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16.1 Brønsted Acids and Bases

Chapter 16 • Acid – proton donor
Acids and Bases • Base – proton acceptor
Insert picture from
First page of chapter • Conjugate base – what remains of the
acid after the donation of a proton
• Conjugate acid – newly formed
protonated species (base)

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p.636
Conjugate Acid-Base Pairs

Producing OH-
H+ or H3O+

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p.637
16.2 The Acid-Base Properties of For pure water at 25 oC
Water K w = [H3O + ][OH− ]
• Autoionization of water – water is
amphoteric, can act as an acid or base K w = (1 x 10 −7 ) x (1 x 10 −7 ) = 1 x 10 −14
Q. What is the concentration of 1L of water at RTP?
Relative amounts determine if the solution is
acid, base, or neutral.

• When [H3O+] = [OH−], the solution is neutral.

• When [H3O+] > [OH−], the solution is acidic.
or • When [H3O+] < [OH−], the solution is basic.
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16.3 The pH Scale
Relative amounts determine if the solution is
acid, base, or neutral.
pH = −log[H + ]
At 25°C
or • When pH = 7, the solution is neutral.
pH = −log[H3 O + ] • When pH < 7.00, the solution is acidic.
• When pH > 7.00, the solution is basic.
or

[H3O+ ] = 10−pH
pH Meter: Laboratory
Measurement of pH
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p.641 p.640

9 10

1.What is the pH of a solution that has a 1.

hydronium ion concentration of 6.5 x 10−5M? pH = −log[H3 O + ]

pH = −log[6.54 x 10 −5 ]

pH = 4.19
2. What is the hydronium ion concentration of
a solution with pH 3.65?
2. [H3O+ ] = 10−pH
[H3O+ ] = 10−3.65
[H3O + ] = 2.2x10 −4

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p.641
Relations among pH, [OH−], pOH, and Kw
pOH = −log[OH− ]

[OH− ] = 10 −pOH

K w = [H3O + ][OH− ]

pK w = pH + pOH = 14.00
So you can tell that the pH range is not confided to 1 to 14 but
can extend to negative values, < 0 ,as well as >14.
13 14

1. What is the pOH of a solution that has a 1.

hydroxide ion concentration of 4.3 x 10−2M? pOH = −log[OH − ]

pOH = −log[4.3 x 10 −2 ]

pOH = 1.37
2. What is the hydroxide ion concentration of a
solution with pOH 8.35? 2.
[OH− ] = 10 −pOH

[OH− ] = 10−8.35

[OH− ] = 4.5x10 −9

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p.644 p.644
16.4 Strong Acids and Bases
• Ionization or dissociation goes to completion –
not considered an equilibrium process
• Concentration of ions in solution is determined
by the stoichiometry of the reaction only
– [H3O+] is equal to starting concentration of the
acid
– [OH−] is equal to starting concentration of the
base (stoichiometry must be considered)
• Only a few acids and bases are strong
Then what about H3PO4, or tartaric acid (HOOC(CH2O)2COOH)?
17 Are they strong acids? 18

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What is the pH of a 0.057 M solution of HBr?

19 20

HBr completely ionizes, and the [H3O+] is What is the pOH of a solution of 0.034 M
equal to the initial concentration of HBr. solution of Ca(OH)2?

HBr (aq) + H2O (l) H3O (aq) + Br (aq)

pH = −log[H3O+ ]

pH = −log[0.057]

pH = 1.24

21 22

Ca(OH)2 completely ionizes, and the [OH−] is p.647

16.5 Weak Acids and Acid
equal to twice the initial concentration of
Ca(OH)2. Ionization Constants
2+ • Weak acids ionize only to a limited extent
Ca(OH)2 (aq) Ca (aq) + 2OH (aq)
in water.
2 mol OH −
[OH− ] = 0.034 M Ca(OH)2 x • The degree to which a weak acid ionizes
1 mol Ca(OH)2
depends on
[OH− ] = 0.068 M – the concentration of the acid
pOH = −log[OH− ] – the equilibrium constant for the
pOH = −log[0.068] ionization called the acid ionization
constant, Ka.
pOH = 1.17
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For a generic weak monoprotic acid p.648

[H3 O + ][A − ]
Ka =
[HA]

or

[H+ ][A − ]
Ka =
[HA]

25 26

Format for solving problems of weak acids ( x )( x )

Ka =
using an equilibrium table Ci − x

which produces a quadratic expression of the form:

x 2 + K a x − K aCi = 0
If the initial concentration and Ka allow, the expression
can be simplified by assuming that x is insignificant
• Fill in initial concentrations when compared to Ci.
• Determine concentration changes in terms of x Ci − x ≈ Ci
• Determine equilibrium concentrations in terms of initial
concentrations (Ci) and x ( x )( x ) x 2
• Substitute into the Ka expression and solve for x Ka = =
Ci Ci
27 28

Calculate the pH at 25°C of a 0.18 M solution

Testing the approximation – it is acceptable to
of a weak acid that has Ka = 9.2 x 10−6.
use this shortcut if the calculated value of x is
less than 5 percent of the initial acid
concentration.

x
5% ≥ x100
Ci

See e.g. on p.649

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x2
9.2 x 10 −6 =
0.18 M
0.18 M 0 0
1.3 x 10 −3 M = x
−x +x +x

0.18 M − x x x Check the approximation:

1.3 x 10 −3 M
( x )( x ) x100 = 0.72%
9.2 x 10 −6
= 0.18 M
0.18 M − x
0.72% < 5%
Use the approximation since Ka is small compared to Ci.
Approximation is valid.
−6 x2
9.2 x 10 = pH = −log(1.3 x 10 −3 M ) = 2.89
0.18 M
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p.652
16.6 Weak Bases and Base For a generic weak base
Ionization Constants
• Weak bases ionize only to a limited extent
in water. [HB + ][OH− ]
Kb =
• The degree to which a weak base ionizes [B]
depends on
– the concentration of the base Solving problems involving weak bases requires the
same approach as for weak acids. Solving for x in a
– the equilibrium constant for the
typical weak base problem gives the hydroxide ion
ionization called the base ionization concentration rather than the hydronium ion
constant, Kb. concentration.
33 34

p.652
Determine the Kb of a weak base if a 0.50 M
solution of the base has a pH of 9.59 at
25°C.

H
N

H N H
H

35 imidazole 36

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pH + pOH = 14.00
9.59 + pOH = 14.00 0.050 M 0M 0M

− 3.89x10-5 M +3.89x10-5 M +3.89x10-5 M

pOH = 4.41 3.89x10-5 M
0.050 M* 3.89x10-5 M

* 0.050 M - (3.89 x 10 -5 M ) ≈ 0.050 M

[OH− ] = 10−pOH
[HB + ][OH− ]
Kb =
[B]
[OH− ] = 10−4.41 = 3.89 x 10−5 M
(3.89x10 −5 M )2
Kb = = 3.0 x 10−9
0.50 M

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p.654
Reciprocal Relationship Between the Strength of an Acid
16.7 Conjugate Acid-Base Pairs or Base and the Strength of its Conjugate

• The conjugate base of a strong acid, is an

example of a weak conjugate base.
• The conjugate base of a weak acid, is an
example of a strong conjugate base.
• Conversely, a strong base has a weak
conjugate acid and a weak base has a
strong conjugate acid. Quantitative Relationship Between Ka and Kb
HCl(aq)
H+(aq) + Cl-(aq)
Cl-(aq) + H2O
HCl(aq) +OH-(aq) Kb ⋅ K a = K w
39 40

Determine Kb of the benzoate ion (C6H5COO−). Benzoate ion is the conjugate base of benzoic acid.

C6H5COOH (aq) + H2O (l) H3O (aq) + C6H5COO (aq)

K a = 6.5 x 10 −5

C6H5COO (aq) + H2O (l) OH (aq) + C6H5COOH (aq)

Kw
Kb =
Ka

1.0 x 10 −14
Kb = = 1.5 x 10 −10
6.5 x 10 −5
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16.8 Diprotic and Polyprotic Acids
p.657

• Diprotic and polyprotic acids undergo

successive ionizations, losing one proton
at a time
• The conjugate base in the first ionization is
the acid in the second ionization.
• Each ionization has a Ka associated with
it.
• Ionization constants are designated by the
step in the ionization involved.
K a1 , K a2 , etc.
43 44

Calculate the concentrations of H2C2O4, H2C2O4 (aq) H (aq) + HC2O4 (aq) K a 1 = 6.5 x 10 -2
H2C2O 4 (aq) H (aq) + HC2O 4 (aq)
HC2O4− , C2O42−, and H+ ions in a 0.20 M
0.20 M
oxalic acid solution at 25°C.
−x +x +x

0.20 M − x x x

− + 2
[HC 2O 4 ][H ] x
K a1 = = = 6.5x10 − 2
[H2C2O 4 ] 0.20 M − x
x 2 + 6.5 x 10 −2 x − 1.3 x 10 −2 = 0
x = 0 .0 8 6 a n d − 0 .1 5 1
[H+]=0.086 M
[HC2O4-]=0.086 M
[H2C2O4]=0.20 M − 0.086 M = 0.11 M
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p.660
HC2O 4 (aq) H (aq) + C 2O 4 (aq) K a 2 = 6.1 x 10 −5
16.9 Molecular Structure and Acid
HC2O 4 (aq) H (aq) + C2O 4 (aq) Strength
0.086 M 0.086 M

−y +y +y
• The strength of an acid is measured by its
0.086 M − y 0.086 M + y y
tendency to ionize.
HX H + X
[C2O4 2- ][H+ ] (0.086 + y )(y) (0.086 M )(y ) • Two factors influence the extent to which
K a2 = = ≈ = 6.1x10 −5
[HC2O4 − ] 0.086 M − y 0.086 M
the acid undergoes ionization.
y = 6.1x10 −5 M – the strength of the H X bond
[H+] = 0.086 M
– polarity of the H X bond
[HC2O4−] = 0.086 M
[C2O42−] = 6.1 x 10−5 M
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Types of Acids
• Hydrohalic Acids – binary acids formed
between hydrogen and the halogens
– the predominant factor in determining
the strength of the hydrohalic acids is
bond strength

HF << HCl < HBr < HI

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To compare oxyacid strengths

• Oxoacids - contain hydrogen, oxygen,
and a central, nonmetal atom • Oxoacids having different central atoms
– contain one or more O H bonds that are from the same group of the
– an electronegative or a high oxidation periodic table and that have the same
state central atom, will attract electrons, oxidation number.
causing the O H bond to be more – acid strength increases with increasing
polar electronegativity of the central atom
– high electronegativity and oxidation
result in stronger acids Example:

51 52

• Carboxylic acids – organic acids with the

• Oxoacids having the same central atom structure
but different numbers of oxygen atoms O
– strength increases with increasing R C O H
oxidation number of the central atom – Ionize to produce a carboxylate anion
O O
Example: R C O
R C O
– Increasing stability of the carboxylate
anion increases acidity
• Stability increases with the number of
electronegative groups in the R group
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a)These two acids have the same central atom but

Indicate which is the stronger acid: (a) HBrO3 differ in the number of attached oxygen atoms. In a
or HBrO4; (b) H2SeO4 or H2SO4. group such as this, the greater the number of
attached oxygen atoms, the higher the oxidation
number of the central atom and the stronger the
acid.
HBrO4 > HBrO3

b) In a group with different central atoms, we must

compare electronegativities. The electronegativities
of the central atoms in this group decrease as
follows: S>Se.
H2SO4 > H2SeO4

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16.10 Acid-Base Properties of Salt Solutions

p.662
• Salt solutions are affected by salt • Acidic salt solutions
hydrolysis, in which ions produced by the – When the cation of a salt is the conjugate
dissociation of a salt react with water to acid of a weak base, a solution of the salt
produce either hydroxide ions or will be acidic.
hydronium ions—thus impacting pH.
• Basic salt solutions - an anion that is the For example:
conjugate base of a weak acid reacts with
water to produce hydroxide ion.

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– Small, highly charged metal ions are hydrated Determine the pH of a 0.25 M solution of
by water molecules and polarization of one of pyridinium nitrate (C5H5NHNO3) at 25°C.
the O-H bonds can produce hydrogen ions. [Pyridinium nitrate dissociates in water to
fig.16.4 (p.665) give pyridinium ions (C5H5NH+), the conjugate
acid of pyridine (Kb = 1.7 x 10−9), and
nitrate ions (NO3− ).]

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C5H5NH (aq) + H2O(l) C 5H5N (aq) + H3O (aq)

0.25 M
C5H5NH (aq) + H2O(l) C5H5N (aq) + H3O (aq) −x +x +x
0.25 − x M x x
K 1.00 x 10−14
Ka = w = = 5.9 x 10−6
Kb 1.7 x 10−9 Kb =
2
x
≅
x 2
= 5.9 x 10 −6
+
(0.25 M − x) (0.25 M )
[C 5 H 5 N][H 3O ]
Ka =
[C 5 H 5 NH + ] x = (5.9 x 10 −6 )(0.25 M ) = 1.2 x 10 −3 M
C5H5NH (aq) + H2O(l) C5H5N (aq) + H3O (aq)
1.2 x 10−3 M
0.25 M
Check: x 100 = 0.49%
0.25 M
−x +x +x
0.25 − x M x x [H3O+ ] = 1.2 x 10 −3 M
pH = −l og(1.2 x 10 −3 M ) = 2.92
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p.665
• Neutral salt solutions
Summary
– A salt composed of the cation of a strong
base and the anion of a strong acid
produces a neutral solution.
– These ions do not hydrolyze in water.

For example:

NaCl or KNO3

63 64

• Salts in Which Both the Cation and the

Predict whether 0.10 M solutions of the
Anion Hydrolyze
following are acidic, basic or nearly neutral.
–pH depends on the relative strengths
of the conjugate acid and base
a) C5H5CNHCl
• When Kb > Ka, the solution is basic.
• When Kb < Ka, the solution is acidic.
b) KF
• When Kb = Ka, the solution is neutral
or nearly neutral.

For example: NH4NO2

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p.667
16.11 Acid-Base Properties of
a) C5H5CNHCl
Oxides and Hydroxides
acidic
C 5H5NH (aq) + H2O(l) C 5H5N (aq) + H3O (aq)

b) KF

basic
F (aq) + H2O(l) HF (aq) + OH (aq)

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• Basic and Amphoteric Hydroxides

• Basic metallic oxides react with water to – All the alkali and alkaline earth metal
form metal hydroxides. hydroxides, except Be(OH)2, are basic.
– Be(OH)2, as well as Al(OH)3, Sn(OH)2,
Pb(OH)2, Cr(OH)3, Cu(OH)2, Zn(OH)2, and
Cd(OH)2, are amphoteric and insoluble in
water.
• Acidic nonmetallic oxides react with water – React with acids
to form acids.
– React with bases

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p.668
16.12 Lewis Acids and Bases A Lewis Acid-Base Reaction

• Lewis base as a substance that can

donate a pair of electrons.
• Lewis acid is a substance that can accept
a pair of electrons.
• A Lewis acid-base reaction is one that
involves the donation of a pair of electrons coordinate covalent bond
from one species to another.
• Most general definition of acids and bases

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• The pH scale
Key Points – Defining equation
– pOH scale
• BrØnsted acids and bases
– Relation among pH, pOH and Kw
– Conjugate acid
• Strong acids and bases
– Conjugate base
• Weak acids and acid ionization constants
• Acid-base properties of water
– Definition of weak acids
– Autoionization of water
– Ka, the acid ionization (equilibrium) constant
– Kw
– Method to solve weak acid equilibrium
– Relation between hydronium and hydroxide
problems
ion concentrations

73 74

• Weak bases and base ionization constants

• Molecular structure and acid strength
– Definition of weak bases
– Hydrohalic acids
– Kb, the base ionization (equilibrium) constant
– Oxoacids
– Method to solve weak base equilibrium problems
– Carboxylic acids
• Conjugate acid-base pairs
• Acid-base properties of salt solutions
– Strength of acid-base pairs
– Basic salts
– Relation between Ka and Kb for conjugate pairs
– Acidic salts
• Diprotic and triprotic Acids
– Neutral salts
– Successive ionization steps
– Complex salts in which both ions hydrolyze
– Associated Ka values
– Solving equilibrium problems
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• Acid-base properties of oxides and

hydroxides
– Oxides
• Metal
• Nonmetal
– Basic and amphoteric hydroxides
• Lewis acids and bases

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