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p.636

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
Water
• Autoionization of water – water is
amphoteric, can act as an acid or base
For pure water at 25 oC
K w = [H3O + ][OH− ]
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.
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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.
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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

49 50

To compare oxyacid strengths

• Oxoacids - contain hydrogen, oxygen,
and a central, nonmetal atom
– contain one or more O H bonds
– an electronegative or a high oxidation
state central atom, will attract electrons,
causing the O H bond to be more
polar
– high electronegativity and oxidation
result in stronger acids
• Oxoacids having different central atoms
that are from the same group of the
periodic table and that have the same
oxidation number.
– acid strength increases with increasing
electronegativity of the central atom
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
53 54

9

Indicate which is the stronger acid: (a) HBrO3
or HBrO4; (b) H2SeO4 or H2SO4.
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16.10 Acid-Base Properties of Salt Solutions
p.662
• Salt solutions are affected by salt
hydrolysis, in which ions produced by the
dissociation of a salt react with water to
produce either hydroxide ions or
hydronium ions—thus impacting pH.
• Basic salt solutions - an anion that is the
conjugate base of a weak acid reacts with
water to produce hydroxide ion.
57
– Small, highly charged metal ions are hydrated
by water molecules and polarization of one of
the O-H bonds can produce hydrogen ions.
fig.16.4 (p.665)
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a)These two acids have the same central atom but
differ in the number of attached oxygen atoms. In a
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
56
• Acidic salt solutions
– When the cation of a salt is the conjugate
acid of a weak base, a solution of the salt
will be acidic.
For example:
58
Determine the pH of a 0.25 M solution of
pyridinium nitrate (C5H5NHNO3) at 25°C.
[Pyridinium nitrate dissociates in water to
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
form metal hydroxides.
• Acidic nonmetallic oxides react with water
to form acids.
– All the alkali and alkaline earth metal
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.
– React with 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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