Lecture Presentation

Chapter 16

Acid–Base
Equilibria

James F. Kirby
Quinnipiac University
Hamden, CT
© 2015 Pearson Education, 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.
• Brønsted–Lowry
– An acid is a proton donor.
– A base is a proton acceptor.
Acids
and
Bases
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 Brønsted–Lowry Acid and Base
A Brønsted–Lowry acid must have at
least one removable (acidic) proton (H+)
to donate.
A Brønsted–Lowry base must have at
least one nonbonding pair of electrons to
accept a proton (H+).

Acids
and
Bases
© 2015 Pearson Education
 What Is Different about Water?
• Water can act as a Brønsted–Lowry base and
accept a proton (H+) from an acid, as on the
previous slide.
• It can also donate a proton and act as an
acid, as is seen below.
• This makes water amphiprotic.

Acids
and
Bases
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 Conjugate Acids and Bases
• The term conjugate means “joined together
as a pair.”
• Reactions between acids and bases always
yield their conjugate bases and acids.

Acids
and
Bases
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 Relative Strengths of Acids
• Acids above the and Bases
line with H2O as
a base are strong
acids; their
conjugate bases
do not act as acids
in water.
• Bases below the line
with H2O as an acid
are strong bases; • The substances between the
their conjugate
lines with H2O are conjugate
acids do not act as
acids in water. acid–base pairs in water. Acids
and
Bases
© 2015 Pearson Education
 Acid and Base Strength
• In every acid–base reaction, equilibrium favors
transfer of the proton from the stronger acid to the
stronger base to form the weaker acid and the weaker
base.
 HCl(aq) + H2O(l) → H3O+(aq) + Cl(aq)
 H2O is a much stronger base than Cl, so the
equilibrium lies far to the right (K >> 1).
 CH3COOH(aq) + H2O(l) ⇌ H3O+(aq) + CH3COO–(aq)
 Acetate is a stronger base than H2O, so the
equilibrium favors the left side (K < 1). Acids
and
Bases
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 Autoionization of Water
• Water is amphoteric.
• In pure water, a few molecules act as bases
and a few act as acids.
• This is referred to as autoionization.

Acids
and
Bases
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 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
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Aqueous Solutions Can Be Acidic,
Basic, or Neutral
• If a solution is neutral, [H+] = [OH–].
• If a solution is acidic, [H+] > [OH–].
• If a solution is basic, [H+] < [OH–].

Acids
and
Bases
© 2015 Pearson Education
 pH
• pH is a method
of reporting
hydrogen ion
concentration.
• pH = –log[H+]
• Neutral pH is 7.00.
• Acidic pH is below 7.00.
• Basic pH is above 7.00.
Acids
and
Bases
© 2015 Pearson Education
 Other “p” Scales

• The “p” in pH tells us to take the –log of

a quantity (in this case, hydrogen ions).
• Some other “p” systems are
pOH: –log[OH]
pKw: –log Kw

Acids
and
Bases
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 Relating pH and pOH
Because
[H3O+][OH] = Kw = 1.0  1014
we can take the –log of the equation
–log[H3O+] + –log[OH] = –log Kw = 14.00
which results in
pH + pOH = pKw = 14.00
Acids
and
Bases
© 2015 Pearson Education
 How Do We Measure pH?
• Indicators, including litmus paper, are
used for less accurate measurements;
an indicator is one color in its acid form
and another color in its basic form.
• pH meters are used for accurate
measurement of
pH; electrodes
indicate small
changes in voltage
to detect pH.
Acids
and
Bases
© 2015 Pearson Education
 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; e.g.,
HA + H2O → H3O+ + A–
• So, for the monoprotic strong acids,
[H3O+] = [acid]

Acids
and
Bases
© 2015 Pearson Education
 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; e.g.,
MOH(aq) → M+(aq) + OH–(aq) or
M(OH)2(aq) → M2+(aq) + 2 OH–(aq)

Acids
and
Bases
© 2015 Pearson Education
 Weak Acids
• For a weak acid, the equation for its dissociation is
HA(aq) + H2O(l) ⇌ H3O+(aq) + A–(aq)
• Since it is an equilibrium, there is an equilibrium
constant related to it, called the acid-dissociation
constant, Ka:Ka = [H3O+][A–] / [HA]

• The greater the value

of Ka, the stronger is
the acid.

Acids
and
Bases
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Comparing Strong and Weak Acids
• What is present in solution for a strong acid
versus a weak acid?
• Strong acids completely dissociate to ions.
• Weak acids only partially dissociate to ions.

Acids
and
Bases
© 2015 Pearson Education
 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]
 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.
 [H3O+] = [HCOO–] = 10–2.38 = 4.2 × 10–3
Acids
and
Bases
© 2015 Pearson Education
 Calculating Ka from pH
Now we can set up a table for equilibrium
concentrations. We know initial HCOOH (0.10 M) and
ion concentrations (0 M); we found equilibrium ion
concentrations (4.2 × 10–3 M); so we calculate the
change, then the equilibrium HCOOH concentration.
[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
© 2015 Pearson Education
 Calculating Ka from pH

• This allows us to calculate Ka by putting

in the equilibrium concentrations.

[4.2  103][4.2  103]

Ka =
[0.10]

= 1.8  104

Acids
and
Bases
© 2015 Pearson Education
 Calculating Percent Ionization
[H3O+]eq
• Percent ionization =  100
[HA]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
© 2015 Pearson Education
Method to Follow to Calculate pH
Using Ka
1) Write the chemical equation for the ionization
equilibrium.
2) Write the equilibrium constant expression.
3) Set up a table for Initial/Change in/Equilibrium
Concentration to determine equilibrium
concentrations as a function of change (x).
4) Substitute equilibrium concentrations into the
equilibrium constant expression and solve for x.
(Make assumptions if you can!)
Acids
and
Bases
© 2015 Pearson Education
 Example
• Calculate the pH of a 0.30 M solution of
acetic acid, HC2H3O2, at 25 C.

1) HC2H3O2 + H2O ⇌ H3O+ + C2H3O2–

2) Ka = [H3O+][C2H3O2–] / [HC2H3O2]
3) Initial
CH3COOH (M)

0.30
H3O+ (M)

0
CH3COO– (M)

0
Concentration (M)

Change in –x +x +x
Concentration (M)

Equilibrium 0.30 – x x x
Concentration (M)
Acids
and
Bases
© 2015 Pearson Education
 Example (concluded)
4) Ka = [H3O+][C2H3O2–] / [HC2H3O2]
= (x)(x) / (0.30 – x)
If we assume that x << 0.30, then 0.30 – x
becomes 0.30. The problem becomes
easier, since we don’t have to use the
quadratic formula to solve it.
Ka = 1.8 × 10–5 = x2 / 0.30, so x = 2.3 × 10–3
x = [H3O+], so pH = –log(2.3 × 10–3) = 2.64
Acids
and
Bases
© 2015 Pearson Education
 Strong vs. Weak Acids—
Another Comparison
• Strong Acid: [H+]eq = [HA]init
• Weak Acid: [H+]eq < [HA]init
• This creates a difference in conductivity
and in rates of chemical reactions.

Acids
and
Bases
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 Polyprotic Acids
• Polyprotic acids have more than one acidic proton.
• It is always easier to remove the first proton than
any successive proton.
• If the factor in the Ka values for the first and second
dissociation has a difference of 3 or greater, the pH
generally depends only on the first dissociation.

Acids
and
Bases
© 2015 Pearson Education
 Weak Bases
• Ammonia, NH3, is a weak base.
• Like weak acids, weak bases have an
equilibrium constant called the base
dissociation constant.
• Equilibrium calculations work the same
as for acids, using the base dissociation
constant instead.

Acids
and
Bases
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 Base Dissociation Constants

Acids
and
Bases
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 Example
• What is the pH of 0.15 M NH3?
1) NH3 + H2O ⇌ NH4+ + OH–
2) Kb = [NH4+][OH–] / [NH3] = 1.8 × 10–5
3) NH3 (M) NH4+ (M) OH– (M)

Initial 0.15 0 0
Concentration (M)

Change in –x +x +x
Concentration (M)

Equilibrium 0.15 – x x x
Concentration (M)

Acids
and
Bases
© 2015 Pearson Education
 Example (completed)

4) 1.8 × 10 – 5 = x2 / (0.15 – x)
If we assume that x << 0.15, 0.15 – x = 0.15.
Then: 1.8 × 10–5 = x2 / 0.15
and: x = 1.6 × 10–3
Note: x is the molarity of OH–, so –log(x) will
be the pOH (pOH = 2.80) and [14.00 –
pOH] is pH (pH = 11.20).
Acids
and
Bases
© 2015 Pearson Education
 Types of Weak Bases
• Two main categories
1) Neutral substances with an
Atom that has a nonbonding
pair of electrons that can
accept H+ (like ammonia and
the amines)
2) Anions of weak acids

Acids
and
Bases
© 2015 Pearson Education
 Relationship between Ka and Kb

For a conjugate acid–base pair, Ka and Kb are

related in this way:
Ka × Kb = Kw
Therefore, if you know one of them, you can
Acids
calculate the other. and
Bases
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 Acid–Base Properties of Salts
• Many ions react with water to create H+
or OH–. The reaction with water is often
called hydrolysis.
• To determine whether a salt is an acid
or a base, you need to look at the cation
and anion separately.
• The cation can be acidic or neutral.
• The anion can be acidic, basic, or
neutral. Acids
and
Bases
© 2015 Pearson Education
 Anions
• Anions of strong acids are neutral. For
example, Cl– will not react with water, so
–
OH can’t be formed.
• Anions of weak acids are conjugate
bases, so they create OH– in water;
e.g., C2H3O2– + H2O ⇌ HC2H3O2 + OH–
• Protonated anions from polyprotic acids
can be acids or bases: If Ka > Kb, the
anion will be acidic; if Kb > Ka, the anion
will be basic. Acids
and
Bases
© 2015 Pearson Education
 Cations
• Group I or Group II (Ca2+, Sr2+, or Ba2+)
metal cations are neutral.
• Polyatomic cations are typically the
conjugate acids of a weak base; e.g., NH4+.
• Transition and post-transition metal cations
are acidic. Why? (There are no H atoms in
these cations!)

Acids
and
Bases
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 Hydrated Cations
• Transition and post-transition metals
form hydrated cations.
• The water attached to the metal is more
acidic than free water
molecules, making the
hydrated ions acidic.

Acids
and
Bases
© 2015 Pearson Education
 Salt Solutions—
Acidic, Basic, or Neutral?
1) Group I/II metal cation with anion of a strong
acid: neutral
2) Group I/II metal cation with anion of a weak
acid: basic (like the anion)
3) Transition/Post-transition metal cation or
polyatomic cation with anion of a strong acid:
acidic (like the cation)
4) Transition/Post-transition metal cation or
polyatomic cation with anion of a weak acid:
compare Ka and Kb; whichever is greater
Acids
dictates what the salt is. and
Bases
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 Factors that Affect Acid Strength

1) H—A bond must be polarized with δ+

on the H atom and δ– on the A atom
2) Bond strength: Weaker bonds can be
broken more easily, making the acid
stronger.
–
3) Stability of A : More stable anion
means stronger acid.
Acids
and
Bases
© 2015 Pearson Education
 Binary Acids
• Binary acids consist of
H and one other element.
• Within a group, H—A
bond strength is
generally the most
important factor.
• Within a period, bond
polarity is the most
important factor to
determine acid strength. Acids
and
Bases
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 Oxyacids
• Oxyacids consist
of H, O, and one
other element,
which is a
nonmetal.
• Generally, as the
electronegativity
of the nonmetal
increases, the
acidity increases
for acids with the
Acids
same structure. and
Bases
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 Oxyacids with Same
“Other” Element
• If an element can form more than one oxyacid,
the oxyacid with more O atoms is more acidic;
e.g., sulfuric acid versus sulfurous acid.
• Another way of saying it: If the oxidation number
increases, the acidity increases.

Acids
and
Bases
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 Carboxylic Acids
• Carboxylic acids are organic acids
containing the —COOH group.
• Factors contributing to their acidic behavior:
 Other O attached to C draws electron
density from O—H bond, increasing
polarity.
 Its conjugate base (carboxylate anion) has
resonance forms to stabilize the anion.

Acids
and
Bases
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 Lewis Acid/Base Chemistry

• Lewis acids are electron pair acceptors.

• Lewis bases are electron pair donors.
• All Brønsted–Lowry acids and bases
are also called Lewis acids and bases.
• There are compounds which do not
meet the Brønsted–Lowry definition
which meet the Lewis definition.
Acids
and
Bases
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 Comparing Ammonia’s Reaction
with H+ and BF3

Acids
and
Bases
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