Acids and Bases

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.
If it can be either…
…it is amphiprotic.
-
HCO3
-
HSO4
H2O (HOH)

Acids
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.
 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.
 pH

These are
the pH
values for
several
common
substances.

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
• Percent Ionization =  100
• In this example [H 3 O +
]eq
[HA]
[H3O ]eq = 4.2  10-3 Minitial
+

[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

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.
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)

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

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

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

Acids
and
Bases
© 2009, Prentice-Hall, Inc.
 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 affect on pH
depends on the Ka and Kb
values. 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.
 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
Acids
and
Bases
© 2009, Prentice-Hall, Inc.