Results and Discussion

Many titrations are now done automatically by instruments which are

calibrated to deliver small increments of titrant between pH measurements.
Titration is one of the techniques by which the characteristics of any substance can
be analyzed. Potentiometric titration is one of them. During titration, pH were
determined and plotted against the buret readings to obtain characteristic curves
that were used to determine the equivalence point/s of the solution [3].
In this experiment a weak acid as sample (coke) and a strong base (NaOH),
sodium hydroxide is commonly known as lye or caustic soda and dissolving NaOH in
water generates considerable heat, was used where three trials made. See
tratment of data (tables) in Appendix A. Data from trial 3 were used thoughout the
discussion. The amount of NaOH used to prepare 1M NaOH was 0.4121 grams (see
calculation in Appendix B). By reading the pH meter, the pH acquired by the sample
is 4.01.
In second year college, students were familiarized with the appearance of a
plot of pH vs. mL of base added in typical titraion. Using these knowledge, the
behavior of the pH at the beginning, at the neuralization and towards the end of
titration were compared with the titration graphs attained from the experiment
using potentiometric titration. Figure 1a and 1b (see reference 4) were used to
compare the graph obtained from the experiment.

Figure 1a. Titration curve for weak acid (ethanoic acid) vs. strong base
(sodium hydroxide). Running acid into alkali.
For the first part of the graph (Figure 1a), there is an excess of sodium
hydroxide. The curve will be exactly the same when an addition of hydrochloric acid

to sodium hydroxide was made. Once the acid is in excess, there will be a
difference. Past the equivalence point, a buffer solution containing sodium
ethanoate and ethanoic acid was gotten. This resists any large fall in pH.

Figure 1b. Titration curve for weak acid (ethanoic acid) vs. strong base
(sodium hydroxide). Running alkali into acid

The start of the graph shows a relatively rapid rise in pH but this slows down
as a buffer solution containing ethanoic acid and sodium ethanoate is produced.
Beyond the equivalence point (when the sodium hydroxide is in excess) the curve is
just the same as that end of the titration graph of strong acid vs. strong base.

Volume vs. pH
14
12
10
8
pH

6
4
2
0
0

0.5

Equi pt
1 1.5 2

2.5

Volume

3.5

4.5

Figure 2. Titration curve from experimental potentiometric titration. (pH

data versus the volume readings of the base.
On the graph shown above the weak acid only partially dissociates from its
salt. The pH raised normally at first, but as it reaches a zone where the solution
seems to be buffered, the slope levels out. After this zone, the pH rises sharply
through its equivalence point and levels out again like the strong acid/strong base
reaction.
There are two main points to notice about this curve. The first is the halfequivalence point. This point occurs halfway through a buffered region where the pH
barely changes for a lot of base added. The half-equivalence point is w hen just
enough base is added for half of the acid to be converted to the conjugate base.
When this happens, the concentration of H+ ions equals the Ka value of the acid.
Take this one step further, pH = pKa. The second point is the higher equivalence
point. Once the acid has been neutralized, notice the point is above pH=7. When a
weak acid is neutralized, the solution that remains is basic because of the acid's
conjugate base remains in solution.

V/m
L
0
1
1.
2
1.3
1.4
5
1.6
1.7
1.8
2.2
2.6
3
3.2
3.5
3.6
4.1
4.3

pH
4.0
1
4.4
6
4.9
5.4
6.1
6.7
7
7.3
5
7.8
3
8.3
3
8.8
4
9.3
8
9.9
2
10.
45
10.
96
11.
46
11.
74

Vmi
d

ph/vol

0.5

0.45

1.1
1.2
5
1.3
75
1.5
25
1.6
5
1.7
5

2.2
5
4.666666
667
4.466666
667
5.8
4.8

1.25

2.4

1.275

2.8

1.35

3.1
3.3
5
3.5
5
3.8
5

2.7
1.766666
667

4.2

1.4

5.1
1

Vmid vs. pH/Vol

7
6
5
4
pH/Vol 3
2
1
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Vmid

This
is
perhaps
the
simplest method for interpreting pH titration data. Because experiments do not
always proceed so neatly, various other methods are often used to determine
equivalence points. For example, since the region of maximum slope contains this
point, a graph of the slope (known as a "derivative" in calculus terminology) versus
the average volume for the slope interval provides a way to zero in on the desired
volume. The slope could be represented as pH/V (i.e., y/x) and Vmid. A plot of
the same data as shown earlier was treated in this way is shown below:

Figure 3. First derivative. The equivalence point corresponds to the

volume at the peak of the curve

Occasionally it is still difficult to judge the equivalence point even by this

method. Sometimes the "peak" is rounded or has a plateau. A second derivative
plot (the change in the slope) may be used in such cases. The values for the plot
are obtained by operating on the first derivative data in the same way as the orig
ginal data was processed. A plot of ratio/V2 vs. V2mid for the same titration data
is shown below:

ratio

V2

V2mid

ratio/V2

V2mid vs. ratio/V2

100
50

ratio/V2

0
0.5 1 1.5 2 2.5 3 3.5 4
-50
-100
-150
V2mid

3.46
0.2
-1.8

0.55
0.1
0.15

0.775
1.1
1.225

0.15

4.6

0.075

-7.5
2.5666
7
-1.1

0.075

1.375
1.487
5
1.562
5

0.125
0.375

1.662
5
1.912
5

6.29090909
1
2
-12
33.3333333
3
61.3333333
3
-100
20.5333333
3
2.93333333

3.8666
67

0.35

2.275

-2.2
-1
2.8

0.15
0.25
0.2

2.525
2.725
2.95

-1.85
0.9166
7
0.9333
3

0.15

3.125

0.25

3.325

0.55

3.725

3
11.0476190
5
14.6666666
7
-4
14
12.3333333
3
3.66666666
7
1.69696969
7

Figure 4. Second Derivative, The euivalence point corresponds to the

volume where the curve crosses the X-axis.

The equivalence point is found at the average volume where the function
crosses y = 0. The downside to the derivative methods is that each involves a
compromise in the accuracy of the volume since the interval chosen for the
derivative requires an average volume. Making the intervals small improves the
accuracy and is a good reason for adding titrant in very small increments in the
vicinity of the equivalence point.
For the reaction of a weak acid, such as the acid used in this experiment, with
a strong base (NaOH), the equivalence point pH is no longer 7 unlike with the
reaction between strong acid and strong base. The equivalence point region on the
titration curve is not centered at pH 7. There is also a more pronounced "level"
region at the beginning of the titration and approaching the equivalence point as
buffering occurs due to the partial neutralization of the acid as base is added, and
the simultaneous formation of substantial amounts of conjugate base.

Conclusion
Potentiometric titration involves the measurement of the potential of a
suitable indicator electrode with respect to a reference electrode as a function of
titrant volume. [5]Potentiometric titrations provide more reliable data than data

from titrations that use chemical indicators and are particularly useful with colored
or turbid solutions and for detecting the presence of unsuspected species.
Weak
acid strong base curve starts at a pH higher than 1 which is generally the case with
strong acids. This is because of the incomplete dissociation of the acid. There is a
partial dissociation of the acid in to H+ and A- ions. A- combines with the B+ of the
base while H+ and OH- get neutralized. The AB salt formed acts as a conjugate acid
and base which will assist further dissociation of weak acid. Once the equivalence
point is reached the strong base affects the increase of pH rapidly.

Recommendation
In this experiment our group recommend that students must have a welltrained hand because it is an important tool. Students should strive to develop good
control of the buret stopcock, delivering single drops with 100% reliability and no
false squirts. Accurately reading the volume on the buret is another important skill.
Be sure the meniscus is at eye-level when recording a volume. Many people find it
helpful to place a card behind the buret with a white/black boundary to help
determine the exact position of the meniscus.

References

[1]
Neumann, Erzsbet. (2010). Advanced Potentiometry: Potentiometric
Titrations and Their
Systematic Errors.
[2]
Skoog, D. ,West D. ,Holler, J. ,Crouch, S. (2004). Fundamentals of Analytic
Chemistry (Philippine
Edition).
[3]
Agbayani, Virgilio. (2014). Laboratory Manual in Physical Chemistry for
Rngineers 1
[4]

http://chemistry.about.com/od/acidsbase1/ss/titrationcurves_2.htm

[5]

http://memo.cgu.edu.tw/hsiu-po/Analytical%20Chem/Lecture%207.pdf

Appendix A

Table 1. Treatment of data for first trial in potentiometric titration

V/m
L
0

pH
4.01

4.57

1.1

4.98

1.35

5.75

1.4

6.48

p
H

0.2
5
0.0
5

0.7
7
0.7
3

1.22
5
1.37
5

0.5
4
0.4
8

1.6

7.5

0.1

2.2

7.97

0.6

2.4

8.44

0.2

0.4
7
0.4
7

2.7

8.97

0.3

0.5
3

0.3

3.7

9.46
10.0
2
10.5
4
11.0
1

4.3

4.65

0.56

1.05

0.1

4.6

0.5

0.1

7.02

3.5

ph/vol

0.5
6
0.4
1

1.5

3.3

Vmid

V2mid

4.1

3.54

0.55

0.775

3.08

-1.02

0.175

1.137
5

14.6

11.52

0.15

1.3

1.45

5.4

-9.2

0.075

1.55

4.8

0.1

1.5

1.9

0.7833333
33

0.35

1.725

2.3

2.35

0.4

2.1

2.55

1.7666666
67

-0.6
4.0166
7
1.5666
67
0.5833
3
0.1333
3
0.2333
33
0.7333
33

0.25

2.425

0.3

2.7

0.3

0.25

3.275

0.2

3.5

0.2

11.5
1

0.6

0.5

11.6
9
11.7
5

0.3
0.0
5

0.1
8
0.0
6

4.45
4.62
5

0.2

V2

1.412
5

0.4
9
0.5
6
0.5
2
0.4
7

0.3

ratio

3.15

1.6333333
33
1.8666666
67

3.4

2.6

3.6

2.35
0.8333333
33

2.85

0.4

3.8

0.6

-0.25
1.5166
7
0.2333
3

0.45

1.2

0.6

0.175

4.225
4.537
5

ratio/V2

6.43636363
6
5.82857142
9
76.8
122.666666
7
-6
11.4761904
8
3.91666666
7
2.33333333
3
0.44444444
4
0.77777777
8
2.93333333
3
-1.25
3.79166666
7
0.51851851
9
3.42857142
9

Graphs Obtained From Table 1

Volume vs. pH
15
10
pH

5
0
0

0.5

1.5

2.5

Volume

3.5

4.5

Vmid vs. pH/vol

20
15
pH/vol 10
5
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Vmid

V2mid vs. ratio/V2

100
50
ratio/V2

0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
-50

trial 1

-100
-150
V2mid

Table 2. Treatment of data for second trial in potentiometric titration

V/mL
0
1

pH
4.01
4.55

pH

Vmid

ph/v
ol

0.54

0.5

0.54

1.1
1.2
1.4

4.95
5.37
5.85

0.1
0.1
0.2

0.4
0.42
0.48

1.05
1.15
1.3

1.5

6.59

0.1

0.74

1.55

7.19

0.05

0.6

ratio

V2

V2mid

4
4.2
2.4

3.46
0.2
-1.8

0.55
0.1
0.15

0.775
1.1
1.225

1.45

7.4

0.15

1.525

12

4.6

0.075

1.375
1.487
5

ratio/V
2

6.290909
091
2
-12
33.33333
333
61.33333
333

-7.5
2.5666
7

0.075

1.562
5

0.125

1.662
5

0.375

1.912
5

4.7

-1.1
3.8666
67

0.35

2.275

2.6
2.85
3.05

2.5
1.5
4.3

-2.2
-1
2.8

0.15
0.25
0.2

2.525
2.725
2.95

0.49

3.2

2.45

0.15

3.125

0.3

0.46

3.45

1.5333
33

0.25

3.325

0.8

0.48

0.6

-1.85
0.9166
7
0.9333
3

0.55

3.725

1.65

7.64

0.1

0.45

1.6

4.5

1.8

7.93

0.15

0.29

1.725

1.9333
33

2.4

8.43

0.6

0.5

2.1

0.8333
33

2.5

8.9

0.1

0.47

2.45

2.7
3
3.1

9.4
9.85
10.28

0.2
0.3
0.1

0.5
0.45
0.43

3.3

10.77

0.2

3.6

11.23

4.4

11.71

Graphs Obtained From Table 2

-100
20.53333
33
2.933333
33
11.04761
905
14.66666
66
-4
14
12.33333
33
3.666666
66
1.696969
69

volume vs. pH
15
10
pH

5
0
0

0.5

1.5

2.5

3.5

4.5

volume

Vmid vs. pH/vol

15
10
pH/vol

5
0
0

0.5

1.5

2.5

3.5

4.5

Vmid

V2mid vs. ratio/V2

100
50
ratio/V2

0
0.5
-50

1.5

2.5

-100
-150
V2mid

3.5

Table 3. Treatment of data for third trial in potentiometric titration

V/mL
0
1
1.2

pH
4.01
4.46
4.9

pH

Vmid

ph/vol

ratio

V2

V2mid

ratio/V2

1
0.2

0.45
0.44

0.5
1.1

0.45
2.2

1.75

0.6

0.8

1.3

5.4

0.1

0.5

1.25

2.8

0.15

1.175

1.45

6.1

0.15

0.7

1.375

6.77

0.15

0.67

1.525

0.3333
-0.2

0.125

1.6

1.312
5
1.45

1.7

7.35

0.1

0.58

1.65

4.6666666
67
4.4666666
6
5.8

0.125

1.8
2.2
2.6
3
3.2
3.5

7.83
8.33
8.84
9.38
9.92
10.45

0.1
0.4
0.4
0.4
0.2
0.3

0.48
0.5
0.51
0.54
0.54
0.53

1.75
2
2.4
2.8
3.1
3.35

3.6

10.96

0.1

0.51

3.55

4.8
1.25
1.275
1.35
2.7
1.7666666
6
5.1

1.3333
33
-1
-3.55
0.025
0.075
1.35
0.9333
3.3333

4.1

11.46

0.5

0.5

3.85

4.3

11.74

0.2

0.28

4.2

1.4

2.91666666
7
18.6666666
7
2.66666666
1.33333333
10.6666666
7
-10
-14.2
0.0625
0.1875
4.5
3.73333333
3
16.6666666
7
13.6666666
1.14285714
3

0.15

0.1
0.25
0.4
0.4
0.3
0.25

1.587
5
1.7
1.875
2.2
2.6
2.95
3.225

0.2

3.45

-4.1

0.3

3.7

0.4

0.35

4.025

Graphs Obtained From Table 3

Volume vs. pH
15
10
pH
5
0
0

0.5

1.5

2.5

3.5

4.5

Volume

Vmid vs. pH/Vol

8
6
pH/Vol 4
2
0
0

0.5

1.5

2.5

Vmid

3.5

4.5

V2mid vs. ratio/V2

30
20
ratio/V2

10
0
0.5
-10

1.5

2.5

3.5

4.5

-20
V2mid

Appendix B
Calculation for the preparation of 0.1M NaOH

g NaOH =( 100mL H 2 O)( 0.1mol / L NaOH )(1 L/(1000 mL))(2539.9969 g/(1mol )NaOH )
g NaOH = 0.399969 grams