Experiment 2: Conductimetric titrations

Introduction:

In solution a compound may dissociate into ions which can carry charge. This conductivity
depends on the amount of ions present as well as their ability to move within the solution. These
in turn are influenced by concentration, degree of dissociation and ion sizes and charge.
Conductimetric titrations show that a dilute solution has the increased ability to conduct as their
concentrations increase. At a given concentration the H+ and OH- ions are much better
conductors than other ions in solution. This is so due to their mobility. The high mobility results
from the rapid transfer of protons between adjacent water molecules and not due to the physical
movement of the ions. Therefore a solution containing excess hydroxyl or hydrogen ions will
have a high conductivity.

Procedure:

The lab was done as outlined in the lab manual.

Results:
 Table # 1: Showing Conductivity readings for Strong Base- Strong Acid (NaOH with HCl)

Volume of HCl used, 1.0M /cm3 Conductance/mV

0.1 1.96
0.2 1.78
0.3 1.75
0.4 1.60
0.5 1.59
0.6 1.46
0.7 1.31
1.0 1.22
Colour change
1.1 1.16
from pale yellow 1.2 2.70
to light pink
1.3 1.85
1.4 2.44
1.5 2.74
1.6 2.90
1.7 3.72

Table #2: Showing Conductivity readings for Weak acid-Strong Base (Acetic acid with NaOH)

Volume of Acetic acid used, 1.0M /cm3 Conductance/mV

0.1 1.53
0.2 1.48
0.4 1.24
0.5 1.17
0.6 1.13
0.8 1.01
Colour change from 0.9 0.99
light pink to
colourless 1.0 1.04
1.1 1.05
1.2 1.04
1.4 1.03
1.5 1.03
1.6 1.02
1.8 1.03
1.9 1.03

Table #3: Showing Conductivity readings for Weak Acid-Weak Base (Acetic acid with NH3)

Volume of NH3 used /cm3 Conductance/mV

0.5 0.61
 1.5 1.25
2.0 1.59
2.2 1.68
2.4 1.77
2.6 1.87
2.8 2.02
3.0 2.2
3.1 2.5
Colour change
3.2 2.53
from light pink to
colourless 3.3 2.78
3.4 2.8
3.5 2.8
3.6 2.8
3.7 2.82

Table #4: Showing Conductivity readings for Strong Acid-Weak Base (H2SO4 with NH3)

Volume of NH3 used /cm3 Conductance/mV

0.5 10.71
1.0 9.97
1.5 9.09
2.0 7.95
2.5 7.08
3.0 6.34
3.5 5.69
Colour change
from light pink to
4.0 5.23
pale yellow 4.5 5.46
5.0 5.51
5.5 5.56
6.0 5.58
6.5 5.68
7.0 5.7
7.5 5.79

Chart # 1: Strong Base- Strong Acid (NaOH with HCl)

Chart #2: Weak acid-Strong Base (Acetic acid with NaOH)
Chart #3: Weak Acid-Weak Base (Acetic acid with NH3)

Chart #4: Strong Acid-Weak Base (H2SO4 with NH3)

Calculations:

Sample for the number of moles and the equivalence point.

Strong Base- Strong Acid (NaOH with HCl)

1000cm3 = 0.01mol
100cm3 = 0.01mol x 100cm3
1000cm3
= 0.001mol
NaOH + HCl → NaCl + H2O
From Equation 1mol NaOH reacts with 1mol HCl
0.001mol NaOH reacts with 0.001mol HCl
Volume of HCl = 0.001mol x 1000
1moldm-3
= 1cm3: Equivalence Point

Weak acid-Strong Base (Acetic acid with NaOH)

1000cm3 = 0.01mol
100cm3 = 0.01mol x 100cm3
1000cm3
= 0.001mol
NaOH + CH3COOH → CH3COONa + H2O
From Equation 1mol NaOH reacts with 1mol
0.001mol NaOH reacts with 0.001mol
Volume of = 0.001mol x 1000
1moldm-3
= 1cm3: Equivalence Point

Weak Acid-Weak Base (Acetic acid with NH3)

1000cm3 = 0.03mol
100cm3 = 0.03mol x 100cm3
1000cm3
= 0.003mol
CH3COOH + NH3 → CH3COONH4
From Equation 1mol reacts with 1mol NH3
0.003mol reacts with 0.003mol NH3
Volume of NH3 = 0.003mol x 1000
1moldm-3
= 3cm3: Equivalence Point

Strong Acid-Weak Base (H2SO4 with NH3)

 1000cm3 = 0.02mol
100cm3 = 0.02mol x 100cm3
1000cm3
= 0.002mol

H2SO4 +2NH3→ ( NH4)2SO4

From Equation 1mol H2SO4 reacts with 2mol NH3
0.002mol NaOH reacts with 0.004mol NH3
Volume of NH3 = 0.004mol x 1000
1moldm-3
= 4cm3 :Equivalence Point

Questions:

1. The following points are possible sources of error that may have occurred in this
experiment, with and estimation of their magnitudes:
• Titration error: This is where the endpoint of the titration is not equal to the
equivalence point. The magnitude of this error may be calculated using the
following: Titration Error = Volume at endpoint - Volume at equivalence point,
where a negative error value indicate the endpoint occurs before the equivalence
point, whilst a positive error values signify the endpoint happens after the
equivalence point. The following magnitudes were calculated: NaOH vs. HCL:
Titration error = 1.2 - 1 = 0.2; NaOH vs. Acetic acid : Titration error = 0.9 - 1 =
-0.1; Acetic acid vs. NH3: Titration error= 3.2 - 3 = 0.2; H2SO4 vs. NH3: Titration
error= 4.0 - 4 = 0
• Use of Electrode: Not submerging the electrode such that the solution of the
beaker covers the opening in the electrode body, yet still allowing the electronics
of the device to remain dry. The magnitude of this error is dependent on the user
as it takes into account the accuracy, precision and technique, each of which can
be relatively high or extremely low where gaining results from the equipment is
concerned.

2. The table below shows the theoretical, indicator and conductivity equivalence points for
the titrations performed in this lab.
 Titration Theoretical Indicator ( volume Conductivity/ Scm-1
equivalence colour change was
point / cm3 observed)/cm3

1.NaOH vs. HCL 1.0 1.2 2.70

2.NaOH vs. Acetic acid 1.0 0.9 0.99

3.Acetic acid vs. NH3 3.0 3.2 2.53

4. H2SO4 vs. NH3 4.0 4.0 5.23

Comparisons between the conductivity and indicator showed that for titrations 1 and 4
the indicator endpoint occurred before the conductivity equivalence point, i.e. a precise
measure of the values, while for titration 2 it occurred at the conductivity equivalence
point. Titration number 3 on the other hand displayed an indicator value that occurred
after the conductivity equivalence point, this may be due to the errors stated above.

3. The strong solution placed in the burette is much more concentrated than that in the
beaker because the strong base is completely dissociated, giving an equivalent OH-
concentration. The weak base will be only partially dissociated and make a much smaller
contribution to the total [OH-] present. The presence of OH-from the strong base will, in
fact, suppress the dissociation of the weak base, since the equilibrium B-+ H2O →BH +
OH- will be shifted to the left. Thus, the first equivalence point gives the volume of the
titrant reacting with the strong base. In a case where a strong base has been titrated. At
this point there exists a solution of the weak base that has been diluted. The difference
between the first and the second equivalence points gives the volume of strong acid
required to react with the weak base. N.B the titration of a base with a strong acid is
just the reverse of the titration of an acid with a strong base.

4. The following explanations state why the graphs presented in the manual have their
specific shape:
• Figure 1-Strong acid Strong base: The reaction between HCl and NaOH is a strong
acid strong base titration. This is represented by Figure 1(pg 7 lab manual). Before
the end point H+ ion is removed from the solution by its reaction with OH- ion and
Na+ ion is added to the solution. Since the relative conductance of H+ (8.5V) is about
7 times that of Na+ (1.2V) the conductance of the solution decreases before the end
point. After the end point no H+ ions are available to react and the conductance of the
solution increases as a result of the addition of Na+ and OH- ions.
 • Figure 2-Strong acid/base Weak acid/base: Looking at the graph one sees the initial
conductivity is high, which is due the presence of the strong acid/base being a strong
electrolyte. What this translates into is a substance the readily dissociate, which will
cause an increase in conductivity as displayed in the graph. On addition of a weak
acid/base the conductivity decrease as ions are being neutralized. After the
equivalence point the conductivity plateaus, because the weak acid/base is a weak
electrolyte and does not easily dissociate, as a result little conductance is seen. The
equivalence point of the titration corresponds to the intersections of the extrapolated
linear portions of the titration cure.
• Figure 3-Weak acid Weak base: Shows a slight decrease in conductance before the
increase due to the suppression of the acid dissociation by the common ion effect
which is essentially the lowering of the degree of ionization of a compound when
another ionisable compound is added to a solution. Since the acetic acid is dissociated
slightly in solution the conductance of the acid solution is initially small. As NaOH is
added the OH- ions react with acid to form water and acetate. The addition of acetate
and Na+ ions to the solution causes conductance to increase. After the end point Na+
and OH- ions are added to the solution. Since the relative conductance of OH- ions is
5 times that of C2H3O2- ions the conductance of the solution after end point increases
more rapidly.

Discussion /Conclusion :

The equivalence point of the titration is the point at which exactly enough titrant has been added
to react with all of the substance being titrated with no titrant left over. What this means is that,
at the equivalence point, the number of moles of titrant added thus far corresponds exactly to the
number of moles of substance being titrated according to the reaction stoichiometry. Based on
the results attained for NaOH (0.01M) VS HCl (1.0M), 1.0cm3 is the theoretical equivalence
point when HCl is added to 100mL NaOH, while the real result of the equivalence point was
found to be 1.1 cm3 as taken off the Chart #1 Plot, with a conductivity value of 2.70mV, the
colour change was seen when 1.2 cm3 of HCl was added to the solution of the beaker. Therefore
a positive Titration error = 0.2 was calculated meaning that the endpoint is after the equivalence
point. The characteristics of the Chart #1 is owing to the high concentration of OH - as a result
high conductivity values , this value begins to decrease as the OH is neutralized by H+ , after
neutralization the conductivity increases again due to an increase excess H+.
In titration 2, of NaOH vs. Acetic acid the Titration error was calculated to be -0.1 cm3, based on
the volume at endpoint being 0.9 cm3 and the volume at equivalence point equalling 1.0 cm3.
This suggested that the endpoint is ahead of the equivalence point. The graphical equivalent
point was found to be 0.8 cm3 with a conductivity value of 0.99 S/cm. It can be seen how a weak
acid reacts with a strong base to produce a shape as shown in Chart #2, where the strong
electrolyte has a high concentration of OH- so high conductivity values, as neutralization takes
place due to the presence of the H+ ions the conductivity value slump to the smallest amount at
the equivalence point. No increase in conductivity can be seen since the acetic acid is not easily
dissociated.
With the titration of Acetic acid vs. NH3, the Titration error was calculated to be 0.2 cm3, based
on the volume at endpoint being 3.2 cm3 and the volume at equivalence point equalling 3.0 cm3.
The graphical equivalent point was found to be 3.3cm3 with a conductivity value of 2.8 S/cm. In
this case when both weak acid and base interact the plot (Chart#3) shows a low initial
conductivity is low since the acetic acid is not readily dissociated and the conductivity begins to
increase on addition of NH4 as it is a to some extent a stronger electrolyte than the acetic acid.
Following the equivalence point it plateaus as the excess of ions no longer significantly influence
the conductivity values.
And finally for the titration of the calculated results shows that no error was incurred meaning
the endpoint value is the same as the equivalence point value of 4.0cm3. The calculation of the
Titration error= 4.0 - 4 = 0 shows this. But from the plot (Chart #4) the equivalence point was
4.ocm3 with a conductivity value of 5.2 S/cm. This titration is very similar to that of the first and
its Chart #4 plot can be treated in the same means.
This lab is not without its fair share of errors those of which include: accuracy and precision on
the experimenter; improper use of the electrode; misreading the volume due to a parallax errors
or error in counting unmarked graduation marks; using contaminated solutions i.e. when two
different solutions are to be dispensed from the same burette and the burette is not rinsed with
distilled water in between; using the wrong amount of indicator since the amount added can shift
end point’ and finally not filling burette properly ,e.g. if there is an air lock in the burette
stopcock it can block the flow of the titrant, but it can also at some moment flow with the titrant;
after that one will have no idea what was the real volume of solution used.
To conclude another method for finding the equivalence point involves using the first derivative
of the data. The equivalence point occurs when the slope of the titration curve is at a maximum.
While it may be possible to find that point using just the titration curve, it is much easier to read
the point of maximum slope from a plot of the first derivative of the data. This lab has shown
how the equivalence point of four acid/base titrations can be determined using conductimetric
titrations.