Analytical Chemistry Laboratory 2

Potentiometric Determination of the Ionization Constant of a Pure Unknown

Weak Acid

Mr. *****

Department of Chemical Engineering and Chemistry, Mapua Institute of Technology

The ionization constant of a weak acid was determined in this experiment. The data was
recorded by using a hydrogen electrode to get the pH of each addition of the titrant NaOH. Two
trials were performed, but only one trial will be examined, in this case, trial 2. The first ionization
constant computed was 2.69x10-3 while the second ionization constant computed was 1.58x10-7.

Objective

The main objective of the experiment is to
determine the ionization constant of a pure
unknown acid by potentiometric titration.
Discussion
Overview
The strength of an acid is defined by its
ability to donate a proton to a base. For
many common acids, we can quantify acid
strength by expressing it as the equilibrium
constant for the reaction in which the acid
donates a proton to the standard base, water,
as shown in the equations below:
HA + H2O ⇔ H3O+ + A-
The equilibrium constant for a reaction of
this type is called the Acid Dissociation
Constant, "Ka", for the acid HA.
A convenient method for determining Ka
is to measure the pH of a solution of the acid
after a strong base has been added to half
neutralize it. We can calculate the amount in
millimoles (mmol) of base added by
multiplying the volume in mL by the
concentration in mmol per mL, which is the
same as the molar concentration
(in moles per liter) since both the numerator
and denominator are divided by 1000. At the
point of half-neutralization, Ka = [H3O+] or
pKa = pH, where
pKa = - log Ka, just as
pH = - log [H3O+].
Two identical unknown sample (25 mL
each) was obtained and 25 mL of water were
each added to it. The analyte was place in
two separate beakers for two separater trials.
A strong base, NaOH, was used as titrant. It
was prepared by dissolving 4 g of NaOH
pellets in 1 L of water.
Methodology
The electrode was rinsed with deionized
water before being standardized. The pH
meter was first calibrated with a pH 7 buffer
solution, and then with a pH 4 buffer
solution. The electrode was then immersed
in the sample solution along with the
magnetic stirring. The buret with the reagent
was put in position so that it can be
delivered without splashing. After
connecting the electrodes to the meter and
commencing stirring, the initial buret
volume and the initial potential (or pH) was 44.2 8.6 0.8
recorded. It is always recorded after each 44.3 8.75 1.5
addition of titrant. The titrant is added by 44.4 8.85 1
batch until a pH of 13 is obtained. 44.5 8.9 0.5
44.6 9.09 1.9
Interpretation 44.7 9.14 0.5
44.8 9.29 1.5
The data obtained in trial 2 is shown 44.9 9.39 1
below including its graphical form. 45 9.5 1.1
45.1 9.58 0.8
VNaOH pH ΔpH/ΔV 45.2 9.67 0.9
0 1.82 45.3 9.77 1
20 3.18 0.068 45.4 9.82 0.5
21 3.53 0.35 45.5 9.9 0.8
21.1 3.59 0.6 45.6 9.94 0.4
21.2 3.68 0.9 45.7 9.98 0.4
21.3 3.72 0.4 45.8 10.04 0.6
21.4 3.87 1.5 45.9 10.08 0.4
21.5 3.99 1.2 46 10.13 0.5
21.6 4.15 1.6 46.1 10.16 0.3
21.7 4.34 1.9 46.2 10.2 0.4
21.8 4.62 2.8 46.3 10.24 0.4
21.9 4.78 1.6 46.4 10.28 0.4
22 4.91 1.3 46.5 10.31 0.3
22.1 5.07 1.6 46.6 10.35 0.4
22.2 5.17 1 46.7 10.38 0.3
22.3 5.24 0.7 46.8 10.41 0.3
22.4 5.33 0.9 46.9 10.43 0.2
22.5 5.38 0.5 47 10.47 0.4
22.6 5.45 0.7 48 10.67 0.2
22.7 5.46 0.1 49 10.83 0.16
22.8 5.52 0.6 50 10.94 0.11
22.9 5.55 0.3 60 11.51 0.057
23 5.58 0.3 70 11.76 0.025
23.1 5.6 0.2 80 11.96 0.02
23.2 5.63 0.3 90 12.07 0.011
23.3 5.66 0.3 100 12.14 0.007
23.4 5.7 0.4
23.5 5.73 0.3
23.6 5.76 0.3
23.7 5.78 0.2 3
2.5
23.8 5.8 0.2 2
23.9 5.83 0.3
pH/V

1.5
1
24 5.84 0.1 0.5
25 6.01 0.17 0
0 50 100 150
30 6.52 0.102 V NaOH added

35 6.91 0.078
40 7.39 0.096
44 8.45 0.265
44.1 8.52 0.7
 14 Conclusion
12
10
8 Potentiometric titration is one important
pH

6
4
technique in determining ionization constant
2 for weak acid and weak base.
0
0 50 100 150
The acid is diprotic, there would be two
V NaOH adde d inflection points in the titration curve above,
and the pKa's would be equal to the pH at
points halfway between 0 and the first
equivalence point, and halfway between the
In order to determine the pH at half- two equivalence points.
neutralization for an unknown acid, we will
measure the pH with a pH meter after each References
addition of base, and create a "Titration
Curve" which resembles the one in the 1. Christian, G.D., Analytical Chemistry, 6th
figure above. edition. New Jersey. John Wiley, 2004.
At the beginning of the titration, from 0
mL to about 20 mL of added base, the pH 2. Filby, G. “Spreadsheets for Chemists,”
changes very little with each addition, and 1 VCH Publishers, New York, 1995, p. 210.
mL of base can be added at a time. But after
about 20 mL, as the titration approaches the 3. Schwartz, L.M. “Advances in Acid-Base
equivalence point, the pH changes Gran Plot Technology,” J. Chem. Educ., 64,
drastically with very small additions of base. 947-950 (1987).
Here it is necessary to add small volumes of
base (≈ 0.1 mL) at a time, in order to get
sufficient points to define the shape of the
curve.
The equivalence point is the volume at
which the slope is greatest, or at which the
inflection point occurs, where the line
changes from upward curvature to
downward curvature. In this titration the
equivalence point occurs when about 10.85
mL of base is added, and the pH is 2.57.
The equivalence point can be determined
visually, or an interesting method developed
in calculus can be used. The "first
derivative" is actually the slope of the line at
a given point. It can be estimated
numerically by calculating the slope of a
line in the region of the point. If the first
derivative of the titration curve is plotted, it
looks like the figure shown above.
The first derivative has a maximum at the
equivalence point where the slope of the
titration curve is greatest, indicating large
pH changes with small volume additions.
Once the equivalence has been
determined, the pH can be read half way to
the equivalence point, and from it the Ka1
which is at 2.69x10-3 while Ka2 is 1.58x10-