Chemistry, The Central Science, 10th edition

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

and Bruce E. Bursten

Chapter 16
Acids and Bases

Acids
and
Bases
 Some Definitions

• Arrhenius

Acid: Substance that, when dissolved in
water, increases the concentration of
hydrogen ions.

Base: Substance that, when dissolved in
water, increases the concentration of
hydroxide ions.

Acids
and
Bases
HCl is an Arrhenius Acid.
HCl gas is a molecular compound
It is very soluble in water and producs
H+ ions
Concentrated acid is 37% by mass and
12M in concentration.
NaOH is an Arrhenius Base
It is an ionic compound
It is soluble in water and produces OH-
ions Acids
and
Bases
 Some Definitions

• Brønsted–Lowry

Acid: Proton donor

Base: Proton acceptor

Acids
and
Bases
Certain substances can be
either…

...it is amphiprotic.

HCO3 −

HSO4−

H2O
Acids
and
Bases
A Brønsted–Lowry acid…

…must have a removable (acidic) proton.

A Brønsted–Lowry base…

…must have a pair of nonbonding electrons.

Acids
and
Bases
• NH3 is a Lowry base

Acids
and
Bases
 H+ ion in water

• A H+ ion is simply a proton with no

surrounding electrons.
• So it can interact strongly with the
nonbonding electron pairs of oxygen in
water to form a hydronium ion H3O+
• Hydronium ion can form additional H
bonds with water and form additional
clusters like H5O2+ and H9O4+ .
Acids
and
Bases
Acids
and
Bases
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
 What happens with NH3
In Aqueous solutions
NH3(aq) + H2O(l)
NH4+(aq) + OH-(aq)

The Bronsted Lowry Acid base concept also

applies to substances that are not in aqueous
solutions:
NH3+ HCl
NH4+ + Cl-
This reaction occurs in gas phase.
Acids
and
Bases
 Conjugate Acids and Bases:

• From the Latin word conjugare, meaning “to

join together.”
• Reactions between acids and bases always
yield their conjugate bases and acids.

Acids
and
Bases
• (a) What is the conjugate base of each of the following acids: HClO4,
H2S, PH4+, HCO3– ?
• (b) What is the conjugate acid of each of the following bases: CN–,
• SO4 2– , H2O, HCO3– ?

Acids
and
Bases
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
Acid and Base Strength
• Substances with
negligible acidity do not
dissociate in water.

Their conjugate bases are
exceedingly strong.

Acids
and
Bases
 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 K is not
measured (K>>1). Acids
and
Bases
 Acid and Base Strength
HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2−(aq)
Acetate is a stronger base than H2O, so the
equilibrium favors the left side (K<1).

Acids
and
Bases
SAMPLE EXERCISE 16.3 Predicting the Position of a Proton-Transfer Equilibrium

For the following proton-transfer reaction, use Figure 16.4 to predict whether the equilibrium lies predominantly
to the left (that is, Kc < 1) or to the right (Kc > 1):

Acids
and
Bases
PRACTICE EXERCISE
For each of the following reactions, use Figure 16.4 to predict whether the equilibrium lies predominantly to the
left or to the right:

Acids
and
Bases
• About Amphoteric and Amphiprotic

Acids
and
Bases
 Auto ionization 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
• This auto ionization of water is very
limited
• About 2 molecules / 109 molecules.

Acids
and
Bases
 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
At 25°C,
Kw = [OH-] [H3O+]
Remember H3O+ and H+ both can be used
interchangeably
= [OH-] [H+]
=1.0 × 10−14

• You need to remember this value!

Acids
and
Bases
SAMPLE EXERCISE 16.4 Calculating [H+] for Pure Water
Calculate the values of [H+] and [OH–] in a neutral solution at 25°C.

In an acid solution [H+] is greater than 1.0 × 10–7 M ; in

a basic solution [H+] is less than 1.0 × 0–7 M.

PRACTICE EXERCISE
Indicate whether solutions with each of the following ion concentrations are neutral,
acidic, or basic:
(a) [H+] = 4 × 10–9 M; (b) [OH–] = 1 × 10–7 M; (c) [OH–] = 7 × 10–13M.

Answers: (a) basic, (b) neutral, (c) acidic

Acids
and
Bases
 SAMPLE EXERCISE 16.5 Calculate the concentration of H+ (aq) in (a) a
solution in which [OH–] is 0.010 M, (b) a solution in which [OH–] is 1.8 × 10–9
M. Note: In this problem and all that follow, we assume, unless stated otherwise,
that the temperature is 25°C.

This solution is basic because

(b) In this instance

This solution is acidic because

Acids
and
Bases
 pH

pH is defined as the negative base-10

logarithm of the hydronium ion
concentration.

pH = −log [H3O+]

Acids
and
Bases
 pH
• In pure water,

Kw = [H3O+] [OH−] = 1.0 × 10−14

• Because in pure water [H3O+] = [OH−],

[H3O+] = (1.0 × 10−14)1/2 = 1.0 × 10−7

Acids
and
Bases
 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
 pH

These are
the pH
values for
several
common
substances.

Acids
and
Bases
• If the pH is say, 3.76
• pH = - log [H+] = 3.76
log [H+] = -3.76
[H+] = 10 -3.76 = 1.7 x 10-4

Acids
and
Bases
 Other “p” Scales

• The “p” in pH tells us to take the

negative log of the quantity (in this case,
hydrogen ions).
• Some similar examples are

pOH −log [OH−]

pKw −log Kw

Acids
and
Bases
Since
[H3O+] [OH−] = Kw = 1.0 × 10−14

If we take a –log of both sides

-log [H3O+] [OH−] = -logKw
logab = loga + logb
therefore
(−log [H3O+]) + (−log [OH−]) = −log Kw
= - log(1.0x10-14)
= 14.00
or, in other words,
Acids
pH + pOH = pKw = 14.00 and
Bases
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

An indicator

Acids
and
Bases
 How Do We Measure pH?

For more accurate

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

Acids
and
Bases
 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
 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
 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
 Dissociation Constants

The greater the value of Ka, the stronger

the acid.

Acids
and
Bases
SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?

Acids
and
Bases
SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?

Acids
and
Bases
 SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?

From the measured pH, we can calculate [H+]:

Acids
and
Bases
 SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?

From the measured pH, we can calculate [H+]:

The equilibrium-constant expression is

Acids
and
Bases
 SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?

From the measured pH, we can calculate [H+]:

The equilibrium-constant expression is

Acids
and
Bases
Acids
and
Bases
We can now insert the equilibrium concentrations into the expression for Ka :

Check: The magnitude of our answer is reasonable because Ka for a weak acid is usually between 10–3 and
10–10.

Acids
and
Bases
 PRACTICE EXERCISE
Niacin, one of the B vitamins, has the following molecular structure:

A 0.020 M solution of niacin has a pH of 3.26. (a) What percentage of the acid is ionized in this solution?
(b) What is the acid-dissociation constant, Ka, for niacin?

Acids
and
Answers: (a) 2.7%, (b) 1.5 × 10–5 Bases
 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+] [HCOO−]
Ka =
[HCOOH]
Acids
and
Bases
 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
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
 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 0.10 − 4.2 × 10−3 4.2 × 10−3 4.2 × 10−3

Equilibrium = 0.0958 = 0.10
Acids
and
Bases
Calculating Ka from pH

[4.2 × 10−3] [4.2 × 10−3]

Ka =
[0.10]

= 1.8 × 10−4

Acids
and
Bases
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

Acids
and
Bases
Calculating Percent Ionization

4.2 × 10−3
Percent Ionization = × 100
0.10

= 4.2%

Acids
and
Bases
 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
 Calculating pH from Ka

The equilibrium constant expression is

[H3O+] [C2H3O2−]
Ka =
[HC2H3O2]

Acids
and
Bases
 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

Acids
compared to 0.30 and can, therefore, be ignored. and
Bases
 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
Calculating pH from Ka

Now
pH = −log [H3O+]
pH = −log (2.3 × 10−3)
pH = 2.64

Acids
and
Bases
• Percent ionization of HC2H3O2
= 0.0023M x 100 = 0.77%
0.30

Acids
and
Bases
 Something Very Important

• If the percent ionization of an acid is

less than 5% then it can be taken as
negligible.
• But if it is more than it, then it needs to
be considered and the quadratic
equations must be used to calculate the
value of x.
Acids
and
Bases
 Strong vs. weak acid

• For 0.30 M solution of acetic acid the

pH would be 2.64
• By comparison the pH of 0.30 M HCl
would be
-log [H+]= - log [0.30] = 0.52 .
Which is more acidic?

Acids
and
Bases
• The percent ionization of the weak acid
decreases as the concentration increases.

Acids
and
Bases
 SAMPLE EXERCISE 16.12 Using Ka to Calculate Percent Ionization

Calculate the percentage of HF molecules ionized in

(a) a 0.10 M HF solution,
(b) (b) a 0.010 M HF solution.
The equilibrium reaction and equilibrium concentrations are as follows:

The equilibrium-constant expression is

When we try solving this equation using the approximation 0.10 – x = 0.10 (that is, by neglecting the
concentration of acid that ionizes in comparison with the initial concentration), we obtain

Acids
and
Bases
SAMPLE EXERCISE 16.12 continued

Because this value is greater than 5% of 0.10 M, we should work the problem without the approximation, using
an equation-solving calculator or the quadratic formula. Rearranging our equation and writing it in standard
quadratic form, we have

This equation can be solved using the standard quadratic formula.

Substituting the appropriate numbers gives

Of the two solutions, only the one that gives a positive value for x is chemically reasonable. Thus,
Acids
and
Bases
SAMPLE EXERCISE 16.12 continued

From our result, we can calculate the percent of molecules ionized:

(b) Proceeding similarly for the 0.010 M solution, we have

The percentage of molecules ionized is

Acids
and
Bases
It is what we would expect from Le Châtelier’s principle. • There are
more “particles” or reaction components on the right side of the
equation than on the left. Dilution causes the reaction to shift in the
direction of the larger number of particles because this counters the
effect of the decreasing concentration of particles.

HF (aq) ⇌ H+ (aq) + CN- (aq)

Acids
and
Bases
 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
Ascorbic Acid
H2C6H6O6

Citric Acid
H3C6H5O7

Acids
and
Bases
 Weak Bases

Bases react with water to produce hydroxide ion.

Acids
and
Bases
 Weak Bases

The equilibrium constant expression for this reaction is

[NH4+] [OH−]
Kb =
[NH3]
Acids
where Kb is the base-dissociation constant. and
Bases
 Weak Bases

Kb can be used to find [OH−] and, through it, pH.

Acids
and
Bases
 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
 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
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
 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
 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
 Calculate
(a) the base-dissociation constant, Kb, for the fluoride ion (F–);
(b) the acid-dissociation constant, Ka, for the ammonium ion
(NH4+).
Solve: (a) Ka for the weak acid, HF, is given in Table 16.2 and Appendix D as Ka = 6.8 × 10–4 . We can use
Equation 16.40 to calculate Kb for the conjugate base, F–:

(b) Kb for NH3 is listed in Table 16.4 and in Appendix D as Kb = 1.8 × 10–5. Using Equation 16.40, we can
calculate Ka for the conjugate acid, NH4+:

Acids
and
Bases
Acid-Base properties of salt
solutions

Acids
and
Bases
• About the discussion on Monday at
11:30!

Acids
and
Bases
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
• If the anion is a base
of a strong acid then
it will be a weak
base and will have
little tendency to
abstract proton from
water.
• Consequently it will
not affect the pH of
the solution.

Acids
and
Bases
• If the anion belongs
to a weak acid it will
consequently be a
relatively strong
base and will
release the OH – ion
from water making it
basic

Acids
and
Bases
Reactions of Cations with Water
• Cations with acidic protons
(like NH4+) will lower the pH of
a solution, by donating a
proton to the water molecule.

NH4+ +H2O
NH3 + H3O+

• Most metal cations that are

hydrated in solution also lower
the pH of the solution.
(details later) Acids
and
Bases
Reactions of Metal 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
 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
 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 higher of the Ka and Kb values.
Acids
and
Bases
 Factors Affecting Acid
Strength
Bond Polarity
Bond strength
H-F though very polar, has a very strong bond
with the bond enthalpy of 567 kJ / mol. So the
HF acid is a weak acid.
Stability of the conjugate base. The more sable
the conjugate base the stronger the acid

Acids
and
Bases
 Binary Acids
• Binary acids are acids between a proton
and one more element.
• In general the H-X bond strength is the
most important factor in determining the
acid strength between the binary acids
of the same group of the periodic table.

Acids
and
Bases
• Bond strength decreases and so acidity increases
down a group.
• Across a group the bond strength does not change
much, so the bond polarity is the factor determining
the acidity across a row.
Acidity increases as the electro negativity increases.
Acids
• Acidity increases from left to right across a row and and
from top to bottom down a group. Bases
 Oxyacids

O
H-O -S- O-H
O

H2SO4

What makes this an acid and not a base Acids

and
Bases
 Factors Affecting Acid Strength
Compounds in which an OH
is bonded to another atom,
Y,
If the Y was an
electropositive metal then the
compound would be a base

In oxyacids, the Y is a
nonmetal and the more
electronegative Y is, the
more acidic the acid.
.
Acids
and
Bases
This happens because:
a. the electron density is drawn towards Y
and it makes the O-H bond weaker.
b. The conjugate base of the acid is an
anion and its stability increases as the
electronegativity of Y increases.

Acids
and
Bases
Factors Affecting Acid Strength

For a series of oxyacids, acidity increases

with the number of oxygens.
Acids
and
Bases
 Carboxylic Acids
Resonance in the conjugate bases of
carboxylic acids stabilizes the base and
makes the conjugate acid more acidic.

Acids
and
Bases
 Lewis Acids

• Lewis acids are defined as electron-pair

acceptors.
• Atoms with an empty valence orbital can be Lewis
acids. Acids
and
Bases
 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
Acids
protons, however. and
Bases