The Chemistry of Acids

and Bases
AP CHEMISTRY
Acid-Base Theories Left: Svante Arrhenius
Right: Gilbert Lewis

“acid” – from Latin acidus, meaning sour Arrhenius Acid-Base Theory – +

◦ Acid – donates a hydrogen ion (H ) in water
“alkali” – Arabic for the ashes that come from -
burning certain plants – in water these ashes ◦ Base – donates a hydroxide ion (OH ) in water
make solutions that feel slippery and taste bitter ◦ Limited. Doesn’t explain how NH3 can be basic.
Bronsted-Lowry Acid-Base Theory –
◦ Acid – donates a proton in water
◦ Base – accepts a proton in water
◦ Better. Explains ammonia as a base.
Lewis Acid-Base Theory –
◦ Acid – accepts an electron pair
◦ Base – donates an electron pair
◦ Best. Explains all traditional acids and bases, gas
phase reactions, coordination compounds. Most
general.
Bronsted-Lowry Acids and Bases
Conjugate acid-base pair – a pair of species Neutral compound as an acid
that differ only by ONE H+ unit

In all acid examples, the hydronium ion forms.

Cation as an acid

Anion as an acid
Bronsted-Lowry Acids and Bases
In all base examples, hydroxide ion forms by Neutral compound as a base
the transfer of a proton from water to the
base.

Anions as bases
Exercise 1
In the following reaction, identify the acid on the left and its CB on the right. Identify the base on
the left and its CA on the right.

HBr + NH3  NH4+ + Br-

What is the CB of H2S?

What is the CA of NO3-?

Acids donate only one proton at a time!
Monoprotic acids –

Diprotic acids –

Polyprotic acids –

Polyprotic bases –

Amphiprotic or amphoteric –
Exercise 2
Write the simple dissociation reaction (omitting water) for each of the following acids:
Hydrochloric acid
Acetic acid
Ammonium ion
Anilinium ion (C6H5NH3+)
Hydrated aluminum ion [Al(H2O)6]3+
Hydrated iron(III) ion [Fe(H2O)6]3+
 Relative Strengths of Acids and Bases
“Strength” is determined by the
position of the equilibrium.
Strong Acids/Strong Bases –
dissociate completely, have very
large dissociation constants
Weak Acids/Weak Bases –
dissociate only slightly, have
very small dissociation constants
Strong Acids vs. Weak Acids
The SIX Strong Acids (memorize!)
HCl
HBr
HI
HNO3
H2SO4
HClO4
Structure and
Acid Strength
Strong Bases
Hydroxides or oxides of group 1 and 2 metals (except Mg and Be, which have solubility issues)
The stronger the acid, the weaker its
conjugate base. (The converse is also true.)
Weak Acids and Bases
The vast majority of acids and bases are weak.
If it’s not on the short list of strong acids and
bases you memorized, it’s WEAK.
Equilibrium is established and it lies far to the
left – reactant favored.
The acid dissociation constant, Ka

Write the Ka expression for acetic acid.

Weak Bases
Bases that do not contain OH-, but produce it by interacting with water.
The reaction between ammonia and water.

Amines are weak bases.

Weak Bases
Weak Bases
The equilibrium expression for bases, Kb

Write the Kb expression for ammonia.

Ka and Kb Expressions
Look similar! H+ vs H3O+
Ka expressions include H3O+ (or H+)
Kb expressions include OH-
Exercise 3
Using the table in the appendix of your book, arrange the following species according to their
strength as bases:
H2O, F-, Cl-, NO2-, CN-

NOTE: Water is a stronger base than the CB of a strong acid, but a weaker base than the CB of a
weak acid.
Water, The Hydronium Ion, Auto-
Ionization, and the pH Scale
Friedrich Kohlrausch, around 1900, found that no matter how pure water is, it still conducts a
minute amount of electric current, proving that water self-ionizes.
Water is amphoteric, and can act as either an acid or a base.

The autoionization constant for water, Kw

Kw = [H3O+][OH-] = 1.008 x 10-14 ≈ 1 x 10-14 (@ 25°C) = Ka x Kb
Kw = Ka x Kb = 1 x 10-14

Allows us to calculate the hydroxide and hydronium ion concentrations for various situations.
[OH-] = [H+] solution is neutral, each of these values is 1 x 10-7 in pure water @25°C
[OH-] > [H+] solution is basic
[OH-] < [H+] solution is acidic
Exercise 5
At 60°C, the value of Kw is 1 x 10-13.
Using LeChatelier’s principle, predict whether the reaction is exothermic or endothermic.

Calculate [OH-] and [H+] in a neutral solution at 60°C.

The pH Scale
Used to designate the hydrogen ion
concentration in aqueous solutions where this
value is small.

pH = -log[H+]
pOH = -log[OH-]
pH + pOH = 14
NOTE: Sig Digs
Report as many decimal places on a pH as there are sig digs in the least accurate measurement
you are given.

[H+] = 1.15, report pH with 3 decimal places.

[H+] = 1.2, report pH with 2 decimal places.
Exercise 6
Calculate either the [H+] or the [OH-] from the information given for each of the following
solutions at 25°C.
1.0 x 10-5 M OH-

1.0 x 10-7 M OH-

10.0 M H+
Exercise 7
Calculate the pH and pOH for each of the following solutions at 25°C.

1.0 x 10-3 M OH-

1.0 M H+
Exercise 8
The pH of a sample of human blood was measured to be 7.41 at 25°C. Calculate pOH, [H+], and
[OH-] for the sample.
Exercise 9
Calculate the pH of 0.10 M HNO3

Calculate the pH of 1.0 x 10-10 M HCl

Exercise 10
Calculate the pH of a 5.0 x 10-2 M NaOH solution.
Calculating the pH of Weak Acid
Solutions
Set up a RICE table!
Calculate the pH of a 1.00 x 10-4 M solution of acetic acid. The Ka of acetic acid is 1.8 x 10-5.
Neglecting x
[HA]o > 100Ka
Exercise 11
Calculate the pH of a 0.10 M solution of acetic acid. The Ka of acetic
acid is 1.8 x 10-5.
Exercise 12
Calculate the pH of a 0.100 M aqueous solution of hypochlorous
acid. (Ka = 3.5 x 10-8)
Solutions Containing More Than One
Weak Acid
Only the acid with the largest Ka value will contribute an appreciable
amount of H+. Determine the pH based on this acid and ignore any
others.

HCN Ka = 6.2 x 10-10

HNO2 Ka = 4.0 x 10-4
Exercise 13
Calculate the pH of a solution that contains 1.00 M HCN (Ka = 6.2x10-10) and 5.00
M HNO2 (Ka = 4.0 x 10-4). Also calculate the concentration of cyanide ion (CN-) in
this solution at equilibrium.
Exercise 14
Calculate the percent dissociation of acetic acid (Ka = 1.8 x 10-5) in each of the following
solutions.
A. 1.00 M acetic acid

B. 0.100 M acetic acid

Exercise 15
In a 0.100 M aqueous solution, lactic acid is 3.7% dissociated. Calculate the value of Ka for this
acid.
pH for a Weak Base
Determination of the pH of a weak base solution is very similar to the determination of the pH
of a weak acid solution.

Write dissociation equation, use RICE table, and solve Kb expression.

Determine [OH-].
Find pOH.
Find pH.
pH = 14 - pOH
Exercise 16
Calculate the pH for a 15.0 M solution of ammonia (Kb = 1.8 x 10-5).
Exercise 17
Calculate the pH of a 1.0 M solution of methylamine (Kb = 4.38 x 10-4).
Calculating pH of Polyprotic Acids
Polyprotic acids ionize in steps.
Each dissociation has its own Ka value.
First dissociation will be the greatest.
Subsequent dissociations have much smaller
equilibrium constants.
As each H+ is removed, remaining acid gets
weaker and therefore has a smaller Ka.
As negative charge on acid increases it becomes
more difficult to remove a positively charged
proton.
The FIRST Ka determines the pH of the solution!
 Calculate the pH of a 5.0 M H3PO4 solution and the
equilibrium concentrations of the species H3PO4, H2PO4-,
Exercise 18 HPO42-, and PO43-.
Exercise 19
Calculate the pH of a 1.0 M H2SO4 solution.
Exercise 20
Calculate the pH of a 1.0 x 10-2 M H2SO4 solution.
Acid-Base Properties of Salts: Hydrolysis
Neutral salts: cation of strong base with anion of strong acid

Basic salts: when the anion is the conjugate base of a weak acid; ex. potassium acetate

Acidic salts: when the cation is the conjugate acid of a weak base; ex. ammonium chloride

If both the cation and the anion contribute to the pH situation, compare Ka and Kb.
If Kb > Ka, solution is basic.
If Ka > Kb, solution is acidic.
Exercise 21
Predict whether an aqueous solution of each of the following salts will be acidic, basic, or
neutral. Write appropriate equations.
NaC2H3O2

NH4NO3

Al2(SO4)3
Relationship between Ka and Kb
Exercise 22
Calculate the pH of a 0.30 M NaF solution. The Ka value for HF is 7.2 x 10-4.
Exercise 23
Calculate the pH of a 0.10 M NH4Cl solution. The Kb value for NH3 is 1.8 x 10-5.
Exercise 24
Calculate the pH of a 0.010 M AlCl3 solution. The Ka value for [Al(H2O)6]3+ is 1.4 x 10-5.
Lewis Acids and Bases
Acid – electron pair acceptor
Base – electron pair donor
Coordinate covalent bonds – covalent bonds in which both electrons come from the same atom
BF3 and NH3
Exercise 25
Determine whether each of the following is a Lewis acid or a Lewis base. Draw structures as
proof.
PH3
BCl3
H2S
SF4
Exercise 26
For each reaction, identify the Lewis acid and Lewis base.
Ni2+(aq) + 6NH3(aq)  [Ni(NH3)6]2+

H+(aq) + H2O(l) H3O+(aq)

Solving Acid-Base Problems
1. List the major species in solution.
2. Look for reactions that can be assumed to
go to completion, for example, a strong acid
dissociating, or H+ reacting with OH-.
3. For a reaction that can be assumed to go to
completion, determine the concentration of
the products and write down the major
species in solution after the reaction.
4. Look at each major component of the
solution and decide if it is an acid or base.
5. Pick the equilibrium that will control the pH.
Use known values of the dissociation
constants for the species to help determine
the dominant equilibrium.
◦ Write the equation for the reaction and the
equilibrium expression.
◦ Compute the initial concentration.
◦ Determine the equilibrium concentrations in
terms of x (RICE table).
◦ Substitute into the equilibrium expression and
solve for x.
◦ Calculate the pH and other concentrations as
required.