CONDUCTOMETRIC TITRATION FOR DETERMINATION OF STRENGTH OF A
SUPPLIED HCl SOLUTION USING A STANDARD NaOH SOLUTION
Theory: In a metallic conductor of length “l” and cross section “a” the resistance “R” is given
by
R= ρ(l/a)
Where ρ is the specific resistance. It is the resistance of a unit length of conductor of unit
cross section. The reciprocal of resistance is termed conductance (λ) and the reciprocal of
specific resistance is called specific conductance or conductivity (L). Hence the specific
conductance
L = 1/ ρ
The conductance of a given solution λ= 1/R= (1/ ρ) (a/l) = L (a/l)
L = (1/R) (l/a)
The resistance is expressed in units of ohm, and the conductance has its unit ohm-1 i.e. mho.
The conductance of solutions is also governed by the same relations if l=1 and a=1
Then L= λ.
The specific conductance is the conductance of the solution enclosed between two
electrodes having a cross sectional area of 1 sq cm separated by a distance of 1 cm.
The conductance of the solution depends upon the number of ions present and hence the
concentration. To compare the conductivity of different solutions, it is necessary to take the
concentration of the solutions into consideration. It is done by using equivalent conductance
λ.
The equivalent conductance is defined as the conductance of the solution containing 1 gm
equivalent of the dissolved electrolyte such that the entire solution is placed between two
electrodes 1 cm apart. Suppose the solution of the electrolyte has a concentration of “c” gm
equivalent /litre. Then the volume of the solution containing 1gm equivalent would be
1000/c
cm3. If this volume be imagined to be placed between two electrodes 1 cm apart the cross
section of the column of the solution or electrodes would be 1000/c sq. cm. Hence the
equivalent conductance of the solution is
λ= (a/l) L= (1000*L)/c where L is the specific conductance
The strength of an acid or a base can be accurately obtained from conductometric
measurements. A known volume of acid is taken in a beaker and its initial conductance is
measured. The alkali is added from a burette in small amounts and the conductance is
measured after each addition. The temperature is maintained constant. The observed
conductances are plotted against the volumes of titre added. Suppose a strong acid HCl is to
be titrated against a strong base NaOH. Since both the acid and base is strong, these remain
completely dissociated. Neutralization would really mean the replacement of H + ions by an
equal number of Na+ ions.
The ionic conductance of H+ is much higher than that of Na+.
Ion l0+ Ion l0-
H+ 349.8 OH- 198
Na+ 50.11 Cl- 76.34
ION CONDUCTANCE AT INFINITE DILUTION (25o C)
As a result, the conductance of the solution will decrease as more and more NaOH are
added. This is shown graphically by the plot of conductance against volume of titre added.
In this way when the entire H+ is removed, the conductance will reach the lowest limit.
Further addition of NaOH means increase in the number of both Na+ and fast moving OH-
ions. These are no longer removed; hence conductance will again increase linearly with
addition of titre. The point of intersection of two lines i.e. the lowest point corresponds to
the minimum conductance which is the exact neutralization point. Some 4 or 5
measurements on either side of the minimum point would give on extension the point of
intersection.
An acid is taken in a beaker and NaOH solution is gradually added to it from a burette. The
reaction occurring during that neutralisation is given by
HCl + NaOH = NaCl + H2O
H+ + Cl- + Na+ + OH- = Na+ + Cl- + H2O
It is now evident from the above equation that as NaOH solution is gradually added, the H+
ion having higher ionic conductance are replaced by the Na+ ion having lower ionic
conductance and hence the conductivity would decrease and reach a minimum. After the
equivalence point , Na+ and OH- would be accumulated in the solution and the conductance
of the solution would increase. If the conductance corresponding to the volume of NaOH
solution added be plotted, two straight lines having opposite slopes would be obtained, i.e.,
V- shaped titration curve. The point of intersection of the two straight lines give the
equivalence point.
Instruments and Apparatus:
1. Digital conductivity meter
2. Conductivity cell
3. Burette
4. Pipette
5. Conical flask
6. Funnel
7. Beaker
Reagents:
Standard oxalic acid solution
Standard NaOH solution
HCl solution
Phenolphthalein indicator
Procedure :
1) 100 ml of standard oxalic acid solution of order (N/10) was prepared.
2) 250 ml of approximately (N/10) NaOH solution was prepared and it was standardised
against a standard oxalic acid solution using phenolphthalein as indicator.
3) 250 ml of an approximately (N/10) solution was prepared.
4) The conductivity cell was rinsed with distilled water and before taking the observed
conductance reading the digital conductivity meter must be calibrated.
5) 25 ml of HCl solution was pipetted out in a 250 ml beaker and 125 ml distilled water was
added.
6) The conductivity cell was placed in the beaker so that the electrodes are completely
immersed in the solution.
7) The cell was connected to the conductivity meter as usual and the conductance of the
solution was measured.
8) NaOH solution was added from a burette dropwise.
9) The conductance of the solution after each addition of the NaOH solution was measured.
The beaker was shaken until it had at least five points beyond the end point.
10) The conductance against the volume of the titrant was plotted. The straight line were drawn
and the point of intersection was obtained and the strength of the HCl solution was
calculated.
PREPARATION OF (N/10) OXALIC ACID SOLUTION:
Oxalic acid: H 2 C 2 O4 .2 H 2 O
Molecular weight: 126
Equivalent weight: 63
1000ml (N) Oxalic acid solution = 63 gm Oxalic acid
1000ml (N/10) Oxalic acid solution = 63/10 Oxalic acid
= 6.3 gm Oxalic acid
TABLE: 1
Initial Final weight Weight Weight to be Factor Strength
weight (gm) taken(A) taken(B) (A/B) ( S¿¿ 1)¿
(gm) (gm) (gm)
PREPARATION OF 250ML OF 250ML(N/10) NaOH SOLUTION(approx.):
Equivalent weight of NaOH = 40
1000ml 1 (N) NaOH solution = 40 gms of NaOH (s)
1000ml of (N/10) NaOH solution = 4 gms of NaOH (s)
250ml of (N/10) NaOH solution contains 1gm NaOH (s)
1gm NaOH (s) was dissolved in 250 ml distilled water.
STANDARDISATION OF NaOH SOLUTION BY STANDARD OXALIC ACID
SOLUTION:
Pipette out 25ml of NaOH solution into a conical flask. Add one drop of phenolphthalein
indicator, the solution turns pink in colour. Titrate with standard Oxalic acid solution
from the burette with continuous stirring, pink colour becomes fainter and fainter until it
is very faint. Continue adding drop wise until with one drop, pink colour just disappears.
Volume of the acid ( v 1 ) × Strenght of a cid ( s 1 )
Strenght of NaOH solution=
Volume of the NaOH solution
TABLE: 2
No Strength of Burette Actual Mean Volume of Strength of NaOH
of Oxalic acid reading Burette volume of NaOH (S¿¿ 2)¿
obs solution Reading Oxalic acid taken(ml)
(S¿¿ 1)¿ (ml) used(ml) (V 2 )
(V 1 )
Initial Final
(ml) (ml)
1.
2.
3.
TABLE: 3
No. of obs Volume of NaOH Total volume of Observed
solution added NaOH solution Conductance (ms)
added
1.
2.
3.
4.
5.
6.
7.
8.
9.
CALCULATIONS:
Intersection point D, gives the volume of NaOH solution (V 2 ) of the strength ( S¿¿ 2)¿
required to neutralize 25ml of the acid (V 3 ). If ( S3 ) be the strength of the supplied acid
solution; then,
V 2 S 2=V 3 S 3
Let us consider that, (V ¿¿ 2 volume)¿ of the NaOH solution was required to neutralize
V 3 volume of the acid.
So, again, V 3= 25 ml (taken), and S3= unknown
V 2 S2
So, S3= (N )
V3
PRECAUTIONS:
1. All electrical connection should be carefully made.
2. As conductance depends on temperature, it should be kept constant during the
experiment. A thermostat should be used for precession work.
3. After each addition to the titrant, the solution should be thoroughly stirred by
taking care that the cell does not break.
4. In the graph, straight line should be carefully drawn. Slight variation in the slope
of the straight lines would cause large error in finding the end point.
Volume of NaOH added ----
Fig: Conductometric titration curve
