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Experiment 7

Potentiometric Titration
Valdosta State University
Purpose
To accurately determine the molar mass and pK
a
of an
unknown weak acid.
Valdosta State University
Background
In this experiment, the pH of a solution will be measured
directly as the sodium hydroxide is added.
The pH will be measured using a glass combination
electrode.
This device measures pH (or [H
3
O
+
]) as voltage.
Valdosta State University
Background
Valdosta State University
pH Combination Electrode
combination refers to the ion sensing cell and the reference
cell.
Background
Valdosta State University
pH Combination Electrode
combination refers to the ion sensing cell and the reference
cell.
Background
Valdosta State University
Consider the following graph:
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12
13
0 5 10 15 20 25 30 35
Volume NaOH (mL)
p
H
Background
Valdosta State University
Consider the following graph:
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4
5
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9
10
11
12
13
0 5 10 15 20 25 30 35
Volume NaOH(mL)
p
H
In this region H
+
dominates, the small change in pH is the result
of relatively small changes in H
+
concentration.
Background
Valdosta State University
Consider the following graph:
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4
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7
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9
10
11
12
13
0 5 10 15 20 25 30 35
Volume NaOH(mL)
p
H
In this region, relatively small changes in H
+
concentration cause
large changes in pH, The midpoint of the vertical region is the
equivalence point.
Background
Valdosta State University
Consider the following graph:
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11
12
13
0 5 10 15 20 25 30 35
Volume NaOH(mL)
p
H
In this region OH
-
dominates, the small change in pH is the result
of relatively small changes in OH
-
concentration.
Background
HA(aq) + NaOH(aq) NaA(aq) + H
2
O(l)

This experiment will use monoprotic acids.
Therefore, at the equivalence point,
moles HA = moles NaOH
Using the definition of moles, the molar mass can be
determined:
Valdosta State University
Background
HA(aq) + NaOH(aq) NaA(aq) + H
2
O(l)

This experiment will use monoprotic acids.
Therefore, at the equivalence point,
moles HA = moles NaOH
Using the definition of moles, the molar mass can be
determined:
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mass molar
weight sample
moles =
Background
HA(aq) + NaOH(aq) NaA(aq) + H
2
O(l)

pK
a
can be determined by using the Henderson-Hasselbach
equation.
Valdosta State University
Background
HA(aq) + NaOH(aq) NaA(aq) + H
2
O(l)

pK
a
can be determined by using the Henderson-Hasselbach
equation.
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+ =
acid weak
base conjugate
pK pH
a
log
Background
HA(aq) + NaOH(aq) NaA(aq) + H
2
O(l)

pK
a
can be determined by using the Henderson-Hasselbach equation.



If the pH is measured at the point where
[conjugate base] = [weak acid]
Valdosta State University
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+ =
acid weak
base conjugate
pK pH
a
log
Background
HA(aq) + NaOH(aq) NaA(aq) + H
2
O(l)

pK
a
can be determined by using the Henderson-Hasselbach
equation.



If the pH is measured at the point where
[conjugate base] = [weak acid]
Valdosta State University
| |
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\
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+ =
acid weak
base conjugate
pK pH
a
log
( )
a
a
pK pH
pK pH
=
+ = 1 log
Background
HA(aq) + NaOH(aq) NaA(aq) + H
2
O(l)

This assumption is valid at the half-titration point.
If the equivalence point is 20.00mL, the half-titration point is
at 10.00mL.
The pH is then obtained directly from the graph.
Valdosta State University
Background
Valdosta State University
3
4
5
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10
11
12
13
0 5 10 15 20 25 30 35
Volume NaOH (mL)
p
H
Background
Valdosta State University
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4
5
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9
10
11
12
13
0 5 10 15 20 25 30 35
Volume NaOH (mL)
p
H
Background
Valdosta State University
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4
5
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8
9
10
11
12
13
0 5 10 15 20 25 30 35
Volume NaOH (mL)
p
H
Procedure Experiment 7
- For this experiment, work in pairs.
Technique - Titration
Clean The Buret
1. Rinse a buret twice with distilled water.
2. Rinse the buret twice with 10-mL portions of your
standardized NaOH solution.
3. Run some of the NaOH solution through the tip of the
buret.
4. Drain the buret, then fill it with the standardized NaOH
solution.
5. Let some NaOH solution run through the tip of the buret so
that all air bubbles are removed.


Technique - Titration
Clean The Buret
Technique - Titration
Prepare the Unknown
1. Weigh 0.300 0.400g of solid unknown or 0.120 0.180g
of liquid unknown to the nearest 0.001 g into a 250mL
beaker.
2. Add approximately 50 mL of distilled water to the beaker
and stir until all the unknown is dissolved.
Technique - Titration
Set-up the pH electrode GLX Computer
Technique - Titration
Set-up the pH meter - Calibration
Get a 400 mL beaker of distilled water to rinse the electrode between
readings. Rinse the electrode with distilled water.
Technique - Titration
Performing The Experiment
1. Put the electrode tip in the unknown acid solution. Start button on
2. Fill the buret to 0.00mL and record this initial pH and buret reading.
3. Slowly add NaOH with stirring until either the pH increases by 0.20
units or 2.0 mL of NaOH have been added, whichever occurs first. Stop
and record both the pH and the buret reading.
4. Repeat step 3 until the pH reaches 12, or until the titration has gone 15
mL past the equivalence point.
Data
mL NaOH pH mL NaOH pH
0.00 4.02 18.80 10.08
2.30 4.36 19.00 10.60
3.00 4.47 19.40 10.98
4.80 4.67 19.92 11.24
6.10 4.81 21.25 11.46
8.48 5.03 23.95 11.69
10.61 5.21 25.10 11.84
12.80 5.42 27.28 11.94
15.08 5.72 28.12 11.94
16.90 6.09 29.80 12.00
17.82 6.47
Mass of unknown: 0.449g
Data
Experiment 7, trial 1
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
Volume NaOH (mL)
p
H
Data
Experiment 7, trial 1
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
Volume NaOH (mL)
p
H
Calculation Molar Mass
NaOH mol
NaOH L
NaOH mol
NaOH mL
NaOH L
NaOH mL 00215 . 0
1
116 . 0
1000
1
50 . 18 =
Calculation Molar Mass
NaOH mol
NaOH L
NaOH mol
NaOH mL
NaOH L
NaOH mL 00215 . 0
1
116 . 0
1000
1
50 . 18 =
unknown mol
NaOH mol
unknown mol
NaOH mol 00215 . 0
1
1
00215 . 0 =
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Calculation Molar Mass


NaOH mol
NaOH L
NaOH mol
NaOH mL
NaOH L
NaOH mL 00215 . 0
1
116 . 0
1000
1
50 . 18 =
unknown mol
NaOH mol
unknown mol
NaOH mol 00215 . 0
1
1
00215 . 0 =
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unknown mol g
unknown mol
unknown g
/ 209
00215 . 0
449 . 0
=
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Calculation - pK
a
Experiment 7, trial 1
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
Volume NaOH (mL)
p
H
Calculation - pK
a
Experiment 7, trial 1
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
Volume NaOH (mL)
p
H
IMPORTANT REMINDER
Save the unused solution in a location identified by your
laboratory instructor.
Valdosta State University
Safety
The NaOH solutions are corrosive. If you get some on your skin,
wash with water for at least five minutes. If any NaOH solution
gets in the eyes IMMEDIATELY wash with water for at least
fifteen minutes. Call for medical assistance!
Valdosta State University
Waste Disposal
All wastes from this experiment can be flushed down the drain
with plenty of running water.
Valdosta State University

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