EXP 3: DETERMINATION OF THE ACID DISSOCIATION CONSTANT OF ACETIC

ACID FROM CONDUCTIVITY MEASUREMENTS

Discussion

Slovacek 1998

Conductance readiness of materials to carry a current

Electrolytic conductors liquids which carry currents
Conductance of a liquid can be defined by its electrical properties:
the ratio of current to voltage between any two points within the liquid
[Meanwhile] Specific conductance or conductivity is a standard measure
that defines the physical parameters of a measurement (Slovacek 1998).

Conductivity is obtained by getting the reciprocal of the resistance in ohms

(Slovacek 1998).

LANCASHIRE 2002
Molar Conductivity and Concentration
The experimentally measured conductance, G, of a solution is that of a certain volume of the solution
contained between the electrodes of the conductivity cell. (These electrodes are the thin metal plates that
can be seen on the inside of the cell, and must be completely covered during measurements). The meter
actually measures the resistance, R, of the solution between the electrodes and converts it to conductance.
G=1/R
In order to use this quantity to compare different solutions we introduce another quantity called specific
conductivity, k and
k = G x cell constant
where the cell constant is a quantity describing the geometry of the cell and
cell constant = l/A
where l is the distance between the electrodes and A is the common electrode area (or the area of one
electrode if both have the same area). The cell constant is not found by measuring distances but is
determined by measuring the conductance of an electrolyte whose specific conductivity is already known.
The molar conductivity,
m = / c
w here c is the molar concentration.
Kohlrausch found an empirical expression for the molar conductivity as
m = mo - k c
where mo is the molar conductivity at infinite dilution and 'k' is a constant whose value depends on the
type of electrolyte used (i.e. MA, M2A, MA2, etc.). The refined, Debye-Onsager theory gives essentially
the same result.
2. Dissociation Constant
Consider the dissociation of acetic acid (a weak acid),
HOAc

(1 - )c

H2O

<=>

H3O+
c

OAc-

(OAc-

= acetate ion)

where is the degree of dissociation and c is the initial concentration of the acid before dissociation. The
dissociation constant, K, is given by

K = 2c / (1- )
If this equation is solved for , and is expressed as the ratio m / mo we get the following equation
1 / m = 1 / mo + c m/ K(mo)2
which is known as the Ostwalds dilution law, and we can see that, from a plot of 1 / m against cm, the
values of mo and K can be obtained from the intercept and slope respectively. Molar Conductivity and
Concentration
The experimentally measured conductance, G, of a solution is that of a certain volume of the solution
contained between the electrodes of the conductivity cell. (These electrodes are the thin metal plates that
can be seen on the inside of the cell, and must be completely covered during measurements). The meter
actually measures the resistance, R, of the solution between the electrodes and converts it to conductance.
G=1/R
In order to use this quantity to compare different solutions we introduce another quantity called specific
conductivity, k and
k = G x cell constant
where the cell constant is a quantity describing the geometry of the cell and
cell constant = l/A
where l is the distance between the electrodes and A is the common electrode area (or the area of one
electrode if both have the same area). The cell constant is not found by measuring distances but is
determined by measuring the conductance of an electrolyte whose specific conductivity is already known.
The molar conductivity,
m = / c
w here c is the molar concentration.
Kohlrausch found an empirical expression for the molar conductivity as
m = mo - k c
where mo is the molar conductivity at infinite dilution and 'k' is a constant whose value depends on the
type of electrolyte used (i.e. MA, M2A, MA2, etc.). The refined, Debye-Onsager theory gives essentially
the same result.
2. Dissociation Constant
Consider the dissociation of acetic acid (a weak acid),
HOAc

(1 - )c

H2O

<=>

H3O+
c

OAcc

(OAc-

= acetate ion)

where is the degree of dissociation and c is the initial concentration of the acid before dissociation. The
dissociation constant, K, is given by
K = 2c / (1- )
If this equation is solved for , and is expressed as the ratio m / mo we get the following equation
1 / m = 1 / mo + c m/ K(mo)2
which is known as the Ostwalds dilution law, and we can see that, from a plot of 1 / m against cm, the
values of mo and K can be obtained from the intercept and slope respectively.

Guide Questions:
1. Why is KCl used to determine the cell constant of the conductivity meter?

2. Can we directly use Kohlrauschs law (instead of Ostwalds dilution law) to

determine the dissociation constant of acetic acid? Why or why not?

3. Compare the limiting molar conductivities and the acid dissociation constant with
literature values. Explain possible sources of errors and their effect on the
calculated parameters.

4. Discuss some other applications of conductivity measurements, especially in

determinations of equilibrium constants.

References
Lancashire R [Internet]. 2002. Experiment 19: Conductivities of Electrolyte
Solutions. Mona Campus, Kingston 7, Jamaica. [cited 2015 Aug 28]. Retrieved from
http://wwwchem.uwimona.edu.jm/lab_manuals/c10expt19.html.

Radiometer Analytical SAS. 2004. Conductivity: Theory and Practice. Villeurbanne

Cedex, France.
Shreiner RH and Pratt KW. 2004. Standard Reference Materials: Primary Standards
and Standard Reference Materials for Electrolytic Conductivity, 2004 ed. NIST
Special Publication 260-142: Gaithersburg, MD.
Slovacek D. 1998. Measurement of Conductivity. Hach Company. Loveland, CO.