CHAPTER 4

EFFECT OF ELECTROLYTES ON CHEMICAL

EQUILIBRIUM :
EFFECT OF ELECTROLYTES ON IONIC
EQUILIBRIUM, THERMODYNAMIC AND
CONCENTRATION EQUILIBRIUM CONSTANTS,
ACTIVITY AND ACTIVITY COEFFICIENTS
1
 In this chapter,

chemical equilibrium including calculations of chemical

composition and of equilibrium concentrations for
monoprotic acid/base systems will be considered.

buffer solutions, which are extremely important in many

areas of science, and describe the properties of these
solutions will be discussed.

2
 THE CHEMICAL COMPOSITION OF
AQUEOUS SOLUTIONS

Electrolytes form ions when dissolved in water (or certain other

solvents) and thus produce solutions that conduct electricity.

Strong electrolytes ionize essentially completely in a solvent,

Weak electrolytes ionize only partially.

Conducting electricity by weak electrolytes <<< strong

electrolyte

3
 *H2SO4 is completely dissociated into HSO42- and H3O+ ions and for
this reason is classified as a strong electrolyte.

HSO42- ion is a weak electrolyte and is only partially dissociated into

SO42- and H3O+.
4
 Brønsted-Lowry Theory

An acid donates protons. A base is a proton acceptor.

only in the presence of a proton only in the presence of a proton

acceptor (base). donor (acid).

A salt is produced in the reaction

of an acid with a base.
NaCl, Na2SO4, NaOOCCH3

Arrhenius acid-base definition

(acid produces H3O+ and base forms OH- in water.)
Lewis acid-base definition
(acid accepts and shares electron and bases share their electrons)
5
A conjugate base is formed when an
acid loses a proton.

conjugate acid/base pair

acid1/base1

A conjugate acid is formed when an

base gains a proton.

conjugate acid/base pair

base2/acid2

A substance acts as an acid only in the presence of a base and vice versa.
6
Neutralization:

HNO2 + NH3  NH4+ + NO2-

NO2- + H2O  HNO2 + OH-

base1 acid2 conjugate conjugate
acid1 base2

NH4+ + H2O  NH3 + H3O+

acid1 base2 conjugate conjugate
base1 acid2

7
 Species that have both acidic and
Amphiprotic Species basic properties are amphiprotic.

 behaves as a base in the presence of a proton donor.

 behaves as an acid in the presence of a proton acceptor.

Water acts as a proton acceptor (base) and as a proton donor (acid):

Amphiprotic solvent 8
The simple amino acids are an important class of amphiprotic
compounds that contain both a weak acid and a weak base functional
group.

an amino acid, undergoes a kind of internal acid/base reaction to

produce a zwitterion—a species that has both a positive and a
negative charge.

acid/base reaction between a carboxylic acid and an amine

9
Water acts as a proton acceptor (base) and as a proton donor (acid):
Amphiprotic solvent

Other common amphiprotic solvents are methanol, ethanol, and

anhydrous acetic acid.

10
Autoprotolysis Amphiprotic solvents undergo self-ionization, or
autoprotolysis, to form a pair of ionic species.
(autoionization)

Water slightly undergoes autoprotolysis at room temperature. Thus,

the hydronium (H3O+) and hydroxide ion(OH-) concentrations in pure
water are only about 10-7 M.
11
 Strengths of Acids and Bases
strong acids: reaction with the solvent is sufficiently complete that
no undissociated solute molecules are left in
aqueous solution.

weak acids: react incompletely with water to give solutions

containing significant quantities of both the parent
acid and its conjugate base.

Note that acids can be cationic, anionic, or electrically neutral.

The same holds for bases.

The common strong acids The common strong bases

include HCl, HBr, HI, HClO4, include NaOH, KOH, Ba(OH)2,
HNO3, the first proton in and the quaternary ammonium
H2SO4, and the organic hydroxide R4NOH, where R is an
sulfonic acid RSO3H. alkyl group such as CH3 or C2H5.
12
Conjugate acids/bases of strong acids/bases do not undergo a
hydrolysis reaction. They are not strong enough to produce
hydronium (H3O+) and hydroxide ion(OH-) .

Conjugate acids/bases of weak acids are strong enough to undergo a

hydrolysis reaction. They are produce hydronium (H3O+) or
hydroxide ion(OH-) and change the pH of the solution.

Note that acids can be cationic, anionic, or electrically neutral.

The same holds for bases.

13
 The tendency of a solvent to accept or donate protons determines the
strength of a solute acid or base dissolved in it.

Water, is a leveling solvent for perchloric, hydrochloric, and nitric

acids because all three are completely ionized in this solvent and
show no differences in strength.

In a leveling solvent, several acids are completely dissociated and

show the same strength. 14
Anhydrous acetic acid acts as a differentiating solvent toward the two
acids by revealing the inherent differences in their acidities.

ClO4

Perchloric acid is, however, about 5000 times stronger than hydrochloric acid
in this solvent.

We conclude that :

 anhydrous acetic acid, is a weaker proton acceptor than water,

neither of HCl and HClO4 undergoes complete dissociation.
 Instead, equilibria such as the above mentioned are established.

In a differentiating solvent, various acids dissociate to different

degrees and have different strengths.

“Only perchloric acid is a strong acid in methanol and ethanol.

Therefore, these two alcohols are also differentiating solvents.”
15
 CHEMICAL EQUILIBRIUM

Many reactions used in analytical chemistry never result in complete

conversion of reactants to products.

They proceed to a state of chemical equilibrium in which the ratio of

concentrations of reactants and products is constant.

Equilibrium- constant expressions:

 describe the concentration relationships among reactants and

products at equilibrium.
 permit calculation of the error in an analysis resulting from the
quantity of unreacted analyte that remains when equilibrium has
been reached.

16
The Equilibrium State

We can follow the rate of this reaction and the extent to which it
proceeds to the right by monitoring the appearance of the orange-red
color of the triiodide ion I3-.

A solution of identical color intensity can be produced by using

appropriate amount of reactants for both reactions.

The final position of a chemical equilibrium is

independent of the route to the equilibrium state.

the concentration relationship at chemical equilibrium (that is, the

position of equilibrium) is independent of the route to the equilibrium state.
17
This relationship is altered by applying stress to the system.

Such stresses include changes in temperature, in pressure (if one

of the reactants or products is a gas), or in total concentration of a
reactant or a product.

These effects can be predicted qualitatively from the

Le Châtelier’s principle.

The mass-action effect is a shift in the position of an equilibrium

caused by adding one of the reactants or products to a system.

This principle states that the position of chemical equilibrium

always shifts in a direction that tends to relieve the effect of
an applied stress.
18
Equilibrium is a dynamic process.

Although chemical reactions appear to stop at equilibrium, in fact, the

amounts of reactants and products are constant because the rates of
the forward and reverse processes are exactly the same.

Chemical thermodynamics is a branch of chemistry that concerns

the flow of heat and energy in chemical reactions. The position of a
chemical equilibrium is related to these energy changes.

19
Equilibrium-Constant Expressions

where the square-bracketed terms are:

1. molar concentrations if they represent dissolved solutes.

2. partial pressures in atmospheres if they are gas-phase reactants
or products.

In such an instance, we will often replace the square bracketed terms

with the symbol p, which stands for the partial pressure of the gases in
atmospheres.

If a reactant or product is a pure liquid, a pure solid, or the solvent

present in excess, no term for this species appears in the equilibrium-
constant expression.
20
 Exact Equilibrium
Approximate Equilibrium constants
constants (thermodynamic)

21
Types of Equilibrium Constants in Analytical Chemistry

22
The formation of Ni(CN)42- is typical in that it occurs in steps as shown.
stepwise formation constants are: K1, K2, …

23
Overall constants are designated by the symbol n.

24
 Applying the Ion-Product Constant for Water
Aqueous solutions contain small concentrations of hydronium and
hydroxide ions as a result of the dissociation reaction.

ion-product constant for water

-log Kw = -log[H3O+] - log [OH-]

p Kw = pH + pOH At 25°C, pKw =14.00.

25
Why [H2O] Does Not Appear in Equilibrium-Constant Expressions
for Aqueous Solutions

In a dilute aqueous solution, the molar concentration of water is

If we have 0.1 mol of HCl in 1 L of water. The presence of this acid will shift the
equilibrium to the left.

Originally, however, there was only 10-7 mol/L OH- to consume the added protons.

Therefore, even if all the OH- ions are converted to H2O, the water concentration
will increase to only

26
 The percent change in
water concentration is
insignificant.

The ion-product constant for water permits us to easily find the

hydronium and hydroxide ion concentrations of aqueous
solutions.

Applying the ION-PRODUCT constant for water

Calculate the hydronium and hydroxide ion concentrations of pure

water at 25°C and 100°C.

Answers:

At 25°C [H3O+] = [OH-] = 1.00×10-7 M

At 100°C [H3O+] = [OH-] = 7.00×10-7 M
27
EXAMPLE : Calculate the hydronium and hydroxide ion concentrations
and the pH and pOH of 0.013 M aqueous KOH at 25 C.

EXAMPLE : Calculate the hydronium and hydroxide ion concentrations

and the pH and pOH of 1.30×10-7 M aqueous KOH at 25 C.

28
EXAMPLE : Calculate the hydronium and hydroxide ion concentrations
and the pH and pOH of 0.023 M aqueous HNO3 at 25 C.

EXAMPLE : Calculate the hydronium and hydroxide ion concentrations

and the pH and pOH of 2.30×10-7 M aqueous HNO3 at 25 C.

29
USING ACID/BASE DISSOCIATION CONSTANTS

1. Dissociation Constants for Conjugate

Acid/Base Pairs

2. Hydronium Ion Concentration of Solutions of

Weak Acids

3. Hydronium Ion Concentration of Solutions of

Weak Bases

30
 Using Solubility-Product Constants

1. The Solubility of a Precipitate in Pure Water

2.The Effect of a Common Ion on the Solubility of a

Precipitate

31