College Practical Chemistry - (Conductometry) PDF

2
Cond uctometry
(1) An electric current may be carried either by electron~ (metals) or by movement of ions
(solutions).
When the current is carried by ions (anions and cations) the conductance is called ionic
or electrolytic conductance.
The conduction obeys Ohm '8 Law.
E
1=-
R
where,
I = Current in amperes
E = Electromotive force in volts
R = Resistance in ohms.
(2) The resistance of any conductor is proportional to the length (1) and inversely
proportional to the area of cross section (a).
1 1
Ra.- ORR=p-
a a
Copyright © 2009. Global Media. All rights reserved.
where, a = Proportionality constant

p = Specific resistance or resistivity.
The reciprocal of resistance is called conductance (C) and the reciprocal of specific
resistance is called specific conductance or conductivity (expressed by K, kappa)..
(3) Conductivity cells employed for conductance work are of various types and shapes.
It consists of two electrodes made of platinum foils kept at a fixed distance. To eliminate the
polarisation effect, the electrodes are coated with a layer of finely divided platinum black.
1 1
K<X -= C·-
p a
Patel, H.N., et al. <i>College Practical Chemistry</i>, Global Media, 2009. ProQuest Ebook Central,
http://ebookcentral.proquest.com/lib/inflibnet-ebooks/detail.action?docID=3011123.
Created from inflibnet-ebooks on 2019-10-25 09:41:51.
Conductometry 11
where, Ie = Specific conductance,

I
- = Cell constant (I = length and a = area)
a
C = conductance,
.. Specific conductance = Cell constant x Conductance
~ Pyrex glass
...... Glass beaker
r----1f--- Holes
~t--- Solution
Coating
of platinum - t - - - F . - -4t-~---+--Platinum foil
black
L-_~===::t---r-Glass plate
Fig. 2.1: Conductivity cell in a solution
The value of cell constant is determined accurately by measuring the conductance of a

standard solution of potassium chloride of known conductivity.
(4) The solutions are usually prepared in conductivity water. Though distilled water is
a poor conductoI of electricity, it has sufficiently high conductance due to dissolved carbon
dioxide and other impurities. Thus, it can affect the results. It is desirable to use water which
is free from such impurities and this water is known as conductivity water.
(5) As the conductivity of solutions varies by about two per cent per degree, the
temperature should be kept constant during the conductance measurements.
(6) Since much of the theory of conductivity is concerned with very dilute solutions and
since their conductivity can be measured with considerable accuracy, it is necessary to make
sure that the concentration of the solutions studied is known accurately.
(7) Important applications of conductance measurements:
(i) Determination of degree of dissociation of weak electrolytes.
(ii) Determination of solubility of sparingly soluble salts.
(iii) Conductometric titrations.
(iv) Determination of degree of hydrolysis of salts.
12 College Practical Chemistry (S. Y. B.Sc.)
TABLE 2.1
SI units
Physical quantity Name of SI unit Symbol for SI SI unit
unit
Electric resistance ohm n n= VIA Kg m 2g-3, A-2
Electrical siemens S S = lin n- I
conductance
l..--.
TABLE 2.2
Specific conductance of KCI (ohm- I cm-I or siemens cm-I )
Temperature Temperature KCI
°C K O.1N
23 296 0.01239
24 297 0.01264
25 298 0.01288
26 299 0.01313
27 300 0.01337
28 301 0.01362
29 302 0.01387
30 303 0.01412
31 304 0.01437
32 305 0.01462
(8) O.IN KCI solution required for the measurement of cell constant is prepared by
dissQlving following quantities of pure KCI:
Weight of KCI in g Normality (N) Volume of KCI solution
0.745 0.1 100 cm 3
1.8625 0.1 250 cm 3
(9) Use of Digital Conductometer:

Conductometric work is simplified by direct reading (digital) conductance meter. Before
the work, refer to the professor in-charge for the working of particular model or to the
instructions in the operation manual of the instrument. The general method for the use of such
digital conductometer is given below:
(i) Put the conductometer on for at least 5 minutes before the begining of actual
measurements.
(ii) Connect the conductivity cell to the terminals provided for the connection (Fig. 2.2).
(iii) Take sufficient solution (40-50 cm 3) in a beaker, so that platinum plates are
completely dipped in it.
(iv) Place the range selector knob at the extreme left range (Le., indicating minimum
conductivity range).
(v) If the reading displayed is I, then it means that the conductance is beyond the range
selected.
(vi) Turn the range selector knob to successive higher range and see the reading
displayed.
(vii) If the reading displayed is 1 again, it means that still the range selected is not proper/
appropriate.
Conductometry
(viii) Turn the range selector knob to next higher range till the reading with maximum
digits displayed is obtained.
(ix) Three ranges on the left side are normally in terms of p u (micro-mhos) and the ranges
at the right side are in terms of mp (millimhos) (Fig. 2.2).
STD
•
10'"
J,
CELL
r···: 1"'.'-,
I \.--.'
)::'..~
>-~ :..- ....:
~u~~1.
~ ....-.;
r"~ r···~
L::. r:::l
..I
I
COND
•
r--
~
200~V- ~2mv
20JiV'-
~~. l-20mtr
2J.t.V" 200m V-
RANGE SELECTOR
Fig. 2.2: Digital conductivity bridge
Experiment No.1
Aim: To verify Ostwald's dilution law using acetic acid.
Requirements: Conductometer and conductivity cell, conductivity water, 100 cm 3 standard
measuring flask, 100 cm 3 beakers, 25 cm3 pipette, 10 cm 3 graduated pipette, O.lN acetic acid,
O.lN KCI solution etc.
Theory: (1) Ostwald's dilution law states that at constant temperature, degree of dissociation
of a weak electrolyte is inversely proportional to the square root of its concentration. The
mathematical form of the law is represented as:
oc2C
K:=-
a 1- oc
(2) In this experiment, the conductance of the acid solution is measured at different
concentrations (C).
(3) Using the conductance of the solution, it is possible to calculate the specific
conductance, equivalent conductance of the solution (Ac)'
(4) It is possible to calculate the degree of dissociation a using the equation,
A<n = Equivalent conductance at infinite dilution and is obtained from Kohlrausch's law.
(5) The dissociation constant (Ka) can be obtained from Ostwald's law. The constant value
of Ka (within reasonable limits) verifies Ostwald's law.
14 College Practical Chemistry (8. Y. B.Sc.)
Procedure:
[If cell constant is provided, proceed to Part II. If it is not provided then proceed as given
in Part I.]
Part I: Determination of Cell constant:
(1) Wash the conductivity cell and a 100 cm3 beaker using conductivity water.
(2) Rinse both the cell and the beaker with a small quantity of O.lN KCI solution.
(3) Take about 50-60 cm 3 of supplied O.lN KCI solution in the rinsed beaker and dip the
conductivity cell in it, so that platinum plates dip in the solution completely.
(4) Connect the cell to the conductometer and determine the conductance ofKCI solution.
Using this conductance, determine the cell constant of the cell. (as shown in the
calculations).
Part II: Measurement of conductance of the prepared acetic acid dilutions:
(1) Wash three 100 em 3 standard measuring flasks with conductivity water. Pipette out
suggested volume of O.lN acetic acid in the flasks as given in the table and dilute
each flask with conductivity water up to the mark. Shake the solutions well.
TABLE 2.3
Preparation of acid solutions
Flask Number Normality (N) Volume of O.1N Acetic acid in cm 3

1 0.05 50.0
2 0.025 25.0
3 0.0125 12.5
(2) Wash the conductivity cell and a 100 em 3 beaker with conductivity water carefully
and then rinse it with O.lN acetic acid solution.
(3) Take about 50-60 em 3 of O.lN acetic acid in the beaker and dip the cell in i~. Determine
the conductance of this solution.
(4) Wash the conductivity cell and the beaker with conductivity water carefully.
(5) Determine the conductance of 0.05, 0.025 and 0.0125N acid solutions in the same
manner.
(6) Calculate the dissociation constant for each acid solution as shown in calculations.
Show all the calculations systematically.
Observations and Calculations: '
Temperature = _ _ _ °C [-K]
Part I:
Determination of cell constant:
(1) Conductance of O.IN KCI solution = mhos lSi
(2) Specific conductance of O.IN KCI solution at experimental temperature. (Refer to
Table 2.3)
= mhos em- l [S em-I]
Conductometry 15
Specific conductance of KCl

(3) Ce11 constant=~-------------------
Conductance of KCl
= ____ cm- l •
Part II:
Calculation of dissociation constant:
(1) Equivalent conductance at infinite dilution (hac) = 390.7 mhos cm 2 eq-l [8 cm 2 eq-l]
(2) Cell constant (from Part I): = ___
Concentration Conductance Specific Equivalent Degree of Dissociation

g.eqldm 3 mhos {S] conductance conductance dissociation constant
K- of solution mhos cm 2 errl
mhos cm-l {S cm2 • errl]
{S em-I]
A 2
a=_c K = a .C
C =
K cell Ac AfIQ II (I-a)
constant x
conductivity
0.1
0.05
0.025 .
0.0125
KII (mean) =___

Results:
Concentration of solution in gm equi lit-3 Value of Dissociation constant

{g dm-3]
C KII
0.1
0.05
0.025
0.0125
Conclusions:
Since the values of Ka are fairly constant, the Ostwald's dilution law is verified.
(Note: Dissociation constant of acetic acid at 25°C or 298 K is 1.74 x lQ-5).
Experiment No.2
Aim: To determine Aw of a strong electrolyte (HClINaCI).
Requirements: Conductometer and conductivity cell, burette, 100 cm 3 standard measuring
flasks, beaker, conductivity water, O.lM HCI or NaCI solution.
Theory: The conductance of a solution is due to the presence of ions. Molar conductance of
an electrolyte increases with increase in dilution, liue to the increase in the degree of
dissociation of the electrolyte. On dilution, the same amount of electrolyte is capable of
furnishing a large number of ions. However, the increase in the number of ions on dilution
is much less than increase in the volume of solution. Therefore, the number of ions per unit
volume actually decreases. Hence the specific conductance decreases although the molar
conductance increases on progressive dilution. The increase in the case of electrolytes like
hydrochloric acid, sodium chloride, potassium chloride etc; is not so large as in the case of acetic
acid or ammonium hydroxide. The electrolytes like HClINaCI etc. are known as strong
electrolytes. In strong electrolytes, there is a tendency for molar conductance to approach to
certain limiting value when the concentration approaches zero. The molar conductance at this
point is known as molar conductance at zero concentration or at infinite dilution. It is denoted
by Ar:JJ'
Infinite dilution is meant a solution so dilute that it has maximum or limiting molar
conductance which does not increase on further dilution. In the case of strong electrolyte, this
value can be obtained by extrapolating the molar concentration graph to zero concentration
as shown in Figure 2.3.
'" Concentration
Fig. 2.3: Variation of molar conductance with dilution.
The molar conductance at infinite dilution can be obtained indirectly using Kohlrausch ~
law.
(Note: molar conductance for HCI or NaCI is same as equivalent conductance).
Procedure:
(If cell constant is provided, proceed to Part II. If it is not provided, then proceed as given
in Part 1).
Part I: Determination of cell constant
Determine cell constant for the supplied conductivity cell by following procedure given
in experiment No.1 on page No. 14.
Conductometry 17
Part II: Measurement of conductance of strong electrolyte (e.g., HCI) solutions:
(1) Wash carefully four 100 cm 3 standard measuring flasks with conductivity water. Wash
and rinse the burette with supplied O.lN HCI solution. Add suggested volume of O.lN HCI
solution from burette in the standard measuring flask as given in the table and dilute each
flask with conductivity water upto the mark. Shake the solutions well.
TABLE 2.4
Preparation of diluted solutions
Flask Molarity Volume of O.1N Final volume
No. M BCI in cm 3 in cm 3
1 0.05 50 100
2 0.025 25 100
3 0.010 10 100
4 0.005 05 100
(2) Wash conductivity cell and a 100 cm 3 beaker several times with conductivity water
carefully.
(3) Take about 40-50 cm 3 of supplied conductivity water in the beaker and dip
conductivity cell in it. Determine conductance as described previously.
(4) Rinse the cell with O.IN HCI solution 2-3 times.
(5) Take about 40-50 ems of O.lN HCI solution in the beaker and determine conductance
of the solution.
(6) Wash the conductivity cell and beaker carefully with conductivity water.
(7) Determine conductance of 0.05, 0.025, 0.01 and 0.005N acid solutions in the same
manner.
(8) Obtain corrected specific conductance of each solution by subtracting specific
conductance obtained for supplied conductivity water from conductance measured for
each solution (KIs = Ks - K,).
(9) Plot the graph of molar conductance of solution against concentration.
Observations and Calculations:
Temperature = ___DC = __ K.
Part I: Determination of Cell constant:
(1) Conductance of O.IN KCI solution = _ _ mho (S).
(2) Specific conductance of O.IN KCI solution at experimental temperature =__ mho
cm- I (8 em-I).
Specific conductance of KCI solution

(3) Cell constant = - - - - - - - - - - - - -
(x) Conductance of KCI solution
= em-I.
Part II: Molar conductance at various concentrations:
Specific Corrected Molar
Concentration conductance K. Specific condllctance Conductance
of solution Conductance K. =Cell constant K>(K.-K,)
= K'
Am -!...
C x conductivity C
Mol. dm-8 mho (S) mho. cm- I (S em-I) mho. cm-I(S em-I) S cm 2 m- I
0.100
0.050
0.025
0.010
0.005
water Kw =
Graph:
Plot the graph of molar conductance, Am against root concentration. Extrapolate to zero
concentration (i.e., y-intercept) to obtain the Aa) value of HC!. (Refer to Fig. 2.3).
Results:
Am for given strong electrolyte (HCI) is = _ _ .
Experiment No.3
Aim: To determine the amount of a strong acid present in the given acid solution by titrating
it against strong base conductometrically.
Requirements: Conductometer and conductivity cell, burette, beaker, pipette, conductivity
water, O.lN NaOH solution etc.
Theory:
Titration of strong acid (HCI) against a strong base (NaOH).
t
§
i I
o
I
I
I
I
I
Iv
•
Volume of strong base added -
Fig. 2.4: Conductometric titration curve
Conductometry 19
(1) The initial conductance is high due to the complete dissociation of strong acid (HCI)
and H+ ions have high conductance value.
(2) The addition of strong base (NaOH) in the acid solution gives the following reaction:
H+ + CI- + Na+ + OH-~ Na+ + CI- + H20
(3) As NaOH is added, H+ ions combine with OH- ions to form undissociated water
molecules and H+ ions get replaced by Na+ ions having much lower conductance value.
Hence, the conductance of the solution goes on decreasing and reaches a minimum
(at equivalence point). Mter the equivalence point, NaOH added remains unreacted.
Being a strong base, it ionises completely producing OH- ions of high conductivity.
Hence, conductance increases again.
(4) A V shaped curve is obtained. The point of intersection of the two segments in the
graph gives the end point of the titration. (Fig. 2.4)
-Procedure:
(1) Dilute the given acid solution using conductivity water to 100 cm 3 in a standard
measuring flask. Shake the solution well.
(2) Rinse and fill the burette with (supplied) O.lN NaOH solution.
(3) Pipette out 10 cm 3 of the diluted solution in a clean 100 cm3 beaker.
(4) Place the conductivity cell in the beaker containing acid solution and add just
sufficient quantity of conductivity water to it, so that platinum plates immerse in
solution completely.
(5) Insert a glass rod and stir the solution well. Do not take it out of beaker till titration
is complete.
(6) Connect the cell to the conductometer and determine the initial conductance of the
solution by selecting the proper range (see instructions).
(7) Add a small volume (say 0.5 cm 3 ) of NaOH solution at a time from the burette, stir
the solution well and note the resultant conductance value.
(8) Repeat step No. 7 until the conductance values start increasing. Take 5 to 6 more
readings.
(9) Plot the graph of conductance against the volume of NaOH added (Fig. 2.4). It gives
a V shaped curve.
(10) The volume corresponding to the intersection of two lines (V), gives the end point
of titration. Note the volume Vx'
(11) Calculate the normality and strength of the acid solution as given in the calculations.
(1) Temperature =__ DC f_KJ
(2) Normality of NaOH solution O.IN =
(3) Volume of the diluted acid pipetted out = 10 cm 3•
(4) Equivalent weight of the acid (HCl) 36.5. =
Observation Table:
Observation Numbers Volume of NaOH added in cm 3 Conductance (1/R) mhos lSi
Calculations:
(1) Volume of NaOH required for end point (V) = - cm 3 [From graph] ... (1)
NNaOH xVx O.lxVx
(2) Normality of HCI = V =
HCI 10
(3) 10 cm 3
of the diluted solution required Vx cm 3 of O.lN NaOH solution.
_ :. 100 cm 3 of the diluted solution will require 10 Vx cm 3 of O.lN NaOH solution .... (2)
1000 cm 3 of IN NaOH = 36.5 g of HCI
36.5 x 10Vx x 0.1
:. 10 Vx cm 3 of O.lN NaOH = 1000 ... (3)
= _ g ofHCI
(Note: While doing calculations, substitute the titration reading obtained in place of Vx ).
Results:
(1) Volume of NaOH required for the end point (V) = _ cm3•
(2) Normality HCI = _ N.
(3) Amount Jf HCI present in the given solution = __ g.
Experiment No.4
Aim: To determine the amount of a weak acid present in the given acid solution by titrating
it against a strong base conductometrically.
Requirements: Conductometer and conductivity cell, burette, beaker, pipette, conductivity
water, O.lN NaOH solution etc.
Theory: Titration of weak acid (.CH 3 COOH) against a strong base (NaOH)
(1) The initial conductance of the solution is due to the partial ionisation of acetic acid.
CH3COOH~CH3COO- + H+ ... (1)
Acetic acid being a weak acid, ionises (reversibly) to a very small extent.
(2) When NaOH is added, initially the conductance of the solution decreases. This is
because free H+ ions produced due to ionisation, having high conductance combine
with OH- ions to form practicaly unionised water.
H+ + OH-~ H 20 ... (2)
(3) The addition of further amount of strong base NaOH in the acid solution shows
gradual increase in conductance. This is because unionised acid, which does not
contribute to the conductance, reacts with NaOH producing CH 3COO- and Na+ ions
which contribute to the conductance.
... (3)
Conductometry 21
(4) This gradual increase in conductance continues till the equivalence point i.e.,
theoretical end point is reached.
(5) Mter the equivalence point, NaOH added remains unreacted. Being strong base, it
ionises completely producing OH- ions having high conducting capacity. Hence,
conductance values increase rapidly.
NaOH ---+ Na+ + OH- ... (4)
(6) The point of intersection of gradual increase segment and rapid increase segment gives
the end point of titration.
Procedure:
(1) Rinse and fill·the burette with the supplied O.IN NaOH solution.
(2) Dilute the given acid solution to 100 cm 3 in a standard measuring flask using
conductivity water. Shake the solution well.
(3) Pipette out 10 cm 3 of the diluted solution in a clean 100 cm 3 beaker.
(4) Insert the conductivity cell in the above beaker and add just sufficient quantity of
conductivity water to immerse the electrodes completely.
(5) Insert a glass rod to stir the solution well. Do not remove it from the solution till
titration is complete.
(6) Connect the cell terminals to the conductometer.
(7) Determine the initial conductance of the solution by selecting the proper range i.e.
range which displays maximum digits.
(8) Add a small quantity (say 0.5 cm 3) ofNaOH solution from the burette. Stir the solution
well and note the resultant conduetance.
(9). Repeat step No.8 until the conductance values start increasing. Take 5 to 6 more
readings.
(10) Plot the graph of conductance against volume of NaOH added (Fig. 2.5).
I
I
I
I
I
I
I Vx
6'
Volume of strong base added •
Fig. 2.5: Conductometric titration curve
(11) Determine the volume of NaOH, Vx corresponding to the end point of titration.
,(12) Calculate the normality and strength of the acid solution as given in the calculations.
(1) Temperature = _ _ °C [_K]
(2) Normality of NaOH solution = O.lN
(3) Volume of the diluted acid pipetted out = 10 em 3
(4) Equivalent weight of the acid (CH 3 COOH) = 60
Observation Table:
Observation Number Volume of NaOH added in cm 3 Conductance (l/R) mhos/{S]
Calculations:
(1) Volume of NaOH required for end point (V,) = __ em 3 [From graph]
NNaOH xVx
(2) Normality of CH 3COOH = v:CH.COOH
(3) Amount of acid present in the given solution.
(a) 10 cm 3 of the diluted solution required Vx em 3 of O.lN NaOH solution.
:. 100 em 3 of the diluted solution required 10 Vx em 3 of O.lN NaOH solution.
1000 em3 of 1N NaOH = 60 g of CH 3COOH
3 _ 60x10Vx xO.l
.. 10 Vx em of O.lN NaOH - 1000 •

g of CH3 COOH =_
(Note: While doing calculations, substitute the actual titration reading obtained in place
of Vx;)'
Results:
(1) Volume of NaOH required for the end point (V,) = __ cm3 .
(2) Normality of CH 3 COOH = __ N.
(3) Amount of CH3 COOH present in the given solution = _ _ g.
000

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2

where, a = Proportionality constant

where, Ie = Specific conductance,

...... Glass beaker

Fig. 2.1: Conductivity cell in a solution

The value of cell constant is determined accurately by measuring the conductance of a

(9) Use of Digital Conductometer:

Fig. 2.2: Digital conductivity bridge

Flask Number Normality (N) Volume of O.1N Acetic acid in cm 3

Specific conductance of KCl

Concentration Conductance Specific Equivalent Degree of Dissociation

KII (mean) =___

Concentration of solution in gm equi lit-3 Value of Dissociation constant

Specific conductance of KCI solution

Fig. 2.4: Conductometric titration curve

Volume of strong base added •

Fig. 2.5: Conductometric titration curve

Observation Number Volume of NaOH added in cm 3 Conductance (l/R) mhos/{S]

.. 10 Vx em of O.lN NaOH - 1000 •

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