Homework

Fundamentals of
Analytical Chemistry

3,

99-15 odd, 18, 19, 21, 25, 27, 32, 34, 38,
43, 44, 45


Problems in green may or may not be part of

the assignment, depending upon the material
that is covered.

Chapter 14
Principles of Neutralization
Titrations

Indicators

Acid/Base


indicators

Acid form has a different color than the base

form of the substance
10x more acid (or greater) acid color
10x more base (or greater) base color
Between these limits color a combination

For ideal behavior, need transition through

colors quickly
Weak acid/base substances
From HendersonHenderson-Hasselbalch,
Hasselbalch, pH = 2 for
transition

Indicators

Titration


Minimize by using low concentration of indicator




any titration, we can consider three

phases


Before the equivalence point, the analyte is in

excess
At the equivalence point, the analyte and
titrant are present in stoichiometrically
equivalent amounts.
After the equivalence point, the titrant is in
excess

MUST BE highly colored for this to work

Ideally, less than 0.02 mL of titrant to cause change

Can also correct with blank

Table



1414-1

List of indicators
pKa can be used to chose correct indicator
Match pKa with pH of equivalence point

Titrations

Strong Acid/Strong Base Titrations

In

Error

Titrant reacts with analyte and indicator

To

determine pH, we have to look at the

composition of the solution after the
reaction has occurred.


I starting conditions
How much stuff do we have before any reaction
occurs

stoichiometric relationships
HOW will the system react
Must follow the stoichiometry

F final conditions
What
Whats in solution after the reaction has gone to
completion

50.0 mL of 0.10 M HCl is titrated

with 0.10M NaOH

Strong Acid/Strong Base Titrations

Consider the following titration:

50.0 mL of
0.10 M HCl is titrated with 0.10M NaOH


Before any titrant is added:

Solution is just the strong acid (HCl
(HCl))
pH = -log 0.10
pH = 1.00

50.0 mL of 0.10 M HCl is titrated

with 0.10M NaOH

After 10.00

mL of titrant is added:

HCl + NaOH  H2O + Na+ +

I 5.00 1.00
~~
0
-1.00 -1.00
~~
~~
F 4.00
~0
~~
~~
pH = -log (4.00/60) = 1.18

Cl0
~~
~~

50.0 mL of 0.10 M HCl is titrated

with 0.10M NaOH

After 45.00

mL of titrant is added:

HCl + NaOH  H2O + Na+ +

I 5.00 4.50
~~
0
-4.50 -4.50
~~
~~
F 0.50
~0
~~
~~
pH = -log (0.50/95) = 2.28

Cl0
~~
~~

After 5.00 mL of titrant is added:

HCl + NaOH  H2O + Na+ + ClI 5.00 0.50

lots
0
0
-0.50 -0.50
~~
~~
~~
F 4.50
~0
~~
~~
~~
pH = -log (4.50/55) = 1.09
[NOTE: ~~ means we don
dont care because these
substances do not affect the pH of the solution]

50.0 mL of 0.10 M HCl is titrated

with 0.10M NaOH

After 25.00

mL of titrant is added:

HCl + NaOH  H2O + Na+ +

I 5.00 2.50
~~
0
-2.50 -2.50
~~
~~
F 2.50
~0
~~
~~
pH = -log (2.50/75) = 1.48

Cl0
~~
~~

50.0 mL of 0.10 M HCl is titrated

with 0.10M NaOH

After 49.98

mL of titrant is added:

HCl + NaOH  H2O + Na+ +

I 5.00 4.998
~~
0
-4.998 -4.998
~~
~~
F 0.002
~0
~~
~~
pH = -log (0.002/99.98) = 4.70

Cl0
~~
~~

50.0 mL of 0.10 M HCl is titrated

with 0.10M NaOH

After 50.0

After 50.02

mL of titrant is added:

50.0 mL of 0.10 M HCl is titrated

with 0.10M NaOH
mL of titrant is added:

Strong Acid/Strong Base Titrations

Summary


HCl + NaOH  H2O + Na+ +

I 5.00 7.00
~~
0
-5.00 -5.00
~~
~~
F ~0
2.00 ~~
~~
pOH = -log (2.00/120) = 1.78
pH = 14.00 1.78 = 12.22

mL of titrant is added:

HCl + NaOH  H2O + Na+ + ClI 5.00 5.002

~~
0
0
-5.00 -5.00
~~
~~
~~
F ~0
0.002 ~~
~~
~~
pOH = -log (0.002/100.02) = 4.70
pH = 14.00 - 4.70 = 9.30

HCl + NaOH  H2O + Na+ + ClI 5.00 5.00

lots
0
0
-5.00 -5.00
~~
~~
~~
F ~0
~0
lots
~~
~~
What do we have affecting the pH?

After 70.0

50.0 mL of 0.10 M HCl is titrated

with 0.10M NaOH

Cl0
~~
~~

Prior to the equivalence point excess

analyte
pH determined by analyte (strong acid or strong
base)

At the equivalence point

Nothing causing a pH from neutral
pH = 7.00
ONLY FOR STRONG ACID/BASE TITRATION!!!
TITRATION!!!

Past the equivalence point excess titrant

pH determined by titrant

Titration Curve

Weak Acid/Strong Base Titration

pH

Strong acid/base

Consider the following titration:

50.0 mL of
a 0.10 M solution of a weak acid (HA, Ka =
1.0 x 10-5) titrated with 0.10 M NaOH.
NaOH.

14
12
10
8
6
4
2

Before any titrant

0

20

40
60
Volume

80

100

is added

Only a weak acid in solution

[ H + ] = K a C HA = (0.10)(1.0 x105 )

[ H + ] = 1.0 x10 3 ; pH = 3.00

50.0 mL of a 0.10 M solution of a weak acid (HA,

Ka = 1.0 x 10-5) titrated with 0.10 M NaOH.
NaOH.

After 5.00

mL of titrant is added

Weak Acid/Strong Base Titration

Differences from strong acid/base


HA + NaOH  A- + Na+ + H2O

I 5.00 0.50
0
~~ ~~
-0.50 -0.50
+0.50 ~~ ~~
F 4.50 ~0
0.50 ~~ ~~
Buffer, pH = pKa + log b/a
pH = 5.00 + log 0.50/4.50 = 4.05

titration

Cannot ignore the products

Will always generate the conjugate base of the
analyte
This produces a buffer solution!

Reverse situation (weak base/strong acid)

Will always generate the conjugate acid of the
analyte
This produces a buffer solution!

Will always titrate

with either a strong acid

or a strong base

50.0 mL of a 0.10 M solution of a weak acid (HA,

Ka = 1.0 x 10-5) titrated with 0.10 M NaOH.
NaOH.

After 25.0

mL of titrant is added

HA + NaOH  A- + Na+ + H2O

I 5.00 2.50
0
~~ ~~
-2.50 -2.50
+2.50 ~~ ~~
F 2.50 ~0
2.50 ~~ ~~
Buffer, pH = pKa + log b/a
pH = 5.00 + log 2.50/2.50 = 5.00

50.0 mL of a 0.10 M solution of a weak acid (HA,

Ka = 1.0 x 10-5) titrated with 0.10 M NaOH.
NaOH.

After 50.0

mL of titrant is added

Weak Acid/Strong Base Titration

For this titration,

25.0 mL gets us way to

the equivalence point


Note that with a weak base/strong acid titration we

still have pH = pKa (and not pKb)

Weak Acid/Strong Base Titration

At


HA + NaOH  A- + Na+ + H2O

I 5.00 5.00
0 ~~ ~~
-5.00 -5.00
+5.00 ~~ ~~
F ~0
~0
5.00 ~~ ~~
Only a weak base in solution

At this point in any weak/strong titration, we

have the same amount of the conjugate acid
and the conjugate base in solution.
At this point pH will ALWAYS equal pKa!

the equivalence point

pH does not equal 7.00
Because the conjugate base is in solution, the pH
is driven by this component and will be basic
For a weak base/strong acid titration, you will have
the conjugate acid in solution at the equivalence
point, and the pH will be acidic

1.0 x10 14 5.00

1.0 x10 5 100

6
[OH ] = 7.1x10 ; pOH = 5.15; pH = 8.85
[OH ] = K b C B =

50.0 mL of a 0.10 M solution of a weak acid (HA,

Ka = 1.0 x 10-5) titrated with 0.10 M NaOH.
NaOH.

After 70.0 mL of titrant is added

Weak Acid/Strong Base Titration

Past


HA + NaOH  A- + Na+ + H2O

I 5.00 7.00
0
~~
~~
-5.00 -5.00
+5.00 ~~
~~
F ~0
2.00
5.00 ~~
~~
Mixture of a weak base and a strong base
Ignore the weak base; [OH-] = 2.00/120
pOH = 1.78; pH = 12.22

the equivalence point

We will assume (and usually properly) that the

contribution to the hydroxide concentration
from the weak base is negligible relative to
the contribution from the strong base
LeChatlier
LeChatliers Principle

Titration Curve

Strong Acid/
Strong Base
Titration Curve

20

40
60
Volume

80

100

80

100

Titration Curve

20

40
60
Volume

80

100

Weak Acid/
Strong Base
Titration Curve

Weak Acid - Strong Base

pH

pH

Weak Acid - Strong Base

14
12
10
8
6
4
2

pH

Strong acid/base

Titration Curve

14
12
10
8
6
4
2

14
12
10
8
6
4
2
0

20

40
60
Volume