Chemistry, The Central Science, 12th edition

Theodore L. Brown, H. Eugene LeMay, Jr.,

and Bruce E. Bursten

Chapter 16
Acids and Bases
 Some Definitions
• Arrhenius
– An acid is a substance that, when
dissolved in water, increases the
concentration of hydrogen ions.
– A base is a substance that, when dissolved
in water, increases the concentration
of hydroxide ions.
• Brønsted-Lowry
– An acid is a proton donor.
– A base is a proton acceptor.
A Brønsted-Lowry acid…
…must have a removable (acidic) proton.

A Brønsted-Lowry base…
…must have a pair of nonbonding electrons.
If it can be either…
…it is amphiprotic.

HCO3-

HSO4-

H2O
What Happens When an Acid
Dissolves in Water?
• Water acts as a
Brønsted-Lowry base
and abstracts a proton
(H+) from the acid.
• As a result, the
conjugate base of the
acid and a hydronium
ion are formed.
 Conjugate Acids and Bases
• The term conjugate comes from the Latin
word “conjugare,” meaning “to join together.”
• Reactions between acids and bases always
yield their conjugate bases and acids.
Acid and Base Strength
• Strong acids are
completely dissociated in
water.
– Their conjugate bases are
quite weak.
• Weak acids only
dissociate partially in
water.
– Their conjugate bases are
weak bases.
Acid and Base Strength
• Substances with
negligible acidity do not
dissociate in water.
– Their conjugate bases are
exceedingly strong.
 Acid and Base Strength

• In any acid-base reaction, the equilibrium will

favor the reaction that moves the proton to
the stronger base.

HCl (aq) + H2O (l)  H3O+ (aq) + Cl- (aq)

• H2O is a much stronger base than Cl-, so

the equilibrium lies so far to the right that K
is not measured (K>>1).
 Acid and Base Strength

• In any acid-base reaction, the equilibrium will

favor the reaction that moves the proton to
the stronger base.

CH3CO2H (aq) + H2O (l) H3O+ (aq) + CH3CO2- (aq)

• Acetate is a stronger base than H2O, so the

equilibrium favors the left side (K<1).
 Autoionization of Water

• As we have seen, water is amphoteric.

• In pure water, a few molecules act as
bases and a few act as acids.

H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)

• This is referred to as autoionization.

 Ion-Product Constant

• The equilibrium expression for this

process is
Kc = [H3O+] [OH-]
• This special equilibrium constant is
referred to as the ion-product constant
for water, Kw.
• At 25C, Kw = 1.0  10-14
 pH

pH is defined as the negative base-10

logarithm of the concentration of
hydronium ion.

pH = -log [H3O+]
 pH
• In pure water,

Kw = [H3O+] [OH-] = 1.0  10-14

• Since in pure water [H3O+] = [OH-],

[H3O+] = 1.0  10-14 = 1.0  10-7

 pH
• Therefore, in pure water,
pH = -log (1.0  10-7) = 7.00
• An acid has a higher [H3O+] than pure water,
so its pH is <7.
• A base has a lower [H3O+] than pure water,
so its pH is >7.
 pH

These are
the pH
values for
several
common
substances.
 Other “p” Scales

• The “p” in pH tells us to take the

negative base-10 logarithm of the
quantity (in this case, hydronium ions).
• Some similar examples are
– pOH: -log [OH-]
– pKw: -log Kw
Because
[H3O+] [OH-] = Kw = 1.0  10-14,
we know that
-log [H3O+] + -log [OH-] = -log Kw = 14.00
or, in other words,
pH + pOH = pKw = 14.00
How Do We Measure pH?
• For less accurate
measurements, one
can use
– Litmus paper
• “Red” paper turns
blue above ~pH = 8
• “Blue” paper turns
red below ~pH = 5
– Or an indicator.
 How Do We Measure pH?

For more accurate

measurements, one
uses a pH meter,
which measures the
voltage in the
solution.
 Strong Acids
• You will recall that the seven strong acids are
HCl, HBr, HI, HNO3, H2SO4, HClO3, and
HClO4.

• These are, by definition, strong electrolytes

and exist totally as ions in aqueous solution.

• For the monoprotic strong acids,

[H3O+] = [acid].
 Strong Bases

• Strong bases are the soluble hydroxides,

which are the alkali metal and heavier
alkaline earth metal hydroxides (Ca2+, Sr2+,
and Ba2+).

• Again, these substances dissociate

completely in aqueous solution.
 Dissociation Constants

• For a generalized acid dissociation,

HA (aq) + H2O (l) A- (aq) + H3O+ (aq)
the equilibrium expression would be
[H3O+] [A-]
Kc =
[HA]
• This equilibrium constant is called the
acid-dissociation constant, Ka.
• Note that H2O is omitted from Ka because it is a pure liquid
 Dissociation Constants

The larger the Ka, the stronger the acid

If Ka >> 1, then the acid is completely ionized

 strong acid
 Dissociation Constants
The greater the value of Ka, the stronger is the acid.
 Calculating Ka from the pH

• pH  [H+] at equilibrium
• Equilibrium [H+]  RICE table
• Use RICE table to find the [other species]
 Calculating Ka from the pH
Sample Exercise 16.10
The pH of a 0.10 M solution of formic acid,
HCOOH, at 25C is 2.38. Calculate Ka for formic
acid at this temperature.
We know that
[H3O+] [HCOO-]
Ka =
[HCOOH]

We can find [H3O+], which is the same as

[HCOO-], from the pH.
 Calculating Ka from the pH

pH = -log [H3O+]
2.38 = -log [H3O+]
-2.38 = log [H3O+]
10-2.38 = [H3O+]
4.2  10-3 = [H3O+] = [HCOO-]
 Calculating Ka from pH

Note that the [HCOOH] remains at 0.10 M at equilibrium

– sig figs. This will become very important later in this chapter.

[4.2  10-3] [4.2  10-3]

Ka =
[0.10]

= 1.8  10-4
Calculating Percent Ionization
Sample Exercise 16.11

A 0.10 M solution of formic acid

(HCOOH) contains 4.2 x 10-3 M H+(aq).
Calculate the percentage of the acid
that is ionized.
 Calculating Percent Ionization
Sample Exercise 16.11
[H3O+]eq
• Percent Ionization = [HA]  100
initial
• In this example
[H3O+]eq = 4.2  10-3 M
[HCOOH]initial = 0.10 M

4.2  10-3
Percent Ionization =  100
0.10
= 4.2%
 Using Ka to Calculate pH

• Using Ka, we can calculate the concentration

of H+ (and hence the pH).

Example: Calculate the pH of a 0.30 M

solution of acetic acid, HC2H3O2, at 25C.

Ka for acetic acid at 25C is 1.8  10-5.

 Using Ka to Calculate pH

1. Write the balanced chemical equation,

clearly showing the equilibrium.

CH3COOH(aq) D H+(aq) + CH3COO-(aq)

 Using Ka to Calculate pH

2. Write the equilibrium expression.

Look up the value for Ka (in a table).

Ka = [H+][ CH3COO-] = 1.8 x 10-5

[CH3COOH]
 Using Ka to Calculate pH

3. Write down the initial and equilibrium

concentrations for everything except pure water.
 Using Ka to Calculate pH
4. Substitute into the equilibrium constant
expression and solve.

Ka = 1.8 x 10-5 = [H+][C2H3O2-] = (x)(x)

[HC2H3O2] 0.30 – x

1.8 x 10-5 = x2
0.30 – x

quadratic
Sometimes solving a quadratic equation to determine
the value of x can be avoided.

• If the Ka value is quite small, we can assume

that x is negligible compared to the initial
concentration.
• It is always necessary to check the validity of
any assumption. Once we have the value of
x, check to see how large it is compared to
the initial concentration.
• If x is < 5% of the initial concentration, the
assumption is probably a good one.
• If x > 5% of the initial concentration, then it
may be best to solve the quadratic equations.
 Using Ka to Calculate pH
4. Substitute into the equilibrium constant expression and solve.

Keep this x

x2 = 1.8 x 10-5
0.30 – x

Neglect this x

 x2 = (1.8 x 10-5 )(0.30) = 5.4 x 10-6

 x2 =  (5.4 x 10-6)

x = 2.3 x 10-3 M = [H+]

 Using Ka to Calculate pH

Check: Compare x with original [HC2H3O2] of 0.30 M:

2.3 x 10-3 M x 100% = 0.77%, which is < 5%

0.30 M
 Using Ka to Calculate pH

5. Convert x ([H+]) to pH.

pH = - log (2.3 x 10-3) = 2.64

 Polyprotic Acids…
…have more than one acidic proton
If the difference between the Ka for the first
dissociation and subsequent Ka values is
103 or more, the pH generally depends only
on the first dissociation.
 Weak Bases
Weak bases remove protons from substances.
They react with water to produce hydroxide ion.
 Weak Bases
The equilibrium constant expression for
this reaction is

[HB] [OH-]
Kb =
[B-]
= [NH4+] [OH-]
[NH3]
where Kb is the base-dissociation constant.
The larger Kb, the stronger the base.
 Weak Bases
Kb can be used to find [OH-] and, through it, pH.
 pH of Basic Solutions
Sample Exercise 16.15 (p. 691)

What is the pH of a 0.15 M solution of NH3?

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

[NH4+] [OH-]
Kb = = 1.8  10-5
[NH3]
 pH of Basic Solutions

Tabulate the data.

[NH3], M [NH4+], M [OH-], M

Initially 0.15 0 0
At Equilibrium 0.15 - x  0.15 x x
 pH of Basic Solutions

(x) 2
1.8  10-5 =
(0.15)
(1.8  10-5) (0.15) = x2
2.7  10-6 = x2
1.6  10-3 = x2
 pH of Basic Solutions

Check the assumption:

1.6  10-3 M x 100% = 1.1%, < 5%
0.15 M
 pH of Basic Solutions

Therefore,
[OH-] = 1.6  10-3 M
pOH = -log (1.6  10-3)
pOH = 2.80
pH = 14.00 - 2.80
pH = 11.20
 Types of Weak Bases

Weak bases generally fall into one of two

categories.
1. Neutral substances with a lone pair of electrons
that can accept protons.

Most neutral weak bases contain nitrogen.

Amines are related to ammonia and have one or more

N–H bonds replaced with N–C bonds
(e.g., CH3NH2 is methylamine).
 Types of Weak Bases

Like NH3, amines can abstract a proton from a water

molecule by forming an additional N-H bond,
as shown in this figure for methylamine.
 Types of Weak Bases

2. Anions of weak acids are also weak bases.

e.g.: ClO– is the conjugate base of HClO (weak acid):

ClO–(aq) + H2O(l) D HClO(aq) + OH–(aq) Kb = 3.3 x 10–7

 Ka and Kb

Ka and Kb are related in this way:

Ka  Kb = Kw

Therefore, if you know one of them, you can calculate the other.

Alternatively, pKa + pKb = pKw = 14.00 (at 25oC)

Acid/Base Properties of Salt
Solutions
Reactions of Anions with Water

• Anions are bases.

• As such, they can react with water in a
hydrolysis reaction to form OH- and the
conjugate acid:

X- (aq) + H2O (l) HX (aq) + OH- (aq)

Reactions of Cations with Water

• Cations with acidic protons

(like NH4+) will lower the pH
of a solution.
• Most metal cations that are
hydrated in solution also
lower the pH of the solution.
Reactions of Cations with Water

• Attraction between nonbonding

electrons on oxygen and the
metal causes a shift of the
electron density in water.
• This makes the O-H bond more
polar and the water more acidic.
• Greater charge and smaller size
make a cation more acidic.
Effect of Cations and Anions

1. An anion that is the

conjugate base of a strong
acid will not affect the pH.
2. An anion that is the
conjugate base of a weak
acid will increase the pH.
3. A cation that is the
conjugate acid of a weak
base will decrease the pH.
 Effect of Cations and Anions

4. Cations of the strong

Arrhenius bases will not
affect the pH.
5. Other metal ions will
cause a decrease in pH.
6. When a solution contains
both the conjugate base
of a weak acid and the
conjugate acid of a weak
base, the effect on pH
depends on the Ka and Kb
values.
 Factors Affecting Acid Strength
(Sec. 16.10-16.11)

• The more polar the H-X bond and/or the weaker

the H-X bond, the more acidic the compound.
• So acidity increases from left to right across a row
and from top to bottom down a group.
Factors Affecting Acid Strength

In oxyacids, in which
an -OH is bonded to
another atom, Y, the
more electronegative
Y is, the more acidic
the acid.
Factors Affecting Acid Strength

For a series of oxyacids, acidity increases

with the number of oxygens.
Factors Affecting Acid Strength

Resonance in the conjugate bases of

carboxylic acids stabilizes the base and
makes the conjugate acid more acidic.
 Comparison of Different Types
of Acids and Bases
Arrhenius (traditional) acids and bases (C19th)
• Acid: compound containing H that ionizes to yield H+ in
solution

• Base: compound containing OH that ionizes to yield OH- in

solution

(Note: does not describe acid/base behavior in solvents

other than water)
Bronsted-Lowry Acids and Bases (1923)

• Acid: H+ (proton) donor

• Base: H+ (proton) acceptor

NH3 + H 2O D NH4+ + OH-

ammonia water ammonium ion hydroxide ion

(B-L base) (B-L acid) (B-L acid) (B-L base)

Note: Every Brønsted-Lowry acid/base is

also a Lewis acid/base.
Lewis Acids and Bases (1920’s)

• Acid: accepts pair of e-‘s

• Base: donates pair of e-‘s

.. ..
H+ + [:O:H] -  H:O:H
.. ..

Lewis acid Lewis base

 Lewis Acids

• Lewis acids are defined as electron-pair

acceptors.
• Atoms with an empty valence orbital can be Lewis
acids.
 Lewis Bases

• Lewis bases are defined as electron-pair donors.

• Anything that could be a Brønsted-Lowry base is
a Lewis base.
• Lewis bases can interact with things other than
protons, however.
 Hydrolysis of Metal Ions

• The Lewis concept may be used to explain

the acid properties of many metal ions.
• Metal ions are positively charged and attract
water molecules (via the lone pairs on the
oxygen atom of water).
• Hydrated metal ions act as acids.
• For example:
Fe(H2O)63+(aq) D Fe(H2O)5(OH)2+(aq) + H+(aq) Ka = 2 x 10–3
 Hydrolysis of Metal Ions

In general:
• The higher the charge, the stronger the M–OH2
interaction.
• Ka values generally increase with increasing
charge
• The smaller the metal ion, the more acidic the ion.
• Ka values generally decrease with decreasing
ionic radius
• Thus the pH of an aqueous solution increases as
the size of the ion increases (e.g., Ca2+ vs. Zn2+) and
as the charge increases (e.g., Na+ vs. Ca2+ and Zn2+
vs. Al3+).