Potentiometric Applications

Author: Mark Eugene A Combalicer

Lab partner: Louise Grace Avena
E-mail: krameugenecombalicer@yahoo.com
The goal of this experiment is to determine the ionization constant of unknown acid,
equivalence point using various graphical methods, and fluoride content of
commercially available products using potentiometry. It also includes how to use
and compare external calibration plot and standard addition plot in determining the
concentration of a sample.

Introduction:
Potentiometric analysis is based on
measuring the potential of
electrochemical cells in which the
current does not flow. Industries
nowadays use potentiometric
methods for different analysis. A
potentiometric titration for example,
includes measurement
of suitable
indicator electrode as a function of the
titrants volume .
Compared to the classical titration
analysis, potentiometric analysis
provides more reliable data especially
in turbid solution wherein endpoints
are hard to determine using chemical
indicators. It is also convenient for
industrial use since it is less time
consuming when compared to that of
the classical method. Potentiometric
measurements are used in the
determination of thermodynamic
equilibrium constants such as Ka, kb,
ksp.
Potentiometric titration uses pH meter
as an electrode which monitors
pH/potential change. It does not need
a chemical indicator to observe

endpoint. Since the hydrogen ion

inside the electrode responds to the
activity of hydrogenion in the analyte
solution, after sometime, sudden
change of pH/potential will signal the
endpoint of the titration.

The direct method to determine the

end point of a potentiometric titration
is to plot potential as a function of
reagent volume wherein the midpoint
in the steeply rising portion of the
curve is estimated visually and taken
as the end point. Another approach to
determine the end point is to calculate
the change in potential per unit
volume of titrant ( E/ V). A plot of
these data as a function of the
average volume V produces a curve
with a maximum that corresponds to
the point of inflection. Alternatively,
this ratio can be evaluated during the
titration and recorded in lieu of the
potential.
The sample is an acid whose ionization
constant is to be determined. This
analysis is performed with the use of

digital pH meter for easy pH

measurement as the base titrant is
added at different volume intervals.
Data gathered will be plotted and the
graph is used for the determination of
the ionization constant.

Materials:
volumetric pipette, Analytical balance,
Hotplate with magnetic stirrer, pH
meter, Fluoride-ion selective
electrode, Burette, Burette clamp
Methods:
I. Determination of Ionization Constant
by Potentiometric titration
-Calibrate the pH meter obtained from
the assistant using buffer solutions
(pH 4, 7 and 9)
Approximation of the equivalence
point
-Pipette a 100 ml aliquot portion of
unknown acid obtained from the
assistant into a 400 ml beaker then
place on top of magnetic stirrer with a
magnetic bar, switch on the stirrer
when titration starts. Set up a burette
above the beaker with standardized
NaOH solution. Titrate the unknown by
adding 5 ml of NaOH at a time and
measure and record the pH of solution
after each addition. Turn off the stirrer
when measuring and wash the
electrode after each measurement.
Repeat the 5 ml addition until total of
30 ml volume was added. Note volume
range in sudden change of pH occurs.

The equivalence point is within that

range.
Differential method Determination of
Equivalence
- Pipette another 100 ml aliquot
portion of the unknown into a 400 ml
beaker and place a magnetic bar.
Place it in top of magnetic stirrer and
below a burette filled with
standardized NaOH solution . Titrate
the unknown by drawing off 1 ml of
NaOH at a time until the volume
before sudden change of pH is
reached. Measure and record the pH
after each addition. During the sudden
change of pH range, change the
volume interval to 0.50 ml of NaOH.
Measure and record its pH after each
addition. If total 30 ml total volume
was added, change the volume
interval to 1 ml of titrant after sudden
change of pH. Prepare two graphical

representation of it is the Normal

titration curve (pH vs. volume of NaOH
added) and the other one the First
Derivative plot (pH/volume NaOH vs
volume titrant which is the average
volume of two successive volumes).
After that, determine the volume at
50% neutralization and the pKa of the
unknown monoprotic acid.
II. Potentiometric determination of
fluoride
Sample Preparation
a. Fluoride
-boil for 2 min a 0.20 g of
sample toothpaste with 50
ml TISAB solution in a 300
ml beaker. Stir it to dissolve
well. Transfer to 100 ml vol
flask, dilute to mark and mix
well after cooling the

suspension. Set aside for

potential measurement
I: APPROXIMATION OF EQUIVALENCE POINT
(GROUP ANALYSIS)
trial 1
trial 2
trial 3
Volum
e of
NaOH
added
, mL
0
5
10
15
20
25
30

pH

3.4
6
3.9
1
4.1
5
4.8
5
7.7
8
8.4
3
9.3
9

p
H

pH

p
H

3.18
0.4
5
0.2
4
0.7

3.9

2.9
3
0.6
5
0.9
6

5.67

4.38
4.67

10.3
6
11.0
6

pH

p
H

2.65
0.7
2
0.4
8
0.2
9
1

3.44

4.6
9
0.7

8.5

3.91
4.26
4.74

10.6
2

0.7
9
0.4
7
0.3
5
0.4
8
3.7
6
2.1
2

b. Tap water
Determination of fluoride from the
sample using external standard
method
-dilute 25 ml of the 100 ppm
standard to 500 ml in vol flask to
prepare a 5 ppm fluoride. Transfer
5,10,15,25 and 50 ml aliquot of it
to 100 ml vol flask, add 50 ml of
TISAB solution then dilute to mark.
Determine the potential of each
solution and prepare the calibration
curve and also the potential of the
samples. From the graph,
determine the concentration of
fluoride in the sample.
Determination of Fluoride from tap
water sample using standard addition
method
-Prepare the following solutions in a
100 mL volumetric flask by pipetting
known volume of previously prepared

standard solution (5 ppm): Soln 1: 50

mL TISAB + 5 mL tap water + 0 mL
standard. Soln 2: 50 mL TISAB + 5 mL
tap water + 10 mL standard. Soln 3:
50 mL TISAB + 5 mL tap water + 15
mL standard. Soln 4: 50 mL TISAB + 5
mL tap water + 20 mL standard. Soln
5: 50 mL TISAB + 5 mL tap water + 25
mL standard. Soln 6: 50 mL TISAB + 5
mL tap water + 30 mL standard. Then
measure the potential of each
solution, plot the E vs (CV)std and
determine
the
concentration
of
fluoride in the sample.

Result and discussion:

Table 1: Approximation of equivalence
point (Group Analysis)

Trial
no
1
2
3
Ave

Equi
v pt
(pH)
6.32
8.02
6.62
6.99

Vol
range(
ml)
15-20
20-25
20-25
20

pKa

4.03
4.53
4.09
4.22

Vol
range(
ml)
5-10
10-15
10-15
10

Graph A: Determination if Equivalence

point

"Volu
me of
NaOH
adde
d
mL"

Table 2: Differential method of

determina tion of equivalence
point

volu
me

V(aver
age)
1.5

2.5

3.5

4.5

5.5

6.5

7.5

8.5

9.5

10

10.5

11

11.5

12

12.5

13

13.5

14

14.5

15

15.5

16

16.5

17

17.5

18

18.5

19

19.5

20

20.25

20.5

0.5

20.75

21

0.5

21.25

21.5

0.5

21.75

22

0.5

22.25

22.5

0.5

22.75

23

0.5

23.25

TRIAL 1
pH
p
H
2.8
2
3.0
0.
3
21
3.2
0.
3
2
3.3
0.
5
12
3.4
0.
9
14
3.6
0.
11
3.7
0.
3
13
3.8
0.
8
15
4
0.
12
4.1
0.
1
11
4.2
0.
3
12
4.3
0.
5
12
4.4
0.
4
09
4.5
0.
5
11
4.6
0.
6
11
4.7
0.
8
12
4.9
0.
1
13
5.0
0.
8
17
5.3
0.
3
25
5.6
0.
8
35
5.9
0.
2
24
5.9
0.
7
05
6.6
0.
4
67
9.6
3
4
10.
0.
2
56
10.
0.
44
24

pH/vol
ume

0.21
0.2
0.12
0.14
0.11
0.13
0.15
0.12
0.11
0.12
0.12
0.09
0.11
0.11
0.12
0.13
0.17
0.25
0.35
0.48
0.1
1.34
6
1.12
0.48

"Volu
me of
NaOH
Adde
d ml

Table3: Differential method of

determination of equivalence
point
Trial 2
volu
me

V(aver
age
1.5

pH

p
H

pH/vol
ume

2.
68
2
1
2.5
2.
0.
0.21
89 21
Table
4:1 Differential
method
3
3.5
3.
0.
0.16 of
05
16
determination of equivalence point
4
1
4.5
3.
0.
0.14
193 14
"Volu
Trial
me5of
1
5.5
3.
0.
0.15
volu
V(avera
pH
p
pH/volu
NaOH
34 15
me
ge
H
me
added
6
1
6.5
3.
0.
0.14
mL"
48 14
1
1.5
2.7
7
1
7.5
3.
0.
0.13
5
61
13
2
1
2.5
3.0
0.3
0.3
8
1
8.5
3.
0.
0.17
5
78 0.1
17
3
1
3.5
3.2
0.19
9
1
9.5
3.
0.
0.06
4
9
4
1
4.5
3.4
0.18
84 0.1
06
2
8
10
1
10.5
3.
0.
0.13
5
1
5.5
3.5
0.09
97 0.0
13
1
9
11
1
11.5
4.
0.
0.16
6
1
6.5
3.6
0.1
0.14
13
16
5
4
12
1
12.5
4. 0.1
0.
0.05
7
1
7.5
3.7
0.1
18
05
5
13
1
13.5
4. 0.1
0.
0.13
8
1
8.5
3.9
0.17
2
7
31
13
9
1
9.5
4.0
0.13
14
1
14.5
4. 0.1
0.
0.06
5
3
37 06
10
1
10.5
4.1
0.1
15
1
15.5
4. 0.1
0.
0.1
5
47
1
11
1
11.5
4.2
0.0
0.08
16
1
16.5
4.
0.
0.16
3
8
63 0.1
16
12
1
12.5
4.3
0.11
17
1
17.5
4.
0.
0.13
4
1
13
1
13.5
4.4
0.09
76 0.0
13
3
9
18
1
18.5
4.
0.
0.13
14
1
14.5
4.5
0.1
89 0.1
13
3
19
1
19.5
5.
0.
0.17
15
1
15.5
4.6
0.1
0.14
06 17
7
4
20
1
20.25
5. 0.1
0.
0.06
16
1
16.5
4.8
0.13
12 06
3
20.5
0.5
20.75
5. 0.1
0.
0.48
17
1
17.5
4.9
0.15
36
24
5
5
18
1
18.5
5.0
0.14
21
0.5
21.25
5. 0.1
0.
0.14
9
4
43
07
19
1
19.5
5.4
0.31
21.5
0.5
21.75
5. 0.3
0.
0.4
1
63
2
20
1
20.25
5.7
0.3
0.32
22
0.5
22.25
7.
1.
3.08
2
2
17 54
20.5
0.5
20.75
5.4
-0.6
22.5
0.5
22.75
8.
1.
2.66
2
0.3
5
33
21
0.5
21.25
5.5
0.1
0.22
21.5

0.5

21.75

22

0.5

22.25

22.5

0.5

22.75

3
5.9
7
6.4
4
7.5

23

0.5

11.5

1
0.4
4
0.4
7
1.0
6
0.5

0.88
0.94
2.12
1

Graph of Differential method of

determination of equivalence point

Differential Method Determination of Equivalence Point

Trial 1
Trial 2
Change in pH over change in volume
Trial 3

Volume of NaOH added, mL

Differential Method Determination of Equivalence Point

12
10
8
pH

6
4
2

Trial 1
Trial 2
Trial 3

Volume of NaOH added, mL

Table 5: External method

Concentrati

Potential(p

Log C

on
0.5
1
1.5
2.5
5

er sample)
168.7
155.2
147.6
136.2
118.6

Conclusion:
-0.301
0
0.1761
0.3979
0.699

Reference:

Potential

Christian, G.D., Analytical

Chemistry, 6th edition, New Jersey,
John Wiley, 2004.

Table 6: Standard addition

solution
1
2
3
4
5
6

CVstd(ppm
)
0
0.5
0.75
1
1.25
1.5

216.8
155.1
142.9
134.4
130.2
128.8

Harris, D.C.,Quantitative Chemical

Analysis, 3rd edition, Freeman,
New York,1991

Acknowledgement:
I would like to acknowledge and
extend my heartfelt gratitude to the
following persons who have made the
completion of this final report
possible: Prof. UREAH THEA A. SEVILLA
(lab instructor), Ms. Tet (lab assistant), Lousie
Grace Avena(Lab partner) and Mapua Institute
of Technology (school).
http://www.slideshare.net/jaNinEbOnjA
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