Chemistry, The Central Science, 11th edition

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

and Bruce E. Bursten

Chapter 9A
Acids and Bases

John D. Bookstaver
Acids
St. Charles Community College and
Bases
Cottleville, MO © 2009, Prentice-Hall, Inc.
Arrhenius
Arrhenius •• Brønsted-
Brønsted- Lewis
Lowry
Lewis
Lowry
acid
acid dissolved
dissolvedininH2O,
H2O, An
Anacid
acidisisaaH+
H+donor
donor Lewis
Lewisacids
acidsare
aredefined
defined
the
theconcentration
concentrationof ofH+ Ex: as
aselectron-pair
H+ Ex:HCl
HCl electron-pair
Ex
Ex:HCl
:HCl acceptors.
acceptors.
Ex:
Ex:BF3
BF3

base
base ininH2O,
H2O, the
the AAbase
baseisisaaH+
H+acceptor
acceptor Lewis
Lewisbases
basesare
aredefined
defined
concentration
concentrationof
ofOH-
OH- Ex:
Ex:NH3
NH3,H2O
,H2O as
aselectron-pair
electron-pairdonors
donors
Ex:
Ex:NaOH
NaOH Ex:
Ex:NH3
NH3,H2O
,H2O
Because
Becausebase
basehave
haveaapair
pair
of
ofnonbonding
nonbondingelectrons
electrons

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Some Definitions

• Brønsted-Lowry
– An acid is a proton donor.
– A base is a proton acceptor.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
A Brønsted-Lowry acid…
…must have a removable (acidic) proton.

A Brønsted-Lowry base…
…must have a pair of nonbonding electrons.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Lewis Acids

• Lewis acids are defined as electron-pair

acceptors.
• Atoms with an empty valence orbital can be Lewis
acids. Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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. Acids
and
Bases
© 2009, Prentice-Hall, Inc.
If it can be either…

amphiprotic. • Amphoterism
– Amphoteric metal
HCO - oxides and
3
hydroxides are
HSO4- soluble in strong acid
or base, because
they can act either as
H2O acids or bases.
– Examples of such
cations are Al3+,
Acids
Zn2+, and Sn2+. and
Bases
© 2009, Prentice-Hall, Inc.
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.
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
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.
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
Acid and Base Strength
• Substances with
negligible acidity do not
dissociate in water.
– Their conjugate bases are
exceedingly strong.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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). Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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).
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
What is the pH of a solution made by dissolving 2.5 g NaOH in 400 mL water?
Determine number of moles of NaOH

 1 mol NaOH 
x mol NaOH = 2.5 g NaOH   = 0.0625 mol NaOH
 40 g NaOH 
Calculate the molarity of the solution

mol 0.0625 mol NaOH

M=  [Recall 1000 mL = 1 L]
L 0.4 L

MNaOH = 0.15625 molar

NaOH Na1+ + OH1-

0.15625 molar 0.15625 molar 0.15625 molar

pOH = -log [OH-] or kW = [H+] [OH-]

pOH = -log [0.15625 M] 1 x 10-14 = [H+] [0.15625 M]
pOH = 0.8 [H+] = 6.4 x 10-14 M
pOH + pH = 14 pH = -log [H+]
0.8 + pH = 14 pH = 13.2 pH = -log [6.4 x 10-14 M]
 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.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 pH

pH is defined as the negative base-10

logarithm of the concentration of
hydronium ion.

pH = -log [H3O+]

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Watch This!
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
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
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.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 How Do We Measure pH?

For more accurate

measurements, one
uses a pH meter,
which measures the
voltage in the
solution.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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].
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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. Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Dissociation Constants
The greater the value of Ka, the stronger is the acid.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Calculating Ka from the pH

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+] [COO-]
Ka =
[HCOOH]

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Calculating Ka from the pH

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.

To calculate Ka, we need the equilibrium

concentrations of all three things.
We can find [H3O+], which is the same as
[HCOO-], from the pH.
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
Calculating Ka from the pH

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

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Calculating Ka from pH

Now we can set up a table…

[HCOOH], M [H3O+], M [HCOO-], M

Initially 0.10 0 0
Change - 4.2  10-3 + 4.2  10-3 + 4.2  10-3
At Equilibrium 0.10 - 4.2  10-3 4.2  10-3 4.2  10-3
= 0.0958 = 0.10

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
Calculating Ka from pH

[4.2  10-3] [4.2  10-3]

Ka =
[0.10]

= 1.8  10-4

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
Calculating Percent Ionization
[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% Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Calculating pH from Ka

Calculate the pH of a 0.30 M solution of

acetic acid, HC2H3O2, at 25C.

HC2H3O2 (aq) + H2O (l) H3O+ (aq) + C2H3O2- (aq)

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

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Calculating pH from Ka

The equilibrium constant expression is

[H3O+] [C2H3O2-]
Ka =
[HC2H3O2]

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Calculating pH from Ka

We next set up a table…

[C2H3O2], M [H3O+], M [C2H3O2-], M

Initially 0.30 0 0
Change -x +x +x
At Equilibrium 0.30 - x  0.30 x x

We are assuming that x will be very small

compared to 0.30 and can, therefore, be ignored.
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Calculating pH from Ka

Now,

(x) 2
1.8  10-5 =
(0.30)
(1.8  10-5) (0.30) = x2
5.4  10-6 = x2
2.3  10-3 = x Acids
and
Bases
© 2009, Prentice-Hall, Inc.
Calculating pH from Ka

pH = -log [H3O+]
pH = -log (2.3  10-3)
pH = 2.64

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Weak Bases

Bases react with water to produce hydroxide ion.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Weak Bases

The equilibrium constant expression for

this reaction is

[HB] [OH-]
Kb =
[B-]

where Kb is the base-dissociation constant.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Weak Bases
Kb can be used to find [OH-] and, through it, pH.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 pH of Basic Solutions

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]

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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. Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 Factors Affecting Acid Strength

• 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. Acids
and
Bases
© 2009, Prentice-Hall, Inc.
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.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
Factors Affecting Acid Strength

For a series of oxyacids, acidity increases

with the number of oxygens.
Acids
and
Bases
© 2009, Prentice-Hall, Inc.
Factors Affecting Acid Strength

Resonance in the conjugate bases of

carboxylic acids stabilizes the base and
makes the conjugate acid more acidic.

Acids
and
Bases
© 2009, Prentice-Hall, Inc.