Chemistry Laboratory Report

Titration of Monoprotic Acid

11 June 2014


Letitia Sarah
061302856
Team member: Masami Hazu



Laboratory in Chemistry
Nagoya University

Preparation prior to the experiment

1. Consult reference books to check the value of the dissociation constant pKa of the weak acid that you will use in
your experiment.
According to Quantitative Chemical Analysis, pKa of acetic acid (CH
3
COOH) at standard condition is 4.756
2. Confirm the exact concentration of the KOH standard solution to be used for the titration (it is labeled on the bottle
and it is specific to each bench) and write it down in your notebook.
The exact concentration of the KOH standard solution is 0.0995 M.
3. Calibrate pH meter by measuring the pH values of the buffer solutions with known pH of 4, 7, 9, respectively and
correct for the deviations in the nominal values as measured by your pH meter.
4. Set up burette to perpendicular to the bench and remove the air bubbles trapped in the tip. Dispense the KOH
standard solution from the reservoir into the burette until the meniscus reaches near zero on the burette. Read the
position of the meniscus up to one tenth of the minimum scale division on the burette

4.1.1 Titration of the monoprotic acids
Experiment 1.1.a Titration of hydrochloric acid
Objective: to determine the precise concentration of the HCl acidic solution by titrating it with a basic solution, KOH
of known concentration
Methods
1. Dispense 10 mL of 0.1 M HCl into 200 mL beaker using volumetric pipette
2. Add 90 mL of water and 2/3 drops of bromothymol blue
3. Put a magnetic stir bar into the beaker. Stir the solution slowly
4. Dip the glass of electrode of the pH meter into the solution. Make sure the electrode does not touch both the beaker
and the stir bar.
5. Add 0.5-1.5 mL of 0.1 M KOH while keeping the pH meter on
6. Read the dispensed volume at the meniscus. Record the amount of KOH solution added and the pH of the solution
10 s after the KOH was added
7. Repeat the 2 previous steps until total KOH added reaches 9 mL
8. Add 0.05-0.1 mL of KOH at a time while watching the color of the solution
9. Repeat the addition of small amount of KOH until the color of indicator does not change
10. When pH starts to stabilize, increase the volume of KOH added to 1 mL
11. Repeat the previous step until the pH is greater than 11.
12. After experiment is finished, wash beaker, stir bar, and glass electrode with deionized water.

Observation
Quantity of KOH (mL) 0 0.70 1.50 2.10 2.80 3.60 4.40 5.20 5.80
pH 1.77 1.78 1.81 1.84 1.88 1.92 1.99 2.06 2.11
Quantity of KOH (mL) 6.80 7.90 8.20 8.50 8.60 8.70 8.80 9.00 9.10
pH 2.22 2.42 2.51 2.58 2.63 2.68 2.73 2.8 2.87
Quantity of KOH (mL) 9.15 9.20 9.30 9.40 9.50 9.60 9.70 9.80 9.85
pH 2.92 2.99 3.06 3.14 3.29 3.43 3.71 4.16 4.71
Quantity of KOH (mL) 9.95 10.00 10.10 11.20
pH 5.3 6.16 6.96 11.1
Table 1 Experiment 1: Sample results for pH at various points in the titration of 10.0 mL HCl with 0.0995 M KOH

Quantity of KOH (mL) 0 0.8 1.8 2.65 3.3 4 4.8 5.7 6.5
pH 1.77 1.78 1.83 1.87 1.91 1.96 2.02 2.1 2.2
Quantity of KOH (mL) 7.2 8.1 8.8 9 9.1 9.15 9.35 9.4 9.5
pH 2.3 2.47 2.71 2.81 2.87 2.93 3.07 3.14 3.26
Quantity of KOH (mL) 9.6 9.8 9.85 9.9 9.95 10 10.15 10.2 10.22
pH 3.47 4.53 4.87 5.13 5.49 5.85 7.64 8.48 9.13
Quantity of KOH (mL) 10.3 10.9 11.1
pH 9.83 10.82 11.06
Table 2 Experiment 2: Sample results for pH at various points in the titration of 10.0 mL HCl with 0.0995 M KOH

Figure 1 Titration Curve of HCl by KOH
Note:
Blue rectangle : pH range of bromothymol blue (6.0-7.6)
Sun : equivalence point
Discussion
In this experiment, 0.0995 M KOH was added to analyte, approximately 0.1 M HCl. The experiment was done two
times and the result was presented in table 1 and 2. During the experiment, indicator bromothymol blue was used.
Bromothymol blue, which is a pair of weak acid and its conjugate base , has pH range from 6.0-7.6. For pH which is
less than 6.0, the indicator will turn the solution yellow. While for pH which is greater than 7.6, the indicator will turn
the solution blue. From both experiments, the solution turned completely blue when KOH added was 10 mL. However,
the pH of the sample at this point for the first experiment was 6.16, while in the second experiment was 5.85. This
change in color indicates the end point of titration. End point is the point at which the indicator changes color of the
solution. In this experiment, the indicator turned the solution into blue even though the pH meter showed pH at that
point was less than 7.6. This might be because the range of indicator slightly is affected by temperature. Pk
ind
is
influenced by change in temperature.
Nevertheless, end point which could be observed does not indicate the exact volume needed to neutralize the reaction.
The exact amount necessary for stoichiometric reaction with the analyte can be only determined from the equivalence
point from the graph. By using graphical method, the equivalence point occurs when 10.1 mL of 0.0995 KOH is added
and the pH is 7.
Questions
1. Determine the accurate concentration of hydrochloric acid and its dissociation constant pKa based on the
results of your experiment
By using the equivalent point from graphical approach which was at the volume of 10.1 mL,
[]
[]

[]
[]

From the calculation, the concentration of HCl is approximately close to the concentration data of the solution,
which was 0.1 M. By using the same geometric method, the mid point of the curve was approximately when
the volume of KOH was 5 mL (pH = 2.0). Assuming that at the mid point pH = pK
a
, pK
a
of HCl will be 2.
However this value is not possible because pK
a
of HCl theoretically less than 1 and the value is very small.
Therefore, we can not determine pK
a
of HCl with this method.
2. Based on the concentration of hydrochloric acid determined in 1, determine the pH at each of the following
stages: I before the addition of the KOH standard solution, ii at the half-neutralization point, iii just before the
neutralization point, iv at the neutralization point, v just after the neutralization point, and vi at the completion
of the titration. Mark these pH values on your titration curve and compare these estimated data with your
experimental results.
(i) Because the solution was diluted with water, the concentration of the diluted HCl before the addition of
KOH was:
[] [

pH of Experimental result: 1.77
(ii) At the half neutralization point, 50% of HCl had been neutralized and []

[].
[

] , [

[]
[]

[]

]
pH of experimental result : 2.06
(iii) Assume that just before the neutralization point, about 10 mL of KOH is added. Therefore,
HCl + KOH KCl + H
2
O
1.00 0.995
-0.995 -0.995 0.9950 0.995
0.005 0.995 0.995
Initial mole of HCl = 0.100 x 10.0 = 1.00 mmol
Initial mole of KOH = 0.0995 x 10.0 = 0.995 mmol
pH= -log [H
+
]= -log [

] = 4.30
pH of experimental result : 6.005 (mean value of 5.85 and 6.16)
(iv) The equation to determine concentration of proton at the neutralization point can be obtained from
[

.
[

pH of experimental result : 6.96
(v) Assume that just after the neutralization point, about 10.15 mL KOH was added
HCl + KOH KCl + H
2
O
1.00 1.01
-1.00 -1.00 1.00 1.00
0 0.01 1.00 1.00
Initial mole of HCl = 0.100 x 10.0 = 1.00 mmol
Initial mole of KOH = 0.0995 x 10.15 = 1.01 mmol
pOH= -log [OH
-
]= -log [

] = 4.00
pH = 14-4 = 10.00
pH of experimental result: 7.64
(vi) Assume at the end of titration, volume of KOH added was 11.15 mL (mean value of 11.10 mL and 11.20
mL)
HCl + KOH KCl + H
2
O
1.00 1.11
-1.00 -1.00 1.00 1.00
0 0.11 1.00 1.00
Initial mole of HCl = 0.100 x 10 = 1.00 mmol
Initial mole of KOH = 0.0995 x 11.15 = 1.11 mmol
pOH= -log [OH
-
]= -log [

] = 2.96
pH = 11.04
pH of experimental result: 11.08 (mean value of 11.1 and 11.06)

3. List other indicators used in titration of acids and bases with their chemical structures and the pH ranges when
the indicators change color.
Indicators pH range Color range Structures
Thymol blue 1.2 - 2.8 Red-yellow

Methyl orange 3.2-4.4 Red-yellow

Bromocresol green 3.8-5.4 Yellow-blue

Methyl red 4.8-6.0 Yellow-red


Experiment 1.1 b Titration of acetic acid
Objective: to determine the precise concentration of the acetic acid solution by titrating it with a basic solution,
KOH of known concentration
Method
1. Dispense 10.0 mL of 0.1 M acetic acid solution into a 200 mL beaker
2. Add 90.0 mL of water and 2 drops of phenolphthalein
3. Repeat step 3-12 in the experiment 1.1 a for this titration
Observation
Quantity of KOH (mL) 0 0.5 1 1.4 1.7 2.1 2.7 2.9 3.3
pH 3.07 3.27 3.49 3.63 3.74 3.86 3.95 4.04 4.11
Quantity of KOH (mL) 3.7 4 4.3 4.9 5.6 5.9 6.5 7 7.4
pH 4.18 4.25 4.3 4.4 4.53 4.58 4.71 4.81 4.9
Quantity of KOH (mL) 8 8.5 8.6 8.8 9 9.2 9.25 9.35 9.4
pH 5.05 5.21 5.26 5.35 5.46 5.56 5.62 5.68 5.76
Quantity of KOH (mL) 9.5 9.55 9.6 9.65 9.7 9.8 9.85 9.9 10
pH 5.83 5.94 6.01 6.08 6.15 6.25 6.53 7.09 7.56
Quantity of KOH (mL) 10.05 10.15 10.2 10.5 10.8 11
pH 8.46 9.15 9.75 10.31 10.81 10.96
Table 3 Experiment 2: Sample results for pH at various points in the titration of 10.0 mL CH
3
COOH with 0.0995 M
KOH
Quantity of KOH (mL) 0 0.6 1 1.55 2.1 3 3.6 3.9 4.6
pH 3.06 3.32 3.52 3.71 3.85 4.07 4.2 4.25 4.38
Quantity of KOH (mL) 5.2 5.7 6.3 7 7.6 8.1 8.3 8.5 8.8
pH 4.48 4.57 4.68 4.81 4.96 5.08 5.16 5.24 5.36
Quantity of KOH (mL) 8.9 9 9.05 9.15 9.3 9.35 9.45 9.55 9.6
pH 5.41 5.45 5.51 5.6 5.67 5.71 5.75 5.89 6.01
Quantity of KOH (mL) 9.65 9.7 9.75 9.8 9.9 9.95 10 10.02 10.1
pH 6.08 6.15 6.24 6.35 6.63 6.84 7.24 7.85 8.35
Quantity of KOH (mL) 10.15 10.4 10.7 11
pH 9.26 10.16 10.7 11.02
Table 4 Experiment 2: Sample results for pH at various points in the titration of 10.0 mL CH
3
COOH with 0.0995 M KOH


Figure 2 Titration Curve of CH
3
COOH by KOH
Discussion
In this experiment, the same concentration of KOH (0.0995 M) was used for the titration. The experiment was also
done 2 times and the values of titration were presented in table 2.
The indicator used in the titration was phenolphthalein and has pH range between 8.2 10.0 and will change color
from colorless to deep pink. In figure 13, the pH range of phenolphthalein was represented by purple rectangle.
From the observation, the color of the solution started to change into pale pink when the volume of KOH added was
10.0 mL (pH = 7.56) in the first experiment and 10.0 mL (pH=7.24) in the second experiment, determining the end
point of the titration. The solution then continued to turn into deep pink. By using geometric method, the equivalent
point of the titration was when the volume of KOH approximately 9.90 mL and the pH of the solution was 7.8.

Question
1. Using the experimental data, estimate the concentration of acetic acid solution used in the experiment and the
value of the dissociation constant pKa of acetic acid
By using the equivalent point from geometrical approach which was at the volume of 9.90 mL,
[

]
[]

From the calculations, the concentration of CH
3
COOH is approximately close to the concentration data of the
solution, which was 0.1 M.
According to the laboratory manual, the value of pK
a
will be the same with pH at the half neutralization point.
By using geometric approach, the half neutralization point is when the volume of KOH added was 4.95 mL and
thus the pH at this point is 4.6. Therefore the pK
a
of acetic acid was 4.6.
2. Based on the concentration of hydrochloric acid determined in 1, determine the pH at each of the following
stages: I before the addition of the KOH standard solution, ii at the half-neutralization point, iii just before the
neutralization point, iv at the neutralization point, v just after the neutralization point, and vi at the completion
of the titration. Mark these pH values on your titration curve and compare these estimated data with your
experimental results.
(i) Because the solution was diluted with water, the concentration of the diluted CH
3
COOH before the addition
of KOH was:
[

] (

) (

)
pH of experimental result: 3.065 (mean value of 3.06 and 3.07)
(ii) At half neutralization point, pH = pK
a
. Therefore,

pH of experimental result: 4.4
(iii) Assume that at the point before equivalent point, 9.8 mL of KOH was added
CH
3
COOH + OH
-
H
2
O + CH
3
COO
-
0.990 0.975
-0.975 -0.975 +0.975 +0.975
0.0150 0.975 0.975
Moles of initial OH
-
= Moles of KOH = 0.0995 x 9.8 = 0.975 mmol
Moles of CH
3
COOH = 0.0990 x 10 = 0.990 mol
pH= pKa + log [

] = 4.74 + 1.816 = 6.56

pH of experimental result: 6.30 (mean value from experiment I and II result)
(iv) At equivalence point
[

pH of experimental result: 7.8
(v) Assume that at the point just after the equivalent point, 10 mL of KOH was added.
CH
3
COOH + OH
-
H
2
O + CH
3
COO
-

0.990 0.995
-0.990 -0.990 0.990 0.990
0.005 0.990 0.990
Moles of initial OH
-
= Moles of KOH = 0.0995 x 10.0 = 0.995 mmol
Moles of CH
3
COOH = 0.0990 x 10 = 0.990 mmol
pH = -log [OH
-
]= -log [

] = 4.301
pOH = 9.699
pH of experimental result: 7.4 (mean value from both experiments)
(vi) At the completion of titration, 11 mL of KOH was added
CH
3
COOH + OH
-
H
2
O + CH
3
COO
-

0.990 1.095
-0.990 -0.990 0.990 0.990
0.105 0.990 0.990
Moles of initial OH
-
= Moles of KOH = 0.0995 x 11.0 = 1.095mmol
Moles of CH
3
COOH = 0.0990 x 10.0 = 0.990 mmol
pH = -log [OH
-
]= -log [

] = 2.98
pOH = 11.02
pOH of experimental result: 10.99 (mean value from both experiments)

Conclusion
The accurate concentration of HCl and CH
3
COOH was obtained from the titration with 0.0995 M KOH. From the
titration, the concentration of HCl was 0.1000 and the concentration of CH
3
COOH was 0.0990 M.
There are several possible errors in this experiment which caused the pH at some points in the experiment differ from
the theoretical pH:
Parallax error when reading the burette scale
Time used to observe pH meter is sometimes too short because at some points of the titration, the value of pH
keeps increasing even after observation time is over
Observation error when identifying the color change at end point. Another source of error regarding end point
might happen when the color of the solution still changes when flask is shaken but that point has already been
regarded as end point.




Reference

Harris, Daniel C. Quantitative Chemical Analysis. 2007. New York: W.H Freeman and Company.
Murata, Shizuaki; Fumi Urano; and Masahiro Yoshimura. Chemistry Laboratory Manual. 2013. Nagoya: Institute of
Liberal Arts and Sciences, Nagoya University.