CHAPTER

8Conductometry
1
Syllabus
Topics to be Covered
1. Introduction about Electrical Conductance
2. Conductance in solution, Some terminologies
3. Conductance of strong and weak electrolytes
4. Conductometric titration
5. Application of direct conductance measurement

• .
2
Measurement units
 Coulomb (C): Quantity of charge
 Converts 0.001118 g of silver ions to silver metal,
 Charge of 6.24 x 1018 electrons.
 Faraday (F): Quantity of charge.
 Charge of one mole (6.023 x 10 23) electrons.
 96490 C
 Ampere (A) : Amount of current.
 Flow of 1 C per Sec
 Volt (V) : potential between two points.
 Produces 1 A current in one ohm resistor.
 Ohm (Ω): Amount of electrical resistance.
 Where 1V potential produces 1A current
 Definition:
 Conductometry is an analytical method which depends
on the movement of ions under an electric field
 No reduction is essential at the electrode (inert)
surface.
 Conductance is the ability of the medium to carry the
electric current.
 In metal wire; flow of electron.
 In solution: migration of cations and anions
 Conductance in
A. Electrolyte Solution B. Metal wire

 Electrolytic (ionic)
 Migration of ions.  Electronic (metallic)
 Transfer of matter.  Migration of electrons.
 Decomposition of electrolyte  No transfer of matter.
occurs/chemical change occurs.  No change in chemical
(electrolytes are acids, bases and salts) properties of conductor.
 Nature of electrolyte  Type of material (nature &
 Inter ionic attraction structure)
 Solvation of ions (size and charge)  No of valence electron/atom
 Viscosity of solvents  Density of metal
 Polarity of solvent  Temperature
 Concentration of electrolyte  Decreases with temperature.
 Temperature
 Increases with temperature.
 Factors affecting the mobility of ions and conductance in solution
 Concentration of charge carrier
 Nature of charge carrier
 Electrical force acting on the ions:-
Electrical force = applied potential × charge on the ion
F=q×V
 Frictional force: + -
Viscosity, nature of ion, ionic strength
 E le ct r o p h o r e t ic E ffe ct
Electrophoretic
Electrophoretic effect;- effect

 Relaxation effect / -
+

(Asymmetric effect):- Symmetric Asymmetric Symmetric

Asymmetric or Relaxation effect

Explanation is done using figure

 Conductance of solution depends on (fixed applied potential):
Velocity of ion/s Number of ions

Nature of ions: Concentration:

 ↑size, ↓ G  ↑C, ↑ Number of ions/vol
 ↑MW, ↓ G
 ↑C, ↑ G (linear relation only for diluted soln).
 ↑T, ↓ interionic attraction ↑ G
 ↑ Charge↑Hydration, ↓ G
 ↑infinite dilution, ↓ interionic attraction is negligible

The electrodes: Temperature:

 Surface area (A) is directly
 ↑T, ↑ G
proportional to the conductance  ↑T, ↑ Energy of ions
(G)  ↓ Viscosity
 ↑ Distance (L ) ↓ conductance (G)  ↓ Hydration

 ↑ 100C ↑ 2% G
 Ohms law: Relation between current, potential and resistance
In metallic
 In electrolyte solution too, Ohm's law is applicable,
conductor:
 In place of resistance conductance is more appropriate
E
I   The reciprocal of resistance is conductance
R
Rl I
V
R

1 1 1A
 0 (CH COOH )  0
(CH 3COO  )
 0
(H  )
R
3

A G 
R  l
l
R A l 1 l
A G     G  
l A R A
Specific conductance (Conductivity)
l
 G
A
 denoted by k (kappa).
 the conductance offered by a cube of side 1
cm3 containing that electrolyteIf L=1cm and A=1cm2;
 Measured in: ohm -1cm-1

κ =G
Effect of dilution:
l/A is called cell constant
 Strong electrolyte:

No of ions per unit vol decreases k decreases.

 Weak electrolyte
Dissociation increases
number of ions 1/cm3 could be increased
k may be increased or decreased
 Equivalent Conductance; Λeq

 The conductance of the electrolyte obtained by dissolving one

gram equivalent of it in V cc of water and keeping the whole
solution between two electrodes which are a cm apart
 If V be the volume of the solution containing one gram
equivalent of the electrolyte is kept between two electrodes
Unit:
which are separated by 1cm, then
  Conduction of V volume of solution ohm cm eqvt. .
-1 2 -1

 V  conduction by 1 cm 3 volume
 V 
1000
 If C be the normality of the solution V cc
C
 volume of solution containing 1 gm. 1000
 
equivalent of electrolyte is C

 Molar Conductance; Λmolar
 The conductance of the electrolyte obtained by dissolving one
mole of it in V cc of water and keeping the whole solution
between two electrodes which are a cm apart. If V be the such
volume
 molar  Conduction of V volume of solution Unit:
 V  conduction by 1 cm3 volume ohm-1cm2mol.-1
 V 
1000
 If Cmolar be the molarity of the solution V  cc
Cmolar
 volume of solution containing 1 gm. 1000
molecule of electrolyte is  molar  
 mol CN Cmolar
 
Hence the molar conductance Z
  eq Cmol
Relation:

Λmolar = z X Λeq , where z =no of equivalent charges/mole of

 Variation of equivalent conduction with dilution
[The eq. conductance at infinite dilution; ]
Strong electrolyte Weak electrolytes
Electrical force between Are feebly dissociated
q1  q2 Contains less number of charge
ions F
r2
decreases carrying ions
This decreases the Inter ionic forces are very less
electrophoretic and before the dilution
relaxation effects Dilution increases the degree of
equivalent conduction dissociation (Debye Huckel Law)
increases Increase magnitude of the
 0eq  lim
C 0  eq equivalent conductance
Following relation is

observed Degree of ionization ( ) 
0
 eq   0eq  b C   eq  b C
 Variation of equivalent conduction with dilution

Strong electrolyte Weak electrolytes

 eq   0eq  b C   eq  b C

 0eq   eq 
lim

Degree of ionization ( ) 
C 0

0

[The Eq. conductance at infinite dilution for strong electrolyte can be obtained
from the plot shown, extrapolation of curve to zero concentration gives Λ0]
 Methods to determine L0 ( incase of weak electrolyte):
1. From the ionic equivalent conductance at infinite dilution,
 Kohlrausch law: 0   0
cation  0
anion
 At infinite dilution weak
 Acetic acid dissociates as electrolyte is completely
CH3COOH CH3COO- + H+ dissociated and ions are
 0 (CH COOH )  0
(CH 3COO )   0  free from each other.
(H )
3

At infintte dilution, Limiting equivalent conductivity  is sum mobilities of ions

2. From the eq. conductance of strong electrolytes:

 If L0 for KCl, CH3COOK 0  0 
( KCl ) (K  ) 0
(Cl  )
& HCl are known,   0 
0 (CH 3COOK ) (K  ) 0 (CH 3COO  )

• Solving 0  0 
(Cl  )
( HCl ) (H  ) 0

   0  0
0 (CH COOH ) 0(CH COOK ) ( HCl ) ( KCl )
3 3
 Ionic mobility is the velocity of an ion under an unit
potential gradient or field strength.
 Therefore, ionic mobility = .
 Depends on the nature of the ion, concentration of the
solution, temperature, and the applied potential gradient.
 Ionic mobilities of some common cations and anions at
infinite diluation  are given below the table,

H+ 349.8 OH- 198.3
NH4+ 73.6 1/2SO42- 80.0 Eq. cond
Measured units
Ag+ 61.9 I- 78.8 S cm2 equiv-1
Li+ 38.7 NO3- 71.5
F- 55.4
Ionic mobility C H COO -
32.4
6 25 −1
the unit: CGS system = cm s /volt cm = cm s volt . In the SI system=
−1 −1 −1

metre2 s−1 volt−1.

The limiting value of ionic mobility is obtained at infinite dilution when
the interionic attraction is totally absent.
 How do we measure conductance of solution
Different parts of arrangement are

 Power supply: induction coil, ac current, requency

between 550 – 5000 Hz and voltage of 6 – 10 volts. Audio
oscillators with frequency of 1000Hz are generally used.
 Resistance Box:
 The null detector consists of a pair of head phone (ear can
respond around 1000Hz) or a magic eye tube or a cathode
ray tube or a micro ammeter.
 Cell: different shapes, electrode is platinized
Specific conductance
Cell Constant 
 Cell constant: Measured conductance

 Temperature control: water or oil bath

Gx = 1/Rx
Devices for measurement of conductance

Re sis tan ce( Rx) Re sis tan ce( AC ) length , AC

 
Re sis tan ce( Rs) Re sis tan ce( BC ) length , BC
length , AC
 Re sis tan ce( Rx)  Re sis tan ce( Rs) X Gx = 1/Rx
length , BC
The cell constant
 specific conductance = conductance × l /A
 The cell constant is a constant when multiplied to the
conductance gives the specific conductance.
 It is equal to the ratio of distance between electrodes and the
cross-section area on the electrode ( l/A).
 KCl is generally used in this purpose. Solution of same
concentration and ionic strength is prepared first and then the
conductance is measured. KCl (M) g KCl/1000g Soln Sp. Cond (298K)
1 71.352 0.113
0.1 7.41931 0.0129
 Application of conductometry
1. Direct or Absolute conductance Measurements
 Qualitative analysis is used for determination any ions
 Quantitative analysis is used for determination of electrolytes
concentration
 The conductivity meter is calibrated, using

Conductance
standard KCl solution
 The conductance of standard solutions were
measured and a calibration curve is plotted
representing the conductance against the
concentration. Concentration
 A solution of exact known concentration of the
substance to be determined is prepared and
checked from the curve.
2. Conductometric titration
 Advantages of direct conductance measurement
 In estimating the purity of water. Specific conductance of the pure
water is 5 x10-8ohm-1cm‑1.
 For control of water treatment process
 To estimate the salinity of the sea water.
 In the detection of ions after the separation from ion exchange
chromatography.
 Determining the concentration of the solution containing single
electrolyte. (Strong). Conductance measured is compared with the
calibration curve plotted.
 To give valuable information about association and dissociation
equilibria if the reacting species are ionic.
 For continuous control of manufactures
 For sewage pollution assessment
 For detecting in chromatography
Installation for reception of the cleared water with
conductometric gauge for water quality assurance
 2. Conductometric Titration
 Conductometric titration depends on the
measurement of conductance as a function of
volume of titrant added ions 104
 The basic requirement is that the conductance K+ 73.52
Na+ 50.11
must vary with the addition of titrant. number Li+ 38.69
of ions and their mobility. H+ 349.82
 The equivalence point in the titration is Ag+ 61.92
Cl- 76.34
obtained from the plot of conductance Br- 78.4

versus volume of titrant. OH- 198

 The curve is a straight line, which changes

its slope after the equivalence point.
Precautions to be Considered in Conductomertic Titrations
Volume correction:
 Upon carrying out the titration; the titrant used must be at least 10
times concentrated as the solution to be determined.
 However a correction factor must be used to compensate for this
dilution. v V
Correction factor = V
V= initial volume of analyte solution.
v = volume of titrant added.
v V
Actual Conductance =  Measured Conductance
V
 e.g. on determination of solution 0.01 N HCl, the titrant NaOH
should be at least 0.1 N.
 Titration of strong acid with strong base
 Before the addition of base the mobility of
H+ is 350
conductance of the acid is high. Cl- is 73
 The conductance of the solution Na+ is 43
OH-
decreases with addition of NaOH. is198
 In doing so highly mobile H+ ions are
replaced by less mobile Na+ ions.
H+ + Cl– + Na+OH– Na+ + Cl– + H2O
in solution from burette in solution
 The conductance decreases linearly up
to the equivalence point as shown in
the figure.
 At the equivalence point all H+ is neutralized
by OH–, that is the concentration of H+ and
OH– is almost zero (10-7M).
H+ + Cl– + Na+OH– Na+ + Cl– + H2O
all reacted in solution
 The conductance at that condition is due to
the Cl– and Na+ as shown in the figure.
 Once the equivalence point is crossed OH– as
well as Na+ ion concentration increases, so the
conductance of the solution increases linearly.
NaOH Na+ + OH–
 The extrapolation of the curves before and
after the equivalence point meets at a sharp
equivalence point
 Titration of weak acid with strong base
 Consider the titration of acetic acid (HOAc) with NaOH.
CH3COOH + Na+ + OH- → CH3COO- + Na+ + H2O
in solution from burette in solution
 Before titration low initial conductance is observed due to low H+ (350)
obtained during dissociation of weak CH3COOH.
 During titration we can observe slight decrease of conductance due to
consumption of H+ .
 During progress of titration we can observe slight increase in
conductancedue to the presence of CH3COO- (41) & Na+ (43) and nearly
constant H+ due to the buffer action of the produced CH3COONa and the
remaining CH3COOH.
 After end point excess NaOH will lead to increase in conductance due to
increasing of Na+ (43) and OH- (198) + OH -

+ CH3COO- + Na+
+ Na+
Titration of weak acid with strong base

 In the titration of weak acid with a strong base, the shape of

the curve will depend on the concentration and the
dissociation constant Ka of the acid.
 Before the addition of the base the conductance of the acid
solution is less due to partial dissociation of the acid as
compared to the strong acid.
 Common ion effect: With the addition of the base ,the salt
sodium acetate, which is formed during the first part of the
titration tends to repress the ionization of the acetic acid still
present so that its conductance decreases.
 The raising of salt concentration will, however, tend to
produce an increase in the conductance.
Titration of weak acid with strong base

 At the end point all the acetic acid is neutralized, after

that the added base increases the concentration of
highly mobile OH– ions and Na+ ions thus the
conductance increases sharply.
 The point where two straight curves cross will give
the end point.
 Titration of strong acid with weak base
 Consider the titration of HCl with NH4OH.
 Titration of strong acid with weak base
 In the beginning HCl being strong electrolyte dissociates completely
furnishing highly mobile H+ ions; analyte solution gives the high
conductance.
 As the base is added conductance decreases due to the consumption

of H+ ions by OH– till equivalence point is reached.

 At the equivalence point, the minimum conductance is due to the Cl –
and NH4+ of the salt.
H+ + Cl– + NH4OH NH4+ + Cl– + H2O
 After the equivalent point conductance remains almost constant with
addition of the base due to common ion effect.
 In presence of strong electrolyte NH4+Cl– the dissociation of added
base NH4OH is suppressed which cannot furnish excess amount of
mobile OH- ions.
 Titration of weak acid with weak base

 Let us suppose CH3COOH is titrated with NH4OH

Titration of weak acid with weak base

 Before addition of the base the acid has very less

conductance.
CH3COOH CH3COO– + H+ (feebly dissociated)
 With addition of the base H+ is consumed which is
replaced by the less mobile cation here, NH4+. And also
due to common ion effect, the conductance decreases
CH3COO– + H+ CH3COO– + Na+
CH3COOH CH3COO– + H+ (dissociation Supressed)
 But due to the continuous increase in the concentration of
the salt NH4+CH3COO– the conductance slowly increases.
Advantage of conductometric
titrations

 Colored solution where no indicator is found to work

satisfactorily can be successfully titrated by this
method.
 Titration of Weak acid with weak base is feasible.
 In ordinary titration where indicators fail to show
color can be titrated.
 Mixture of weak acid and strong acid can be titrated
by strong base.
 More accurate results are obtained because end point
is determined graphically.
 Titration of mixture of strong and weak
acids with strong base
 (e.g. HCl + CH3COOH) with NaOH
Mixture of strong acid and weak acid aganist strong base.
e.g. HCl/CH3COOH mix with NaOH

Theinitial conductivity is high it is due to HCl which by

common ion effect suppress the ionization of CH3COOH.
 Upon titration; decrease in conductivity occurs due to
replacement of H+ ion with mobility 350
by Na+ ion with mobility 43 , till all the H+
ions from HCl are neutralized.
CH3COOH will thus ionize and

react with NaOH.

The change in conductivity will take

place in similar way as described above. HCl e.p.

for acetic acid.
Precepitation Titrations

 Itis important to choose the suitable titrant which gives

sharp change of conductance after the equivalence
point.

 Titrantmust have mobility that varies greatly from the

sample because the products are weakly ionizable
leading to decrease in conductance during titration till the
endpoint.
e.g. Titration of NaCl ≠ AgNO3
NaCl + AgNO3  AgCl + NaNO3
Na+ + Cl‑ + Ag+ + NO3‑  AgCl + NO3- + Na+

During titration of NaCl against AgNO3, Ag+ precipitate Cl- as

AgCl and NO3- replace Cl- in the medium.
As mobility of NO3- (71.5) is nearly equal that of Cl- (76.3) we
observe nearly no change in conductance during titration.
After complete precipitation of Cl- ,
+ Ag+
exx Ag (61.9) and NO3 (71.5) will
+ -
+ NO3-
- Cl-
increase conductance of solution. + NO3-
The measured conductance of o.1 N solu. of a drug I
s0.0563 ohm-1 at 250c. The cell constant is 0.52 cm-1, what
is the specific conductance? And what is the equivalent
conductance at that concentration? (0.0293 ohm-1cm-1) (293 ohm-1
cm2 /eq)

 A certain cell was filled with 0.01M KCl, (K= 0.001409 ohm-1cm-1), it had a

resistance of 161.8 ohm at 250 C, and when filled with 0.005M NaOH it had a

resistance of 190 ohm. What is the equivalent conductance of the NaOH

solution? (240 ohm -1cm2/ eq.)

So as: the equivalent wt of the substances ↑
their equivalent conductances (λ) ↓

e.g. The λ of HCl (eq.wt. 36.5) is higher than NaCl

(eq.wt. 58.5)

 Equivalent conductance is used to express the ability

of individual substance to conduct electric current.
Thank you