Experiment No 9: DETERMINATION OF DEGREE OF DISSOCIATION ANDDISSOCIATION

CONSTANT OF ACETIC ACID BY CONDUCTOMETRIC METHOD

Objectives:

 To determine the dissociation constant of acetic acid by conductometric method

 To measure the conductivity (mS/cm2) of acetic at different concentrations
 To determine the degree constant k from the degree of dissociation α

Glassware/Apparatus:

 Conductometer
 Pipette
 Volumetric flask
 Beakers

Chemicals:

 Acetic acid
 Distilled water

Scope/Rationale:

The study of the conductivity of electrolyte solutions is important for the

development of electrochemical devices, for the characterization of the dissociation
equilibrium of weak electrolytes and for the fundamental understanding of charge
transport by ions.

Theoretical Explanation:

Typically, the conductivity of electrolyte solutions is measured for electrolyte

solutions with concentrations in the range of 10 -3 to 10-1 mol L-1, as solutions in this
range of concentrations can be easily prepared. The molar conductivity (Λ m) of strong
electrolyte solutions can be nicely fit by the Kohlrausch equation,

Λm = Λmᴏ - K √c (1)

Where, m is the molar conductivity at infinite dilution and c is the concentration of the
solution. K is an empirical proportionality constant to be obtained from the experiment.

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The molar conductivity of weak electrolytes, on the other hand, is dependent on the
degree of dissociation of the electrolyte. At the limit of very dilute solutions, the Ostwald
dilution law is expected to be followed,

1 1 Λm CA
= o
+ (2)
Λm Λm (Λom)2 Kd

Where, CA is the analytical concentration of the electrolyte and Kd is the dissociation

constant.
The molar conductivity at infinite dilution can be decomposed into the contributions of
each ion,
Λ mᴏ = v + λ + - v - λ - (3)

Where, λ+ and λ– are the ionic conductivities of the positive and negative ions,
respectively, and ν+ and ν– are their stoichiometric coefficients in the salt molecular
formula. From the concentration dependence of the molar conductivity of each salt, it
is possible to obtain the molar conductivities at infinite dilution through Equation 1.

The molar conductivity of strong electrolytes is expected to follow the

Kohlrausch law (Equation 1). For sufficiently dilute solutions, however, Λ mᴏ >> K √c,
and thus the molar conductivity is expected to be approximately constant and equal to
the molar conductivity at infinite dilution Λm ≈ Λmᴏ. In other words, since к = Λmc, if one
plots the conductivity κ as a function of the concentration, a linear correlation with slope
Λmᴏ is expected.

Conductance of solution depends upon ions in the solution when water is added to
acetic acid, it dissociates into ions
CH3COOH ↔ CH3COO− + H+

[CH3COO−] + [H+]
K= = 1.8 × 10−5 at 25°C
[CH3COOH]

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The conductivity of the solution increases with increase in temperature of
solution. And as concentration of ions increase the conductance also increases.
In this experiment, we calculated the conductivity of different concentrations of
acetic acid and calculated the degree of dissociation and equilibrium constant.
The movement of ions through its solution to electrodes is known as conductance.

When electrodes are placed in a solution, the cations are attracted to the negatively-
charged cathode while the anions move towards the positively-charged anode. This
conductance may be affected by changes in ionic concentration and differs between
compounds.

For a strong electrolyte, there is complete dissociation into mobile ions. At infinite
dilution, the distance between neighboring ions is significant; therefore, only the effect
of the applied electric field is experienced by individual ions. However, in a
concentrated solution, each ion is surrounded by other ions. The ions are close enough
to be influenced by both the electric field applied by the electrodes as well asthat by
their surrounding ions.

Principle:

Basic principle is the change in conductivity of a solution when no. of ions that are
responsible for conduction of electricity are changing.

Procedure:

1. Prepare a stock solution of 0.1 M acetic acid in 250 ml Volumetric flask.

2. Dilute the solution with distilled water to get the following concentrations: 0.001,
0.002, 0.003, 0.004 and 0.005 M concentrations by dilution formula.
M1V1 = M2V2
3. Fill the beaker with distilled water and measure its conductivity.
4. Check the conductivity of each solution with the help of conductometer.
5. Calculate the equivalent conductance as
 = L × 10-3/ C
Where, L is conductivity in micro-S/cm2

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6. Determine the degree of Degree of dissociation can be calculated as, where the
value of Λo is 383.5 µScm-2/mol
α = Λ /Λo
7. The apparent rate constant for dissociation is given as under:
K= α2C / (1 – α)
Observations and Calculations:

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 Table 1: Concentration and conductivity measurements.

S/No [CH3COOH] Recorded Conductivity

( ) ( )
1
2
3
4
5
6

Results and discussion:

Table 2: parameters for calculation of degree of dissociation and rate constant

conc/ Conductivity/ Equivalent Degree of k= α2C / (1 –α)
( )
( ) Conductance/ dissociation
( ) (α)

Average k =

Where Degree of dissociation, α = Λ /Λo

Plot a graph between degree of dissociation constant vs concentration.

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Conclusion:

Precautions:
 To prepare the various concentrations of solutions, successive dilutions were
carried out carefully. This must be done with utmost precision:
 After the preparation of the solutions, conductivity measurements are carried
out with a dip cell. When not in use, the dip cell is placed in a beaker filled
with deionized water to ensure it is reasonably stowed.
 Prior to each measurement, the electrodes on the dip cell are rinsed a few
times with a dropper containing the solution to be tested. This displaces any
residual ions that may be on it. For the same reason, the beaker is also rinsed
several times with the solution for which conductance is to be measured.
 Temperature during the experiment should be kept constant as conductance
depends on temperature.
 Stirring should be done after each addition of titrant.

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