CHEM 3420 EXPERIMENT 5

Conductometric Titration of Hydrochloric Acid and

Acetic Acid with Sodium Hydroxide

Conductance (G) is the reciprocal of electrical resistance (R).

G = 1/R

It is a measure of the ability of a solution to conduct electricity. The conductance

of a solution is the sum of the conductances of all of the ions that are in the
solution.

G = ΣG i

The conductance of a particular ion in solution depends upon the concentration of

the ion, the charge on the ion, and the size of the ion. As the concentration or the
charge of the ion increases, the conductance of the solution increases. In general
as the size of the solvated ion decreases, its mobility through the solution
increases and consequently the conductance of the solution increases. In water
the ion which has the greatest conductance is H+. Of the common, negative ions,
OH– has the greatest conductance. The relative conductances (relative to acetate)
of the species that are involved in the experiment are listed in the table.
Molecular species (uncharged substances) do not contribute to the conductance of
a solution.

Relative conductances of the species which are involved in the experiment.

Species Relative conductance

H+ 8.5
OH– 4.8
Cl – 1.9
Na + 1.2
C2H3O2– 1.0
HC2H3O2 0
H2O 0
CHEM 3420 EXPERIMENT 5

During the titration of hydrochloric acid with sodium hydroxide, the reaction that
takes place in the titration vessel is

Na + OH–
H+ + Cl– > H2O + Cl– + Na +

Before the end point, H + is removed from the solution by reaction with OH– , and
Na + is added to the solution. Since the relative conductance of H+ is about seven
times that of Na +, the conductance of the solution decreases prior to the end point.
After the end point, no H+ is available to react, and the conductance of the solution
increases as a result of the addition of Na+ and OH– . Consequently the titration
curve has a V-shape as shown in the figure. The end point of the titration
corresponds to the intersection of the extrapolated linear portions of the titration
curve.

Diagrams of the conductometric titration curves. A, the titration of HCl with

NaOH; B, the titration of HC2H3O2 with NaOH. The slight decrease in
conductance at the start of the acetic acid titration is due to suppression of the acid
dissociation by the common-ion effect.

Since acetic acid is dissociated slightly (Ka = 1.8 x 10– 5) in aqueous solution, the
conductance of the acetic acid solution is initially small. As sodium hydroxide is
added, the hydroxide reacts with the acid to form water and acetate.
HC2H3O2 > H2O + Na+ + C 2H3O2–

H+ + C 2H3O2–
CHEM 3420 EXPERIMENT 5

The addition of C2H3O2– and Na+ to the solution causes the conductance of the
solution to increase. After the end point, Na+ and OH– are added to the solution.
Since the relative conductance of OH– is nearly five times that of C H O – , the
2 3 2
conductance of the solution after the end point increases more rapidly than it did
before the end point. The end point corresponds to the intersection of the
extrapolated linear portions of the curve.

Conductance is usually measured with an alternating current between two

identical, platinized platinum electrodes. Use of an alternating current prevents
the buildup of reaction products around either electrode and consequently
prevents polarization of the solution. The electrodes must be rigidly held at a fixed
distance apart during the titrations in order to prevent changes in conductance
that result from an altered solution volume between the electrodes.

Reference

R.D. Braun, “Introduction to Chemical Analysis”, McGraw-Hill, New York, 1982,

pp. 329-335.

Procedure

1. Dry the potassium hydrogen phthalate in a 110°C oven for at least 1 hour.
After the drying period remove the compound from the oven and allow it to
cool to room temperature in a desiccator.

2. Add about 6 mL of 50% sodium hydroxide solution to a 1 L volumetric flask.

Dilute the solution to near the mark with distilled or deionized water. The
resulting solution contains 0.1 M sodium hydroxide.

3. Weigh to the nearest 0.1 mg, between 0.7 and 0.9 g of the cooled potassium
hydrogen phthalate into each of three, labeled, 250 mL Erlenmeyer flasks.
Record the mass of the solid that is in each flask.

4. Add 30 mL of distilled or deionized water and two drops of phenolphthalein

solution to each flask. Fill the 50 mL buret with the sodium hydroxide
solution. Titrate the solution which is in each Erlenmeyer flask to the end
CHEM 3420 EXPERIMENT 5

point with the sodium hydroxide solution. The end point color change is
from colorless to light pink. Record the three endpoint volumes to the nearest
0.01 mL.

5. Obtain at least 35 mL of an acetic acid solution and at least 35 mL of a

hydrochloric acid solution from the instructor. Record the sample numbers.

6. Use a pipet to add 10 mL of the hydrochloric acid solution to the 250 mL, tall-
form beaker. Add about 140 mL of distilled or deionized water and a stirring
bar to the beaker. Place the beaker on a magnetic stirrer. Use a clamp to
suspend the electrodes in the solution. The platinum electrodes must be
completely submerged in the solution, but they should not interfere with
operation of the stirring bar. Adjust the stirring rate to yield a smoothly
stirred solution.

7. Refill the buret with sodium hydroxide solution. Measure the initial
conductance of the stirred solution. Add 1 mL portions of the sodium
hydroxide solution to the stirred solution. Record the conductance of the
titrand solution and the total volume (to the nearest 0.01 mL) of the added
titrant solution after each addition. Continue the titration until the end point
has been passed by 100%, i.e., until a total volume that is twice the endpoint
volume has been added.

8. Similarly dilute and titrate two, more 10 mL portions of the hydrochloric acid
solution, and three, 10 mL portions of the acetic acid solution.

9. After the titrations have been completed, store the electrodes in water.

Calculations

1. Use the mass of potassium hydrogen phthalate (MW 204.23) that was in each
flask and the corresponding endpoint volume of the sodium hydroxide
solution to calculate three values of the concentration (M) of the sodium
hydroxide solution. Determine the mean concentration and the standard
deviation of the results.
CHEM 3420 EXPERIMENT 5

2. For each conductometric titration, plot conductance (y axis) as a function of

the volume of the added sodium hydroxide solution. Draw a straight line
through each of the two, linear portions in each titration curve. Determine
the endpoint volume of each titration from the intersection of the two straight
lines.

3. Use the endpoint volumes and the mean sodium hydroxide concentration to
calculate three values of the concentration of the original hydrocholoric acid
solution and three values of the concentration of the original acetic acid
solution.

4. Determine the mean hydrochloric acid concentration and the standard

deviation of the results. Determine the mean acetic acid concentration and
the standard deviation of the results.