Intro/purpose:

The purpose of this experiment was to determine the identity of the unknown acid that was
given, whether it be acetic acid (CH3COOH), monochloroacetic acid (CClH2COOH),
dichloroacetic acid (CCl2HCOOH), or trichloroacetic acid (CCl3COOH). This was done by
experimentally determining the Ka value of the reaction HA + H2O -> H3O+ + A-, through the pH
meter titration that was completed and the formula Ka = ([H3O+][A-]) / [HA]. The formula for ka

k w / }

k w / }
H 3 O+
(KA = (C A V A )/(V A +V B){[(C B V B)/( V A+V B)]+ )
H 3 O+
H 3 O+ {[( C B V B)/(V A+ V B)]+

was also derived using several simple formulas, which included The identification of the acid
was also done through a qualitative method, using various indicators, such as thymol blue,
malachite green, and crystal violet, to determine the initial pH of the solution. From the initial
pH of the solution and the other unknown acids, it could be determined which acid was which
based on their relative strength, and thus which of the four was the unknown solution (21).

Experiment Procedure:

The pH meter was calibrated using three buffer solutions of pH 4, 7, and 10 with the
assistance of the teachers assistance. 25mL of the unknown acid was pipeted into a 100mL
beaker and titrated with a solution of NaOH. A magnetic bar was then used to continuously stir
the solution and adjusted it so that the magnetic bar did not hit the pH electrodes. The first 3mL
was titrated in approximately 0.25mL increments. After a noticeable increase in pH, 20mL were
then titrated in 1mL increments. At around 4-5 pH, titrate the unknown acid at one drop
increments. After the equivalence point, the titration was continued at 1mL increments. After
each increment was added to the acid, the burette reading and pH were recorded.
5mL of four different acids were added into four separate test tubes. 5mL of the unknown acid
(number 21) was also added to a separate test tube. 5 drops of thymol blue were then added into
the test tubes and observations were then recorded. This set-up was then replicated two more
times, but the indicators malachite green and crystal violet were used instead and the
observations were recorded again.
Observations:
Table 1: Quantitative Identifications
Unknown acid number
Concentration of NaOH (M)
Temperature (oC) ( 0.3 oC)

21
0.10002
22.8

Table 2: Quantitative results for the identification of an unknown acid

Burette
Reading
4.26
4.79
5.08
5.35
5.60
5.84
6.10

Volume of
base (mL) pH
0.00
0.53
0.82
1.09
1.34
1.58
1.84

delta V(mL) delta pH

2.06
2.02
2.02
2.03
2.03
2.05
2.06

0.53
0.29
0.27
0.25
0.24
0.26

-0.04
0.00
0.01
0.00
0.02
0.01

delta pH/
delta V
-0.08
0.00
0.04
0.00
0.08
0.04

average V
(mL)
0.26
0.68
0.96
1.22
1.46
1.71

6.37
6.65
6.89
7.15
7.41
7.93
8.42
8.93
9.41
9.93
10.41
10.92
11.95
13.00
13.99
15.00
16.00
17.01
18.03
19.01
19.98
21.00
22.01
23.04
24.00
25.01
25.97
27.00
27.96
28.87
29.10
29.20
29.28
29.35
29.41
29.49
29.52
29.59
29.71
29.79
29.93
30.06
30.25

2.11
2.39
2.63
2.89
3.15
3.67
4.16
4.67
5.15
5.67
6.15
6.66
7.69
8.74
9.73
10.74
11.74
12.75
13.77
14.75
15.72
16.74
17.75
18.78
19.74
20.75
21.71
22.74
23.70
24.61
24.84
24.94
25.02
25.09
25.15
25.23
25.26
25.33
25.45
25.53
25.67
25.80
25.99

2.08
2.08
2.10
2.12
2.13
2.15
2.18
2.20
2.24
2.27
2.29
2.31
2.38
2.43
2.49
2.55
2.60
2.67
2.74
2.81
2.87
2.94
3.01
3.11
3.20
3.30
3.45
3.61
3.89
4.55
5.02
5.50
5.81
6.30
6.77
8.26
9.14
9.49
9.87
10.12
10.36
10.47
10.63

0.27
0.28
0.24
0.26
0.26
0.52
0.49
0.51
0.48
0.52
0.48
0.51
1.03
1.05
0.99
1.01
1.00
1.01
1.02
0.98
0.97
1.02
1.01
1.03
0.96
1.01
0.96
1.03
0.96
0.91
0.23
0.10
0.08
0.07
0.06
0.08
0.03
0.07
0.12
0.08
0.14
0.13
0.19

0.02
0.00
0.02
0.02
0.01
0.02
0.03
0.02
0.04
0.03
0.02
0.02
0.07
0.05
0.06
0.06
0.05
0.07
0.07
0.07
0.06
0.07
0.07
0.10
0.09
0.10
0.15
0.16
0.28
0.66
0.47
0.48
0.31
0.49
0.47
1.49
0.88
0.35
0.38
0.25
0.24
0.11
0.16

0.07
0.00
0.08
0.08
0.04
0.04
0.06
0.04
0.08
0.06
0.04
0.04
0.07
0.05
0.06
0.06
0.05
0.07
0.07
0.07
0.06
0.07
0.07
0.10
0.09
0.10
0.16
0.16
0.29
0.72
2.04
4.80
3.88
7.00
7.83
18.62
29.33
5.00
3.17
3.12
1.71
0.85
0.84

1.98
2.25
2.51
2.76
3.02
3.41
3.92
4.42
4.91
5.41
5.91
6.40
7.18
8.22
9.24
10.24
11.24
12.24
13.26
14.26
15.24
16.23
17.24
18.26
19.26
20.24
21.23
22.22
23.22
24.16
24.72
24.89
24.98
25.06
25.12
25.19
25.24
25.30
25.39
25.49
25.60
25.74
25.90

31.26
32.27
33.28
34.30
35.32
36.30
37.30
38.29
39.32
40.25
41.31
42.29
43.31
44.28
45.29

27.00
28.01
29.02
30.04
31.06
32.04
33.04
34.03
35.06
35.99
37.05
38.03
39.05
40.02
41.03

10.99
11.13
11.23
11.29
11.34
11.36
11.40
11.42
11.44
11.44
11.47
11.48
11.48
11.50
11.50

1.01
1.01
1.01
1.02
1.02
0.98
1.00
0.99
1.03
0.93
1.06
0.98
1.02
0.97
1.01

0.36
0.14
0.10
0.06
0.05
0.02
0.04
0.02
0.02
0.00
0.03
0.01
0.00
0.02
0.00

0.36
0.14
0.10
0.06
0.05
0.02
0.04
0.02
0.02
0.00
0.03
0.01
0.00
0.02
0.00

26.50
27.50
28.52
29.53
30.55
31.55
32.54
33.54
34.54
35.52
36.52
37.54
38.54
39.54
40.52

Table 3: Qualitative Identification of Acids

Acid
1

2
3
4

Unknown Compound
21

Colour change with

Thymol Blue
Bright, clear yellow
solution

Colour change with

Malachite
Light blue
(aquamarine) clear
solution
Pink/red clear solution Faint green tint, clear
solution
Pink/red clear solution Faint green tint, clear
solution
Orange/red clear
Light blue
solution
(aquamarine) clear
solution
Orange/red clear
Light blue
solution
(aquamarine) clear
solution

Colour change with

Crystal Violet
Violet (Purple/blue)
clear solution
Turquoise clear
solution
Teal clear solution
Medium blue clear
solution
Medium blue clear
solution

Table 4: Qualitative Identification of Acids

Acid
1
2
3
4

Order of Strength
Weakest
Strongest
Second Strongest
Third Strongest

Identity
Acetic acid
Trichloroacetic acid
Dichloroacetic acid
Monochloroacetic acid

Unknown Compound 21

Third Strongest

Monochloroacetic acid

Calculations:
Based on both graphs and table 5, it can be seen that the point of equivalence was at an average
of 25.245 mL of the added base and at the pH of 9.14.
To find the concentration of the acid at the equivalence point, the formula CAVA=CBVB was used:
CA = (CBVB)/ VA
= [(0.10002 M)(25.245 mL)] / (25.00 mL)
= 0.1010 M
The error of this calculation is then:
CA = CA [(VA / VA)2 + (CB / CB)2 + (VB / VB)2]1/2
= (0.1010 M) [(0.03 / 25 mL)2 + (0 / 0.10002 M)2 + (0.03 / 25.245 mL)2]1/2
= 0.0002 M
Therefore, the concentration of the acid was 0.1010 0.0002 M

During the experiment, several chemical equations were needed, which include the following:
1. KA = ([A-][H3O+]) / [HA]
2. Kw = [H3O+][OH-]
3. [Na+] = (CBVB) / (VA + VB)

4. [HA] + [A-] = (CAVA) / (VA + VB)

5. [Na+] + [H3O+] = [A-] + [OH-]
[A-] = [(CBVB) / (VA + VB)] + [H3O+] - [OH-]
Then by subbing equation 5 into equation 4, the equation becomes the following:
[HA] = (CAVA) / (VA + VB) - {[(CBVB) / (VA + VB)] + [H3O+] - [OH-]}
Finally, by subbing this new equation into equation 1, the final equation becomes:
k w / }

k w / }
H 3 O+
(C
A
V
A
)/(V
A
+V
B){[(C
B V B)/(V A+V B)]+
KA =
H 3 O+
H 3 O+ {[(C B V B)/ (V A+ V B)]+

To find the pH of the H3O+, the formula [H3O+] = 10-pH, was used
(At equivalent point)
[H3O+] = 10-pH
= 10-(9.14)
= 7.24 x 10-10 M
= 7.2 x 10-10 M
Then the error is:
[H3O+] = pH x pH x [H3O+]
= (0.01)(9.14)(7.2 x 10-10)
= 7 x 10-11 M
Therefore the concentration of hydronium ions was 7.2 x 10-10 7 x 10-11 M

To calculate ka at the equivalence point, the following calculations were completed

at 100% Titration Point

CA = 0.1010 M
CB = 0.10002 M
VA = 25.00 mL
VB = 25.245 mL
pH at equivalence point = 9.14
[H3O+] = 10-pH = 10-9.14 = 7.2 x 10-10 M
Ka =

[7.2 x 1010 M ]{[(0.10002 M x 25.245 mL)/(25.00 mL+25.245 mL)]+[7.2 x 1010 M ] (1.0 x 1014 M /[7.2 x 10
(0.1010 M x 25.00 mL)/(25.00 mL+25.245 mL){[(0.10002 M x 25.245)/(25.00 mL +25.245 mL)]+[7.2 x 1010 M ] (1.0 x 10

ka = - 9.2 x 10-8 M

The error of this result is then:

Error of CBVB: = CBVB [(CB / CB)2 + (VB / VB)2]1/2
= (2.525)[(0 / 0.10002)2 + (0.03 / 25.245)2]1/2
= 3 x 10-3
Error of CAVA: = CAVA [(CA / CA)2 + (VA / VA)2]1/2
= 2.525 [(0.0002 / 0.1010)2 + (0.03 / 25.00)2]1/2
= 6 x 10-3

Error of VA + VB: = [(VA)2 + (VB)2]1/2

= [(0.03)2 + (0.03)2]1/2
= 0.04
Error of (CBVB) / (VA + VB): = (CBVB) / (VA + VB) [(CBVB / CBVB)2 + (VA + VB / VA + VB)2]1/2
= (0.050258) [(3 x 10-3 / 2.525)2 + (0.04/ 50.245)2]1/2
= 7 x 10-5
Error of kw / [H3O+]: = kw / [H3O+] [(kw / kw)2 + ([H3O+] / [H3O+])2]1/2
= 1.4 x 10-5[(0 / 1 x 10-14)2 + (7 x 10-11 / 7 x 10-10)2]1/2
= 1.4 x 10-26
Error of (CAVA) / (VA + VB): = (CAVA) / (VA + VB) [(CAVA / CAVA)2 + (VA + VB / VA + VB)2]1/2
= (0.0502) [(6 x 10-3 / 2.525)2 + (0.04 / 50.245)2]1/2
= 1 x 10-4
Error of [(CBVB) / (VA + VB)] + [H3O+] (kw / [H3O+])]: = [([(CBVB) / (VA + VB)])2 + [H3O+]2 (
kw / [H3O+])2]1/2
= [(7 x 10-5)2 + (7 x 10-11)2 + (1.4 x 10-26)2]1/2
= 7 x 10-5
Total error: = (formula for ka)[(numerator / numerator)2 + (denominator / denominator)2]1/2
= (-9.2 x 10-8) [((5.024 x 10-4) / (3.6173 x 10-5))2 + ((1.94 x 10-6) / (1.379 x 10-5)2)]1/2
= 9 x 10-6

Table 5: Tabulated results

Titration point (%)

Average
pH ( 0.01)
volume of
Base added
(mL) ( 0.03)

[H3O+] (M)

Ka of the unknown
acid (M)

2.060

20

4.935

2.020

40

11.435

2.345

60

15.500

2.575

80

20.490

2.905

100

25.245

9.140

8.7 x 10-3
2 x 10-4
9.5 x 10-3
2 x 10-4
4.5 x 10-3
1 x 10-4
2.7 x 10-3
7 x 10-5
1.2 x 10-3
4 x 10-5
7.2 x 10-10
7 x 10-11

-8.7 x 10-3
3 x 10-5
4.3 x 10-3
7 x 10-5
4.8 x 10-3
3 x 10-4
5.2 x 10-3
7 x 10-5
6.0 x 10-3
2 x 10-4
- 9.2 x 10-8
9 x 10-6

The average ka value is then: 5.1 x 10-3 1.6 x 10-4

Discussion:
Titration curves are graphs based on the titration of an acid and a base with the x-axis
containing the volume of the titrant (NaOH in this case) and the y-axis containing the pH of the
solution. The reason for these graphs are so that the equivalence point can be located1. The
equivalence point is when the amount of titrant (in this case, the base) is equal and thus
neutralizes the acid in the solution2. Thus, from using the equivalence point, and several other
pieces of data, the ka can then be found, which is known as the equilibrium constant for the
dissociation of the weak acid3. From this background info, the ka of the unknown acid was
calculated to be 5.1 x 10-3 1.6 x 10-4, which is closest to the ka of monochloroacetic acid, which
was seen to be 1.36 x 10-3. The ka value is temperature dependant, which is based on the vant
Hoff equation, where the ka decreases in exothermic reactions as the temperature increases and
increases in endothermic reactions as the temperature decreases4. It is also known that each acid
has its own unique ka because it indicates the probability that an acid molecule would react with
a water molecule, to form an anion and a hydronium ion5, which is different for each molecule
based on their composition, structure and other unique properties.

This was also supported with the qualitative analysis, where three different indicators (thymol
blue, malachite green, and crystal violet) were used on the four possible acids (acetic acid
(CH3COOH), monochloroacetic acid (CClH2COOH), dichloroacetic acid (CCl2HCOOH), or
trichloroacetic acid (CCl3COOH)) as well as the unknown acid, to determine which the unknown
acid was closest to based on the colour change. Based on table 4, the data also supports that the
unknown acid was monochloroacetic acid. Several indicators were used most likely to increase
the precision of the results, and to tell the difference between certain acids that obtained the same
results when only one indicator was used. The indicators are really weak acids that contain two
forms, the acid form and the conjugate base form. Within a certain range of pH, the equilibrium
of the indicator shifts rapidly from acid to conjugate base (or vice-versa)6. There is usually a
colour change associated with the shift, which is due an atom in the structure that accepted a
proton, which altered the resonant frequencies of the entire chain of double bonds that are
usually present in indicators. This resulted in a slightly different wavelength absorption profile,
and thus a color change4.
This also shows that the experiment was quite accurate, especially since the difference
between the ka values was only 3.74 x 10-3. Some errors that could have created this discrepancy
may have included adding more than the recommended amount of base at a time. From there, the
equivalence point could have been passed slightly, and thus the pH at the equivalence point could
have been slightly inaccurate. In order to solve this dilemma, smaller amounts of the titrant could
have been added as the pH increased rapidly in order to obtain more data points and to obtain a
more accurate equivalence point. Another source of error could have been that the pH meter was
not properly calibrated, which could give a pH reading that is slightly inaccurate. To improve
this, a second pH meter could be used to check the reading for consistency.

Conclusion:
Therefore, based on the calculated ka (5.1 x 10-3 1.6 x 10-4) of unknown acid 21, that the
most accurate assumption would be that the acid is monochloroacetic acid. This is also supported
by referring to the known ka value of monochloroacetic acid the qualitative analysis that was
done using several indicators to determine the strength of the acids.

References
1. "Titration curve -." Wikipedia, the free encyclopedia. Web. 08 Feb. 2010.
<http://en.wikipedia.org/wiki/Titration_curve>.
2. "Equivalence point -." Wikipedia, the free encyclopedia. Web. 08 Feb. 2010.
<http://en.wikipedia.org/wiki/Equivalence_point>.
3. "Acids and Bases - Table of Common Ka values." Chemistry - Periodic Table, Chemistry
Projects, and Chemistry Homework Help. Web. 08 Feb. 2010.
<http://chemistry.about.com/od/chartstables/a/pkatable.htm>.
4. "Acid dissociation constant -." Wikipedia, the free encyclopedia. Web. 08 Feb. 2010.
<http://en.wikipedia.org/wiki/Acid_dissociation_constant>.
5. "NetLogo Models Library: Weak Acid." The Center for Connected Learning and
Computer-Based Modeling. Web. 08 Feb. 2010.
<http://ccl.northwestern.edu/netlogo/models/WeakAcid>.
6. "How do acid/base indicators work? - Yahoo! Answers." Yahoo! Answers - Home. Web.
07 Feb. 2010. <http://answers.yahoo.com/question/index?
qid=20070528191849AAFKQVc>.
CHM 140Y5Y Course Manual. University of Toronto Mississauga. Print.

S. S. Zumdahl "Chemical Principles," 6th edition, Houghton Mifflin, Boston, MA (2008)