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Introduction:
Electrolytes are substances which break up into cations and anions when dissolved in water. This process
is known as ionization. The degree to which the electrolytes ionize categorizes them as strong or weak.
Strong electrolytes ionize 100% in solution. That is, the compound exists in water only as individual ions
and there are no intact molecules at all. Due to the nature and presence of these two oppositely charged
ions, the molar conductivity of the strong electrolyte is inversely proportional to the concentration of the
solution. The inverse relation is a result of the asymmetric effect and the electrophoretic effect.
Λm=Λ0-(A+BΛ0) √c (1)
Weak electrolytes ionize partially in solution. That is, the compound exists in water as a mixture of
individual ions and intact molecules. At a degree of ionization α , the Kolrausch’s Law becomes:
K= α 2c/1- α (3)
Procedure:
Gradient = 1/KΛo
1/K(277.8)2 = 0.0015
K = 8.64 x 10-3 moldm-3
Indirect Method:
NaCl Λ0 = 126.4 Scm2mol-1
HCl Λ0 = 426.0 Scm2mol-1
Sodium Mandelate Λ0 = 84.0 Scm2mol-1
Λ0Mandelic Acid = Λ0 HCl +Λ0Sodium Mandelate - Λ0NaCl
Λ0Mandelic Acid = 426.0 + 84.0 – 126.4 (Scm2mol-1)
= 383.6 Scm2mol-1
Table 3: Data values required for graph of Λm vs √c for NaCl
1. Looking at the data given with respect to the cations of Group 1 of the periodic table, the
H+ ion has a highest conductivity value. This due to the hydrogen ion approaching the
H2O molecule to form a hydrogen bond. As the ion gets closer to the H2O an actual
covalent bond forms, which in turn causes the water molecule to release another
hydrogen ion. This process called the proton switch mechanism continues onward and is
carried out quite quickly, thereby leading to hydrogen cation having a high conductivity
value.
With the other cations, as on descends down the group, the size of the ion increases by
one shell, and all they all contain a single positive charge that remains unchanged. Both
these factors affect the charge density, therein causing it to decrease as you descend down
the group. This decrease in charge density and decrease in the value of frictional force
and increases the ability of the ion to conduct an electrical charge within an infinite dilute
solution, i.e. ions are able to move more easily as the group is descended.
For the anions, the hydroxide ion can attract an H+ ion from H2O molecules, forming
another hydroxide ion. By doing this hydroxide ion causes an increase in the
conductivity of the hydroxide ion in an infinitely dilute solution. Looking at the other
halide ions in this group the conductivity is seen to increase down the group but at values
less than those of the Group 1 cations as the nucleus has less control of the outer
electrons of these negative ions. This lack of control of the outer electrons reduces the
ability of the ions to conduct electricity. Consequently the increase in conductivity down
the group is a great deal smaller than that of the group 1 metals because as an outer
electron is lost the nucleus still has control of the other electrons.
2. The cell constant can be determined by measuring the conductance when the cell is filled
with a solution whose conductivity is accurately known or alternatively by comparing the
measured conductance with that obtained from a cell of known cell constant when both
cells contain the same solution (i.e. potassium chloride) at the same temperature.
Bearing the above in mind the following equation can be employed to determine the cell
constant of a conductivity cell:
let A/B = K;
K = (α2 c) / (1- α)
The conductivity of the strong electrolyte NaCl was found to be 135.6 Scm2mol-1, which is larger
than the theoretical value of 126.4 Scm2 mol-1 mainly due to experimental errors. This may have
been a result of unclean apparatus which may have contained ions which contributed to the
conductivity of the solution, parallax errors when making up the different concentrations to
measure the conductance, as well as graphical errors due to extrapolation.
The conductivity of the weak electrolyte was found to be 277.8 S cm2 mol-1 using Graph 2, which
is higher than the value obtained using the indirect method (383.6 S cm 2 mol-1). The indirect
method is more accurate since the value of Λ0 is closer to the theoretical value of 397 S cm2 mol-
1
. The calculated equilibrium constant K for Mandelic Acid (8.64 x 10-3 moldm-3).
Depending on the concentration of the dilute solutions the molar conductivity varied. This is due
to the fact that in solution there are varying amounts of free ions which isn’t proportionally equal
to concentration. For it is seen that for a weak electrolyte doubling the concentration does not
result in a doubling of the number of free ions. Also, because strong interactions between ions,
the conductivity does not relate directly to the number of ions present.
For strong electrolytes the molar conductivity is slightly dependant on the concentration whereas
for weak electrolytes the molar conductivities is at its maximum when the concentrations are
close to zero and falls as the concentration increases.
At infinite dilutions the distance between ions are relatively large that the only effect of an
applied electric field is on the individual ions whereas at high concentrations each ion is fairly
surrounded by other ions and the effect of the electric field is on ion groups. Due to size and
charge on ions their ability to aid in conductivity will vary; large ions will offer greater resistivity
while smaller ones won’t.
During the experiment it is very important that the dilutions are made up to accurate amounts and
concentrations, so the use of auto pipettes would have greatly reduce precision errors. Bearing
the former in mind and noting that pipette fillers were used one should remember to get at eye
level when filling the pipette to the appropriate mark and always remember to use de-ionized
water. One should also ensure to blot the conductivity probe dry before the next measurement to
avoid water droplets and diluting or contaminating the next sample to be tested. Ensure to
submerge the probe into the liquid being measured.