Determination of the dissociation constant and molar conductivity at infinite dilution of a

weak acid
Physical Chemistry Report

Introduction

Conductivity is a measure of electrical conduction; it can be measured by using a conductivity

cell. A solution is able to conduct electricity due to the presence of ions. The behavior of the ions
in a solution is studied by applying an alternating voltage to one of the conductivity electrodes.
This causes the ions in the solution to move towards the electrodes. The dip type conductance
cell used consists of two platinum electrodes and the meter measures the conductance of the
volume of solution between the electrodes. The unit of measurement for conductivity is Siemens
(S). Since the electrode geometry varies, G will differ for different cells. Therefore, a cell
constant is calculated to compensate for variations in electrode dimensions.

A pH meter can be used to measure the pH change during a titration, these readings enable us to
plot a graph. Where the equivalence point can be determined accurately from the pH curve.
Additionally, the dissociation constant Ka can be determined from the half neutralization point of
the solution where the concentration of acid is equal to the concentration of salt. This point is the
pKa which is equal to pH. Using the Ka and the concentration calculated from the pH curve, the
molar conductivity of a weak acid can be calculated from a straight line graph that can be plotted
in order to find ❑∞. Extrapolation of the molar conductivities to infinite dilution enables the
analysis of ionic conductivities. The preparation of the dilute solutions could lead to inadequate
readings, due to small electrolyte contaminations which in turn can dominate the conductivity of
the solutions.

Experimental
Apparatus and Chemicals

 Conductance meter
 dip type cell
 150 cm3 narrow tall beakers
 100 cm3 volumetric flasks or 50 cm3 volumetric flasks
 10 cm3 pipette
 bulb pipette filler
 conical flask
 burette
 clamp and stand
 distilled water
 magnetic stirrer

1
  stirrer bar
 KCl solution (0.100 mol dm–3)
 distilled water
 NaOH (0.10 mol dm–3)
 pH = 4 and 7 buffer solutions
 solution of unknown weak acid.

Material name Hazard statement Precautionary Disposal

statement

Sodium Hydroxide Causes severe skin Wear protective gloves, Liquid- down the sink
burns and eye damage protective clothes, eye with plenty of water
protection, face
protection
If in eyes: rinse
cautiously with water
for several minutes.
Hydrochloric Acid Maybe corrosive to Liquid- down the sink
metals with plenty of water
Ethanoic Acid Not a hazardous Not a hazardous Liquid- down the sink
substance substance with plenty of water
Unknown Weak acid Toxic if swallowed Wear protective gloves, Liquid- aqueous waste
Toxic in contact with protective clothes, eye
skin protection, face
Causes severe skin protection
burns and eye damage
May cause respiratory
irritation
Very toxic to aquatic
life
If in eyes: rinse
cautiously with water
for several minutes.

If swallowed:
Immediately call poison
center.
Potassium Chloride Not a hazardous Not a hazardous Liquid- down the sink
substance substance with plenty of water

2
Identify the hazard of the work Identify the risks arising from the work
Breakage of glass- graduated flasks/ beakers Cuts/injection of substances from glass fragments

Use of the hazardous substances- corrosive Skin irritation/ eye damage; Fire
acids/bases, flammable liquids (ethyl ethanoate)

Electrical equipment (magnetic stirrer plates, PH Electrocution

meters and conductance meters)

Method

To determine the concentration and the dissociation constant of the unknown acid solution-

1. pH calibration procedure. Before beginning ensure the temperature reading of the pH

meter is adjusted to room temperature. Begin by placing around 30 cm3 of the pH 7
buffer solution into a beaker. Immerse the tip of the pH probe in the solution, and adjust
the control knob on the pH meter to get a reading of exactly 7.0.
1. Rinse the pH probe thoroughly in distilled water to prevent any contamination. Proceed
to immerse the pH probe in pH 4 buffer solution and adjust the control knob on the pH
meter to get a reading of exactly 4.0.
2. Repeat these processes while ensuring to wash the pH probe thoroughly each time, until
the pH meter reads exactly 7.0 in the pH 7 buffer and 4.0 in the pH 4 buffer solution.

1.
Accurately pipette 25 cm3 of the unknown acid solution and place it into a beaker. Drop a
magnetic stirrer into the solution and place the beaker on top of a magnetic stirrer to
ensure the solution is being stirred evenly.
2. Pour the standard sodium hydroxide solution (0.10 mol dm–3) into a burette. Next align
the beaker under the burette, and carefully place the pH probe into the solution.
3. Titrate and record the pH after the addition of each 2.0 cm3 aliquot of NaOH and stop at
20.0 cm3. In the equivalence point range, from 20.0 cm3-30.0 cm3, record the pH after
each addition of each 0.5 cm3aliquot of NaOH. From 30.0 cm3 onwards continue to take
pH readings after the addition of each 2.0 cm3 aliquot of NaOH until reaching the final
volume of 40.0 cm3.

To determine the cell constant of the dip type conductivity cell-

1. Fill a beaker about halfway with a solution of KCl (0.1 mol dm- 3), and immerse the dip
type cell in this solution. Ensure it is fully immersed by using the black line as a guide,
and ensure there are no trapped air bubbles. Measure the conductance (G) of this solution

3
 at room temperature. The reading must be obtained to three significant figures.
2. Repeat this process, in order to have two conductance readings.

To determine the molar conductivity at infinite dilution for the unknown acid-

1. Prepare ten 150 cm3 narrow tall beakers holding dilute solutions of the unknown acid at
the concentration of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, and 0.1 M.

2. Determine the conductance of each of these solutions by immersing the cell into each of
these solutions. Ensuring to rinse the cell thoroughly using distilled water after each
reading, in order to prevent contamination.

3. Record two conductance readings for each solution.

Results

pH Titration Curve
14.00

12.00

10.00

8.00
pH

6.00

4.00

2.00

0.00
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0

Vol NaOH / cm3

1. Concentration and the dissociation constant of the unknown acid solution.

Figure 1. pH titration graph

4
pH=pKa

pKa= -log Ka

Ka=10−pKa

pH at half equivalence point= 2.57

Dissociation constant Ka= 10−2.57 = 2.69 ×10−3

Concentration of the unknown acid solution:

Cb ×V b 0.10 ×25
C a= = = 0.1 mol dm−3
Va 25

2. The cell constant of the dip type conductivity cell.

Reading 1 K (0.1 M KCl) = 16.19 mS

Reading 2 K (0.1 M KCl) = 16.27 mS
Average(G) 16.23 mS Table 1. cell constant data

Conductivity (K) of 0.100 mol dm- 3 KCl= 1.29 S m-1

Cell constant = K/G

1.29
= −3
=79.4824 m−1
16.23× 10

= 79.5 m−1

5
 Concentration of Reading 1 G Reading 2 G Average G k λ 1
2
unknown acid ( (mS) (mS) (S) ( Sm−1) ( Sm mol−1) λ2
mol dm−3 ) ( Sm2 mol−1

0.01 0.161 0.164 1.65 ×10−4 0.0131 1.31 0.583

0.02 0.233 0.231 2.32 ×10−4 0.0184 0.920 1.181
0.03 0.284 0.278 2.81 ×10−4 0.0223 0.743 1.811
0.04 0.330 0.338 3.34 ×10−4 0.0226 0.665 2.261
0.05 0.369 0.365 3.67 ×10−4 0.0292 0.584 2.932
0.06 0.411 0.391 4.01 ×10−4 0.0319 0.532 3.533
0.07 0.447 0.429 4.38 × 10−4 0.0348 0.497 4.048
0.08 0.475 0.479 4.77 × 10−4 0.0379 0.474 4.451
0.09 0.501 0.503 5.02 ×10− 4 0.0399 0.443 5.096
0.10 0.515 0.523 5.19 ×10−4 0.0413 0.413 5.863

3. The molar conductivity at infinite dilution for the unknown acid.

Table 3. Data for Molar conductivity

0.12
Concentration of uknown acid (mol dm-3)

0.1

0.08

0.06

0.04

0.02

0
0 1 2 3 4 5 6 7

1 / ^2 (Sm2mol-1 )

Figure 2.

6
 2
❑
Ka = c ( )
❑∞

1
C = Ka ❑∞ 2  2
❑

Gradient (m) = Ka ❑∞ 2 = 0.017056

Gradient
❑∞ =
√ Ka

0.017
❑∞ =
√ 2.69 ×10−3
= 2.518

=2.52 Sm2mol-1

Conclusion

The value of the Ka was found to be 2.69 ×10−3 this value is small indicating that the acid only
partially dissociates which is expected from a weak acid. Weak electrolytes have lower molar
conductivity.