CHEMICAL EQUILIBRIUM

MODULE-3

TOPIC OVERVIEW

 Acids and base

 Ionisation constant of weak acids and base

 Ionic product of water

 pH

 Assignments

 Links

IONIC EQUILIBRIUM

 Electrolytes are substances that dissociate in aqueous solutions and are responsible for
conducting electricity due to movement of ions. Strong electrolytes are completely
dissociated.

 Weak electrolytes however are only partially dissociated and an equilibrium is established
between the un-dissociated molecule of a weak electrolyte & its ions. This is known as the
ionic equilibrium.

ACIDS AND BASES

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I) Arrhenius acids & bases -

Acids are substances that produce H + ions and bases are substances that produce OH -

ions in aqueous solutions.

H O
Eg HCl 
2
 H + (aq) + Cl – (aq) &

H O
NaOH 
2
 Na + (aq) + OH – (aq)
II) Bronsted Lowry Acids & bases-

Acids are proton donors while bases are proton acceptors.

Eg-

 The pair of acids and bases which are formed from each other by gain or loss of a proton is
called conjugate acid base pair.

 In order to find conjugate base of a species, subtract one H+ from that species and in order
to find conjugate acid of a species add one H+ to that species.

 Stronger the acid, weaker will be its conjugate base and vice versa.

 Substances which can accept as well as donate a proton are called amphoteric
[Link]: H 2O , HCO 3-, HSO4-, HS -,, NH 3 etc.

(III) Lewis acids & bases-

 Lewis acids are electron deficient species which is capable of accepting a pair of
electrons.

 Lewis base are electron rich species which are capable of donating a pair of electrons.

Lewis bases are electron donors while Lewis acids are electron acceptors.

Examples of Lewis acids

 (a) Molecule having an atom with incomplete octet. e.g.: BF 3 & AlCl 3

(b) Simple cations - H  , Ag 

(c) Molecules in which central atom has vacant orbitals and may acquire more
than an octet of valence electrons. e.g.: SiF 4

Examples of lewis base

(a) Neutral molecules having one or more unshared pairs of electrons.


(b) Anions – Such as CN , OH  , Cl 

IONIZATION CONSTANTS OF WEAK ACIDS & BASES

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For weak acids HX the dissociation may be shown as-

HX (aq) + H2 O(l) H 3 O + (aq) + X - (aq)

Ka 
H O  X 
3
 
where Ka is the ionization constant of weak acids.
HX 
The equilibrium constant can also be expressed as-

HX (aq) + H2 O(l) H 3 O + (aq) + X - (aq)

Initial conc c 0 0

Equili conc c (1- α ) c α c α,

where α is a degree of dissociation.

Ka 
c 2
c1   

Ka  c 2   1

1/ 2
 Ka 
  
 c 

Similarly for weak bases,

 MOH (aq)+ H2O M +
(aq) + OH - (aq)

Kb = c α2
1/ 2
 Kb 
&   
 c 

where Kb is the ionization constant of weak bases .

POLYBASIC ACIDS & POLYACIDIC BASES

 Acids & bases having more than one ionisable H + &

OH- ions are known as polybasic acids
and poly acidic bases. For eg-

H2 X (aq) H + (aq) + HX -(aq) , Ka 1

HX -(aq) H + (aq) + X -(aq) , Ka 2

 The magnitude of successive ionization constants decreases as the ionization becomes

increasingly difficult because it is difficult to remove H +
from a negative charged species..

IONISATION CONSTANT OF WATER (IONIC PRODUCT) kw

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H2 O + H2 O H3 O + + OH -
(acid) (base)

K
H O  OH 
3
 

H 2O
K x const = [ H 3 O + ] [ OH - ]

Kw = [ H 3 O + ] [ OH - ] = 1x10 -14 at 298K

 The value of Ionic product of water Kw increases with increase in temperature.

In neutral solutions [𝑯𝟑 𝑶 ] = [𝑶𝑯 ] = 𝟏 × 𝟏𝟎 𝟕 𝑴

In acidic solution [𝑯𝟑 𝑶 ] > [𝑶𝑯 ] But Kw remains constant
In basic solutions [𝑯𝟑 𝑶 ] < [𝑶𝑯 ]

pH SCALE

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 It is the measure of the acidity or the basicity of a solution.

pH - It is the negative logarithm of hydrogen ion concentration.

pH = - log [ H + ] ;

For neutral solutions, [ H + ] = 1x10 -7 & pH = 7

For acidic solutions pH < 7

For basic solutions pH > 7 .

pOH - It is the negative logarithm of OH - ion conc.

Note:

pOH = - log [ OH + ]

pKw = - log Kw

pKa = - log Ka

pKb = - log Kb .

 Larger the value of Ka , smaller the value of pKa, and stronger the acid.

 Larger the value of Kb , smaller the value of pKb, and stronger the base

We know Kw = [H +] [OH -] = 10 -14

Therefore, pKw = pH + POH = 14;

RELATION BETWEEN Ka & Kb

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𝐵 (𝑎𝑞 ) + 𝐻 𝑂(𝑙 ) ⇔ 𝐵𝐻 (𝑎𝑞 ) + 𝑂𝐻 (𝑎𝑞 )

base conjugate acid

[𝐵𝐻 ][𝑂𝐻 ]
𝐾 =
[𝐵]
As the concentration of water remains constant it has been omitted from the denominator
and incorporated within the dissociation constant. Then, multiplying and dividing the above
expression by [H +], we

[𝐵𝐻 ][𝑂𝐻 ][𝐻 ]

𝐾 =
[𝐵][𝐻 ]

[𝐵𝐻 ]
= {[𝑂𝐻 ][𝐻 ]}
[𝐵][𝐻 ]

𝐾
=
𝐾

𝑜𝑟𝐾 = 𝐾 × 𝐾
For a pair of conjugate acid & base,

Ka x Kb = Kw,

pKa + pKb = pKw = 14 at 298K

SOLVED QUESTIONS

Q1. Calculate the degree of dissociation and concentration of H 3O+ ions in 0.01 M solution of
formic acid. K a = 2.1 × 10 -4 at 298 K.

Ans: HCOOH + H 2O ⇔ H3O+ + HCOO-

Let 𝛼 be the degree of ionisation. Then

HCOOH + H 2O ⇔ H 3O+ + HCOO -

Initial conc. 0.01 0 0

Conc. at eqm. 0.01(1 - 𝛼) = 0.01 0.01 𝛼 0.01 𝛼

[ 𝛼 𝑖𝑠 𝑣𝑒𝑟𝑦 𝑠𝑚𝑎𝑙𝑙 𝑎𝑛𝑑 𝑐𝑎𝑛 𝑏𝑒 𝑛𝑒𝑔𝑙𝑒𝑐𝑡𝑒𝑑 𝑖𝑛 𝑐𝑜𝑚𝑝𝑎𝑟𝑖𝑠𝑖𝑜𝑛 𝑡𝑜 1]

Thus, K a = = 0.01 × 𝛼 2 = 2.1 × 10 -4

. × .
.

𝛼 2 = 2.1 × 10 -4 / 0.01 = 2.1 × 10 -2

Degree of ionisation = √2.1 × 10 -2 = 0.14

Concentration of H 3O+ = C 𝛼 = 0.14 × 0.01 = 1.4 ×10 -3 mol L -1

Q2. The ionization constant of HF at 298 K is 6.8 ×10 -4. Calculate the ionization constants of
the corresponding conjugate base.
Ans. The ionization constants of conjugate acid-base pair are related as:
Kw
K a  K b  K w or Kb 
Ka
(i) HF

Kw 10 14
Kb for F  
K a 6.8  10  4
 1.47  10 11  1.5  10 11

Q3. The species: H 2O, HCO, HSO and NH 3 can act both as Bronsted acids and bases. For each
case, give the corresponding conjugate acid and base.
Ans. Specie Conjugate Acid Conjugate Base
H 2O H 3O  OH 
HCO3 H 2CO3 CO32 
HSO4 H 2 SO4 SO42 
NH 3 NH 4 NH 2

Q4. Calculate the H 3O+ and OH - ion concentration at 25 0C in 0.02 M HCl solution.

Ans: HCl completely ionizes as: HCl + H 2O → H 3O+ + Cl -

[H3O+] = [HCl] = 0.02 M = 2 ×10 -2 M

Now, as [H 3O+] [OH -] = K w = 10 -14

[OH-] = K W / [H 3O+] = 10 -14/ 2× 10 -2 = 5× 10 -13 M

Q5. The ionization constant of acetic acid is 1.74×10 -5. Calculate the degree of dissociation of
acetic acid in its 0.05 M solution. Calculate the concentration of acetate ion in the
solution and its pH.

Ans. Acetic acid being a weak acid, Ostwald’s dilution law is applicable.
 Ka 1.74  10 5
   0.0186
c 0.05
Ac  

cKa  0.05  1.74  10 5
 9.3  10 4 M  0.00093M
H   Ac   9.3 10 M
  4

pH   logH    log 9.3  10

 4
 3.03.
Q6. Calculate the degree of ionization of 0.05M acetic acid if its pKa value is 7.74. How is the
degree of dissociation affected when its solution also contains (a) 0.01 M (b) 0.1 M in
HCl?

Ans: Given c = 0.05 M; pKa = 4.74 = -log Ka

Ka = antilog (-4.74) = 1.82 ×10 -5

Ka 1.82  10 5
   0.019  1.9  10 2
c 0.05

In presence of 0.01 M HCl

HAc ⇋ H+ + Ac-

0.05 (1-α) 0.05 α 0.05 α

HCl → H+ + Cl ̅

0 0.01M 0.01M

Ka 
H Ac 
 

HAc
H   0.01  0.05 ≅ 0.01


[HAc] = 0.05 (1- α) ≅ 0.05

0.01 0.05
1.82  10 5 
0.05
1.82  10 5
  1.82  10  3
0.01
Q7. A solution is found to contain 0.63 g of nitric acid per 100 ml of the solution. What is
the pH of the solution if the acid is completely dissociated?

Ans: Concentration of HNO 3 solution = 0.63 g per 100 ml

 = 6.3 g per litre = 6.3/63 mol L -
= 10 -1 M

Now, HNO 3 completely ionizes as: HNO 3 + H 2O → H 3O+ + NO3-

[H3O+] = [HNO 3] = 10 -1 M

pH = -log [H 3O+] = -log 10 -1 = 1

pH = 1

Q8. 4.0 g of NaOH are dissolved per litre. Find i) Molarity of solution ii) OH - concentration
iii) pH value of the solution (At. Masses: Na = 23, O = 16, H = 1)

Ans: i) Calculation of Molarity : Mass of NaOH dissolved = 0.4 g/litre

Mol. Mass of NaOH = 40

Molarity of the solution = = = 0.1 M

/ .
.

ii ) Calculation of the OH - ion concentration

NaOH completely ionizes as: NaOH → Na + + OH-

∴[OH-] = [NaOH] = 0.1M = 10 -1 M

iii) Calculation of pH:

[H 3O+] [OH -] = K w = 1.0 x 10 -14

[H 3O+] = = 1.0 x 10 -14 / 0.1 = 10 -13 M

[ ]

pH = - log [H 3O+] = 13

Q9. Calculate the pH of a solution obtained by mixing equal volumes of the solutions with
pH = 3 and pH = 5.

Ans: pH = 3 means [H +] = 10 -3 M and pH = 5 means [H +] = 10 -5 M

On mixing equal volumes, in the final solution,

[H+] = (10 -3 + 10 -5) / 2 = 0.505 × 10 -3 M = 5.05 × 10 -4 M

pH = -log (5.05 × 10 -4) = 4 – 0.7033 = 3.3

pH = 3.3

Q10. The value of K w is 9.55 × 10 -14 at a certain temperature. Calculate the pH of water at this
temperature.

Ans: Kw = 9.55 × 10 -14

For water, [H 3O+] = [OH -] ∴ Kw = [H 3O+] [H 3O+] = [H3O+]2
 i.e. [H 3O+]2 = 9.55 × 10 -14 or [H 3O+] = (9.55 x 10 -4)1/2 = 3.09 x 10 -7

pH = - log [H 3O+] =-log (3.09 x 10 -7) = 6.51 Thus, pH = 6.51

Q11. How many grams of NaOH must be dissolved in 1 litre of the solution to give it a pH
value of 12?

Ans: pH = - log [H 3O+] ∴ log [H 3O+] = -pH = -12 ∴ [H 3O+] = 10 -12 g ions/litre
[H3O+] [OH -] = K w = 10 -14 ∴ [OH -] = K w/ [H 3O+] = 10 -2 g ions/litre

Since NaOH is a strong electrolyte it undergoes complete ionization as:

NaOH → Na + + OH-

[H3O+] [NaOH] = 10 -2 M

Mol. Mass of NaOH = 40 ∴ Amount of NaOH dissolved per litre = 10 -2 ×40 = 0.4 g

Q12. Calculate the pH of 10 -10 M NaOH solution.

Ans: [OH-] from NaOH = 10 -10 M, [OH -] from H 2O = 10 -7 M

Total [OH -] = 10 -10 + 10 -7 = 10 -7 (1 + 10 -3) = 1.001 × 10 -7 M

pOH = -log (1.001 × 10 -7) = 7 – log 1.001 = 7- 0.0004 = 6.9986

pH = 14 – 6.9986 = 7.0004

pH = 7.0004

Q13. An acid having pH = 6 is diluted 1000 times. What will be the pH of the final solution?

Ans: pH = 6 means [H 3O+] = 10 -6 M

After diluting 1000 times, [H 3O+] = 10 -6/1000 = 10 -9 M

∴ [H 3O+] from water cannot be neglected.

Total [H 3O+] = 10 -9 + 10 -7 = 10 -7(1 + 10 -2) = 10 -7(1.01)

pH = - log (1.01 ×10 -7) = 7 – 0.0043 = 6.9957

Q14. Calculate the pH of the resultant mixtures:

(i) 10 mL of 0.1 M H 2SO4 + 10 mL of 0.1 M KOH

Ans: (i) Mixture of 10 mL of 0.1 M H 2SO4 + 10mL of 0.1 M KOH

H2SO4 and KOH react in 1 : 2 molar ratio as

H 2 SO4  2 KOH 
 K 2 SO4  2 H 2O
 10 mL of 0.1 M H 2SO4 contains 10 ×0.1 = 1mmol H 2SO4

10 mL of 0.1 M KOH contains 10×0.1 = 1mmol KOH

1 m mol KOH would neutralize 0.5 mmol H 2SO4

Unreacted H 2SO4 = 1 – 0.5 = 0.5 mmol

Volume of mixture solution = 10 + 10 = 20 mL

0.5
Concentration of H 2SO4   0.025M
20
Since 1 mol H 2SO4 gives 2 mol H +

[H+] = 2 [H 2SO4 ] = 2 ×0.025 = 0.05 M

pH = - log [H +] = - log 0.05 = 1.301

ASSIGNMENT

MCQ

1. The compound that is not a Lewis acid is:

a) AlCl3
b) BF3
c) NH3
d) SiF 4

2. How will the ionic product of water change on increasing the temperature?
a) Increases
b) Decreases
c) May increase or decrease
d) Remains same
3. A solution of NaOH contain 0.04 g of NaOH per litre. Its pH is:
a) 10
b) 9
c) 11
d) 12
4. pH of 1 M HCl is:
a) zero
b) -2
c) 7
d) 14
5. Which is incorrect?
a) Conjugate acid of H 2O is H 3O+
b) Conjugate base of HCO 3- is CO 32-
c) Conjugate base of NH 3 is NH 2-
d) Conjugate base of HOCl is Cl -
6. Which of the following acid is a stronger acid?
a) Acid having larger value of Ka
b) Acid having smaller value of pKa
c) Acid having larger value of pKa
d) Both a) and b)
7. The dissociation constant of 0.01 M CH 3COOH is 1.8 x 10 -[Link] will be the dissociation
constant of its conjugate base(CH 3COO -) ?
a) 2.4 x10 -10
b) 1.6 x10 -5
c) 6.7 x 10 -6
d) 5.6 x 10 -10
8. Which of the following statements is correct?
a) For polybasic acids, K a = Ka1 x K a2 x Ka3 ……
b) For polyacidic bases, K b = Kb1 x Kb2 x K b3…
c) Ca(OH) 2 is a polyacidic base
d) All of the above statements are correct
9. The pH of a solution is increased from 3 to 6, its H +
concentration will be:
a) Reduced to half
b) Doubled
c) Reduced by 1000 times
d) Increased by 1000 times

CONCEPTUAL QUESTIONS

1. BF3 does not have a proton but still acts as an [Link]?

2. What happens to the ionic product of water when some acid is added into water?
3. Will the pH of water be same at 4 0C and 25 0C? Explain.
4. Ionization constant K a for formic acid and acetic acid are 17.7 ×10 -5 and 1.77 ×10 -5. Which acid
is stronger and why?
5. Explain why pH of 0.1 molar solution of acetic acid will be higher than 0.1 molar solution
of HCl?
6. How does the degree of dissociation of a weak electrolyte vary with concentration of the
solution? Name the law called?
7. Why is NH 3 termed as base though it does not contain OH - ions?
NUMERICAL QUESTIONS

1. A 0.01 M solution of acetic acid is 1.34% ionized (degree of dissociation = 0.0134) at 298 K.
what is the ionization constant of acetic acid?
2. Calculate the concentration of H +(aq) in 0.2 M solution of HCN. Given the dissociation
constant of HCN in water is 4.9 ×10 -10.
3. 0.049 g of H 2SO4 is dissolved per litre of a given solution. Calculate the pH of the solution.
4. Calculate the pH value of a solution of 0.1 M NH 3 (K b = 1.8 ×10 -5).
5. What would be the pH of a solution obtained by mixing 100 ml of 0.1 N HCl and 9.9 ml of
NaOH solution?
6. The pH of a solution obtained by dissolving 0.1 mole of an acid HA in 100 ml of the aqueous
solution was found to be 3.0. Calculate the dissociation constant of the acid.
7. The pH of blood serum is 7.4. What is the [H +] of blood serum?
8. Calculate the pH of a solution obtained by diluting 25 ml of N/100 HCl to 500 ml of H 2 O.
9. The ionization constant of propanoic acid is 1.32 ×10 -5
. Calculate the degree of ionization if
its solution is 0.05 M. What will be its degree of ionization if its solution is 0.01 M in HCl
also?
10. A 50 ml solution of pH = 1 is mixed with 50 ml solution of pH = 2. What will be the pH of
the mixture?

NCERT EXERSICE QUESTIONS

Solve the question no. 7.35 to 7.57

LINKS –

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