EXPERIMENT 8

THE ACID DISSOCIATION CONSTANT, KA

Assigned Concentration ____________

Goals – gain experience preparing solutions of specified concentration, experimentally

determine the dissociation constant, Ka, of acetic acid, observe the effect of the initial
acetic acid concentration on the value of Ka, calculate the classes’ average Ka, calculate
the molarity of acetic acid in vinegar.

Purpose – the purpose of this experiment is to determine the equilibrium constant, Ka,
for acetic acid by measuring the pH of several concentrations. The classes’ average value
of Ka will be calculated. Next the pH of vinegar is measured and the molarity of acetic
acid in vinegar is calculated.

Introduction - Weak acids only partially dissociate into ions in solution. For acetic acid,
the reaction that occurs is:

HC2H3O2 (aq) ⇔ H+ (aq) + C2H3O2 - (aq) (1)

The equilibrium expression is:

[H + ]eq[C2H3O2 - ]eq
Ka = (2)
[HC2H3O2]eq

where the subscript, eq, represents the equilibrium concentration. By examining Eq. 1 it
can be seen that when acetic acid is added to distilled water:

[H+]eq = [C2H3O2 -(aq)]eq (3)

Acetic acid is a weak acid, and only a small fraction ionizes. It can thus be
approximated that the equilibrium concentration of acetic acid equals the initial
concentration:
[HC2H3O2 (aq)]eq ≈ [HC2H3O2 (aq)]i (4)

where the subscript, i, indicates the initial concentration. The percentage of ionization
can be calculated from:

⎛ [H + ]eq ⎞
% ionization = ⎜⎜ ⎟⎟(100%) (5)
⎝ [HC2H3O2]i ⎠

As a general rule, if the % ionization is less than 5%, the assumption

[HC2H3O2(aq)]eq ≈ [HC2H3O2 (aq)]i is valid.
 The pH of an aqueous solution can be found from the concentration of H+ ions,
+
[H ], using the following equation:
pH = - log[H+] (6)

By taking the antilog of this equation, [H+] can be found from the pH:

[H+] = 10-pH (7)

In this experiment, 100 mL of acetic acid solution with the assigned concentration,
[C2H3O2 -(aq)]i, is prepared by dilution. The starting solution is 2.0M acetic acid. The pH
is then measured. Equation (7) is used to calculate [H+]eq, which equals [C2H3O2 -(aq)]eq.
These values are substituted into Eq.(2) to find Ka.
Each group will prepare one solution, measure its pH, and calculate Ka. The
results of the entire class are collected and the average Ka is calculated.
Lastly, the pH of vinegar is measured, and the molarity of acetic acid in vinegar is
calculated.

Example 1 - How should one prepare 100 mL of 0.75 M HA starting with 2.0M HA?

Solution - This is a dilution problem: MdVd=McVc

where Md = molarity of the dilute solution = 0.75 M HA

Vd = volume of the dilute solution = 100 mL
Mc = molarity of the concentration solution = 2.0M HA
Vc = volume of the concentrated solution needed to prepare the dilute solution =?
Vc = MdVd/Mc = (0.75M)(100 mL)/(2.0M) = 37.5 mL

To prepare this solution, add 37.5 mL of 2.0M HA to enough water to make 100 mL of
solution

Example 2 - The pH of a 0.75 M HA solution was found to be 4.5. Calculate [H+]eq, [A-
(aq)]eq, and Ka. Is the assumption [HA(aq)]eq ≈ [HA (aq)]i valid?

Solution - The dissociation reaction that occurs is: HA ⇔ H+ + A-

[H+]eq = [A-]eq = 10-pH = 10-4.5 = 3.16 x 10-5

Assume [HA]eq = [HA]i = 0.75 M

-5 -5
[H+ ]eq[A - ]eq (3.16 x 10 )(3.16 x 10 )
Ka = = = 1.33 x 10-9
[HA]eq (0.75 M )
⎛ [H+ ]eq ⎞ ⎛ 3.15 x 10−5 ⎞
The % ionization = ⎜ ⎜ ⎟(100% ) = ⎜⎜ ⎟(100%) = 0.0042%
[HA]i ⎟ 0.75 ⎟
⎝ ⎠ ⎝ ⎠
Since the % ionization is less than 5%, the assumption that [HA (aq)]eq ≈ [HA(aq)]i is valid.
Example 3 – Suppose a chemistry class finds an average value of Ka = 2 x 10-5 for acetic
acid. The pH of vinegar is then found to be pH = 3.0. Find the molarity of the acetic acid
in the vinegar.

Solution – [H+]eq = 10-3.0 = 1 x 10-3M = [C2H3O2 -]eq

⎛ [H+ ][C2H3O2- ] ⎞ ⎛ (1x10−3 )2 ⎞

Rearranging Eq. 2 gives: [HC2H3O2] = ⎜⎜ ⎟=⎜
⎟ ⎜ 2 x 10-5 ⎟
⎟ = 0.05M
⎝ K a
⎠ ⎝ ⎠

The assumption that the equilibrium concentration of acetic acid approximately equals
the initial concentration is valid since the % ionization is only 2%.

Materials - Computer, Vernier computer interface, LoggerPro, Vernier pH Sensor

electrode, 100-mL beaker, 2.0M HC2H3O2, distilled water, 100-mL volumetric flask,
pipets, pipet bulb, thermometer.

Procedure –
1. Wear a lab coat and safety glasses
2. Pour ~50 mL of distilled water into a clean 100-mL volumetric flask
3. Calculate the volume of 2.0M acetic acid needed to prepare 100 mL of acetic acid
solution at the assigned concentration. Show the calculations to the instructor before
making the solution.
4. Prepare the assigned solution using a pipet, pipet bulb and 100-mL volumetric flask.
5. Prepare the computer to monitor the pH by connecting the pH Sensor probe to the
computer interface. Prepare the computer for data collection by opening the file “27
Acid Dissociation Ka” from the Chemistry with Vernier folder of LoggerPro. The
meter window will display the live pH readings.
6. Determine the pH of the solution as follows:
a. Use about 40 mL of distilled water in a 100 mL beaker to rinse the pH Sensor.
b. Pour about 30 mL of your prepared solution into a clean 100 mL beaker and use it
to thoroughly rinse the sensor.
c. Dispose of the solution down the drain, and refill with 30 mL of solution. Swirl
the solution vigorously. (Note: Readings may drift without proper swirling!)
d. Record the measured pH reading. Record the temperature
e. When done, place the pH Sensor in distilled water.
7. Repeat step 6 to determine the pH of vinegar.
8. At the completion of experiment, rinse the pH Sensor and return it to the sensor
storage solution.
Data and Results
Table 1
Data and Calculations for Your Assigned Concentration
Assigned Concentration ______ M
Volume of 2.0 M acetic acid ______ mL
Measured pH ______
[H+]eq ______ M
-
[C2H3O2 ]eq ______ M
[H C2H3O2]eq ______ M
Ka calculation

Temperature ____ 0C Ka = _________

% ionization calculation

Is the assumption used valid? _____ % ionization = _________

Collect data from your classmates and complete Table 2. Include all results, even if more
than one group was assigned a concentration.
Table 2
Class Values of Assigned Concentrations, Measured pH, and Calculated Ka
Assigned Concentration of Measured [H+]eq (M) Calculated Ka
Acetic acid (M) pH
0.2

0.3

0.4

0.5

Average Ka =

Measured pH of vinegar
Find the molarity of the acetic acid in vinegar.
Show all calculations
Discussion Hints:
1. Discuss your results and compare it to the class average.
2. Fill in the following statement with: increases, decreases, or remains the same.
From Table 2, it can be seen that as the concentration increases:
pH _____________, [H+]eq ___________, and Ka _____________, within experimental
error.