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2018
Experiment Number : 07
1. How to determine the solubility product of a sparingly soluble salt using conductometry.
2. How to perform a conductometric titration and use the results for calculation of
concentration of an unknown electrolyte.
Theory:
Conductance is simply the reciprocal of resistance and for a solution it depends on the number of
ions in solution and how mobile they are to make use of the change in conductance. Conductivity
(K) (or specific conductance) of an electrolyte solution is a measure of its ability to conduct
electricity. This is dependent on temperature. Cell constant (Kcell) is a function of the electrode
areas, the distance between the electrodes and the electrical field pattern between the electrodes.
It’s a parameter of the conductivity cell.
These 3 parameters are related by the following equation,
1
𝐺 = (𝐾 )𝐾
𝑐𝑒𝑙𝑙
Where; the cell constant, Kcell depends on the geometry of the conductivity cell and is defined by
𝑙
𝑘𝑐𝑒𝑙𝑙 = 𝑎 l = distance between the electrodes
A = area of the electrodes of the conductivity cell
As the conductivity of a solution depends on the temperature, the following equation summarizes
the variation of conductivity of a 0.1 mol dm-3 aqueous solution as a function of temperature, t,
around 20℃.
Κ = [1.167 – 0.024 (20 – t / ℃)] Sm-1
Conductivity of a solution is due to all the ions present in that solution. Therefore, for a pure
aqueous solution of an electrolyte,
Ksolution=Kelectrolyte+Kwater
Now, Consider a solution of a strong electrolyte of the form Av+ Bv- [e.g. AICl3, where ѵ+ = 1 and v-
= 3] which dissociates according to
+ → + + −
− + −
Neglecting the conductivity due to water, we can relate the conductivity of +, − to its
molar conductivity, , by
𝐾𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒
𝛬= 𝐶
Where C = molar concentration of the electrolyte in solution.
Molar conductivity of the electrolyte is related to the molar conductivities of the ions by
= + + --
Where and - are the molar conductivities of the cation and the anion. The highest ionic mobility
of a given ion at a given temperature in a given solvent is attained when the electrolyte
concentration goes to zero. This is called the ionic mobility at infinite dilution. This is because the
ionic mobility decreases with increasing concentration of ions in solution. Therefore, for a sparingly
soluble salt like PbSO4, the saturated solution is so dilute that the molar conductivity of the ions
may take to be equal to their respective values at infinite dilution.
The concentration of a sparingly soluble salt can be given by the following equation
𝐾
𝐶 = 𝜈 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒
𝜆0 +𝜈 𝜆0
+ + − −
At 25 we have
Conductance / mS Temperature / ℃
1. Κ = [1.167 – 0.024 (20 – t / ℃)] Sm-1 = [1.167 – 0.024 (20 –33.6/ ℃)] Sm-1
n = 1.4934 S m-1
1
2. 𝐺 = (𝐾 )𝐾
𝑐𝑒𝑙𝑙
1 1
𝐾𝑐𝑒𝑙𝑙 = (𝐺) 𝐾 = 13.89×10−3×1.4934Sm-1 =104.416m-1
4. Conductance of the CO2 free de-ionized water = 0.00272 mS at 29.4 Conductivity of free
CO2 de-ionized water = Kcell G
= 104.416 0.00272
= 0.28 × 10-3 S m-1
5. Ksolution=Kelectrolyte+Kwater
Kelectrolyte=Ksolution-Kwater
𝐾 0.004095𝑆𝑚−1
b. C =𝜈 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒 = (1×0.0138𝑆𝑚−2 𝑚𝑜𝑙−1 )+(1×0.0160𝑆𝑚−2 𝑚𝑜𝑙−1 ) = 0.137mol m-3
𝜆0 +𝜈 𝜆0
+ + − −
=0.000137mol dm-3
Strong Acid – Strong Base Weak Acid – Strong Base (Strong Acid + Weak Acid)
Titration
Volume of Titration – Strong Base Titration
NaOH Conductance of the Conductance of the Conductance of the
added/ cm3 Mixture / mS Mixture / mS Mixture / mS
0.00 3.30 0.176 3.69
21.00 1.678
22.00 1.726
23.00 1.807
24.00 1.952
25.00 2.15
26.00 2.30
27.00 2.45
28.00 3.58
29.00 3.72
30.00 3.85
3
Conductance / mS
2.5
1.5
0.5
0
0 5 10 15 20 25
volume of NaOH cm3
Conductance / mS 1.5
0.5
0
0 5 10 15 20 25
volume of NaOH
NaOH: CH3COOH
1 : 1
3
2.5
2
1.5
1
0.5
0
0 5 10 15 20 25 30 35
Volume of NaOH
Volume of base added at the end point of HCl = 10 cm3
NaOH: HCl
1 : 1
NaOH: CH3COOH
1 : 1
1.0×10−3
Therefore, % of HCl in the mixture = 2.7×10−3×100 %
= 37.037 %
1.7×10−3
Therefore, % of CH3COOH in the mixture = = 2.7×10−3×100 %
= 62.96 %
1. About 100 mL of water was added in to the conductivity cell to make sure that the probe is
properly immersed in the solution.
3. Carbonic acid which can also contribute to the conductance if we do not remove CO 2. The ions
produced due to the weak dissociation of carbonic acid boost the conductivity readings, thus
giving rise to errors. Therefore we boil the water to liberate the dissolved CO2.
4. In titrations when use an indicator, it is difficult to identify the end point but in conductometric
titrations gives a direct end point and it is easily identify.
5. We should make sure all solutions are made by deionized water if not other ions dissolved in the
water will contribute to the conductance.
The conductometer must be calibrated accurately. If not it will cause errors in the conductance
measurements.
Discussion:
The conductivity of an electrolyte in a solution is defined as the sum of conductivities of the ions
produced by that electrolyte in that solution. The conductivity of an ionic species depend on the
ionic mobility, the molar charge and the molar concentration. The ionic mobility in turns depends
on the total electrolyte concentration in solution, the temperature and the solvent.
Conductometric determination of an endpoint of a reaction is fast, precise and easy than a normal
titration method because there is no colour change to detect. We can directly get the endpoint
using the change of the conductance. However, a disadvantage of the technique is that it cannot be
used when the solution contains high concentration of ions other than those to be determined.
The conductivity cell changes due to the change in the composition due to the reaction and the
dilution brought about by the added volume of titrant. The conductance of a solution varies with
the concentration.
Therefore dilution reduces the number of ions present and it decreases the conductance. When
considering the hydrogen and hydroxyl ions, we see their ionic mobilities are very much higher at
infinite dilution in aqueous solution compared to any other ionic species. Here the hydrogen ion
jumps from a hydronium ion to a neighboring water molecule. In the same way a hydrogen ion can
jump from a water molecule to a neighboring hydroxyl ion. These two processes are fast enough to
give high ionic mobilities to hydrogen and hydroxyl ions.
In this experiment we have to use infinite solutions this could be a difficult task and this can create
an error and the temperature fluctuations also can be an error in this experiment. It is to be noted
that conductometric titration is seldom used for the titration involving redox reaction. In redox
titration, besides active reactant there is a presence of large excess of electrolytes e.g. acids and the
change in conductance during titration is often low, and the location of end point becomes difficult.
A very weak acid where other method of titration fails can be successfully titrated by conductometric
method. Moreover, very dilute solution can be titrated by conductometric method.
A mixture of weak and strong acids can be analyzed by a single titration. No need to take special
precaution as the end point approaches since the end point is located by utilizing the titration
readings of several observations graphically. Owing to this more accurate and reliable result
can be obtained by conductometric method.
Experiment 7
Determination of end point of a
Titration and Solubility Product of a
Sparingly soluble salt using Conductometry
S.H.M.C.S.Herath
164517
BP25
Experiment 16
Measurement of Transport Numbers by Hittorf
Methods
S.H.M.C.S.Herath
164517
14.05.2018