Experiment 1: The Conductance of Strong and Weak Electrolytes

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.

The combined effects results in the Kolrausch’s Law:

Λm=Λ0-(A+BΛ0) √c (1)

Λm –molar conductivity; Λ0 –conductivity at infinite dilution; A&B –constants; c–concentration.

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:

Λm= α [(Λ0-(A+BΛ0) √ αc)] (2)

If α c is small then, Λm≈ α Λ0 and the equilibrium constant, K, becomes:

K= α 2c/1- α (3)

Combining equation (2) and (3) to form Oswald’s Dilution Law:

1/ Λm= Λm c/K Λ20 + 1/ Λ0

Procedure:

The lab was done as outlined in the lab manual.

Results:

Table 1: Conductivity of the strong electrolyte NaCl at varying dilutions

Solution Vol. of Conc. of Vol. of Conductivity Average

number stock used solution in conductivity Ascending Descending Conductivity
(mL) boiling tube water (µS) (µS) (µS)
(mM) (mL)
1 20 20.00 0 2350 2630 2355
2 20 16.00 5 1880 1878 1883
3 20 13.33 10 1561 1552 1556.5
4 10 10.00 10 1132 1171 1151.5
5 10 6.67 20 841 832 836.5
6 5 4.00 20 512 502 507
7 2 1.82 20 234 241 237.5

Mass of NaCl used = 0.1188g

Table 2: Conductivity of the weak electrolyte Mandelic acid at varying dilutions

Solution Volume of Conc. of Vol. of Conductivity Average

number stock used solution in conductivity Ascending Descending Conductivity
(mL) boiling tube water (µS) (µS) (µS)
(mM) (mL)
1 20 20.00 0 1028 1031 1029.5
2 20 16.00 5 920 906 913
3 20 13.33 10 829 824 826.5
4 10 10.00 10 700 698 699
5 10 6.67 20 525 511 518
6 5 4.00 20 419 416 417.5
7 2 1.82 20 278 276 277

Mass of Mandelic acid used = 0.3055g

Calculations:

Mass of Sodium Chloride For Solution

1000cm3 = 0.02moles NaCl
100cm3 = 0.02moles /1000cm3x 100cm
= 0.002 moles
Mr of NaCl = 58.44gmol-1
Mass of NaCl = 0.002mol x 58.44gmol-1
= 0.1169g

Mass of Mandelic Acid For Solution

1000cm3 = 0.02moles C8H8O3
100cm3 = 0.02moles /1000cm3x 100cm
= 0.002 moles
Mr of Mandelic Acid = 152.14gmol-1
Mass of Mandelic Acid Used = 0.002mol x 152.14gmol-1
= 0.3043g

Molar Conductivity,Λm = (G x K cell ) / c

= (2355 x10-6S x 1 cm-1) / 20 x 10-3 x 10-3 molcm-3
= 117.75 Scm2mol-1

From graph 1 Λo for NaCl is 135.6 Scm2mol-1

From graph 2 1/Λo = 0.0036Scm2mol-1
Λo = 1/0.0036Scm2mol-1
Λo = 277.8Scm2mol-1

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

Solution Conc. of Average Molar √c

number solution in Conductivity conductivity (mM)
boiling tube (µS) Λm
(mM) (Sm2mol-1)
1 20.00 2355 117.75 4.47
2 16.00 1883 117.69 4.00
3 13.33 1556.5 116.77 3.65
4 10.00 1151.5 115.15 3.16
5 6.67 836.5 125.41 2.58
6 4.00 507 126.75 2.00
7 1.82 237.5 130.49 1.35

Graph 1: Plot of Λm vs √c for NaCl

 Table 4: Data values required for graph of Graph of 1/Λm vs Λmc for Mandelic Acid

Solution Conc. of Average Molar 1/Λm ΛmC

number solution in Conductivity conductivity *10-4
boiling tube (µS) Λm
(mM) (Sm2mol-1)
1 20.00 1029.5 51.48 0.019 10.30
2 16.00 913 57.06 0.018 9.13
3 13.33 826.5 62.00 0.016 8.26
4 10.00 699 69.90 0.014 6.99
5 6.67 518 77.66 0.013 5.18
6 4.00 417.5 104.38 0.010 4.18
7 1.82 277 152.20 0.007 2.77

Graph 2: Plot of 1/Λm vs Λmc for Mandelic Acid

Questions:

The conductivity at infinite dilution is represented by Λo . After carrying out the

experiment and performing the relevant calculations Λo for NaCl was found to be 135.6
Scm2mol-1 , while Λo for Mandelic Acid was 333.3 Scm2mol-1 as ascertained from the
respective graphs. The Λo value of the weak electrolyte was more than that of the Λo
value strong electrolyte. From theory the value of the NaCl conductivity at infinite
dilution is 126.4Scm2mol -1. The experimental value obtained for NaCl was higher than
the theoretical value.
Regarding the values obtained for Mandelic Acid, Λ0 was found to be 383.6 Scm2mol-1
via the indirect method and 277.8 Scm2mol-1 via Graph 2. The difference in the two
values could be due to the fact that extrapolation is inaccurate for weak electrolytes. The
calculated equilibrium constant K for Mandelic Acid was found to be 8.64 x10-3 moldm-3
which was 8.242 x 10 -3 times the theoretical value of 3.98 x 10-4 moldm-3. In addition, K
was not the same due to non-ideality of the solution used.

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:

Using equation (2): Λm = α[(Λo – ( A + BΛo )√ αc)]

where Λm ≈ αΛo
αΛo= α[(Λo – (A + BΛo) √αc
= α(Λo - A√αc + BΛo) √αc)
αΛo= αΛo - αA√αc + αBΛo√αc)
αΛo + αA√αc = αΛo + αBΛo√αc

let A/B = K;
K = (α2 c) / (1- α)

3. Conductivity/ conductance is the ability of a material to conduct electric current. The

conductance, G, of a solution is the inverse of its resistance R: G = l/R, and with its units
in siemens, S. The principle by which instruments measure conductivity is simple-two
plates are placed in the sample, a potential is applied across the plates, and the current
that passes through the solution is measured.
For example when a conductivity meter/cell is being used to make a conductivity reading
the device should be calibrated with a standard solution before using. The meter usually
has a menu item that allows users to enter the calibration mode or a setting on the side
that you can adjust with a small screwdriver or tool. Place the probe in a solution with a
known conductivity value and temperature and set the meter to that conductivity. To test
the conductance of a solution, the handheld probe of the meter should be immersed in the
solution to be measured, the meter then applies voltage between two electrodes inside the
probe. Electrical resistance from the solution causes a drop in voltage, which is read by
the meter. The meter converts this reading to milli- or micromhos or milli- or
microSiemens per centimeter. This value indicates the total dissolved solids. Total
dissolved solids is the amount of solids that can pass through a glass-fiber filter. If the
user wishes to test additional solutions the handheld probe should dried with tissue
between each measurement.
Discussion and Conclusion:

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.