Chapter 16

Overview:
Definitions
Arrhenius
Bronsted -- Conjugate Pairs
Hydronium Ion
Relative Strengths
Strong/Weak acids and reactions
Strong/Weak bases and reactions
K
a
s and K
b
s
pH and H
2
O Ionization
Calculating Equilibrium Concentrations
Hydrolysis
Acidic and Basic Salts
Polyprotic Acids
Molecular Structure/Bonding
Lewis Acids and Bases
Acids
sour
corrosive
reddens blue vegetable colors
react with bases
Bases
bitter
soapy
restores vegetable colors reddened by acids
react with acids
Arrhenius Acid:
substance that releases or produces H
+

HCl
(aq)
H
+
(aq)
+ Cl
-
(aq)

Arrhenius Base:
substance that releases or produces OH
-

NaOH
(aq)
Na
+
(aq)
+ OH
-
(aq)

Bronsted Acid:
substance that donates a H
+
to another
HNO
3(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ NO
3
-
(aq)

Bronsted Base:
substance that accepts a H
+
from another
CO
3
2-
(aq)
+ H
2
O
(l)
HCO
3
-
(aq)
+ OH
-
(aq)

Water Dissociation:
2H
2
O H
3
O
+
+ OH
-

Hydronium Ion -- because
bare protons are unlikely
H
+
transfer
H O
H
H O
H
H O
H
H O
H
+
d+ d -
-
+
pH and Water Ionization:
2H
2
O
(l)
H
3
O
+
(aq)
+ OH
-
(aq)

K
w
= [H
3
O
+
][OH
-
] = 1.0 x 10
-14


Reactant Favored
ion-product constant for water
(at 25C)
K = [H
3
O
+
][OH
-
] = K [H
2
O]
2
= [H
3
O
+
][OH
-
]
[H
2
O]
2


pH = - log [H
+
] = - log [H
3
O
+
]
neutral solution: [H
3
O
+
] = [OH
-
]

2H
2
O H
3
O
+
+ OH
-


1.0 x 10
-14
= [H
3
O
+
][OH
-
] = [H
3
O
+
]
2
[H
3
O
+
] = 1.0 x 10
-7
M
pH = - log (1.0 x 10
-7
) = 7.0
non-neutral solutions:
[H
+
] > [OH
-
]
acidic solutions:
pH < 7.0
basic solutions:
[H
+
] < [OH
-
]
pH > 7.0
pH of Strong Acid and Base Solutions:
Calculate the pH of a solution containing 0.00100 M of
a strong acid such as HCl.
HCl
(aq)
H
+
(aq)
+ OH
-
(aq)

0.00100 0.00100 0.00100
pH = - log (0.00100) = 3.00
but. . . .
What about H
3
O
+
from water?
2 H
2
O H
3
O
+
+ OH
-

initial 0.00100 0
change +x +x
equil. 0.00100 + x x
1 x 10
-14
= (0.00100 + x)(x)
x = H
3
O
+
and OH
-
from disso. of water
[H
3
O
+
] (1.0 x 10
-11
) = 1.0 x 10
-14

[H
3
O
+
] = 1.0 x 10
-3
M
pH = 3.0
1 x 10
-14
= (0.00100 + x)(x)
x = 1.00 x 10
-11
M = [OH
-
]


K
w
= [H
3
O
+
] [OH
-
]
0
x is very small
compared to
0.00100 & can be
neglected
[H
+
] [H
3
O
+
]
the conc. of H
+
in a
solution of a strong
acid is the conc. of
the strong acid
pOH = 11.0
Note: pH + pOH = 14.0
Bottom Line:
[H
+
] = [H
3
O
+
] = [H
5
O
2
+
] = [H
9
O
4
+
] hydrated
hydrogen ions
neutral solution [H
3
O
+
] = [OH
-
] pH = 7
acidic solution [H
3
O
+
] > [OH
-
] pH < 7
basic solution [H
3
O
+
] < [OH
-
] pH > 7
the concentration of [H
3
O
+
] in a strong acid
is the concentration of the acid
Calculate the pH of a solution containing
0.010 M KOH.
KOH K
+
(aq)
+ OH
-
(aq)

0.010 M 0.010 M 0.010 M
1.0 x 10
-14
= [H
+
] (0.010 M)
[H
+
] = 1.0 x 10
-12
M
pH = 12.0
strong base, complete rxn, stoichiometric
contribution of [H
+
] from
dissociation of H
2
O is
negligible
Calculate the [H
+
] and [OH
-
] in a
solution that has a pH = 8.60
- log [H
+
] = pH
- log [H
+
] = 8.60
log [H
+
] = -8.60
[H
+
] = anti log (-8.60)
[H
+
] = 1.8 x 10
-4
M
[OH
-
] = 5.6 x 10
-11
M
Basic
Neutral
Acidic
pH [H
3
O
+
] [OH
-
] pOH
7.0 10
-7
10
-7
7.0
14 10
-14
1 0
0 1 10
-14
14
vinegar, cola
milk
ammonia
human blood
Measuring pH:
pH meter -- electrodes measure pH
most precise method
acid-base indicators
less precise but good when a pH meter is not
available
substances which are differently colored at
different pH values
litmus, phenolphthalein, thymol blue
Arrhenius Acid:
substance that releases or produces H
+

HCl
(aq)
H
+
(aq)
+ Cl
-
(aq)

Arrhenius Base:
substance that releases or produces OH
-

NaOH
(aq)
Na
+
(aq)
+ OH
-
(aq)

Bronsted Acid:
substance that donates a H
+
to another
HNO
3(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ NO
3
-
(aq)

Bronsted Base:
substance that accepts a H
+
from another
CO
3
2-
(aq)
+ H
2
O
(l)
HCO
3
-
(aq)
+ OH
-
(aq)

Examples:
NH
4
+
(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ NH
3(aq)

acid base
conjugate
acid
conjugate
base
PO
4
3-
(aq)
+ H
2
O
(l)
HPO
4
2-
(aq)
+ OH
-
(aq)


H
+
base
acid
conjugate
acid
conjugate
base
H
+
conjugate pair
conjugate pair
HCO
3
-
(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ CO
3
2-
(aq)

HCO
3
-
(aq)
+ H
2
O
(l)
H
2
CO
3(aq)
+ OH
-
(aq)

Some species can act as an acid or base:
acid base
conjugate
acid
conjugate
base
base
acid
conjugate
acid
conjugate
base
HCO
3
-
is an amphiprotic substance
H
+
H
+
You Must Know:
what an acid and a base is and how to
identify both
know definitions and properties
the reaction of an acid and a base with
water
how to identify acid, base, conjugate
acid and conjugate base
what the hydronium ion is and the
ionization reaction of water
Problems: HX + H
2
O H
3
O
+
+ X
-


A B CA CB
What is the conjugate base of:
H
2
S
NH
4
+

NH
3

H
2
O
OH
-
HS
-
NH
3

NH
2
-

OH
-
O
2-

What is the conjugate acid of:
NO
3
-

HPO
4
2-

H
2
SO
4
HNO
3

H
2
PO
4
-

H
3
SO
4
+

Relative Strengths:
HCl + H
2
O H
3
O
+
+ Cl
-

equilibrium is a competition between the bases
H
2
O and Cl

-
-- the equilibrium will lie toward
the direction of the weaker acid and base
in this case, H
2
O is a stronger base than Cl
-
as
it competes much more effectively for the H
+

stronger B weaker B stronger A weaker A
HCN + H
2
O H
3
O
+
+ CN
-

H
2
O < CN
-

weaker B weaker A stronger A stronger B
Which is the weaker acid:
H
2
S + CN
-
HCN + HS
-


HCO
3
-
+ SO
4
2-
HSO
4
-
+ CO
3
2-

HClO
4
+ H
2
O H
3
O
+
+ ClO
4
-


NH
4
+
+ H
2
O H
3
O
+
+ NH
3


HCN
HCO
3
-

H
3
O
+

NH
4
+

The stronger the acid the weaker its conjugate base:
strongest acid
weakest acid
strongest
conjugate base
weakest
conjugate base
Given the following, which is the weaker
conjugate:
HCl > CH
3
CO
2
H
HCN < H
3
PO
4

H
2
SO
4
> H
2
SO
3

NH
3
> H
2
O
HSO
4
-
< CO
3
2-

H
-
> NH
3

acids
bases
Cl
-
CH
3
CO
2
-
<
CN
-
H
2
PO
4

-
>
HSO
4

-

HSO
3
-
<
NH
4
+

H
3
O
+
<
H
2
SO
4
HCO
3

-
>
H
2

NH
4
+
<
Predicting Direction of Acid/Base Rxns.
CH
3
CO
2
H + CN
-
HCN + CH
3
CO
2

-

stronger A weaker A
weaker B
stronger B
HSO
4
-
+ NH
3
NH
4
+
+ SO
4
2-

stronger A weaker A
stronger B weaker B
Strong Acids and Bases
Strong Acids
HCl
HNO
3

HClO
4

HClO
3

H
2
SO
4

HBr
HI
Strong Bases
Grp I hydroxides
Grp II hydroxides
(except Be)
HX + H
2
O H
3
O
+
+ X
-
MOH M
+
+ OH
-

essentially complete rxns.
Weak Acids and Bases:
HX + H
2
O H
3
O
+
+ X
-

B

+ H
2
O BH
+
+ OH
-

K
a
= [H
3
O
+
][X
-
]
[HX]
K
b
= [BH
+
][OH
-
]
[B]
< 1
< 1
Weak Acids Can Be:
cations NH
4
+
or [Cu(H
2
O)
6
]
2+

anions H
2
PO
4
-
or HCO
3
-

neutral CH
3
CO
2
H or HCO
2
H
Weak Bases Can Be:
anions CO
3
2-
or CN
-



neutral NH
3
or (CH
3
)
3
N
You Must:
Be able to determine direction of rxn
based on acid or base relative strengths
Know the strong acids and strong bases
Be able to recognize weak acids and bases
Know water ionization rxn, constant and
expression
Know what pH is and how to calculate it
Know how to calculate equil. conc., pH,
pOH for weak acids and bases
Problem 1: A 0.015 M solution of an
unknown base has a pH of 10.09. Is it a strong
or weak base? What is the K
b
, if it is weak?
Problem 2: What are the equil. conc. of
H
3
O
+
, acetate ion, acetic acid in a 0.20 M
aqueous solution of acetic acid, CH
3
CO
2
H?
Use the approximation whenever possible: When the initial
weak acid/base conc. > 100 * K
a/b
neglect x when it is added
to or subtracted from the initial conc.
If this were a strong base then
[OH
-
] = 0.015 M and pOH = 1.8 and pH = 12.2.
pH = 10.09 and pOH = 3. 91 [OH
-
] = 1.2 x 10
-4

K
b
= [HB
+
][OH
-
] = (1.2 x 10
-4
)
2


[B] (0.015)
B + H
2
O HB
+
+ OH
-

= 9.6 x 10
-7
Answer 1:
CH
3
CO
2
H + H
2
O H
3
O
+
+ CH
3
CO
2
-

initial 0.20 0 0
change -x +x +x
equil. 0.20 -x x x
K
a
= 1.8 x 10
-5
= [H
3
O
+
][CH
3
CO
2
-
]
[CH
3
CO
2
H]
K
a
= 1.8 x 10
-5
= (x)(x) x
2
= 3.6 x 10
-6

(0.20 -x) x = 1.9 x 10
-3

[CH
3
CO
2
-
]=[H
3
O
+
] = 1.9 x 10
-3
M
[CH
3
CO
2
H] = 0.20 M
pH = 2.7
Answer 2:
What is the percent ionization?
% ion = [H
3
O
+
] x 100
[CH
3
CO
2
H]

= 0.95 %
Polyprotic Acids and Bases:
H
3
PO
4
+

H
2
O H
3
O
+
+ H
2
PO
4
-
K
a1

H
2
PO
4
-
+

H
2
O H
3
O
+
+ HPO
4
2-
K
a2

HPO
4
2-
+

H
2
O H
3
O
+
+ PO
4
3-
K
a3
H
3
PO
4
+

3H
2
O 3H
3
O
+
+ PO
4
3--

(7.5 x 10
-3
)(6.2 x 10
-8
)(3.6 x 10
-13
) = 1.7 x 10
-22
K
a tot
= K
a1
K
a2
K
a3
Weak Bases:
Can be anions such as:
CN
-
, HSO
3
-
, SO
3
2-
, HCO
3
-
, CO
3
2-
, etc.
Can be N-containing compounds, such as:
NH
3
, (CH
3
)NH
2
, (CH
3
)
2
NH, (CH
3
)
3
N, etc.
React with water
B
-
+ H
2
O HB + OH
-
or
B + H
2
O HB
+
+ OH
-

Have base dissociation constants, K
b


NH
3
+ H
2
O NH
4
+
+ OH
-

initial 0.20 M 0 0
change -x +x +x
equil. 0.20 -x x x
K
b
= 1.8 x 10
-5
= [NH
4
+
][OH
-
]
[NH
3
]
K
b
= 1.8 x 10
-5
= (x)(x) x
2
= 3.6 x 10
-6

(0.20 -x) x = 1.9 x 10
-3

[NH
4
+
]=[OH
-
] = 1.9 x 10
-3
M
[NH
3
] = 0.20 M
pOH = 2.7
pH = 12.3
Example:
CO
3

-2
+ H
2
O OH
-
+ HCO
3
--
K
b1

HCO
3

--
+ H
2
O OH
-
+ H
2
CO
3
K
b2
CO
3
+ 2H
2
O 2OH
--
+ H
2
CO
3
2--

K
b tot
= K
b1
K
b2

(2.1 x 10
-4
)(2.4 x 10
-8
) = 5.0 x 10
-12

Relationship of an acid K
a
and the K
b

of its conjugate base:
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
= 1.8 x 10
-5

NH
4
+
+ H
2
O NH
3
+ H
3
O
+
K
a
= 5.6 x 10
-10

2H
2
O H
3
O
+
+ OH
-
K
w
= 1 x 10
-14

For Conjugate Acid/Base Pairs:
K
b
K
a
= K
w
or pK
b
+ pK
a
= pK
w

conjugate pair rxns with water
Find K
a
for the conjugate acids of
the following bases: K
a
= K
w
/K
b

NH
3
1.8 x 10
-5

C
5
H
5
N 1.7 x 10
-9

HS
-
1.8 x 10
-7

CO
3
2-
1.8 x 10
-4

Base K
b
Conj. Acid K
a

NH
4
+
5.6 x 10
-10

C
5
H
5
NH
+
5.9 x 10
-6

H
2
S
5.6 x 10
-8

5.6 x 10
-11
HCO
3
-

Acid/Base Hydrolysis
Many salts produce solutions that are acidic or basic
Why?
because either (or both) the cation or anion of the salt
acted as a weak acid or a weak base
HX + H
2
O H
3
O
+
+ X
-

or
B + H
2
O BH
+
+ OH
-

weak acid
weak base
Which cations will not hydrolyze?
Cations of strong bases -- Grp I and II (except
Be)
Li
+
Na
+
K
+
Rb
+
Cs
+
Mg
2+
Ca
2+
Sr
2+
Ba
2+

Anions of strong acids --
ClO
4
-
ClO
3
-
SO
4
2-
NO
3
-
Cl
-
Br
-
I
-

All other cations and anions will hydrolyze
Which cations will hydrolyze?
Conjugate acids of weak bases:
NH
4
+
Al
3+
Cu
2+
etc.
Conjugate bases of weak acids:
CO
3
2 -
CH
3
CO
2
-
NH
3
F
-
etc.
What is the pH of the following salt solutions?
NaCl
NaF
NH
4
Cl
Na
2
CO
3

Cr(NO
3
)
3

KNO
3

NaC
3
H
2
O
4

NH
4
CH
3
CO
2

Na
+
-- neutral Cl
-
-- neutral
Na
+
-- neutral F
-
-- basic
NH
4
+
-- acidic Cl
-
-- neutral
Na
+
-- neutral CO
3
2-
-- basic
Cr
3+
-- acidic NO
3
-
-- neutral
K
+
-- neutral NO
3
+
-- neutral
Na
+
-- neutral C
3
H
2
O
4
-
-- basic
NH
4
+
-- acidic CH
3
CO
2
-
-- basic
N
B
A
B
A
N
B
?
Is NH
4
CH
3
CO
2
acidic or basic?
NH
4
+
+ H
2
O H
3
O
+
+ NH
3

K
a
= 5.6 x 10
-10

CH
3
CO
2
-
+ H
2
O CH
3
CO
2
H + OH
-

K
b
= 5.6 x 10
-10

weak acid & weak base strength equal -- neutral soln.
You Must:
Know what hydrolysis is
Know which cations hydrolyze or produce acidic
solutions
Know which anions hydrolyze or produce basic
solutions
Be able to estimate and calculate the pH of a
salt solution
Know how to determine K
a
s & K
b
s of conjugate
pairs
Strength of Acids:
Can be increased by anything that facilitates
the loss of a Proton (H
+
)
Bond Strength
Polarity or D electronegativity
Central Atom Charge or Oxidation #
Examples:
IVA VA VIA VIIA
row 2 CH
4
NH
3
H
2
O HF
row 3 SiH
4
PH
3
H
2
S HCl
Increasing acid strength
I
n
c
r
e
a
s
i
n
g

a
c
i
d

s
t
r
e
n
g
t
h

HClO
4

HClO
3

HClO
2

HClO
I
n
c
r
e
a
s
i
n
g

a
c
i
d

s
t
r
e
n
g
t
h

Acid Cl ox. #
+7
+5
+3
+1
K
a

strong
strong
1.1 x 10
-2

3.0 x 10
-8

HClO
HBrO
HIO

I
n
c
r
e
a
s
i
n
g

a
c
i
d

s
t
r
e
n
g
t
h

Acid K
a

3 x 10
-8

2.5 x 10
-9

2.3 x 10
-11

Organic Acids:
C C O
-

O
H
H
H
C C O
O
-

H
H
H
Acetate ion
resonance
C C OH
O
H
H
H
Trifluoroacetic Acid
K
a
= 5.0 x 10
-1

C C OH
O
F
F
F
Acetic Acid
K
a
= 1.8 x 10
-5

Lewis Acids and Bases:
Lewis Acid -- accepts a pair of electrons
Lewis Base -- donates a pair of electrons
formation of a coordinate covalent bond
N
H
H
H
B
F
F
F
N
H
H
H
H
+

NH
4
+

NH
3
+ H
+
Lewis Base --
donates a pair of
electrons
Lewis Acid --
accepts a pair of
electrons