12/10/2021

IONIC EQUILIBRIA

Acid-Base Equilibria (Recap)

Acids:
Arrhenius acid: Any substance that, when dissolved in water,
increases the concentration of hydroxonium ion (H3O+)
Bronsted-Lowry acid: A proton donor
Lewis acid: An electron pair acceptor
Bases:
Arrhenius base: Any substance that, when dissolved in water,
increases the concentration of hydroxide ion (OH-)
Bronsted-Lowery base: A proton acceptor
Lewis base: An electron pair donor

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Brønsted-Lowry Theory of Acids & Bases

Conjugate Acid-Base Pairs

General Equation

Conjugate Acid-Base Pairs

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Acid Dissociation Constant

Base Dissociation Constant

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Ionization of Water
conjugate pair

H2O + H2O HO- + H3O+

ACID BASE conj base conj acid

conjugate pair

Autoionization of Water
H2O(l) + H2O(l) H3O+ + OH-

[H3O+][OH-]
Kc =
[H2O]2

The ion-product for water, Kw:

Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 (at 25°C)

For pure water the concentration of hydroxyl and hydronium ions

must be equal:
[H3O+] = [OH-] = 1.0 x 10-14 = 1.0 x 10 -7 M (at 25°C)

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pH Scale
 pH is a measure of how acidic or basic a solution is.
 The pH scale ranges from 0 to 14.
 Acidic solutions have pH values below 7
 A solution with a pH of 7 is neutral.
 Pure water has a pH of 7.
 Basic solutions have pH values above 7.

Manipulating pH
Algebraic manipulation of:
pH = - log [H3O+]
allows for:
[H3O+] = 10-pH
If pH is a measure of the hydronium ions
concentration then the same equations could be
used to describe the hydroxide (base)
concentration since [H+] = [OH-]
[OH-] = 10-pOH pOH = - log [OH-]
thus:
pH + pOH = 14 ; the entire pH range!

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pH Practice

[H3O+] [OH-] pH pOH

0.015 M 6.61x10-13 1.82 12.18

8.41

2.16

3.7 x 10-8 M

Calculate the pH of 0.10-M HNO3 solution.

HNO3 + H2O  H3O+ + NO3-

HNO3 is a strong 0.10 M ---- ----
acid - Ka is large!
It dissociates - 0.10 + 0.10 + 0.10
completely.
---- 0.10 M 0.10 M
Thus, [H3O+] = 0.10 M
pH = - log (0.10) = 1.00

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Finding the Ka of a Weak Acid from the pH

of its Solution–I
Problem: The weak acid hypochlorous acid is formed in bleach
solutions. If the pH of a 0.12 M solution of HClO is 4.19, what is the
value of the Ka of this weak acid.
Plan: We are given [HClO]initial and the pH which will allow us to find
[H3O+] and, hence, the hypochlorite anion concentration, so we can
write the reaction and expression for Ka and solve directly.
Solution:

Calculating [H3O+] : [H3O+] = 10-pH = 10-4.19 = 6.46 x 10-5 M

Concentration (M) HClO(aq) + H2O(l) H3O+(aq) + ClO -(aq)

Initial 0.12 ---- ------- -------

Change -x ---- +x +x
Equilibrium 0.12 -x ---- +x +x
[H3O+] = [ClO-] from the equation

BUT since HClO is a weak acid, we assume 0.12 M - x = 0.12 M

Finding the Ka of a Weak Acid from the pH of

its Solution–II
HClO(aq) + H2O(l) H3O+(aq) + ClO -(aq)

x = [H3O+] = [ClO-] = 6.46 x 10-5 M

[H3O+] [ClO-] (6.46 x 10-5 M) (6.46 x 10-5 M)

Ka = = = 3.48 x 10 -8
[HClO] 0.12 M

Ka = 3.48 x 10-8 In text books it is found to be: 3.5 x 10-8

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Determining Concentrations from Ka and Initial [HA]

Problem: Hypochlorous acid is a weak acid formed in laundry bleach.
What is the [H3O+] of a 0.125 M HClO solution? Ka = 3.5 x 10-8
Plan: We need to find [H3O+]. First we write the balanced equation and
the expression for Ka and solve for the hydronium ion concentration.
Solution:
HClO(aq) + H2O(l) H3O+(aq) + ClO-(aq)

[H3O+] [ClO-]
Ka = = 3.5 x 10-8
[HClO]

Concentration (M) HClO H 2O H3O+ ClO-

Initial 0.125 ---- 0 0

Change -x ---- +x +x
Equilibrium 0.125 - x ---- x x

(x)(x) assume 0.125 - x = 0.125

Ka = = 3.5 x 10-8
0.125-x x2 = 0.4375 x 10-8 x = 0.661 x 10-4 M

HF (Weak acid): What is the pH of 0.15 M

HF
HF + H2O  H3O+ + F-
0.15 M ---- ----
-x +x +x
0.15 - x x x

4 [ H O  ][ F  ] 6.7 x10 4 
x2
K a  6.7 x10  3 0.15
[ HF ]
x = 0.0097 M = [H3O+]
x2
6.7 x10 4 
0.15  x pH = {- log (0.0097)} = 2.01
Since Ka is small let’s assume
that x << 0.15 M

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pH of a Strong Base
Calculate the pH of a 2.0 x 10-3 M solution of NaOH.

Since NaOH is a strong base, it will dissociate 100% in water.

NaOH(aq) Na+(aq) + OH-(aq)

Since [NaOH] = 2.0 x 10-3 M , [OH-] = 2.0 x 10-3 M

The concentration of [H+] can be calculated from Kw:

Kw 1.0 x 10-14
[H+] = [OH-] = = 5.0 x 10-12 M
2.0 x 10-3

pH = - log [H+] = - log( 5.0 x 10-12) = 11.7

Determining pH from Kb and Initial [B]–I

Problem: Ammonia is commonly used cleaning agent in households and
is a weak base, with a Kb of 1.8 x 10-5. What is the pH of a 1.5 M NH3
solution?
Plan: Ammonia reacts with water to form [OH-] and then calculate
[H3O+] and the pH. The balanced equation and Kb expression are:

NH3 (aq) + H2O(l) NH4+(aq) + OH-(aq)

[NH4+] [OH-]
Kb =
[NH3]

Concentration (M) NH3 H2O NH4+ OH-

Initial 1.5 ---- 0 0

Change -x ---- +x +x
Equilibrium 1.5 - x ---- x x

making the assumption: since Kb is small: 1.5 M - x = 1.5 M

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Determining pH from Kb and Initial [B]–II

Substituting into the Kb expression and solving for x:

[NH4+] [OH-] (x)(x)

Kb = = = 1.8 x 10 -5
[NH3] 1.5

x2 = 2.7 x 10-5 = 27 x 10-6

x = 5.20 x 10-3 = [OH-] = [NH4+]

Calculating pH:
Kw 1.0 x 10-14
[H3O+] = = = 1.92 x 10 -12
[OH-] 5.20 x 10-3

pH = -log[H3O+] = {- log (1.92 x 10-12)} = 11.72

The Relation Between Ka and Kb of a Conjugate

Acid-Base Pair

Acid HA + H2O H3O+ + A-

Base A- + H2O HA + OH-

2 H2 O H3O+ + OH-

[H3O+] [A-] [HA] [OH-]

[H3O+] [OH-] = x
[HA] [A-]

Kw = Ka x Kb

Ka = 4.5 x 10-4

For HNO2 Ka x Kb = (4.5 x 10-4)(2.2 x 10-11) = 9.9 x 10-15

Kb = 2.2 x 10-11 or ~ 10 x 10-15 = 1 x 10 -14 = Kw

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