Analytical

Chemistry
For Chemical Engineering
Chem-2074
Chapter – II B
Ionic Equilibria
2024/25
November 23, 2024 1
Outlines
 Acid-base equilibria

Acid-base theories

Common ion effect

Hydrolysis of salt

Buffer solutions
 Solubility & Solubility product principle

November 23, 2024 2

Acid-base Equilibria

 What is an acid?
 Explain the theories of acids and bases.
 Discuss the properties of an acid you know.
 What is a base?
 Discuss the properties of a base you know.
 Determine acid-base equilibrium constants.

November 23, 2024 3

Theories of acids and bases
A. Arrhenius acid and base theory (Aqueous concept)
 Svante Arrhenius, a Swedish chemist, advanced the first
modern approach to an acid-base concept
 An acid:- is a substance, that increases the concentration of
hydrogen ion, H+(aq) when dissolved in water.
E.g. HClO4 + H2O → H3O+ + ClO4 -(aq), HClO4 is acid.
 A base :- is a substance that increases the concentration of
hydroxide ion, OH-(aq) when dissolved in water.
E.g. 2NaOH + H2O →2Na+(aq) + 4OH- (aq), NaOH is base.

November 23, 2024 4

 Cont’d...
Limitations:

 The theory defines in terms of aqueous solution and was not

comprehensive enough to include non-aqueous solvents (like
liquid ammonia, liquid SO2 etc,).
 The concept also leaves the dissociated hydrogen ion at large
and doesn’t elaborate on its fate in solution.
 The existence of bare proton in solution is improbable.
 The concept restricts bases merely to hydroxides, thus metal
oxides would not be regarded as bases.
 It offered no satisfactory explanation for the acid properties of
various salts such as:
• AlCl3
• NH4NO3, etc.
November 23, 2024 5
Cont’d...
B. The Bronsted-Lowry theory of acid and bases (The protonic
concept)
 Bronsted -Lowry proposed in 1923 a new concept, which is
independent of solvents.
 According to them,
 An acid :- is a compound or ion that gives up or donates a proton.
 A base :- is a substance (compound or ion), which accepts a
proton (from an acid).
 This concept makes acid-base reactions independent of solvent.
 Neutral compounds or even ions could be designated as acids or
bases according to protonic concept.
 The relation in general can be represented as:

That is, for every acid there exists a base, which is produced
when the acid loses its proton.
November 23, 2024 6
Cont’d...
 When an acid donates a proton, there must be some base to accept
it and vice versa.

 Consider the following examples:

 When an acid releases a proton, the residue must be a base & this
base can take up proton to form the original acid.

 Therefore, any acid base reaction involves two acids and two
bases, thus forming a conjugate pair.
November 23, 2024 7
Cont’d...
Conjugate acid base pairs
Conjugate Pair

Acid + Base Base + Acid

Conjugate Pair
• Eg.
 NH4+ + H2O NH3 + H3O+
 HSO4- + H2O SO42- + H3O+
 HS- + H2O S2- + H3O+
 Thus (NH4 and NH3), (HSO4- and SO42-), (HS- and S2-), are
examples of conjugate pairs.
 A conjugate base of an acid is the part left after the proton is
lost.
 A conjugate acid of a base is the species formed on the addition
of a proton to the base.
November 23, 2024 8
Cont’d...

• Autoprotolysis (auto-ionization)

 Amphoteric solvents undergo self-ionization, to

form a pair of ionic species as illustrated by the
following equations.

November 23, 2024 9

Cont’d...

November 23, 2024 10

Cont...
Exercise 1
1. Compare the strength of the conjugate base of the ff
acids?
A. HBr
B. H2SO4
C. HCOOH
D. HCO3-
2. Compare the strength of the conjugate acid of the ff
bases?
A. S2-
B. NO3-
C. F-
D. HPO42-

November 23, 2024 11

Cont’d...
C. Lewis acid-base theory (The electronic theory)

 According to Lewis theory:

 A base:- is an electron pair donor and;

An acid:- is an electron pair acceptor.

 An acid, therefore, combines with a base leading to a coordinate
link or bond from the base to an acid.

 An acid must have a vacant orbital into which an electron pair

donated by a base can be accommodated.

 A base then is a substance, which has at least one unshared (lone)

pair of electrons.
November 23, 2024 12
Cont’d...
The acceptor has got less than a full octet:
BF3+ :NH3→H3N→BF3
ii) The acceptor has got incomplete orbital:
 Ag+ + 2:NH3→Ag (:NH3)2
iii) The acceptor has got double bond:
 O = C= O + :OH2→ O2C:OH2 or H2CO3
 An acid as a substance which can accept negative ion and a base as a
substance which can provide a negative ion as exemplified in the
following reaction
SO2 + Ca2+O2- → Ca2+ + SO32–
Thus SO2 is an acid and CaO is a base.
November 23, 2024 13
Cont’d...
Limitation

• No simple measure of the relative strengths of the bases as electron donors or

of acids as electron acceptors.

• Dissociation constants of acids (Ka) are invaluable guides to their relative acid
character (strength).

Acid/base strength

 Strong acid or base is the one completely ionized in the water

E.g. strong acid: H2SO4, HCl ….

Strong base: KOH, NaOH

 Weak acid or base is the one partially ionized in the water

E.g. Weak acid: CH3COOH, CHOOH….

Weak base: NH4OH……

November 23, 2024 14
Dissociation of Strong Monoprotic acids and bases
 The process acid /base reacts with water to produce hydronium ion
( H+) or hydroxide (OH-).
 The conjugate acid and base ion respectively is called ionization
or dissociation of acid or base.
 Strong monoprotic acids are those that lose their one proton (HCl,
HNO3).
 Strong monoprotic bases are molecules that dissociate completely
that can accept a proton (NaOH, KOH).
 In solutions of a strong monoprotic acid/base, the amount of H+
/OH- contributed to the solution by the acid is determined by the
specified concentration of the acid/base.
 Thus if a solution is labeled 0.02 M HNO3, it contributes 0.02 M
H+ and 0.02 M NO3-.
E.g. HCl + H2O → H3O++ Cl-
November 23, 2024 NaOH + H2O → Na+ + OH- 15
Cont’d...
E.g:
1) Calculate the concentration of hydrogen ion and hydroxide ion at
25 oC in a) 0.15 M HNO3 b) 0.010 M Ca(OH)2
Solution
 A strong acid or base is fully ionized in solution so you can use its
formula and molar concentration to determine H+ (or OH-) ion
concentration.
 Any contribution to this ion concentration from the self-ionization
of water is negligible.
a) Every mole of HNO3 contributes one mole of H+, so the H+
concentration is 0.15 M. and Kw = [H+][OH-], Kw = 10-14
10-14 = 0.15 M x [OH-]
[OH-] = 10-14/0.15 M = 6.7 x 10-14 M
 Therefore; The concentration of OH- in 0.15 M HNO3 is:
November 23,
6.7 2024x 10
–14 M.
16
Cont’d...
b) Ca(OH)2(s) + H2O Ca2+ (aq) + 2OH- (aq)
 Every mole of Ca(OH)2 dissolves to yield two moles of OH-.
 Therefore, 0.010 M Ca(OH)2 contains 2 x 0.010 M OH- = 0.020
M OH-.
 The H+ concentration is obtained from Kw = [H+][OH-], = 5.0
x 10-13 M
 The above relation tells us that in aqueous solution the
concentrations of H+ and OH- are inversely proportional to each
other.
 The ion product Kw = 1 x 10-14 hold true at 25oC for any dilute
aqueous solutions regardless of whether it is acid, a base or a
salt solution.

November 23, 2024 17

Dissociation of Weak Monoprotic Acids and Bases
 Weak acids and bases mean that their reactions with water don’t
go to completion (CH3COOH, HF, NH4OH…).
 Consider an aqueous solution of the weak acid, acetic acid,
CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO-(aq)
 The reaction involves the transfer of a proton from acetic acid to
water.
 The equilibrium constant expression for this reaction is:

 Thus, Ka equals [H2O] Kc.

 We can also simplify this some what by using H+ in place of H3O+.

November 23, 2024 18

Cont’d...
 Consider weak base NH4OH dissociation in water
NH4OH + H2O NH4+ + OH-
 The equilibrium constant expression for this reaction is:

 In general, acids and bases with larger value of Ka and Kb are

stronger than acids and bases with smaller values of Ka and Kb,
respectively.
 The degree of dissociation of a weak acid (base) depends on
both Ka (Kb) and the concentration of the acid (base) solution.
 For a given concentration, the larger Ka (Kb), the greater is the
degree of dissociation.
 Percent dissociation is defined as:

November 23, 2024 19

Cont’d...

November 23, 2024 20

Cont’d...

November 23, 2024 21

Cont’d...

November 23, 2024 22

 Cont’d...
The Relationship between Ka and Kb for an Acid-Base Conjugate
Pairs
 Kw = Ka.Kb or Ka. Kb = [H+][OH-]
 This can be easily seen if we consider the pairs NH4+ and NH3.
 For the NH4+ the expression corresponding to Ka is

 and for ammonia(NH3) the expression for Kb is

= [H+][OH-] = Kw
November 23, 2024 23
Cont’d...
 Note: pKa = -logKa; pKb = -logKb and in general, pX = -logX

 Thus pKa + pKb = pKw = 14 for conjugate pairs at 25oC

 The larger value of pKa, the weaker the acid is.

 Conversely the smaller the value of pKa the stronger the acid is.

 The same is true for bases.

Example

1. A 0.01 M NH3 solution was prepared and it was determined that

NH3 has undergone 4.2% dissociation. Calculate the base
ionization constant, Kb, for ammonia.

November 23, 2024 24

Cont’d...

November 23, 2024 25

Cont’d...

November 23, 2024 26

Cont’d...

November 23, 2024 27

Cont’d...
 Because [H3O+] [OH-] is a product of ion concentrations, Kw is
called the ion product for water (ionization constant or
dissociation constant of water).
 It is more convenient to describe acidity in terms of pH, which is
defined as negative logarithm of the molar hydrogen ion
concentration.
pH = log(1/[H+]) = -log[H+]
or pOH = log(1/[OH-]) = -log [OH-]

November 23, 2024 28

Cont’d...
 From Kw = [H+] [OH-] taking logarithm of both sides,
logKw = log[H+] + log[OH-]
 Multiplying both sides by negative,
-logKw = -log [H+] - log [OH-]
pKw = pH + pOH
 Since Kw = 1.0 x 10-14, pKw = -log [1.0 x 10-14] = 14.
 Hence, pH + pOH = 14 at 25oC.
 In terms of pH we have the following:
*Neutral solution: [H+] = 10-7 M; pH = 7 at 25oC.
*Acidic solution: [H+] > 10-7 M; pH < 7 at 25oC.
*Basic solution: [H+] < 10-7 M; pH > 7 at 25oC.
November 23, 2024 29
Cont’d...
Examples:

1) A sample of orange juice has a hydrogen ion concentration of 2.9

x 10-4 M at 25oC. What is the pH. Is the solution acidic?

Solution: pH = -log [H+] = -log (2.9 x 10-4) = 3.54

 Since the pH of the solution is less than 7, the solution is acidic.

2) The pH of human arterial blood is 7.40. What is its hydrogen ion

concentration?

Solution: [H+] = antilog (-pH) = 10-pH = 10-7.40 = 4.0 x 10-8 M

November 23, 2024 30

 Break for
next topic!!

November 23, 2024

 Common ion effect in Acid-Base Equilibria

 In a solution of weak acid or weak base, some ions common to the

acid or base are added, the degree of dissociation of base or acid is
suppressed.

 Thus, if in to a solution of CH3COOH, some CH3COO- ions are

added in the form of CH3COONa, the dissociation of acetic acid is
very much reduced.

 Similarly, H+ added in the form of HCl(aq) will also suppress the

dissociation of the acid.

November 23, 2024 32

Cont’d...
 Thus, addition of strong electrolyte containing a common ion to a
solution of a weak electrolyte decreases the degree of dissociation
of the weak electrolyte and the concentration of the uncommon
ion of the weak electrolyte.

 For example, the addition of HCl to a solution of H2S decreases

the concentration of S-2 and the degree of ionization of H2S.
Examples:
1. The degree of ionization of acetic acid in a 0.1 M aqueous solution
at 25oC is 0.013 and the dissociation constant of the acid at this
temperature is 1.75 x 10-5. Calculate the degree of ionization of a
0.1 M solution of acetic acid when a 0.01 M HCl solution is
added to it.
November 23, 2024 33
Cont’d...
Solution:
 The hydronium ion concentration contributed by acetic acid can be
neglected in comparison to that of HCl (0.01 M).

 The starting concentrations are [CH3COOH] = 0.1 M, [H3O+] =

0.01 M (from HCl) and [CH3COO-] = 0.

The acetic acid ionizes to give additional x mol/L of acetate ion.

November 23, 2024 34

Cont’d...

November 23, 2024 35

Cont’d...

November 23, 2024 36

Cont’d...
Table 1. The Effect of Added Acetate Ion on the Dissociation of Acetic
Acid

[CH3COOH]init [CH3COO-]added % Dissociation* [H3O+] pH

0.10 0.00 1.3 1.3x10-3 2.89

0.10 0.050 0.036 3.6x10-5 4.44

0.10 0.10 0.018 1.8x10-5 4.74

0.10 0.15 0.012 1.2x1015 4.92

[CH3COO-]dissoc
* % Dissociation = x 100
[CH3COOH]init

November 23, 2024 37

 Buffer solutions
 A buffer solution is a solution, which resists change in
hydronium ion concentration (pH) when small amount of either
a strong acid or base is added to the solution.
 Buffer solution can be prepared by mixing a weak electrolyte
and its salt.

 An acid-base buffer usually consists of a conjugate acid-base

pair where both species are present in appreciable quantities in
solution.

 An acid-base buffer is therefore a solution of a weak acid and

its conjugate base, or a weak base and its conjugate acid.
November 23, 2024 38
Cont’d...
 For example, it contains either a mixture of a weak acid and its

salt such as:

 CH3COOH and CH3COONa or CH3COONH4,

 NH4OH and NH4Cl.

 It can be immediately suggested that such solutions should

contain as their constituents, substance which can consume H+
or OH- ions producing only very weakly dissociated acid or
bases such that the original pH of the buffer solution are not
affected to any appreciable extent.

November 23, 2024 39

Cont’d...
How a Buffer Works
 The buffer components (HA and A-) are able to consume
small amounts of added OH- or H3O+ by a shift in
equilibrium position.
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Added OH- reacts with Added H3O+ reacts with

CH3COOH, causing a shift to CH3COO-, causing a shift
the right. to the left.

 The shift in equilibrium position absorbs the change in [H3O+]

or [OH-], and the pH changes only slightly.
November 23, 2024 40
Cont’d...
Buffer capacity
 The resistance of a solution in the change of pH or hydrogen ion
concentration upon an addition of an acid or a base is termed as a
buffer action.
 Buffer capacity(ß):- is the number of moles of strong acid or
base required to cause a unit change in the pH in a liter of
solution.

 Buffer capacity depends on the amount of acid and its conjugate

base in the solution or amount of a base and conjugate acid.
 The greater the buffer capacity, the more resistance the solution to pH change.
November 23, 2024 41
Cont’d...

November 23, 2024 42

Cont’d...
Calculation of pH Values of Buffer Solution:
Q. How do you prepare a buffer of a given pH?

 A buffer must be prepared from a conjugate acid-base pair in

which the acid-ionization constant is approximately equal to the
desired H+ concentration (pKa = pH).

 When the buffer pH equals the pKa of the acid component, the
buffer has its highest capacity.

November 23, 2024 43

 Cont’d...
(a) For Acidic Buffer Mixture (Henderson–Hasselbalch
equation):
 Suppose it is required to calculate the pH of an acid buffer
mixture, obtained by mixing a weak acid HA and its salt
with a strong base, BA.
 The former being weak dissociates to a small extent
whereas the latter being strong electrolyte dissociates
almost completely in the solution i.e. we have
• HA H+ + A -

• BA → B+ + A-

November 23, 2024 44

Cont’d...

Applying the law of chemical equilibrium to the

dissociation equilibrium of the weak acid, we get:

Ka = (i)

(ii)

 Suppose the concentration of the acid and the salt taken

originally in the buffer solution are c1 and c2 moles/liter,
respectively.

 As the salt BA dissociates completely, we have

November 23, 2024 [A]- = [BA] = c2 moles/litre (iii) 45
Cont’d...

Also as HA dissociates to a very small extent, the

concentration of HA at equilibrium will be almost
same as the original concentration, i.e

[HA] = c1 moles/litre (iv)

Substituting the values of [A-] and [HA] from

equations (iii) and (iv) in equation (ii), we get:
or (v)

November 23, 2024 46

Cont...

(vi)

 (b) For Basic Buffer Mixture: Proceeding exactly in a similar

manner as above, the expression for the pOH of a basic buffer
mixture (BOH + BA) can be obtained.

 Analogous to the expression (vi), we get:

(vii)

where Kb is the dissociation constant of the base.

November 23, 2024 47
Cont’d...
 This equation was derived by Henderson (1908) and is,
therefore, usually known as Henderson equation.

 Using this equation, the pH of an acid buffer mixture can

be calculated from the known concentrations of the acid
and salt provided the dissociation constant of the acid is
known.

 Similarly, knowing the dissociation constant of the acid,

the ratio of the concentrations of the salt and the acid can
be calculated which will give the desired value of pH.
November 23, 2024 48
Cont’d...
Example 1. What will be the pH value of a solution obtained by
mixing 5 g of acetic acid and 7.5 g of sodium acetate
and making the volume to 500 mL. (Ka = 1.8 x 10-5 at
25 oC)

 Describe how could you prepare a ‘phosphate buffer’ of pH =

7.4.

November 23, 2024 49

Hydrolysis of salts
 When a salt is dissolved in water, the solution is not always
neutral in reaction.
 Interaction occurs with the ions of water and the resulting
solution may be neutral, acidic or alkaline according to the
nature of the salt.
 Hence the hydrolysis of salts is defined as the reaction occurs
between the ions of the salt and ions of water to form weak acid
or weak base or both.
 Salt + H2O Acid + Base
 Salts are divided into four classes depending on their reactions
with water. These four classes are:

November 23, 2024 52

Cont’d...
1) Type I salt: Salts derived from strong acid and strong base
 Hydrolysis is caused by the shift of the dissociation equilibrium
of water due to the formation of slightly ionized compounds.
 If such compounds don’t result, that is, if both the acid and the
base that form a salt are strong, no hydrolysis takes place.
 E.g. NaCl, KCl, KI, NaNO3

NaCl + H2O Na+ + Cl-

Na+ + H2O No reaction
Cl- + H2O No reaction
 Since conjugate acids and bases of strong base and acids are
weak and results neutral salt solution.
November 23, 2024 53
Cont’d...
2) Type II salt: Salts derived from weak acid and strong base
 For example, sodium acetate formed between the weak acetic
acid and the strong base NaOH is a basic salt.
 When the salt is dissolved, ionization takes place:
CH3COONa ↔ Na+ + CH3COO-
 In the presence of water, CH3COO- (generally anions)
undergoes hydrolysis:
H2O + CH3COO- ↔ CH3COOH + OH-

 And the equilibrium constant for this reaction is Kb of the

conjugate base CH3COO- of the acid CH3COOH.
November 23, 2024 54
Cont’d...

November 23, 2024 55

Cont’d...

November 23, 2024 56

Cont’d...

November 23, 2024 57

Cont’d...
 Thus, pH= ½ pKw + ½ pKa + ½ Log Csalt

Example 1:
Calculate the [CH3COO-], [H+], [OH-] and pH of a solution of
0.100 M CH3COONa (at 298 K). (Ka = 1.8×10-5).

November 23, 2024 58

Cont’d...

November 23, 2024 59

Cont’d...
3) Type III salt; salts derived from strong acids and weak bases

 A salt formed between a strong acid and a weak base is an acid

salt.

 Ammonia is a weak base, and it’s salt with any strong acid gives
a solution with a pH lower than 7.

 For example, let us consider the reaction:

HCl + NH4OH ↔ NH4+ + Cl- + H2O

 In the solution, the NH4+ ion (generally cations) reacts with

water (called hydrolysis) according to the equation:

NH4+ + H2O ↔ NH3+ H3O+

November 23, 2024 60
Cont’d...

November 23, 2024 61

Cont’d...
Example 2:

What is the concentration of NH4+, NH3, and H+ in a 0.100 M

NH4NO3 solution? (Ka = 5.7×10-10)

 Solution: Assume that [NH3] = [H3O+] = x, and using the

reaction table:

NH4+ + H2O ↔ NH3 + H3O+

Initial 0.1 0 0

Change -x +x +x

Final 0.1-x +x +x
November 23, 2024 62
Cont’d...

November 23, 2024 63

Cont’d...
4) Type IV Salts: salts derived from weak acid and weak base

 In this type of salts, the cation of the salt combines with OH- and
anions with hydronium ion forming a feebly dissociating base and
acid, respectively.

 Therefore the resultant solution could be neutral, acidic or basic

depending on the relative strength of the cation as an acid and the
anion as a base (depending on the degree of hydrolysis of the
cation and the anion).

E.g. CH3COONH4, HCOONH4, NH4CN, etc.

November 23, 2024 64

Cont’d...
 Conditions for acidity and alkalinity of salts derived from
weak acid and weak base
 Case 1:- If Ka = Kb, the solution is neutral (pH = 7).
Example: CH3COONH4
Ka (CH3COOH) = l.75 x 10-5, Kb (NH3) = 1.80 x 10-5
 Since the ionization constants of NH3 (Kb) and CH3COOH (Ka) are
almost equal, the hydronium and hydroxyl ions must be bound
(removed) to the same extent and, therefore, the solution remains
practically neutral (pH = 7).
 The pH of the solution is determined by the pH of water used
to prepare the solution.

November 23, 2024 65

Cont’d...
 Reaction of solution of the salts will be neutral only if the base
and the acid formed in the hydrolysis have close ionization
constants.

CH3COO-(aq) + H2O (l) CH3COOH (aq) + OH-(aq)

 NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)

November 23, 2024 66

Cont’d...
 Case 2:- If Ka > Kb, the solution is acidic.
Example: HCOONH4
Kb (NH3) = 1.80 x 10-5, Ka (HCOOH) = 1.8 x 10-4
HCOO-(aq) + H2O (l) HCOOH (aq) + OH-(aq)
NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)
 Case 3:- If Kb > Ka, the solution is basic, for example,
NH4CN
Kb (NH3) = 1.80 x 10-5, Ka (HCN) = 7.2 x 10-10
NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)
CN-(aq) + H2O (l) HCN (aq) + OH-(aq)

November 23, 2024 67

Cont’d...
 Note: - Spectator ions are those ions which do not react with
water.

 When soluble compounds containing one of these spectator ions

dissolves in water we can ignore the spectator ion.

 Soluble compounds of two spectator ions have no direct effect on

the pH of water.

 If you memorize the spectator ions, you can always identify the
strong acids, strong bases, and neutral salts.

November 23, 2024 68

Cont’d...

Spectator Cations: Spectator Anions:

Li+ lithium ion Cl- chloride ion

Na+ sodium ion Br- bromide ion

K+ potassium ion I- iodide ion

Rb+ rubidium ion NO3- nitrate ion

perchlorate
Sr2+ strontium ion ClO4-
ion

Ba2+ barium ion SO42- sulfate ion

November 23, 2024 69
Cont’d...
Look the following table for the category of salts:

November 23, 2024 70

Cont’d...
Example: - Write equations to predict whether aqueous solution of the
following salts are acidic, basic or neutral:
a) KNO2 c) KClO4
b) CrCl3 d) C6H5COONa
Solution: - a) to predict weather the salt is acidic, basic or neutral; first the
hydrolysis of the salt must be determined.

 KNO2 + H2O K+ + NO2- (since K+ is a spectator ion it doesn’t

react with water, so the only ion which hydrolyzed in water is NO2- and
KNO2 completely dissolves in water.

 Hence, NO2- + H2O (l) HNO2 + OH-.

 The nitrite ion, NO2-, is a weak base and the solution will be basic.
November 23, 2024 71
Cont’d...
 c) KClO4 + H2O (l) K+ + ClO4- (both K+ and ClO4- are
spectator ions).
 Hence, none of these ions undergo hydrolysis therefore; KClO4
completely dissolves in water, forming a neutral salt solution.
So,
a) KNO2 (Basic) c) KClO4 (Neutral)
b) CrCl3 (Acidic) d) C6H5COONa (Basic)

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Solubility Product Principle

 Solubility: - Solubility of a solute in a solvent refers to the amount

of a solute that can be dissolved in a given amount of the solvent,
which is usually taken as 100 g of a solvent, at specified
temperature.

 Solubility Equilibria and solubility product: - slightly soluble

electrolytes do produce some ions in solution.

 The reaction to produce ions from the solid solute is a reversible

one, and in a saturated solution there is equilibrium between the
ions in solution and the undissolved solute.
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Solubility, solubility equilibria and solubility product

 Solubility: - Solubility of a solute in a solvent refers to the

amount of a solute that can be dissolved in a given amount of
the solvent, which is usually taken as 100 g of a solvent, at
specified temperature.
 Solubility Equilibria and solubility product: - slightly
soluble electrolytes do produce some ions in solution.
 The reaction to produce ions from the solid solute is a
reversible one, and in a saturated solution there is equilibrium
between the ions in solution and the undissolved solute.

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Cont’d...
 An equilibrium of this type may be shifted either by a change in
temperature, or by change in concentration of the ions involved
in the equilibrium.
 In general, for a slightly soluble ionic compound, MpXq,
composed of ions Mn+ and Xz-, the equilibrium reaction is:
MpXq(s) + nH2O (l) pMn+(aq) + qXz-(aq)

 and the corresponding equilibrium constant expression is:

Ksp = [Mn+]p[Xz-]q

where Ksp is known as the solubility product constant.

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Cont’d...
Examples: - Write solubility product expression for:

a) Magnesium carbonate (MgCO3)

b) Calcium phosphate (Ca3 (PO4)2)
c) Ferric hydroxide (Fe (OH) 3)
d) Arsenic (III) sulphide (As2S3)

Solution:
a) MgCO3(s) + H2O (l) Mg2+(aq) + CO32-(aq)
Then Ksp = [Mg2+][CO32-]
b) Ca3 (PO4)2(s) + H2O (l) 3Ca2+(aq) + 2PO43-(aq)
Then Ksp = [Ca2+]3[PO43-]2
c) Fe(OH) 3(s) + H2O (l) Fe3+(aq) + 3OH-(aq)
Then Ksp = [Fe3+][OH-]
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Cont’d...
Calculations Involving the Solubility Product Constant
Calculating solubility product constant from solubility:-
 The value of Ksp can be obtained from the solubility and vice-
versa.
 The solubility’s of ionic compounds are determined
experimentally.

Example: 1) The solubility of AgCl is 0.0015 g/L. Calculate the

solubility product constant (Ksp) of AgCl. (Formula weight of
AgCl = 143.5 g/mol

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Cont’d...

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Cont’d...

November 23, 2024 79

Cont’d...
Exercises:
1. Lead sulphate, PbSO4, is used as a white pigment in paints and
as key component in common lead-acid batteries. Its solubility
in water at 25oC is 4.25 x 10-3 g/100 mL of solution. What is
the Ksp of the lead sulphate? (Formula weight of PbSO4 is
303.3 g/mol)
2. the solubility of barium sulphate (BaSO4) (F.Wt = 233) at 25oC
is 0.0023 mg/mL of solution. Calculate the value of its Ksp?

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Cont’d...
Calculation of solubility from solubility product constant
 The reverse of the previous problems type involves finding the
solubility of a compound based on its formula and Ksp value.
 Hence, the solubility product constants can be used to calculate
solubility values if the ionization reactions and the formula
weights are known.
Examples:
1. calculate the solubility of SrC2O4 in gram per liter (analytical
(g/L), if the Ksp is 1.4 x 10-7.

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Cont’d...

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Cont’d...
 The solubility in grams per liter = (molar solubility)
(formula weight)
 The solubility in grams per liter = 3.7 x 10-4 mol/L x 176 g/mol
= 0.065 g/L

Exercise
1. The Ksp of Mg(OH)2 is 3.4 x 10-11. Calculate the concentration
of hydroxide ion in a saturated solution of Mg (OH) 2 and the pH
of the resulting solution (Formula weight of Mg(OH)2 = 58.3197
g/mol).

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Cont’d...
Factors affecting solubility
1. Common ion effect:
 The presence of a common ion decreases the solubility of a
slightly soluble ionic compound.

 For instance, how is the solubility of Pb(IO3)2 affected if we

add Pb(IO3)2 to a solution of 0.10 M Pb(NO3)2?

 We begin by setting up a table to help us keep track of the

concentrations of Pb2+ and IO3–in this system.

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Cont’d...
PbI2(s) Pb2+(aq) + 2IO3–(aq)

Initial concentration solid 0.10 0

Change in concentration solid +x +2x
concentration solid 0.10+x=x 0+2x=2x
 Substituting the equilibrium concentrations into the solubility product
expression;

Ksp = [Pb2+][IO3-]2

= (0.10+x)(2x)2 = 2.5110–13 but 0.10+x ≈ 0.10

= (0.10)(2x)2 = 2.5110–13 = 0.40x2 = 2.510–13
x = 7.9110–7M

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Cont’d...
 The solubility of Pb(IO3)2 is equal to the additional
concentration of Pb2+ in solution, or 7.9x10–7mol/L.

 As expected, the solubility of Pb(IO3)2 decreases in the presence

of a solution that already contains one of its ions.

 This is known as the common ion effect.

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Cont’d...
Example:
1. What is the solubility of silver chromate, Ag2CrO4, in g/L,
in a 0.1 M solution of K2CrO4? The Ksp of Ag2CrO4 is 9 x 10-12.
Solution: i) before adding K2CrO4 (solubility of Ag2CrO4 in pure
water)

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Cont’d...

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Cont’d...
2. Salt Effect

 The presence of ions from either KNO3 or K2SO4 increases the

solubility of compound and as a result, the value for its
solubility product.

 But the effect is greater in the presence of ions from K2SO4 than
of ions produced by KNO3.

 This difference is attributed to the doubly charged SO42-, which

have more effect upon the solubility than the nitrate ion with a
single charge.

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Cont’d...
3. Acidity (pH) Effect
 The hydronium ion concentration can have a profound effect on
the solubility of an ionic compound.

 If the compound contains the anion of a weak acid, addition of

H3O+ (from a strong acid) increases its solubility.

 The Le Chatelier’s principle can be used to explain it.

 For example, in a saturated solution of calcium carbonate, CaCO3,

we have:

CaCO3(s) Ca2+(aq) + CO32-(aq)

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Cont’d...
 According to the Le Chatelier’s principle if we add which
increase the concentration of Ca2+ and CO32-, the equilibrium will
shift the direction into the backward; i.e formation of CaCO3.

 If we decrease the concentration of Ca2+ and CO32-, it will shift

the direction into the forward to increase the concentration of
Ca2+ and CO32-; i.e it will increase solubility of CaCO3.

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 Cont’d...
 Adding strong acid introduces a large amount of H3O+, which
immediately reacts with the carbonate ion to form a weak acid,
HCO3-

 CO32-(aq) + H3O+(aq) → HCO3-(aq) + H2O(l)

 If enough acid is added, further reaction occurs to form carbonic

acid, which decomposes immediately to CO2 and H2O:

HCO3-(aq) + H3O+(aq) → H2CO3(aq) + H2O(l) → CO2(g) +

2H2O(l)

 Thus, the net effect of added strong acid (H3O+) is a shift in

equilibrium position to the right, and more CaCO3 dissolves.
November 23, 2024 92
Cont’d...

 In contrast, adding H3O+ to a saturated solution of a compound

with strong-acid anion, such as silver chloride has no effect on the

equilibrium position and hence the solubility:

 AgCl(s) Ag+(aq) + Cl-(aq)

 Because Cl- ion is a conjugate base of strong acid (spectator ion),

HCl, it ordinarily coexists in solution with high [H3O+]. Since Cl-

is not removed from the system, the equilibrium position is not

affected.

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 Thank you !!

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