Hydrolysis of CH3COO- will take place : pH > 7
(iii) salts of strong acid and weak base is acidic e.g., NH4Cl : Hydrolysis of NH4+ will take place : pH<7
(iv) salts of weak acid and weak base, e.g., CH COONH : Hydrolysis of both the ions will take place
as both ion come from weak acid/base. : pH = 7 + 1/2 (pKa -pKb) (pH value is nearly 7)
pH = 7 + 1/2(pKa – pKb )

Q. The pKa of acetic acid and pKb of ammonium hydroxide are 4.76 and 4.75 respectively. Calculate the pH
of ammonium acetate solution.

pH = 7 + ½[pKa - pKb = 7 + ½[4.76 - 4.75] = 7 + ½[0.01] = 7 + 0.005 = 7.005

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