Date : 11.06.

2018

Experiment Number : 07

Experiment Title : Determination of End Point of a Titration and Solubility Product of a

Sparingly soluble salt using Conductometry.
Objectives:

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

= 1.39 10-2 Sm2 mol- Sm2 mol-1

Limiting molar conductivity of an ion increases by approximately 2% per 1 degree rise in
temperature.
Solubility product of + − is defined by
Ksp = [ + +[ −] -=( + C) + ( - C) - 𝐾𝑠𝑝 = [𝐴𝑧+ ]𝜈+ [𝐵 𝑧− ]𝜈− = (𝜈+ 𝐶)𝜈+ (𝜈− 𝐶)𝜈−
Procedure :

• Determination of cell constant

A 0.01 M KCl solution was prepared in a 100.0 cm3 of volumetric flask using distilled water. A
volume of about 100 mL of the 0.1 M KCl solution was transferred in to the conductivity cell, and
the conductance was recorded. The temperature of the KCl solution was recorded.
• Determination of the Solubility product of Lead Sulphate at Room Temperature
Two beakers containing de-ionized water were boiled to remove CO2 and then was left to cool. A
small amount of lead Sulphate was placed in a large conical flask. It was shaken with about 100
cm3 of warm CO2 free de-ionized water for 3 times. After each shaking, it was left for some time
and after a while the water was decanted to remove soluble impurities. About 250 cm3 of the
CO2 free distilled de-ionized was added to the lead sulphate and the flask was closed with a
watch glass to prevent CO2 dissolving. It was allowed to stand for about ½ an hour to ensure
saturation at room temperature. The mixture was swirled in every 10 minutes during this period.
A volume of about 10 cm3 of the saturated solution was filtered in to a 250 mL conical flask using
a funnel and filter paper. The filtrate was swirled and then discarded. The remainder of the
solution was continued filtering without disturbing the solution. A beaker was washed with de-
ionized and with about 10 cm3 of filtrate. About 100 cm3 of the filtrate was poured in to this
beaker and the conductance and temperature were measured. The last step was repeated using
a fresh sample of the same solution. Next the conductivity cell was filled with CO 2 free de-ionized
water and the conductance was measured.
• Titration of a Strong Acid with a Strong Base – HCl vs NaOH Titration
A volume of 10.00 cm3 of 0.1 M HCl was pipetted out in to a beaker and 100 cm3 of de- ionized
water was added. The magnetic flea was placed inside the beaker and the beaker was placed on
the magnetic stirrer and the stirrer was started. The conductance of the HCl solution was read
using the conductometer. Using a burette 1.00 cm3 of 0.1 M NaOH solution was added. The
conductometer was read when the reading is constant (when the screen displays ready). Repeat
the last two steps until the total added volume of NaOH solution is 20.00 cm3 .
• Titration of Weak Acid with Strong Base – Acetic Acid vs NaOH titration
The above procedure was repeated using approximately 0.100 M acetic acid solution in place of
HCl.
• Titration of a Mixture of a Strong and a Weak Acid with a Strong Base – HCl + Acetic acid vs
NaOH titration
The above procedure was repeated using a mixture of 5.00 cm3 of 0.1 M HCl and 10.00 cm3 0.1
M acetic acid solution.
Results and Calculations:

Conductance / mS Temperature / ℃

CO2 free de-ionized water 0.00272 32.7

Lead Sulphate filtrate 0.0419 33.6

0.1 M KCl 13.89 29.4

• Solubility of Lead Sulphate

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

3. Conductance of the lead sulphate solution = 0.0419S

Conductivity of lead sulphate = Kcell × G = 104.416 0.0419 = 4.375× 10-3 S m-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

Κ = 0.004375 – 0.00028 = 0.004095 S m-1

6.Limiting molar conductivity of an ion increases by approximately 2 % per 1 degree rise in

temperature.
Temperature = 33.6
Temperature rise = 33.6 – 25 = 8.6
 2
Percentage for 8.6 degree rise in temperature = × 8.6 = 0.172%
100
0.172
Therefore, = 1.39 × 10−2 + ( 100 × 1.39) = 0.0138 S m2 mol-1
0.172
Therefore, 𝜆0𝑠𝑜2− = 1.60 × 10−2 + ( 100 × 1.60) = 0.0160 S m2 mol-1
4

a. The concentration of a sparingly soluble salt

𝐾 𝐾𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒
𝐶 = 𝜈 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒 =
𝜆0 +𝜈 𝜆0
+ + − − 1𝜆0+ +𝜈− 𝜆−
0

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

Ksp = ( + C) + ( - C) -=( 000137)1 (1 000137) =1.8769×10-8 mol2 dm-6

Acid Base Titrations.

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

1.00 3.03 0.158 3.39

2.00 2.72 0.205 3.04

3.00 2.45 0.266 2.80

4.00 2.20 0.335 2.52

5.00 1.46 0.405 2.24

6.00 1.466 0.471 1.927

7.00 1.215 0.534 1.686

8.00 1.026 0.598 1.466

9.00 0.958 0.663 1.258

10.00 0.984 0.724 1.199

11.00 1.110 0.788 1.213

12.00 1.389 0.854 1.250

13.00 1.54 0.912 1.297

14.00 1.678 1.076 1.343

15.00 1.819 1.228 1.397

16.00 1.961 1.389 1.444

 17.00 2.40 1.570 1.497

18.00 2.58 1.715 1.546

19.00 2.71 2.08 1.589

20.00 2.86 2.24 1.642

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

Strong acid - strong base

Conductance / mS Vs volume of NaOH cm3

3.5

3
Conductance / mS

2.5

1.5

0.5

0
0 5 10 15 20 25
volume of NaOH cm3

Volume of base added at the end point = 9.0 cm3

Concentration of the NaOH = 0.1 M
9
Moles of NaOH = 0.1 mol ×1000 = 0.9×10-3mol
NaOH: HCl
1 : 1
Therefore, number of moles of HCl = 0.9 × 10-3 mol
Volume of HCl = 9.0 cm3
0.9×10−3
Therefore concentration of HCl = 10.00×10−3 = 0.09 mol dm-3
Weak Acid – Strong Base Titration

Conductance / mS Vs volume of NaOH

2.5

Conductance / mS 1.5

0.5

0
0 5 10 15 20 25
volume of NaOH

Volume of base added at the end point = 13 cm3

Concentration of the NaOH = 0.1 M
13
Moles of NaOH = 0.1 mol ×1000 = 1.3×10-3mol

NaOH: CH3COOH
1 : 1

Therefore, number of moles of CH3COOH = 1.3 × 10-3 mol

Volume of CH3COOH = 10.00 cm3
1.3×10−3
Therefore concentration of CH3COOH == 10.00×10−3= 0.13 mol dm-3

Mixture of Strong Acid and Weak Acid – Strong Base Titration

Conductance / mS Vs Volume of NaOH

4.5
4
3.5
Conductance / mS

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

Concentration of the NaOH = 0.1 M

10
Moles of NaOH = 0.1 mol ×1000 = 1.0×10-3mol

NaOH: HCl
1 : 1

Therefore, number of moles of HCl = 1.0 × 10-3 mol

Volume of base added at the end point of CH3COOH = 27 cm3
Volume consumed for CH3COOH = 27 – 10 = 17 cm3
Concentration of the NaOH = 0.1 M
17
Moles of NaOH = 0.1 mol 0.1 mol ×1000 = 1.7×10-3mol

NaOH: CH3COOH
1 : 1

Therefore, number of moles of CH3COOH = 1.7 10-3 mol

Total number of moles = (1.0 10-3) + (1.7 10-3) = 2.7 10-3 mol

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 %

Post Laboratory Questions:

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.

2. HCl with NaOH

 Before the addition of NaOH, the conductance is high due to the presence of hydrogen ions.
When NaOH is added, the conductance falls due to the H+ ions reacting with OH − ions to form
water. This decrease in the conductance continues till the end point. When the reaction reaches
the end point, the conductance increases due to the large conductivity of OH- ions.

Acetic acid with NaOH

Acetic acid is a weak acid and dissociates partially. The hydrogen ion concentration is low
therefore, the conductance is low. On the addition of base, the conductance increases as
CH3COONa is formed which is a strong electrolyte. This increase in conductance continues until
the end point. After the end point, the conductance increases more rapidly due to the highly
conducting OH– ions.

Mixture of HCl and Acetic acid with NaOH

In this curve there are two break points. The first break point corresponds to the neutralization
of HCl. The second break point corresponds to the neutralization of acetic acid. When the HCl
has been completely neutralized, the weak acid starts to neutralize. After both acids have been
neutralized, the conductance increases due to the excess of OH– ions.

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.

Advantages of Conductometric Titrations

Conductometric titration has several advantages over classical titration with the use of chemical
indicator, which may be listed as follow:
Conductometric titration can be performed even for a colored solution since the color of the solution
does not interfere in the measurement of conductance. With chemical indicator method highly
colored solution cannot be titrated.

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