Station # 4

Identification of an Unknown Acid by pH Titration

Submitted By: Annu Dhami

Submitted To: Qasim Saleem
Date: February 25th, 2009
Practical Session: PRA0701

Introduction:
The main purpose of this lab is to determine the identity of an unknown acid through the use of quantitative
and qualitative analysis. First, the KA value for the reaction: HA + H2O H3O+ + A- is calculated through
the use of pH titration, since KA = [H3O+][ A-]/[HA]. The calculated KA value would be compared with the
known KA values for one of the following acids: acetic acid, monochloroacetic acid, dichloroacetic acid,
and trichloroacetic acid; since there are three chloro substituted derivatives of acetic acid, each with a
different KA value for the carboxylic acid proton. Next, in a qualitative analysis, the identity of an unknown
acid is determined by using various different indicators to conclude the initial pH of the unknown acid
solution.
Observations:
1. Quantitative Identification
Number of Unknown Solution: 199
Concentration of NaOH: 0.09993 mol/L= 9.993 x 10-2 mol/L
Temperature of Solution: 20.4 C
Table l: pH of solution at each burette reading, after a certain volume of NaOH has been added
Volume of NaOH (mL)
Burette Reading (mL)
pH of solution
0.00
5.00
1.88
0.20
5.20
2.01
0.50
5.50
2.23
0.90
5.90
2.42
1.20
6.20
2.55
1.60
6.60
2.67
1.90
6.90
2.75
2.30
7.30
2.89
2.60
7.60
2.93
2.90
7.90
2.99
3.20
8.20
3.04
3.30
8.30
3.04
3.50
8.50
3.06
3.70
8.70
3.06
4.00
9.00
3.06
4.60
9.60
3.08
4.90
9.90
3.12
5.10
10.10
3.16
5.30
10.30
3.17

5.70
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
14.00
15.10
16.10
17.00
18.00
19.00
20.00
21.00
21.30
21.60
22.00
22.30
23.40
23.45
23.50
23.60
23.70
23.80
23.90
24.00
24.10
24.20
24.30
24.40
24.50
24.60
24.65
24.70
24.75
24.80
24.85
24.90
25.00
25.05
25.10
25.15
25.20

10.70
11.00
12.00
13.00
14.00
15.00
16.00
17.00
18.00
19.00
20.10
21.10
22.00
23.00
24.00
25.00
26.00
26.30
26.60
27.00
27.30
28.40
28.45
28.50
28.60
28.70
28.80
28.90
29.00
29.10
29.20
29.30
29.40
29.50
29.60
29.65
29.70
29.75
29.80
29.85
29.90
30.00
30.05
30.10
30.15
30.20

3.24
3.26
3.39
3.49
3.58
3.60
3.75
3.83
3.93
4.00
4.10
4.18
4.26
4.41
4.46
4.57
4.70
4.74
4.80
4.86
4.90
5.15
5.18
5.19
5.21
5.24
5.28
5.32
5.36
5.39
5.44
5.45
5.51
5.56
5.62
5.65
5.68
5.70
5.74
5.78
5.82
5.87
5.95
6.01
6.08
6.15

25.30
25.35
25.40
25.45
25.50
25.55
25.60
25.65
25.70
25.75
25.80
25.90
25.95
26.00
26.05
26.10
26.15
26.20
26.25
26.30
26.35
26.40
26.45
26.50
26.55
26.60
26.65
26.70
26.75
26.80
26.85
26.90
27.00
27.50
28.00
29.00
30.00
31.00
32.00
33.00
34.00
35.00
36.00
37.00
38.00
39.00

30.30
30.35
30.40
30.45
30.50
30.55
30.60
30.65
30.70
30.75
30.80
30.90
30.95
31.00
31.05
31.10
31.15
31.20
31.25
31.30
31.35
31.40
31.45
31.50
31.55
31.60
31.65
31.70
31.75
31.80
31.85
31.90
32.00
32.50
33.00
34.00
35.00
36.00
37.00
38.00
39.00
40.00
41.00
42.00
43.00
44.00

6.23
6.32
6.44
6.59
6.79
7.08
7.74
9.18
9.74
10.01
10.24
10.37
10.47
10.58
10.65
10.71
10.77
10.82
10.87
10.89
10.93
10.96
11.00
11.03
11.06
11.08
11.10
11.13
11.15
11.17
11.18
11.21
11.23
11.33
11.45
11.59
11.69
11.75
11.82
11.86
11.90
11.92
11.96
12.00
12.01
12.04

40.00
45.00
12.05
41.00
46.00
12.07
42.00
47.00
12.09
43.00
48.00
12.11
44.00
49.00
12.12
45.00
50.00
12.14
Table 1: Displays the pH of the solution at each burette reading, after the unknown solution is titrated with
a certain amount of NaOH
2. Qualitative Identification
Table 2: Observations made when performing a series of qualitative tests, using indicators, in order to
determine the identity of the unknown solution
Acid
Colors with

1
2
3

Thymol Blue

Malachite Green

Crystal Violet

More red/orange in
color
Magenta pink in
color

Light green in color

Navy blue in color

Paler, & lighter

green than #1(lime
green)
Turquoise in color

Aqua green in color

Yellow /orange in
Royal purple in
color
color
4
Similar to #2, but a
Similar to #2, but a
Similar to #2, but a
bit darker magenta
bit darker in color,
little bit darker in
in color, than #2
than #2
color, than #2
Unknown #:199
Yellow/orange in
Turquoise in color
Royal purple in
color (perfect match (perfect match with color (perfect match
with Acid #3)
Acid #3)
with Acid #3)
Table 2: Displays the observations made when performing a series of qualitative tests, in order to determine
the identity of the unknown solution. During this qualitative analysis, the unknown compound was treated
with three different types of indicators (Thymol Blue, Malachite Green, & Crystal Violet) and then
compared to the results of the four different unlabelled acids, which were each treated with the same three
types of indicators
Calculations:
Qualitative Identification:
According to the various qualitative tests done, in order to determine the identity of the unknown solution,
it was later determined that the unknown acid is a perfect match with unknown acid #3, which was the
weakest of the four unknown acids, according to the lab manual.

Quantitative Identification:
Figure 1:

Figure 1: This graph displays the acid-base titration of a weak acid with a strong base. The steep slow in
the middle refers to the equivalence point where the moles of the base added equals the moles of the acid
present
Figure 2:

Figure 2: This graph displays the derivative plot of the acid-base titration of a weak acid with a strong
base. The steep point in the middle of the graph (where the two ends meet) is the equivalence point,
corresponding to the volume of NaOH at the equivalence point
At Equivalence Point:
pH = (7.74 + 9.18) / 2
pH = 8.46
Volume of NaOH= (25.60 + 25.65) / 2

Volume of NaOH= 25.625 mL=2.5625 x 10-2 L

Volume of Acid= 25 mL= 2.5 x 10-2 L
Moles of Acid present = Moles of Base added
CAVA = CBVB
CA= (CBVB) / VA
CA = (0.09993 mol/L) * (2.563 x 10-2 L) / (2.5 x 10-2 L)
CA = 0.1024 mol/L = [HA]
Reactions for Weak Acid & Strong Base Titration:
HA + H2O H3O+ + AA- + H2O HA + OHNaOH Na+ + OH2H2O H3O+ + OHSpecies Available at Equilibrium:
HA, A-, H3O+, OH-, Na+
Mass Balance:
Charge Balance: [H3O+] + [Na+] = [OH-] + [A-]
Simultaneous Equations:
1. KA = [H3O+][A-] / [HA]
2. Kw = [ H3O+][OH-]
3. [HA] + [A-] = CAVA / VA+VB
4. [Na+] = CBVB / VA+VB
5. [ H3O+] + [Na+] = [OH-] + [A-]
At 0% Titration Point:
KA = [H3O+][A-] / [HA]
[H3O+] can determined using the initial pH of the acid, since 0 mL of NaOH has been added
pH = 1.88
[H3O+] = 10-1.88
[H3O+] = 1.32 x 10-2 mol/L
Since [H3O+] = [A-] = 1.32 x 10-2 mol/L and CA = 0.1024 mol/L = [HA]
KA = [1.32 x 10-2 mol/L][ 1.32 x 10-2 mol/L] / [0.1024 mol/L]
KA = 1.70 x 10-3
the KA at the 0% titration point is 1.70 x 10-3
At 20% Titration Point:
KA = [H3O+][A-] / [HA]
VB added = 20% of 25.625 mL = 0.2(25.625 mL) = 5.125 mL = 5.13 x 10-3 L
[H3O+] can determined by taking the average of the pH values of the volumes 5.10 mL and 5.30 mL where
pH = (3.16 + 3.17) / 2 = 3.165

[H3O+] = 10-3.165
[H3O+] = 6.84 x 10-4 mol/L
From the Simultaneous Equations, #2, 4, & 5
[A-] = [ H3O+] + [Na+] - [OH-]
[A-] = [ H3O+] + [CBVB / VA+VB] - Kw / [ H3O+]
[A-] = [6.84 x 10-4 mol/L] + [(0.09993 mol/L) x (5.13 x 10-3 L) / (2.5 x 10-2 L + 5.13 x 10-3 L)] [(1.0 x 1014
) / (6.84 x 10-4 mol/L)]
[A-] = 1.77 x 10-2 mol/L
From the Simultaneous Equation, #3
[HA] + [A-] = CAVA / VA+VB
[HA] = [CAVA / VA+VB] - [A-]
[HA] = [(0.1024 mol/L) x (2.5 x 10-2 L) / (2.5 x 10-2 L + 5.13 x 10-3 L)] [1.77 x 10-2 mol/L]
[HA] = 6.73 x 10-2 mol/L
KA = [6.84 x 10-4 mol/L][ 1.77 x 10-2 mol/L] / [6.73 x 10-2 mol/L]
KA = 1.80 x 10-4
the KA at the 20% titration point is 1.80 x 10-4
At 40% Titration Point:
KA = [H3O+][A-] / [HA]
VB added = 40% of 25.675 mL = 0.4(25.625 mL) = 10.25mL = 1.03 x 10-2 L
[H3O+] can determined by taking the average of the pH values of the volumes 10.00 mL and 11.00 mL
where pH = (3.60 + 3.75) / 2 = 3.675
[H3O+] = 10-3.675
[H3O+] = 2.11 x 10-4 mol/L
From the Simultaneous Equations, #2, 4, & 5
[A-] = [ H3O+] + [Na+] - [OH-]
[A-] = [ H3O+] + [CBVB / VA+VB] - Kw / [ H3O+]
[A-] = [2.11 x 10-4 mol/L] + [(0.09993 mol/L) x (1.03 x 10-2 L) / (2.5 x 10-2 L + 1.03 x 10-2 L)] [(1.0 x 1014
) / (2.11 x 10-4 mol/L)]
[A-] = 2.94 x 10-2 mol/L
From the Simultaneous Equation, #3
[HA] + [A-] = CAVA / VA+VB
[HA] = [CAVA / VA+VB] - [A-]
[HA] = [(0.1024 mol/L) x (2.5 x 10-2 L) / (2.5 x 10-2 L + 1.03 x 10-2 L)] [2.94 x 10-2 mol/L]
[HA] = 4.31 x 10-2 mol/L
KA = [2.11 x 10-4 mol/L][ 2.94 x 10-2 mol/L] / [4.31 x 10-2 mol/L]
KA = 1.44 x 10-4
the KA at the 40% titration point is 1.44 x 10-4

At 60% Titration Point:

KA = [H3O+][A-] / [HA]
VB added = 60% of 25.625 mL = 0.6(25.625 mL) = 15.38 mL = 1.54 x 10-2 L
[H3O+] can determined by taking the average of the pH values of the volumes 15.10 mL and 16.10 mL
where pH = (4.10 + 4.18) / 2 = 4.14
[H3O+] = 10-4.14
[H3O+] = 7.24 x 10-5 mol/L
From the Simultaneous Equations, #2, 4, & 5
[A-] = [ H3O+] + [Na+] - [OH-]
[A-] = [ H3O+] + [CBVB / VA+VB] - Kw / [ H3O+]
[A-] = [7.24 x 10-5 mol/L] + [(0.09993 mol/L) x (1.54 x 10-2 L) / (2.5 x 10-2 L + 1.54 x 10-2 L)] [(1.0 x 1014
) / (7.24 x 10-5 mol/L)]
[A-] = 3.82 x 10-2 mol/L
From the Simultaneous Equation, #3
[HA] + [A-] = CAVA / VA+VB
[HA] = [CAVA / VA+VB] - [A-]
[HA] = [(0.1024 mol/L) x (2.5 x 10-2 L) / (2.5 x 10-2 L + 1.54 x 10-2 L)] [3.82 x 10-2 mol/L]
[HA] = 2.52 x 10-2 mol/L
KA = [7.24 x 10-5 mol/L][ 3.82 x 10-2 mol/L] / [2.52 x 10-2 mol/L]
KA = 1.10 x 10-4
the KA at the 60% titration point is 1.10 x 10-4
At 80% Titration Point:
KA = [H3O+][A-] / [HA]
VB added = 80% of 25.625 mL = 0.8(25.625 mL) = 20.5 mL = 2.05 x 10-2 L
[H3O+] can determined by taking the average of the pH values of the volumes 20.00 mL and 21.00 mL
where pH = (4.57 + 4.70) / 2 = 4.635
[H3O+] = 10-4.635
[H3O+] = 2.32 x 10-5 mol/L
From the Simultaneous Equations, #2, 4, & 5
[A-] = [ H3O+] + [Na+] - [OH-]
[A-] = [ H3O+] + [CBVB / VA+VB] - Kw / [ H3O+]
[A-] = [2.32 x 10-5 mol/L] + [(0.09993 mol/L) x (2.05 x 10-2 L) / (2.5 x 10-2 L + 2.05 x 10-2 L)] [(1.0 x 1014
) / (2.32 x 10-5 mol/L)]
[A-] = 4.50 x 10-2 mol/L
From the Simultaneous Equation, #3
[HA] + [A-] = CAVA / VA+VB

[HA] = [CAVA / VA+VB] - [A-]

[HA] = [(0.1024 mol/L) x (2.5 x 10-2 L) / (2.5 x 10-2 L + 2.05 x 10-2 L)] [4.50 x 10-2 mol/L]
[HA] = 1.13 x 10-2 mol/L
KA = [2.32 x 10-5 mol/L][ 4.50 x 10-2 mol/L] / [1.13 x 10-2 mol/L]
KA = 9.24 x 10-5
the KA at the 80% titration point is 9.24 x 10-5
At 100% Titration Point:
KA = [H3O+][A-] / [HA]
VB added = 100% of 25.625 mL = 1.0(25.625 mL) = 25.63 mL = 2.563 x 10-2 L
[H3O+] can determined by taking the average of the pH values of the volumes 25.60 mL and 25.65 mL
where pH = (7.74 + 9.18) / 2 = 8.46
[H3O+] = 10-8.46
[H3O+] = 3 x 10-9 mol/L
From the Simultaneous Equations, #2, 4, & 5
[A-] = [ H3O+] + [Na+] - [OH-]
[A-] = [ H3O+] + [CBVB / VA+VB] - Kw / [ H3O+]
[A-] = [3 x 10-9 mol/L] + [(0.09993 mol/L) x (2.563 x 10-2 L) / (2.5 x 10-2 L + 2.563 x 10-2 L)] [(1.0 x 1014
) / (3 x 10-9 mol/L)]
[A-] = 5.06 x 10-2 mol/L
From the Simultaneous Equation, #3
[HA] + [A-] = CAVA / VA+VB
[HA] = [CAVA / VA+VB] - [A-]
[HA] = [(0.1024 mol/L) x (2.5 x 10-2 L) / (2.5 x 10-2 L + 2.563 x 10-2 L)] [5.06 x 10-2 mol/L]
[HA] = -3.71 x 10-5 mol/L
KA = [3 x 10-9 mol/L][ 5.06 x 10-2 mol/L] / [-3.71 x 10-5 mol/L]
KA = -4.10 x 10-6
the KA at the 100% titration point is -4.10 x 10-6
Since the calculated KA values vary slightly, an average can be taken to determine one value for the
equilibrium constant.
KA avg = [(1.70 x 10-3) + (1.80 x 10-4) + (1.44 x 10-4) + (1.10 x 10-4) + (9.24 x 10-5)] / 5
KA avg = 4.45 x 10-4
The corresponding KA values of acetic acid and its three chloro substitutes are:
Acetic Acid: 1.9 x 10-5
Monochloroacetic Acid: 1.6 x 10-3
Dichloroacetic Acid: 5 x 10-2
Trichloroacetic Acid: 2 x 10-1
(* taken from http://www.lsbu.ac.uk/biology/biolchem/acids.html)

Therefore, according to the known KA values of acetic acid and its three chloro substitutes, the identity of
the unknown acid is acetic acid, since the known KA value of acetic acid is the closest to the calculated KA
value of the unknown acid. However, because of possible errors made during the titration of the weak acid
and NaOH, the two KA values are a bit off.
Conclusion:
The main purpose of performing the experiment was to determine the identity of an unknown acid through
qualitative analysis, and by experimentally calculating the KA value for the reaction. After carrying through
the lab, and performing the calculations, it was determined that the KA value of the unknown acid is 4.45 x
10-4, and therefore the identity of the unknown acid is acetic acid, whose KA value is 1.9 x 10-5. This was
determined by calculating the KA value of the reaction at 0%, 20%, 40%, 60%, 80%, and 100% titration
points, and then finding the average of the five values. The identity of the unknown acid was further proven
by the qualitative analysis since the results of the unknown acid matched the results of Acid #3, which
proved to be the weakest acid present, such as acetic acid. The calculated KA value of the unknown acid
was a bit off from the known KA value of the acetic acid due to possible errors and miscalculations made
during the acid-base titration.