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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
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
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:
ratio
V2
V2mid
ratio/V2
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
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
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
Volume vs. pH
15
10
pH
5
0
0
0.5
1.5
2.5
Volume
3.5
4.5
0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
-50
trial 1
-100
-150
V2mid
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
-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
5
0
0
0.5
1.5
2.5
3.5
4.5
Vmid
0
0.5
-50
1.5
2.5
-100
-150
V2mid
3.5
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
Volume vs. pH
15
10
pH
5
0
0
0.5
1.5
2.5
3.5
4.5
Volume
0.5
1.5
2.5
Vmid
3.5
4.5
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