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Buffers

and
Acid/Base
Titration
50
40
30
20
10
0
Reaction of Weak Bases with Water
The base reacts with water, producing its
conjugate acid and hydroxide ion:
CH
3
NH
2
+ H
2
O CH
3
NH
3
+
+ OH
-
K
b
= 4.38 x 10
-4

4
3 3
3 2
[ ][ ]
4.38 10
[ ]
b
CH NH OH
K x
CH NH
+

= =
K
b
for Some Common Weak Bases
Base Formula
Conjugate
Acid
K
b

Ammonia NH
3
NH
4
+
1.8 x 10
-5

Methylamine CH
3
NH
2
CH
3
NH
3
+
4.38 x 10
-4

Ethylamine C
2
H
5
NH
2
C
2
H
5
NH
3
+
5.6 x 10
-4

Diethylamine (C
2
H
5
)
2
NH

(C
2
H
5
)
2
NH
2
+
1.3 x 10
-3

Triethylamine (C
2
H
5
)
3
N

(C
2
H
5
)
3
NH
+
4.0 x 10
-4

Hydroxylamine HONH
2
HONH
3
+

1.1 x 10
-8

Hydrazine H
2
NNH
2
H
2
NNH
3
+

3.0 x 10
-6

Aniline C
6
H
5
NH
2
C
6
H
5
NH
3
+

3.8 x 10
-10

Pyridine C
5
H
5
N C
5
H
5
NH
+
1.7 x 10
-9

Many students struggle with identifying weak
bases and their conjugate acids.What patterns
do you see that may help you?
Reaction of Weak Bases with Water
The generic reaction for a base reacting
with water, producing its conjugate acid and
hydroxide ion:
B + H
2
O BH
+
+ OH
-

[ ][ ]
[ ]
b
BH OH
K
B
+
=
(Yes, all weak bases do this DO NOT
endeavor to make this complicated!)
Buffered Solutions

A solution that resists a change in
pH when either hydroxide ions or
protons are added.
Buffered solutions contain either:
A weak acid and its salt
A weak base and its salt
Acid/Salt Buffering Pairs
Weak Acid
Formula
of the acid
Example of a salt of the
weak acid
Hydrofluoric HF KF Potassium fluoride


Formic HCOOH KHCOO Potassium formate


Benzoic C
6
H
5
COOH NaC
6
H
5
COO Sodium benzoate
Acetic CH
3
COOH NaH
3
COO Sodium acetate


Carbonic H
2
CO
3
NaHCO
3

- Sodium bicarbonate
Propanoic HC
3
H
5
O
2
NaC
3
H
5
O
2

- Sodium propanoate

Hydrocyanic HCN KCN - potassium cyanide


The salt will contain the anion of the acid,
and the cation of a strong base (NaOH, KOH)
Base/Salt Buffering Pairs
The salt will contain the cation of the base,
and the anion of a strong acid (HCl, HNO
3
)
Base
Formula of
the base
Example of a salt of the weak
acid
Ammonia NH
3
NH
4
Cl

- ammonium chloride
Methylamine CH
3
NH
2
CH
3
NH
2
Cl methylammonium chloride

Ethylamine C
2
H
5
NH
2
C
2
H
5
NH
3
NO
3
-

ethylammonium nitrate

Aniline C
6
H
5
NH
2
C
6
H
5
NH
3
Cl aniline hydrochloride

Pyridine C
5
H
5
N C
5
H
5
NHCl pyridine hydrochloride
1
2
3
4
5
6
7
8
9
10
11
12
13
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
milliliters NaOH (0.10 M)
p
H
Titration of an Unbuffered Solution
A solution that is
0.10 M CH
3
COOH
is titrated with
0.10 M NaOH
1
2
3
4
5
6
7
8
9
10
11
12
13
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
milliliters NaOH (0.10 M)
p
H
Titration of a Buffered Solution
A solution that is
0.10 M CH
3
COOH and
0.10 M NaCH
3
COO is
titrated with
0.10 M NaOH
Comparing Results
Graph
0
2
4
6
8
10
12
14
0 5 10 15 20 25 30 35 40 45
mL 0.10 M NaOH
p
H
Buffered
Unbuffered
Comparing Results
1
2
3
4
5
6
7
8
9
10
11
12
13
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
milliliters NaOH (0.10 M)
p
H
1
2
3
4
5
6
7
8
9
10
11
12
13
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
milliliters NaOH (0.10 M)
p
H
Unbuffered
Buffered
In what ways are the graphs different?
In what ways are the graphs similar?
Henderson-Hasselbalch Equation
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =

] [
] [
log
] [
] [
log
acid
base
pK
HA
A
pK pH
a a
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =
+
] [
] [
log
] [
] [
log
base
acid
pK
B
BH
pK pOH
b b
This is an exceptionally powerful tool, and its use
will be emphasized in our problem solving.
1
2
3
4
5
6
7
8
9
10
11
12
13
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
milliliters NaOH (0.10 M)
p
H
Weak Acid/Strong Base Titration
A solution that is
0.10 M CH
3
COOH
is titrated with
0.10 M NaOH
Endpoint is above
pH 7
1
2
3
4
5
6
7
8
9
10
11
12
13
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
milliliters NaOH (0.10 M)
p
H
Strong Acid/Strong Base Titration
A solution that is
0.10 M HCl is
titrated with
0.10 M NaOH
Endpoint is at
pH 7
1
2
3
4
5
6
7
8
9
10
11
12
13
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
milliliters HCl (0.10 M)
p
H
Strong Acid/Strong Base Titration
A solution that is
0.10 M NaOH is
titrated with
0.10 M HCl
Endpoint is at
pH 7
It is important to
recognize that
titration curves are
not always
increasing from left
to right.
1
2
3
4
5
6
7
8
9
10
11
12
13
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
milliliters NH3 (0.10 M)
p
H
Strong Acid/Weak Base Titration
A solution that is
0.10 M HCl is
titrated with
0.10 M NH
3
Endpoint is below
pH 7
Selection of Indicators
Indicator Transitions
Indicator Low pH color Transition pH range High pH color
Gentian violet (Methyl violet 10B) yellow 0.02.0 blue-violet
Leucomalachite green (first transition) yellow 0.02.0 green
Leucomalachite green (second transition) green 11.614 colorless
Thymol blue (first transition) red 1.22.8 yellow
Thymol blue (second transition) yellow 8.09.6 blue
Methyl yellow red 2.94.0 yellow
Bromophenol blue yellow 3.04.6 purple
Congo red blue-violet 3.05.0 red
Methyl orange red 3.14.4 orange
Bromocresol green yellow 3.85.4 blue
Methyl red red 4.46.2 yellow
Methyl red red 4.55.2 green
Azolitmin red 4.58.3 blue
Bromocresol purple yellow 5.26.8 purple
Bromothymol blue yellow 6.07.6 blue
Phenol red yellow 6.88.4 red
Neutral red red 6.88.0 yellow
Naphtholphthalein colorless to reddish 7.38.7 greenish to blue
Cresol Red yellow 7.28.8 reddish-purple
Phenolphthalein colorless 8.310.0 fuchsia
Thymolphthalein colorless 9.310.5 blue
Alizarine Yellow R yellow 10.212.0 red
Litmus red 4.5-8.3 blue
Source: Wikipedia