Chapter 3 Acids & Bases

Copyright 2011 Pearson Education, Inc.
Chapter 15
Acids and
Bases

Chapter 16
Ionic Equilibrium

CHM096
CHAPTER 3: ACID-BASE EQUILIBRIUM

3.1 Definitions of Acids and Bases
Arrhenius Theory
Bronsted-Lowry Concept
Conjugate Acid-Base Relationship
Lewis Acids and Bases
3.2 Strength of Acids and Bases
pH and Acid strength
Self-Ionisation of Water
Acid and Base Ionisation Costants
Hydrolysis of Salts
3.3 Buffer Solutions and Acid-Base Titrations
Properties of Buffer Solutions
The Henderson-Hasselbalch Equation
Titration Curves
Acid-Base Indicators

Tro: Chemistry: A Molecular Approach 2
Structures of Acids
3
Binary acids have acid hydrogens attached to a
nonmetal atom
HCl, HF

Tro, Chemistry: A Molecular Approach, 2/e
Structure of Acids
4
Oxy acids have acid hydrogens attached to an
oxygen atom
H
2
SO
4
, HNO
3
Structure of Acids
5
Carboxylic acids have
COOH group
HC
2
H
3
O
2
, H
3
C
6
H
5
O
7

Only the first H in the
formula is acidic
the H is on the COOH
Common Acids
6 Tro, Chemistry: A Molecular Approach, 2/e
Properties of Bases
7
Also known as alkalis
Taste bitter
alkaloids = plant product tHAt is
alkaline
often poisonous
Solutions feel slippery
Change color of vegetable dyes
red litmus turns blue
React with acids to form ionic salts
neutralization
Common Bases
Arrhenius Theory
Bases dissociate in water to produce OH
ions and cations

ionic substances dissociate in water
NaOH(aq) Na
+
(aq) + OH
(aq)

Acids ionize in water to produce H
+
ions and anions
because molecular acids are not made of ions, they cannot
dissociate
they must be pulled apart, or ionized, by the water
HCl(aq) H
+
(aq) + Cl
(aq)
in formula, ionizable H written in front
HC
2
H
3
O
2
(aq) H
+
(aq) + C
2
H
3
O
2
(aq)
Arrhenius Theory
HCl ionizes in water,
producing H
+
and Cl
ions
NaOH dissociates in water,
producing Na
+
and OH
ions
Hydronium Ion
The H
+
ions produced by the acid are so reactive they cannot
exist in water
H
+
ions are protons!!
Instead, they react with water molecules to produce complex
ions, mainly hydronium ion, H
3
O
+

H
+
+ H
2
O H
3
O
+

Arrhenius AcidBase Reactions
The H
+
from the acid combines with the OH
from the base

to make a molecule of H
2
O
it is often helpful to think of H
2
O as H-OH

The cation from the base combines with the anion from the
acid to make a salt
acid + base salt + water
HCl(aq) + NaOH(aq) NaCl(aq) + H
2
O(l)
Limitations of Arrhenius Theory
Does not explain why molecular substances, such as NH
3
,
dissolve in water to form basic solutions even though they
do not contain OH
ions
Does not explain how some ionic compounds, such as
Na
2
CO
3
or Na
2
O, dissolve in water to form basic solutions
even though they do not contain OH
ions
Does not explain why molecular substances, such as CO
2
,
dissolve in water to form acidic solutions even though they
do not contain H
+
ions
Does not explain acidbase reactions that take place in non-
aqueous solution
Brnsted-Lowry Theory
In a Brnsted-Lowry acidbase reaction, a proton (H
+
)
is transferred
The acid is an H
+
donor
The base is an H
+
acceptor
base structure must contain an atom with an unsHAred pair of
electrons (lone pairs)
In a Brnsted-Lowry acid-base reaction, the acid
molecule gives an H
+
to the base molecule
HA + :B :A
+ HB
+

Brnsted-Lowry Acids
Brnsted-Lowry acids are H
+
donors
any material that has H can potentially be a
Brnsted-Lowry acid

When HCl dissolves in water, the HCl is the acid because
HCl transfers an H
+
to H
2
O, forming H
3
O
+
ions
water acts as base, accepting H
+

HCl(aq) + H
2
O(l) Cl
(aq) + H
3
O
+
(aq)
acid base
Brnsted-Lowry Bases
Brnsted-Lowry bases are H
+
acceptors
any material that has atoms with lone pairs can potentially be a
Brnsted-Lowry base

When NH
3
dissolves in water, the NH
3
(aq) is the base
because NH
3
accepts an H
+
from H
2
O, forming OH
(aq)
water acts as acid, donating H
+
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
(aq)
base acid
Examples of Molecules with Lone Pairs
You need to be able to recognize when an atom in a molecule has lone
pair electrons and when it doesnt!
CH4 has no lone pair
Examples of Molecules with Lone Pairs
18
HClO
HCO
3

Amphoteric Substances
Amphoteric substances can act as either an acid or a
base
because they have both a transferable H and an atom with lone
pair electrons
Water acts as base, accepting H
+
from HCl
HCl(aq) + H
2
O(l) Cl
(aq) + H
3
O
+
(aq)
Water acts as acid, donating H
+
to NH
3

NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
(aq)
Therefore, water is amphoteric
Brnsted-Lowry
Acid-Base Reactions
One of the advantages of Brnsted-Lowry theory is that it
allows reactions to be reversible
HA + :B :A
+ HB
+
The original base has an extra H
+
after the reaction, so it
will act as an acid in the reverse process

And the original acid has a lone pair of electrons after the
reaction so it will act as a base in the reverse process
:A
+ HB
+
HA + :B

Conjugate Pairs
In a Brnsted-Lowry acidbase reaction, the original base
becomes an acid in the reverse reaction, and the original
acid becomes a base in the reverse process
Each reactant and the product it becomes is called a
conjugate pair
In an acid-base reaction, there are two aid-base conjugate
pairs.
For the reaction: HA + :B :A
+ HB
+
:A

is the conjugate base of HA
HB
+
is the conjugate acid of :B
Brnsted-Lowry
AcidBase Reactions
HA + :B :A
+ HB
+
acid base conjugate conjugate
base acid
HCHO
2
+ H
2
O CHO
2
+ H
3
O
+
base acid
H
2
O + NH
3
HO
+ NH
4
+
base acid
Conjugate Pairs
In the reaction H
2
O + NH
3
HO

+ NH
4
+

H
2
O and HO
constitute an
acid/conjugate base pair
NH
3
and NH
4
+
constitute a
base/conjugate acid pair
Practice Write the formula for the conjugate acid of
the following
H
2
O
NH
3
CO
3
2
H
2
PO
4
1
H
2
O H
3
O
+

NH
3
NH
4
+

CO
3
2
HCO
3

H
2
PO
4
1
H
3
PO
4

Practice Write the formula for the conjugate base
of the following
H
2
O
NH
3
CO
3
2
H
2
O HO

NH
3
NH
2

CO
3
2
because CO
3
2
does not have an H, it
cannot be an acid
H
2
PO
4
1
HPO
4
2
Example 15.1a: Identify the Brnsted-Lowry acids and bases, and
their conjugates, in the reaction
H
2
SO
4
+ H
2
O HSO
4
+ H
3
O
+
base acid
H
2
SO
4
+ H
2
O HSO
4
+ H
3
O
+

When the H
2
SO
4
becomes HSO
4
, it loses an H
+
so H
2
SO
4
must
be the acid and HSO
4
its conjugate base

When the H
2
O becomes H
3
O
+
, it accepts an H
+
so H
2
O must be
the base and H
3
O
+
its conjugate acid
Example 15.1b: Identify the Brnsted-Lowry acids and bases and
their conjugates in the reaction
HCO
3
+ H
2
O H
2
CO
3
+ HO

base acid conjugate conjugate
acid base
HCO
3
+ H
2
O H
2
CO
3
+ HO

When the HCO
3
becomes H
2
CO
3
, it accepts an H
+
so HCO
3

must be the base and H
2
CO
3
its conjugate acid
When the H
2
O becomes OH
, it donats an H
+
so H
2
O must be
the acid and OH
its conjugate base

Practice Identify the Brnsted-Lowry acid, base, conjugate
acid, and conjugate base in the following reaction
HSO
4
(aq)
+ HCO
3
(aq)
SO
4
2
(aq)
+ H
2
CO
3(aq)

Base
Conjugate
Acid
Acid Conjugate
Base
Practice Write the equations for the following reacting with
water and acting as a monoprotic acid & label the conjugate
acid and base
HBr + H
2
O Br
+ H
3
O
+

Acid Base Conj. Conj.
base acid
HSO
4
+ H
2
O SO
4
2
+ H
3
O
+

Acid Base Conj. Conj.
base acid
HBr
HSO
4

Comparing Arrhenius Theory and Brnsted-Lowry Theory
30
BrnstedLowry theory

HCl(aq) + H
2
O(l) Cl
(aq) + H
3
O
+
(aq)
HF(aq) + H
2
O(l) F
(aq) + H
3
O
+
(aq)
NaOH(aq) Na
+
(aq) + OH
(aq)
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
(aq)
Arrhenius theory

HCl(aq) H
+
(aq) + Cl
(aq)
HF(aq) H
+
(aq) + F
(aq)
NaOH(aq) Na
+
(aq) + OH
(aq)
NH
4
OH(aq) NH
4
+
(aq) + OH
(aq)

Lewis AcidBase Theory
Lewis AcidBase theory focuses on transferring an electron
pair
lone pair bond
Does NOT require H atoms
The electron donor is called the Lewis Base
electron rich, therefore nucleophile
The electron acceptor is called the Lewis Acid
electron deficient, therefore electrophile
Anions are better Lewis Bases than neutral atoms or
molecules
N: < N:

Generally, the more electronegative an atom, the less willing
it is to be a Lewis Base
O: < S:

Lewis AcidBase Reactions
The base donates a pair of electrons to the acid
Generally results in a dative bond forming
H
3
N: + BF
3
H
3
NBF
3

No H transfer
The product that forms is called an adduct
Arrhenius and Brnsted-Lowry acidbase reactions are
also Lewis acidbase reactions
Examples of Lewis AcidBase Reactions
Examples of Lewis AcidBase Reactions
Ag
+
(aq)
+ 2 :NH
3(aq)
Ag(NH
3
)
2
+
(aq)

Lewis
Acid
Lewis
Base
Adduct
Practice
Identify the Lewis Acid and Lewis Base in Each Reaction
35
Lewis
Base
Lewis
Base
Lewis
Acid
Lewis
Acid
Strong or Weak
A strong acid is a strong electrolyte
practically all the acid molecules ionize,
A strong base is a strong electrolyte
practically all the base molecules form OH
ions, either
through dissociation or reaction with water,
A weak acid is a weak electrolyte
only a small percentage of the molecules ionize,
A weak base is a weak electrolyte
only a small percentage of the base molecules form OH

ions, either through dissociation or reaction with water,
Strong Acids
37
HCl H
+
+ Cl

HCl + H
2
O H
3
O
+
+ Cl

0.10 M HCl = 0.10 M H
3
O
+

The stronger the acid, the more
willing it is to donate H
+

we use water as the standard base
to donate H
+
to
Strong acids donate practically all
their H
+
s
100% ionized in water
strong electrolyte
[H
3
O
+
] = [strong acid]
[X] means the molarity of X

HF H
+
+ F

HF + H
2
O H
3
O
+
+ F

0.10 M HF 0.10 M H
3
O
+

Weak Acids
38
Weak acids donate a small
fraction of their H
+
s
most of the weak acid molecules do
not donate H
+
to water
less than 1% ionization in water
[H
3
O
+
] << [weak acid]

Strong & Weak Acids
Copyright 2011 Pearson Education, Inc. Tro, Chemistry: A Molecular Approach, 2/e
Autoionization of Water
Water is actually an extremely weak electrolyte
therefore there must be a few ions present
About 2 out of every 1 billion water molecules form ions
through a process called autoionization or self-ionisation
H
2
O H
+
+ OH

H
2
O + H
2
O H
3
O
+
+ OH

All aqueous solutions contain both H
3
O
+
and OH

the concentration of H
3
O
+
and OH
are equal in water

[H
3
O
+
] = [OH
] = 10
7
M @ 25 C
Ion Product Constant of Water
In any aqueous solution, the product of the [H
3
O
+
] and
[OH
] concentrations is always a constant number

The number is called the Ion Product Constant of
Water and has the symbol K
w

[H
3
O
+
] x [OH
] = K
w
= 1.00 x 10
14
@ 25 C

if you measure one of the concentrations, you can calculate the
other
As [H
3
O
+
] increases, the [OH
] must decrease so the

product stays constant
Acidic and Basic Solutions
All aqueous solutions contain both H
3
O
+
and OH
ions
Neutral solutions have equal [H
3
O
+
] and [OH
]
[H
3
O
+
] = [OH
] = 1.00 x 10
7

Acidic solutions have a larger [H
3
O
+
] than [OH
]
[H
3
O
+
] > 1.00 x 10
7
; [OH
] < 1.00 x 10
7

Basic solutions have a larger [OH
] than [H
3
O
+
]
[H
3
O
+
] < 1.00 x 10
7
; [OH
] > 1.00 x 10
7

Practice Complete the table
[H
+
] vs. [OH
]
OH

H
+
H
+
H
+
H
+
H
+
OH

OH

OH

OH

[OH
]
[H
+
] 10
0
10
1
10
3
10
5
10
7
10
9
10
11
10
13
10
14
Practice Complete the table [H
+
] vs. [OH
]
OH

H
+
H
+
H
+
H
+
H
+
OH

OH

OH

OH

[OH
]10
14
10
13
10
11
10
9
10
7
10
5
10
3
10
1
10
0
[H
+
] 10
0
10
1
10
3
10
5
10
7
10
9
10
11
10
13
10
14
Even though it may look like it, neither H
+
nor OH
will ever be 0
The sizes of the H
+
and OH
are not to scale

because the divisions are powers of 10 rather than units
Acid
Base
Example 15.2b:
Calculate the [OH
] at 25 C when the [H
3
O
+
] = 1.5 x 10
9
M,
and determine if the solution is acidic, basic, or neutral
46
the units are correct; the fact tHAt the
[H
3
O
+
] < [OH
] means the solution is basic

[H
3
O
+
] = 1.5 x 10
9
M
[OH
]
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
[H
3
O
+
] [OH
]
Practice: Determine the [H
3
O
+
] when the [OH
] = 2.5 x 10
9
M
Practice :
Determine the [H
3
O
+
] when the [OH
] = 2.5 x 10
9
M
48
the units are correct; the fact that
[H
3
O
+
] > [OH
] means the solution is acidic

[OH
] = 2.5 x 10
9
M
[H
3
O
+
]
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
[OH
] [H
3
O
+
]
Measuring Acidity: pH
49
The acidity or basicity of a solution is
often expressed as pH
pH = log[H
3
O
+
]

exponent on 10 with a positive sign
pH
water
= log[10
7
] = 7
need to know the [H
3
O
+
] concentration
to find pH
pH < 7 is acidic; pH > 7 is basic, pH = 7 is
neutral
[H
3
O
+
] = 10
pH

[H
3
O
+
] and [OH
] in a
Strong Acid or Strong Base Solution
There are two sources of H
3
O
+
in an aqueous solution of a
strong acid the acid and the water
There are two sources of OH
in an aqueous solution of a
strong acid the base and the water
For a strong acid or base, the contribution of the water to the
total [H
3
O
+
] or [OH
] is negligible
the [H
3
O
+
]
acid
shifts the K
w
equilibrium so far that [H
3
O
+
]
water

is too
small to be significant
except in very dilute solutions, generally < 1 x 10
4
M
Finding pH of a Strong Acid or Strong Base
Solution
For a monoprotic strong acid [H
3
O
+
] = [HA]
for polyprotic acids, the other ionizations can generally be ignored
0.10 M HCl HAs [H
3
O
+
] = 0.10 M and pH = 1.00
For a strong ionic base, [OH
] = (number OH
)x[Base]
for molecular bases with multiple lone pairs available, only one lone
pair accepts an H, the other reactions can generally be ignored
0.10 M Ca(OH)
2
HAs [OH
] = 0.20 M and pH = 13.30

Example 15.3b: Calculate the pH at 25 C when the [OH
] = 1.3 x 10
2

M, and determine if the solution is acidic, basic, or neutral
52
pH is unitless; the fact that the pH > 7 means the
solution is basic
[OH
] = 1.3 x 10
2
M
pH
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
[H
3
O
+
] [OH
] pH
Practice Determine the pH @ 25 C of a solution
that has [OH
] = 2.5 x 10
9
M
Practice Determine the pH @ 25 C of a solution that has
[OH
] = 2.5 x 10
9
M
54
pH is unitless; the fact that the pH < 7 means
the solution is acidic
[OH
] = 2.5 x 10
9
M
pH
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
[H
3
O
+
] [OH
] pH
Practice Determine the [OH
] of a solution with a
pH of 5.40
55
because the pH < 7, [OH
] should be less
tHAn 1 x 10
7
; and it is
pH = 5.40
[OH
], M
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
[H
3
O
+
] pH [OH
]
pOH
56
Another way of expressing the acidity/basicity of a solution is
pOH
pOH = log[OH
],
[OH
] = 10
pOH
pOH
water
= log[10
7
] = 7
need to know the [OH
] concentration to find pOH

pOH < 7 is basic; pOH > 7 is acidic, pOH = 7 is neutral
pH + pOH = 14.0
Relationship between pH and pOH
pH + pOH = 14.00
at 25 C
you can use pOH to find pH of a solution
57

[H
3
O
+
][OH
] = K
w
= 1.0 10
14
log [H
3
O
+
][OH
]
( ) ( )
= log 1.0 10
14
( )
log [H
3
O
+
]
( ) ( )
+ log [OH
]
( ) ( )
= 14.00
pH+ pOH= 14.00
Example: Calculate the pH at 25 C when the [OH
] = 1.3 x
10
2
M, and determine if the solution is acidic, basic or neutral
58
pH is unitless; since t pH > 7, the solution is
basic
[OH
] = 1.3 x 10
2
M
pH
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
pOH [OH
] pH
Practice Determine the pOH at 25 C of a solution that has
[H
3
O
+
] = 2.5 x 10
9
M
59
pH is unitless; the fact tHAt the pH < 7 means
the solution is acidic
[H
3
O
+
] = 2.5 x 10
9
M
pOH
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
pH [H
3
O
+
] pOH
Example 15.11: Calculate the pH at 25 C of a 0.0015 M
Sr(OH)
2
solution and determine if the solution is acidic, basic,
or neutral
pH is unitless; the fact tHAt the pH > 7 means
the solution is basic
[Sr(OH)
2
] = 1.5 x 10
3
M
pH
Check:
Solution:
Conceptual
Plan:
Relationships:
Given:
Find:
[H
3
O
+
] [OH
] pH [Sr(OH)
2
]
[OH
]=2[Sr(OH)
2
]
[OH
]
= 2(0.0015)
= 0.0030 M
Practice Calculate the pH of the following strong
acid or base solutions
0.0020 M HCl
0.0015 M Ca(OH)
2

[H
3
O
+
] = [HCl] = 2.0 x 10
3
M
pH = log(2.0 x 10
3
) = 2.70
[OH
] = 2 x [Ca(OH)
2
] = 3.0 x 10
3
M
pOH = log(3.0 x 10
3
) = 2.52
pH = 14.00 pOH = 14.00 2.52
pH = 11.48
Finding the pH of a Weak Acid
There are also two sources of H
3
O
+
in an aqueous solution
of a weak acid the acid and the water
However, finding the [H
3
O
+
] is complicated by the fact HA
the acid only undergoes partial ionization
Calculating the [H
3
O
+
] requires the use of K
a
for the
equilibrium :

HA + H
2
O A
+ H
3
O
+

Acid Ionization Constant, K
a
Acid strength measured by the size of the equilibrium
constant when reacts with H
2
O
HA(aq) + H
2
O() A
(aq) + H
3
O
+
(aq)

The equilibrium constant for this reaction is called the
acid ionization constant, K
a

larger K
a
= stronger acid [A

] [H
3
O
+
]
K
a
=
[HA

]

Copyright 2011 Pearson Education, Inc. 65 Tro, Chemistry: A Molecular Approach, 2/e
[HNO
2
] [NO
2
] [H
3
O
+
]
initial 0.200
0 0
change
equilibrium
Example 15.6: Find the pH of 0.200 M HNO
2
(aq) solution @
25 C, given that K
a
for HNO
2
= 4.6 x 10
4

66
represent the change in
the concentrations in
terms of x
sum the columns to find
the equilibrium
concentrations in terms
of x
substitute into the
equilibrium constant
expression
+x
+x x
0.200 x
x x
HNO
2
+ H
2
O
(l)
NO
2
(aq)
+ H
3
O
+
(aq)


2
(aq) solution @
25 C, given that K
a
for HNO
2
= 4.6 x 10
4
using simplifying approximation method

67
because K
a
is very small,
approximate the [HNO
2
]
eq

= [HNO
2
]
init
and solve for
x
[HNO
2
] [NO
2
] [H
3
O
+
]
initial 0.200
0 0
change
x +x +x
equilibrium
0.200
x x
0.200 x
2
(aq) solution @
25 C
68
check if the
approximation is
valid by seeing if
x < 5% of [HNO
2
]
init

K
a
for HNO
2
= 4.6 x 10
4

[HNO
2
] [NO
2
] [H
3
O
+
]
initial 0.200
0 0
change
x +x +x
equilibrium
0.200
x x
the approximation is valid
x = 9.6 x 10
3

2
(aq)
solution at 25 C
69
substitute x into
the equilibrium
concentration
definitions and
solve
K
a
for HNO
2
= 4.6 x 10
4

[HNO
2
] [NO
2
] [H
3
O
+
]
initial
0.200
0 0
cHAnge x +x +x
equilibrium 0.200x
x x
x = 9.6 x 10
3

[HNO
2
] [NO
2
] [H
3
O
+
]
initial
0.200
0 0
change x +x +x
equilibrium 0.190 0.0096 0.0096
2
(aq)
solution at 25 C
70
substitute [H
3
O
+
]
into the formula for
pH and solve
[HNO
2
] [NO
2
] [H
3
O
+
]
initial 0.200
0 0
change
x +x +x
equilibrium
0.190 0.0096 0.0096
Determining [H
3
O
+
] of a weak acid from K
a

using the direct approach

For a weak acid HA with [HA] = c mol/L

[A
] [H
3
O
+
]
K
a
=
[HA

]

Since [A
] = [H
3
O
+
]

[HA

] x K
a
= [H
3
O
+
]

[H
3
O
+
] = c x K
a

[H
3
O
+
] = \ c x K
a


Practice What is the pH of a 0.012 M solution of nicotinic
acid, HC
6
H
4
NO
2
?
(K
a
= 1.4 x 10
5
at 25 C)

[HC
6
H
4
NO
2
] = 0.012 M = c

[H
3
O
+
] = \ c x K
a

[H
3
O
+
] = \ 0.012 x 1.4 x 10
5
= 4.1 x 10
4
M

pH = log(4.1 x 10
4
) = 3.39

Example 15.8: What is the K
a
of a weak acid if a
0.100 M solution has a pH of 4.25?
73
use the pH to find the
equilibrium [H
3
O
+
]
write the reaction for
the acid with water
Compute K
a

HA + H
2
O A
+ H
3
O
+

K
a
= [H
3
O
+
] / c
= (5.6 x 10
5
)/0.100
= 3.1 x 10
8

Practice
What is the K
a
of nicotinic acid, HC
6
H
4
NO
2
, if
a 0.012 M solution of nicotinic acid has a pH
of 3.40?

(Answer: 1.3 x 10
5
)
Weak Bases
75
NH
3
+ H
2
O NH
4
+
+ OH

In weak bases, only a small fraction
of molecules accept Hs
weak electrolyte
most of the weak base molecules
do not take H from water
much less than 1% ionization in
water
[HO
] << [weak base]

Finding the pH of a weak base
solution is similar to finding the pH of
a weak acid
Base Ionization Constant, K
b
Base strength measured by the size of the equilibrium
constant when a base B reacts with H
2
O
:B + H
2
O OH
+ H:B
+

The equilibrium constant is called the base ionization
constant, K
b

larger K
b
= stronger base
Copyright 2011 Pearson Education, Inc. 77 Tro, Chemistry: A Molecular Approach, 2/e
Structure of Amines
pK
Another way of expressing the strength of a weak acid or
weak base is pK
pK
a
= log(K
a
), K
a
= 10
pKa
The stronger the acid, the smaller the pK
a

larger K
a
= smaller pK
a

because it is the log
pK
b
= log(K
b
), K
b
= 10
pKb

The stronger the base, the smaller the pK
b

larger K
b
= smaller pK
b

Determine pKa
a) HF has Ka = 3.5 x 10
4
. Calculate the pKa.
pKa = logKa = log(3.5 x 10
4
) = 3.455

b) The pKb of ethylamine, C2H5NH2 = 3.25. What is its Kb value?
pKb = 3.25 Kb = 10
pK
b
= 10
3.25

= 5.62 x 10
4

Example 15.12: Find the pH of 0.100 M NH
3
(aq)
81
determine the value of
K
b
from Table 15.8
because K
b
is very
small, approximate the
[NH
3
]
eq
= [NH
3
]
init
and
solve for x
K
b
for NH
3
= 1.76 x 10
5

[NH
3
] [NH
4
+
] [OH
]
initial 0.100
0 0
change
x +x +x
equilibrium
0.100
x x
0.100 x
Example 15.12: Find the pH of 0.100 M NH
3
(aq)
82
Example 15.12: To find pH of 0.100 M NH
3
(aq)
From previous calculation, obtained:
x = 1.33 x 10
3

Practice Find the pH of a 0.0015 M morphine solution, K
b
=
1.6 x 10
6
using direct approximation method

B + H
2
O BH
+
+ OH

Taking [B] = c, and [BH
+
] = [OH
]

[BH
+
][OH
] [OH
]
K
b
= =
[B] c

[OH
] = \(c x K
b
) = \(0.0015 x 1.6 x 10
6
)
= 4.9 x 10
5

pOH = log(4.9 x 10
5
) = 4.31
pH = 14 pOH = 14 4.31
= 9.69

AcidBase Properties of Salts: Salt Hydrolysis
Salts are water-soluble ionic compounds

Basic salts
Salts that contain the cation of a strong base and an anion
that is the conjugate base of a weak acid are basic
NaF solutions are basic
Na
+
is the cation of the strong base NaOH
F
is the conjugate base of the weak acid HF. F
sligthly
hydrolyse in water to give OH

F
(aq) + H
2
O(l) HF(aq) + OH
(aq)

SALTS
Acidic Salts
Salts that contain cations that are the conjugate acid of a
weak base and an anion of a strong acid are acidic
NH
4
Cl solutions are acidic
NH
4
+
is the conjugate acid of the weak base NH
3

NH
4
+
under goes hydrolysis to produce slight excess of H
+

NH
4
+
(aq) + H
2
O(l) NH
4
OH(aq) + H
+
(aq)

Cl
is the anion of the strong acid HCl. No hydrolysis.

Neutral Salts
Salts that contain cations that are the conjugate acid of a strong base
and an anion of a strong acid are neutral. Examples: NaBr, KNO3

Example 15.13: Use the table to determine if the given
anion is basic or neutral
a) NO
3

the conjugate base of a
strong acid, HNO3,
therefore neutral

b) NO
2

the conjugate base of a
weak acid, HNO2 therefore
basic
Relationship between K
a
of an Acid and K
b
of Its
Conjugate Base
Many reference books only give tables of K
a
values
because K
b
values can be found from them
when you add
equations, you
multiply the Ks
At 25
o
C, Kw = 1 x 10
14

Example 15.14: Find the pH of 0.100 M
NaCHO
2
(aq) solution

Na
+
is the cation
of a strong base
pH neutral. The
CHO
2
is the
anion of a weak
acid pH basic
write the reaction
for the anion with
water
construct an ICE
table for the
reaction
enter the initial
concentrations
assuming the
[OH
] from water
is 0
CHO
2
+ H
2
O HCHO
2
+ OH

[CHO
2
] [HCHO
2
] [OH
]
initial
0.100 0 0
change
equilibrium
[CHO
2
] [HCHO
2
] [OH
]
initial 0.100 0 0
change
equilibrium
0.100 x
Example 15.14: Find the pH of 0.100 M
NaCHO
2
(aq) solution
91
represent the
change in the
concentrations in
terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
Calculate the value
of K
b
from the value
of K
a
of the weak
acid from Table 15.5
substitute into the
equilibrium constant
expression
+x +x x
x x
Example 15.14: Find the pH of 0.100 M NaCHO
2
(aq)
92
because K
b
is very
small, approximate
the [CHO
2
]
eq
=
[CHO
2
]
init
and
solve for x
K
b
for CHO
2
= 5.6 x 10
11

[CHO
2
] [HCHO
2
] [OH
]
initial
0.100 0 0
change x +x +x
equilibrium 0.100 x x
0.100 x
2
(aq)
93
check if the
approximation is
valid by seeing if
x < 5% of
[CHO
2
]
init

x = 2.4 x 10
6

K
b
for CHO
2
= 5.6 x 10
11

[CHO
2
] [HCHO
2
] [OH
]
initial
0.100 0 0
change x +x +x
equilibrium 0.100
x x
[CHO
2
] [HCHO
2
] [OH
]
initial
0.100 0 0
cHAnge x +x +x
equilibrium 0.100 2.4E-6 2.4E-6
2
(aq)
94
substitute x into
the equilibrium
concentration
definitions and
solve
x = 2.4 x 10
6

K
b
for CHO
2
= 5.6 x 10
11

[CHO
2
] [HCHO
2
] [OH
]
initial
0.100 0 0
x +x +x
equilibrium
2
(aq)
95
use the [OH
] to
find the [H
3
O
+
]
using K
w

substitute [H
3
O
+
]
into the formula
for pH and solve
K
b
for CHO
2
= 5.6 x 10
11

[CHO
2
] [HCHO
2
] [OH
]
initial
0.100 0 0
change x +x +x
2
(aq)
97
check by
substituting the
equilibrium
concentrations
back into the
equilibrium
constant
expression and
comparing the
calculated K
b
to
the given K
b

though not exact,
the answer is
reasonably close
K
b
for CHO
2
= 5.6 x 10
11

[CHO
2
] [HCHO
2
] [OH
]
initial
0.100 0 0
cHAnge x +x +x
equilibrium 0.100 2.4E6 2.4E6
If a 0.0015 M NaA solution HAs a pOH of
5.45, what is the K
a
of HA?
Na
+
is the cation of a
strong base pOH
neutral. Because
pOH is < 7, the
solution is basic. A

is basic.
write the reaction for
the anion with water
construct an ICE
table for the reaction
enter the initial
concentrations
assuming the [OH
]
from water is 0
A
+ H
2
O HA + OH

[A
] [HA] [OH
]
initial
0.100 0 0
change
equilibrium
98
Practice If a 0.15 M NaA solution HAs a pOH of 5.45,
what is the K
a
of HA?
use the pOH to
find the [OH
]

use [OH
] to fill
in other items
[A
] [HA] [OH
]
initial
0.15 0 0
cHAnge 3.6E6
+3.6E6 +3.6E6
[A
] [HA] [OH
]
initial
0.15 0 0

equilibrium
calculate the
value of K
b
of A

[A
] [HA] [OH
]
initial 0.15 0 0
change
3.6E6 +3.6E6 +3.6E6
equilibrium
0.15 3.6E-6 3.6E-6
100
Practice If a 0.15 M NaA solution HAs a pOH of 5.45,
what is the K
a
of HA?
use K
b
of A

to
find K
a
of HA
101
Practice If a 0.15 M NaA solution HAs a pOH
of 5.45, what is the K
a
of HA?
[A
] [HA] [OH
]
initial 0.15 0 0
change
3.6E6 +3.6E6 +3.6E6
equilibrium
0.15 3.6E-6 3.6E-6

K
b
= 8.3910
11
Polyatomic Cations as
Weak Acids
Some cations can be thought of as the conjugate acid of a
weak base
others are the counter-ions of a strong base
Therefore, some cations can potentially be acidic. They
undergo hydrolysis
MH
+
(aq) + H
2
O(l) MOH(aq) + H
3
O
+
(aq)
The stronger the base is, the weaker the conjugate acid
is
a cation that is the counter-ion of a strong base is pH
neutral
a cation that is the conjugate acid of a weak base is acidic
NH
4
+
(aq) + H
2
O(l) NH
3
(aq) + H
3
O
+
(aq)
because NH
3
is a weak base, the position of this equilibrium favors
the right

Metal Cations as Weak Acids
Cations of small, highly charged metals are weakly acidic
alkali metal cations and alkali earth metal cations are
pH neutral
cations are hydrated
Al(H
2
O)
6
3+
(aq) + H
2
O(l) Al(H
2
O)
5
(OH)
2+

(aq) + H
3
O
+
(aq)
Example 15.15: Determine if the given cation is
acidic or neutral
a) C
5
N
5
NH
+

the conjugate acid of the weak base pyridine, C
5
N
5
N
therefore acidic
b) Ca
2+

the counter-ion of the strong base Ca(OH)
2
, therefore
neutral
c) Cr
3+

a highly charged metal ion, therefore acidic
Classifying Salt Solutions as
Acidic, Basic, or Neutral
If the salt cation is the counter-ion of a strong base and the
anion is the conjugate base of a strong acid, it will form a
neutral solution
NaCl Ca(NO
3
)
2
KBr
If the salt cation is the counter-ion of a strong base
and the anion is the conjugate base of a weak
acid, it will form a basic solution
NaF Ca(C
2
H
3
O
2
)
2
KNO
2

If the salt cation is the conjugate acid of a weak
base and the anion is the conjugate base of a
strong acid, it will form an acidic solution
NH
4
Cl
If the salt cation is a highly charged metal ion and
the anion is the conjugate base of a strong acid, it
will form an acidic solution
Al(NO
3
)
3

If the salt cation is the conjugate acid of a weak
base and the anion is the conjugate base of a
weak acid, the pH of the solution depends on the
relative strengths of the acid and base
NH
4
F because HF is a stronger acid than NH
4
+
, K
a
of
NH
4
+
is larger than K
b
of the F
; therefore the solution

will be acidic

Example 15.16: Determine whether a solution of the
following salts is acidic, basic, or neutral
a) SrCl
2

Sr
2+
is the counter-ion of a strong base, pH neutral
Cl
is the conjugate base of a strong acid, pH neutral

solution will be pH neutral
b) AlBr
3

Al
3+
is a small, highly charged metal ion, weak acid
Cl

solution will be acidic
c) CH
3
NH
3
NO
3

CH
3
NH
3
+
is the conjugate acid of a weak base, acidic
NO
3

solution will be acidic
Example 15.16: Determine whether a solution of the
following salts is acidic, basic, or neutral
d) NaCHO
2

Na
+
CHO
2
is the conjugate base of a weak acid, basic

solution will be basic
e) NH
4
F
NH
4
+
is the conjugate acid of a weak base, acidic
F
is the conjugate base of a weak acid, basic

K
a
(NH
4
+
) > K
b
(F
); solution will be acidic

Copyright 2011 Pearson Education, Inc. Tro: Chemistry: A Molecular Approach 110
Practice Determine whether a solution of
the following salts is acidic, basic, or neutral
KNO
3

CoCl
3

Ba(HCO
3
)
2

CH
3
NH
3
NO
3
the solution is pH neutral
Co
3+
is a highly charged cation, pH acidic
111
K
+
NO
3
is the counter-ion of a strong acid, pH neutral

Cl

the solution is pH acidic
Ba
2+
HCO
3
is the conjugate of a weak acid, pH basic

the solution is pH basic
CH
3
NH
3
+
is the conjugate of a weak base, pH acidic
NO
3

the solution is pH acidic
KNO
3

CoCl
3

Ba(HCO
3
)
2

CH
3
NH
3
NO
3
Chapter 16
Aqueous Ionic
Equilibrium
Buffers
Buffers are solutions that resist changes in pH when an acid
or base is added
They act by neutralizing acid or base that is added to the
buffered solution
Acidic buffers are made by mixing a solution of a weak acid
with a solution of a salt containing its conjugate base anion
Mixing acetic acid, HC
2
H
3
O
2
with sodium acetate, NaC
2
H
3
O
2

Basic buffers are prepared by mixing a solution of a weak
base with a solution of a salt containing its conjugate acid
cation
Mixing aqueous NH3 with ammonium chloride solution NH4Cl

113 Tro: Chemistry: A Molecular Approach, 2/e
Making an Acid Buffer
Basic Buffers
B:
(aq)
+ H
2
O
(l)
H:B
+
(aq)
+ OH
(aq)
Buffers can also be made by mixing a weak base, (B:),
with a soluble salt of its conjugate acid, H:B
+
Cl

H
2
O
(l)
+ NH
3

(aq)
NH
4
+
(aq)
+ OH
(aq)
How Acid Buffers Work:
Addition of Base
HA
(aq)
+ H
2
O
(l)
A
(aq)
+ H
3
O
+
(aq)
Buffers work by applying Le Chteliers Principle to weak
acid equilibrium
Acid Buffer solutions contain significant amounts of the
weak acid molecules, HA
These molecules neutralize the added base OH
(aq)
HA(aq) + OH
(aq) A
(aq) + H
2
O(l)
you can also think of the H
3
O
+
combining with the OH
to make
H
2
O; the H
3
O
+
is then replaced by the shifting equilibrium
How Acid Buffers Work:
Addition of Acid
HA
(aq)
+ H
2
O
(l)
A
(aq)
+ H
3
O
+
(aq)
The buffer solution also contains significant
amounts of the conjugate base anion, A

These ions combine with added acid, H
+
(aq) to
make more HA
H
+
(aq) + A
(aq) HA(aq)

Common Ion Effect
HA
(aq)
+ H
2
O
(l)
A
(aq)
+ H
3
O
+
(aq)
Adding a salt, NaA containing the anion, A
(aq)
which is the
conjugate base of the acid (the common ion), shifts the
position of equilibrium to the left, lowering the H
3
O
+
ion
concentration
This causes the pH to be higher than the pH of the acid
solution
Example 16.1: What is the pH of a buffer that is
0.100 M HC
2
H
3
O
2
and 0.100 M NaC
2
H
3
O
2
?
119
write the reaction
for the acid with
water
construct an ICE
table for the
reaction
enter the initial
concentrations
assuming the
[H
3
O
+
] from
water is 0
HC
2
H
3
O
2
+ H
2
O C
2
H
3
O
2
+ H
3
O
+
[HA] [A
] [H
3
O
+
]
initial
0.100 0.100 0
change
equilibrium
Tro: Chemistry: A Molecular Approach, 2/e
[HA] [A
] [H
3
O
+
]
initial
0.100 0.100 0
change
equilibrium
Example 16.1: What is the pH of a buffer that is 0.100 M
HC
2
H
3
O
2
and 0.100 M NaC
2
H
3
O
2
?
120
represent the
cHAnge in the
concentrations in
terms of x
sum the columns
to find the
equilibrium
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
+x +x x
0.100 x 0.100 + x
x
HC
2
H
3
O
2
+ H
2
O C
2
H
3
O
2
+ H
3
O
+
Example 16.1: What is the pH of a buffer that is
0.100 M HC
2
H
3
O
2
and 0.100 M NaC
2
H
3
O
2
?
121
determine the
value of K
a

because K
a
is very
small, approximate
the [HA]
eq
= [HA]
init

and [A
]
eq
= [A
]
init
,
then solve for x
[HA] [A
] [H
3
O
+
]
initial
0.100 0.100 0
change x +x +x
equilibrium 0.100 0.100
x
0.100 x 0.100 +x
K
a
for HC
2
H
3
O
2
= 1.8 x 10
5

HC
2
H
3
O
2
and 0.100 M NaC
2
H
3
O
2
?
122
check if the
approximation
is valid by
seeing if x <
5% of
[HC
2
H
3
O
2
]
init

K
a
for HC
2
H
3
O
2
= 1.8 x 10
5

x = 1.8 x 10
5

[HA] [A
] [H
3
O
+
]
initial
0.100 0.100 0
cHAnge x +x +x
equilibrium 0.100 0.100
x
HC
2
H
3
O
2
and 0.100 M NaC
2
H
3
O
2
?
123
substitute x
into the
equilibrium
concentration
definitions
and solve
x = 1.8 x 10
5

[HA] [A
] [H
3
O
+
]
initial
0.100 0.100 0
change x +x +x
equilibrium 0.100 0.100 1.8E-5 0.100 + x
x
0.100 x
HC
2
H
3
O
2
and 0.100 M NaC
2
H
3
O
2
?
124
substitute [H
3
O
+
]
into the formula
for pH and solve
[HA] [A
] [H
3
O
+
]
initial
0.100 0.100 0
change x +x +x
equilibrium 0.100 0.100 1.8E5
Practice What is the pH of a buffer that is 0.14 M
HF (pK
a
= 3.15) and 0.071 M KF?
125
write the
reaction for the
acid with water
construct an
ICE table for
the reaction
enter the initial
concentrations
assuming the
[H
3
O
+
] from
water is 0
HF + H
2
O F
+ H
3
O
+
[HA] [A
] [H
3
O
+
]
initial 0.14 0.071 0
change
equilibrium
[HA] [A
] [H
3
O
+
]
initial
0.14 0.071 0
cHAnge
equilibrium
Practice What is the pH of a buffer that is 0.14 M HF (pK
a
=
3.15) and 0.071 M KF?
126
represent the
cHAnge in the
concentrations in
terms of x
sum the columns
to find the
equilibrium
concentrations in
terms of x
substitute into
the equilibrium
constant
expression
+x +x x
0.14 x 0.071 + x
x
HF + H
2
O F
+ H
3
O
+
pK
a
for HF = 3.15 K
a
for HF = 7.0 x 10
4

Practice What is the pH of a buffer that is 0.14 M and 0.071
M KF?
127
determine the
value of K
a

because K
a
is
very small,
approximate the
[HA]
eq
= [HA]
init

and [A
]
eq
= [A
]
init

solve for x
[HA] [A
] [H
3
O
+
]
initial
0.14 0.071 0
cHAnge x +x +x
equilibrium 0.012
0.100
x
0.14 x 0.071 +x
HF (pK
a
= 3.15) and 0.071 M KF?
128
check if the
approximation
is valid by
seeing if
x < 5% of
[HC
2
H
3
O
2
]
init

K
a
for HF = 7.0 x 10
4

x = 1.4 x 10
3

[HA] [A
] [H
3
O
+
]
initial
0.14 0.071 0
change x +x +x
equilibrium 0.14 0.071 x
HF (pK
a
= 3.15) and 0.071 M KF?
129
substitute x into
the equilibrium
concentration
definitions and
solve
x = 1.4 x 10
3

[HA] [A
] [H
3
O
+
]
initial
0.14 0.071 0
change x +x +x
equilibrium 0.14 0.072 1.4E-3 0.071 + x
x
0.14 x
Practice WHAt is the pH of a buffer tHAt is
0.14 M HF (pK
a
= 3.15) and 0.071 M KF?
130
substitute
[H
3
O
+
] into the
formula for pH
and solve
[HA] [A
] [H
3
O
+
]
initial
0.14 0.071 0
change x +x +x
equilibrium 0.14 0.072 1.4E3
Henderson-Hasselbalch Equation
Calculating the pH of a buffer solution can be simplified by
using an equation derived from the K
a
expression called
the Henderson-Hasselbalch Equation
The equation calculates the pH of a buffer from the pK
a

and initial concentrations of the weak acid and salt of the
conjugate base
as long as the x is small approximation is valid
Deriving the Henderson-Hasselbalch Equation
HC
7
H
5
O
2
and 0.150 M NaC
7
H
5
O
2
?
133
assume the [HA] and [A
]
equilibrium
concentrations are the
same as the initial
substitute into the
Henderson-Hasselbalch
Equation
check the x is small
approximation
HC
7
H
5
O
2
+ H
2
O C
7
H
5
O
2
+ H
3
O
+
K
a
for HC
7
H
5
O
2
= 6.5 x 10
5

HF (pK
a
= 3.15) and 0.071 M KF?
134
find the pK
a
from the
given K
a
assume the [HA] and
[A
] equilibrium
same as the initial
substitute into the
Henderson-
Hasselbalch equation
approximation
HF + H
2
O F
+ H
3
O
+
The Henderson-Hasselbalch equation is written for a
chemical reaction with a weak acid reactant and its
conjugate base as a product
The chemical equation of a basic buffer is written with a
weak base as a reactant and its conjugate acid as a
product
B: + H
2
O H:B
+
+ OH

To apply the Henderson-Hasselbalch equation, the
chemical equation of the basic buffer must be looked at like
an acid reaction
H:B
+
+ H
2
O B: + H
3
O
+

this does not affect the concentrations, just the way we are looking
at the reaction
Henderson-Hasselbalch Equation for Basic Buffers
Relationship between pK
a
and pK
b
Just as there is a relationship between the K
a
of a weak
acid and K
b
of its conjugate base, there is also a
relationship between the pK
a
of a weak acid and the pK
b
of
its conjugate base
K
a
- K
b
= K
w
= 1.0 x 10
14
log(K
a
- K
b
) = log(K
w
) = 14

log(K
a
) + log(K
b
) = 14
pK
a
+ pK
b
= 14

NH
3
(pK
b
= 4.75) and 0.20 M NH
4
Cl?
137
find the pK
a
of the
conjugate acid (NH
4
+
)
from the given K
b

assume the [B] and
[HB
+
] equilibrium
same as the initial
substitute into the
Henderson-
HAsselbalch equation
approximation
NH
3
+ H
2
O NH
4
+
+ OH

The Henderson-HAsselbalch equation is written for a
chemical reaction with a weak acid reactant and its
conjugate base as a product
The chemical equation of a basic buffer is written with a
weak base as a reactant and its conjugate acid as a
product
B: + H
2
O H:B
+
+ OH

We can rewrite the Henderson-HAsselbalch equation for
the chemical equation of the basic buffer in terms of pOH

Henderson-HAsselbalch Equation for Basic Buffers
NH
3
(pK
b
= 4.75) and 0.20 M NH
4
Cl?
139
find the pK
b
if given K
b

assume the [B] and
[HB
+
] equilibrium
same as the initial
substitute into the
Henderson-HAsselbalch
equation base form,
find pOH
approximation
calculate pH from pOH
NH
3
+ H
2
O NH
4
+
+ OH

Buffering Effectiveness
A good buffer should be able to neutralize moderate
amounts of added acid or base
However, there is a limit to how much can be added
before the pH changes significantly
The buffering capacity is the amount of acid or base a
buffer can neutralize
The buffering range is the pH range the buffer can be
effective
The effectiveness of a buffer depends on two factors (1)
the relative amounts of acid and base, and (2) the
absolute concentrations of acid and base
Buffering Capacity
a concentrated
buffer can
neutralize
more added
acid or base
tHAn a dilute
buffer
Effectiveness of Buffers
A buffer will be most effective when the
[base]:[acid] = 1
equal concentrations of acid and base
A buffer will be effective when 0.1 <
[base]:[acid] < 10
A buffer will be most effective when the [acid] and
the [base] are large
Buffering Range
We have said that a buffer will be effective when
0.1 < [base]:[acid] < 10
Substituting into the Henderson-Hasselbalch equation
we can calculate the maximum and minimum pH at
which the buffer will be effective
Lowest pH Highest pH
Therefore, the effective pH range of a buffer is pK
a
1
When choosing an acid to make a buffer, choose one whose
is pK
a
closest to the pH of the buffer
Formic acid, HCHO
2
pK
a
= 3.74
Example 16.5a: Which of the following acids would be the
best choice to combine with its sodium salt to make a
buffer with pH 4.25?
Chlorous acid, HClO
2
pK
a
= 1.95
Nitrous acid, HNO
2
pK
a
= 3.34
Hypochlorous acid, HClO pK
a
= 7.54
The pK
a
of HCHO
2
is closest to the desired pH of the
buffer, so it would give the most effective buffering
range
Example 16.5b: What ratio of NaCHO
2
: HCHO
2
would be
required to make a buffer with pH 4.25?
145
Formic acid, HCHO
2
, pK
a
= 3.74
To make a buffer with pH
4.25, you would use 3.24
times as much NaCHO
2
as
HCHO
2

Practice What ratio of NaC
7
H
5
O
2
: HC
7
H
5
O
2
would be required
to make a buffer with pH 3.75?
Benzoic acid, HC
7
H
5
O
2
, pK
a
= 4.19
to make a buffer with
pH 3.75, you would use
0.363 times as much
NaC
7
H
5
O
2
as HC
7
H
5
O
2

Buffering Capacity
Buffering capacity is the amount of acid or base that can
be added to a buffer without causing a large change in pH
The buffering capacity increases with increasing absolute
concentration of the buffer components
As the [base]:[acid] ratio approaches 1, the ability of the
buffer to neutralize both added acid and base improves
Buffers that need to work mainly with added acid generally
have [base] > [acid]
Buffers that need to work mainly with added base
generally have [acid] > [base]
Titration
In an acid-base titration, a solution of unknown
concentration (titrant) is slowly added to a solution of
known concentration from a burette until the reaction is
complete
when the reaction is complete we have reached the
endpoint of the titration
An indicator may be added to determine the endpoint
an indicator is a chemical that changes color when the
pH changes
When the moles of H
3
O
+
= moles of OH
, the titration has

reached its equivalence point

Titration
Titration Curve
A plot of pH vs. amount of added titrant
The inflection point of the curve is the equivalence point of the
titration
Prior to the equivalence point, the known solution in the flask is
in excess, so the pH is closest to its pH
The pH of the equivalence point depends on the pH of the salt
solution
equivalence point of neutral salt, pH = 7
equivalence point of acidic salt, pH < 7
equivalence point of basic salt, pH > 7
Rapid pH change from about pH = 3 to pH = 11

Titration Curve:
Unknown Strong Base Added to Strong Acid
Before Equivalence
(excess acid)
After Equivalence
(excess base)
Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH
Equivalence Point
equal moles of
HCl and NaOH
pH = 7.00
-
Because the
solutions are equal
concentration, and
1:1 stoichiometry, the
equivalence point is
at equal volumes
HCl NaCl NaOH
mols before 2.50E-3 0 5.0E-4
mols cHAnge
5.0E-4 +5.0E-4 5.0E-4
mols end
2.00E-3 5.0E-4 0
molarity, new
0.0667 0.017 0
HCl NaCl NaOH
mols cHAnge
mols end
molarity, new
HCl NaCl NaOH
mols cHAnge
5.0E-4 +5.0E-4 5.0E-4
mols end
2.00E-3 5.0E-4 0
molarity, new
5.0 x 10
4
mole NaOH added
HCl
(aq)
+ NaOH
(aq)
NaCl
(aq)
+ H
2
O
(l)

Initial pH = log(0.100) = 1.00
Initial mol of HCl = 0.0250 L x 0.100 mol/L = 2.50 x 10
3

Before equivalence point added 5.0 mL NaOH
HCl
(aq)
+ NaOH
(aq)
NaCl
(aq)
+ H
2
O
(aq)

To reach equivalence, the added moles NaOH = initial moles
of HCl = 2.50 x 10
3
moles
At equivalence, we have 0.00 mol HCl and 0.00 mol NaOH
left over
Because the NaCl is a neutral salt, the pH at equivalence =
7.00

Practice Calculate the pH of the solution that results when
10.0 mL of 0.15 M NaOH is added to 50.0 mL of 0.25 M
HNO
3

HNO
3
NaNO
3
NaOH
mols cHAnge
1.5E-3 +1.5E-3 1.5E-3
mols end
1.1E-3 1.5E-3 0
molarity, new
HNO
3
NaNO
3
NaOH
mols cHAnge
1.5E-3 +1.5E-3 1.5E-3
mols end
1.1E-3 1.5E-3 0
molarity, new
0.018 0.025 0
HNO
3

HNO
3
(aq) + NaOH(aq) NaNO
3
(aq) + H
2
O(l)
Initial pH = log(0.250) = 0.60
Initial mol of HNO
3
= 0.0500 L x 0.25 mol/L=1.25 x 10
2
Before equivalence point
added 10.0 mL NaOH
HNO
3
NaNO
3
NaOH
mols cHAnge
1.25E-2 +1.25E-2 1.25E-2
mols end
0 1.25E-2 0.0025
molarity, new
0 0.0833 0.017
HNO
3
NaNO
3
NaOH
mols change
1.25E-2 +1.25E-2 1.25E-2
mols end
0 1.25E-2 0.0025
molarity, new
HNO
3

HNO
3
(aq) + NaOH(aq) NaNO
3
(aq) + H
2
O(l)
Initial mol of HNO
3
= 0.0500 L x 0.25 mol/L=1.25 x 10
2
After equivalence point
added 100.0 mL NaOH
Titration of a Strong Base with a Strong Acid
If the titration is run so
that the acid is in the
burette and the base
is in the flask, the
titration curve will be
the reflection of the
one just shown
Titration of a Weak Acid with a Strong Base
Titrating a weak acid with a strong base results in
differences in the titration curve at the equivalence point and
excess acid region
The initial pH is determined using the K
a
of the weak acid
The pH in the excess acid region is determined as you
would determine the pH of a buffer
The pH at the equivalence point is determined using the K
b
of the conjugate base of the weak acid
The pH after equivalence is dominated by the excess strong
base
the basicity from the conjugate base anion is negligible
Titrating Weak Acid with a Strong Base
The initial pH is that of the weak acid solution
calculate like a weak acid equilibrium problem
e.g., 15.5 and 15.6
Before the equivalence point, the solution becomes a
buffer
Half-neutralization pH = pK
a
At equivalence point, pH 9
and rapid change of pH from about pH = 7 to pH = 11
Titration of 25 mL of 0.100 M HCHO
2
with 0.100 M NaOH
HCHO
2(aq)
+ NaOH
(aq)
NaCHO
2(aq)
+ H
2
O
(aq)
Initial pH
[HCHO
2
] [CHO
2
] [H
3
O
+
]
initial
0.100 0.000 0
change
x +x +x
equilibrium
0.100 x x x
K
a
= 1.8 x 10
4

2
with 0.100 M NaOH
HCHO
2(aq)
+ NaOH
(aq)
NaCHO
2

(aq)
+ H
2
O
(aq)

Initial mol of HCHO
2
= 0.0250 L x 0.100 mol/L = 2.50 x 10
3

Before equivalence
added 5.0 mL NaOH
HA A
OH

mols before 2.50E-3 0 0
mols added
5.0E-4
mols after
2.00E-3 5.0E-4 0
HA A
OH

mols before 2.50E-3 0 0
mols added
2.50E-3
mols after
0 2.50E-3 0
[HCHO
2
] [CHO
2
] [OH
]
initial
0 0.0500 0
cHAnge
+x x +x
equilibrium
x 5.00E-2-x x
2
with 0.100 M NaOH
added 25.0 mL NaOH
CHO
2
(aq)
+ H
2
O
(l)
HCHO
2(aq)
+ OH
(aq)

K
b
= 5.6 x 10
11

[OH
] = 1.7 x 10
6
M
HCHO
2(aq)
+ NaOH
(aq)
NaCHO
2

(aq)
+ H
2
O
(aq)

Initial mol of HCHO
2
= 0.0250 L x 0.100 mol/L = 2.50 x 10
3

At equivalence
added 35.0 mL NaOH
0.00100 mol NaOH xs
pH = 12.22
initial HCHO
2
solution
0.00250 mol HCHO
2

pH = 2.37
added 5.0 mL NaOH
0.00200 mol HCHO
2

pH = 3.14
added 10.0 mL NaOH
0.00150 mol HCHO
2

pH = 3.56
added 25.0 mL NaOH
equivalence point
0.00250 mol CHO
2

[CHO
2
]
init
= 0.0500 M
[OH
]
eq
= 1.7 x 10
6

pH = 8.23
added 30.0 mL NaOH
0.00050 mol NaOH xs
pH = 11.96
added 20.0 mL NaOH
0.00050 mol HCHO
2

pH = 4.34
added 15.0 mL NaOH
0.00100 mol HCHO
2

pH = 3.92
added 12.5 mL NaOH
0.00125 mol HCHO
2

pH = 3.74 = pK
a

HAlf-neutralization
Adding NaOH to HCHO
2

added 40.0 mL NaOH
0.00150 mol NaOH xs
pH = 12.36
added 50.0 mL NaOH
0.00250 mol NaOH xs
pH = 12.52
Titrating Weak Acid with a Strong Base
At the equivalence point, the mole HA = mol Base, so the
resulting solution has only the conjugate base anion in it before
equilibrium is established
mol A
= original mole HA
calculate the volume of added base as you did in
Example 4.8
[A
]
init
= mol A
/total liters
calculate like a weak base equilibrium problem
e.g., 15.14
Beyond equivalence point, the OH is in excess
[OH
] = mol MOH xs/total liters

[H
3
O
+
][OH
]=1 x 10
14

Example 16.7a: A 40.0 mL sample of 0.100 M HNO
2
is
titrated with 0.200 M KOH. Calculate the volume of KOH at
the equivalence point.
166
write an equation for
the reaction for B
with HA
use stoichiometry to
determine the volume
of added B
HNO
2
+ KOH NO
2
+ H
2
O

Example 16.7b: A 40.0 mL sample of 0.100 M HNO
2
is
titrated with 0.200 M KOH. Calculate the pH after adding
5.00 mL KOH.
167
write an
equation for the
reaction for B
with HA
determine the
moles of HA
before

& moles of
added B
make a
stoichiometry
table and
determine the
moles of HA in
excess and
moles A
made
HNO
2
+ KOH NO
2
+ H
2
O

HNO
2
NO
2
OH

mols before
0.00400 0 0
mols added

0.00100
mols after
0
0.00300
0.00100
2
is
titrated with 0.200 M KOH. Calculate the pH after adding
5.00 mL KOH.
168
write an
equation for the
reaction of HA
with H
2
O
determine K
a

and pK
a
for HA
use the
Henderson-
Hasselbalch
equation to
determine the
pH
HNO
2
+ H
2
O NO
2
+ H
3
O
+
HNO
2
NO
2
OH

mols before
0.00400 0 0
mols added
0.00100
mols after 0.00300 0.00100
0
Table 15.5 K
a
= 4.6 x 10
4

2

is titrated with 0.200 M KOH. Calculate the pH at
the half-equivalence point.
169
write an
equation for the
reaction for B
with HA
determine the
moles of HA
before

& moles of added
B
make a
stoichiometry
table and
determine the
moles of HA in
excess and
moles A
made
HNO
2
+ KOH NO
2
+ H
2
O

HNO
2
NO
2
OH

mols before
0.00400 0 0
mols added

0.00200
mols after
0
0.00200
0.00200
at HAlf-equivalence, moles KOH = mole HNO
2

2
is
titrated with 0.200 M KOH. Calculate the pH at
the half-equivalence point.
170
write an equation
for the reaction of
HA with H
2
O
determine K
a
and
pK
a
for HA
use the
Henderson-
Hasselbalch
equation to
determine the pH
HNO
2
+ H
2
O NO
2
+ H
3
O
+
HNO
2
NO
2
OH

mols before
0.00400 0 0
mols added

0.00200
mols after
0.00200 0.00200
0
Table 15.5 K
a
= 4.6 x 10
-4

At equivalence point, pH 5

Rapid change of pH range between pH = 3 to pH = 7
Titrating Weak Base with a Strong Acid
Titration Curve of a Weak Base with a Strong Acid
Practice Titration of 25.0 mL of 0.10 M NH
3
with 0.10 M
HCl. Calculate the initial pH of the NH
3
(aq)
173
NH
3(aq)
+ HCl
(aq)
NH
4
Cl
(aq)

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

[HCl] [NH
4
+
] [NH
3
]
initial
0 0 0.10
cHAnge
+x +x x
equilibrium
x x 0.10x
pK
b
= 4.75
K
b
= 10
4.75
= 1.8 x 10
5

3
(pK
b
= 4.75)
with 0.10 M HCl. Calculate the pH of the solution at
equivalence.
3
(pK
b
= 4.75)
equivalence.
175
NH
3(aq)
+ HCl
(aq)
NH
4
Cl
(aq)

Initial mol of NH
3
= 0.0250 L x 0.100 mol/L = 2.50 x 10
3

At equivalence mol NH
3
= mol HCl = 2.50 x 10
3
added 25.0 mL HCl
NH
3
NH
4
Cl HCl
mols change
2.5E-3 +2.5E-3 2.5E-3
mols end
0 2.5E-3 0
molarity, new
0 0.050 0
3
(pK
b
= 4.75)
equivalence.
176
NH
3(aq)
+ HCl
(aq)
NH
4
Cl
(aq)

at equivalence [NH
4
Cl] = 0.050 M
[NH
3
] [NH
4
+
] [H
3
O
+
]
initial
0 0.050 0
change
+x x +x
equilibrium
x 0.050x x
NH
4
+
(aq)
+ H
2
O
(l)
NH
3(aq)
+ H
3
O
+
(aq)

Indicators
Many dyes change color depending on the pH of the
solution
These dyes are weak acids, establishing an equilibrium
with the H
2
O and H
3
O
+
in the solution
HInd
(aq)
+ H
2
O
(l)
Ind
(aq)
+ H
3
O
+
(aq)
The color of the solution depends on the relative
concentrations of Ind
:HInd
when Ind
:HInd 1, the color will be mix of the colors of Ind
and
HInd
when Ind
:HInd > 10, the color will be mix of the colors of Ind

when Ind
:HInd < 0.1, the color will be mix of the colors of HInd
Phenolphthalein
Methyl Red
C
C C
H
CH
C
H
C
H
C
C
H
C
H
C
C
H
C
H
(CH
3
)
2
N N N N
H
NaOOC
C
C C
H
CH
C
H
C
H
C
C
H
C
H
C
C
H
C
H
(CH
3
)
2
N N N N
NaOOC
H
3
O+ OH-
Monitoring a Titration with an Indicator
For most titrations, the titration curve shows a very
large change in pH for very small additions of
titrant near the equivalence point
An indicator can therefore be used to determine
the endpoint of the titration if:
pK
a
of indicator pH at equivalence point
it changes color within the same range as the rapid
change in pH
Acid-Base Indicators

Chapter 3 Acids &amp; Bases

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Chapter 3 Acids &amp; Bases

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ions and cations

from the base

its conjugate base

its conjugate base

are equal in water

] concentrations is always a constant number

] must decrease so the

are not to scale

] means the solution is basic

] means the solution is acidic

] = 0.20 M and pH = 13.30

] concentration to find pOH

] << [weak base]

is the conjugate base of the weak acid HF. F

is the anion of the strong acid HCl. No hydrolysis.

; therefore the solution

is the conjugate base of a strong acid, pH neutral

is the conjugate base of a strong acid, pH neutral

is the conjugate base of a strong acid, pH neutral

is the conjugate base of a weak acid, basic

is the conjugate base of a weak acid, basic

); solution will be acidic

is the counter-ion of a strong acid, pH neutral

is the counter-ion of a strong acid, pH neutral

is the conjugate of a weak acid, pH basic

is the counter-ion of a strong acid, pH neutral

, the titration has

] = mol MOH xs/total liters

:HInd 1, the color will be mix of the colors of Ind

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Chapter 3 Acids & Bases

Chapter 3 Acids & Bases