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CONDUCTOMETRIC
METHODS OF
ANALYSIS
By;- SANCHIT DHANKHAR
2
Introduction
Ohm’s law.
Conductometric measurements.
Factor affecting conductivity.
Application of conductometry.
2.Conductometric titration-:
 Introduction.
Types of conductometric tiration.
Advantages of conductometric tiration.
3.Recent devlopement
4.References .
Content
s
Conductometry:
is the simplest of the electroanalytical
techniques; by Kolthoff in 1929.
Conductivity is:
“the ability of the medium to carry
electric current”.
Introduction
Conductors are:
either metallic (flow of electrons) or
electrolytic (movemenmt of ions).
Conductance of electricity:
migration of positively charged ions towards the
cathode and negatively charged ones towards the
anode
(i.e.) current is carried by all ions present in solution.
Conductance depends on the number of ions in solun.
Introduction
5
Introduction
Factors affecting conductance:
1- Temperature:
(1C increase in temperature causes 2 %
increase in conductance).
2- Nature of ions
Size, molecular weight and number of
charges.
3- Concentration of ions:
As the number of ions increases, the
conductance increases.
4- Size of electrodes
Conductance is directly proportional to
the cross sectional area (A).
Specific conductance (K)
Conductance is directly proportional to the
cross section area A
and is inversely proportional to the length of
a uniform conductor,
Thus,
G  A/l so G =KA/L
where K is the specific conductance
(the conductance when A and L are
numerically equal).
When unit of A and L is centimeter, K is:
“the conductance of a cube of liquid one
centimeter on a side” its unit is Ohm-1 Cm-1
Equivalent conductance (o ):
“It is the conductance of a solution of
one-gram equivalent of solute (with no
respect of its volume) contained
between two electrodes placed 1 cm
apart.”
Due to the interionic effects,
the equivalent conductance (o) is
concentration dependant.
The value of (o)
(equivalent conductance at infinite
dilution)
is used for comparison purposes.
The magnitude of (o) is determined
by the charge, size and degree of
hydration of the ion.
(o) is also known as
limiting ionic conductance
or
ionic mobility.
Table 6, shows limiting ionic
conductances or ionic mobilities
(o) in water at 25C for many ions.
10
Conductivity measurements
1.Electrodes
Two parallel platinized Pt. foil electrodes or Pt. black with
electrodeposited a porous Pt. film which increases the surface area of
the electrodes and further reduces faradaic polarization.
2.Primary standard solutions
Primary standard KCl solution ,at 25℃, 7.419g of KCl in 1000g of
solution has a specific conductivity of 0.01286Ω-1/cm.
11
3. Conductivity Cell :
Avoid the change of temperature during determination
4.Wheat stone bridge :
Conductivity Cell and Wheat stone Bridge
Factors affecting conductivity:
 Size of ions
 Temperature
 Number of ions
 Charge of ions
 Specific conductivity:-It is conductivity offered by a
substance of 1cm length and 1sq.cm surface area. units
are mhos/cm.
 Equivalent conductivity:-it is conductivity offered by a
solution containing equivalent weight of solute in it.
12
Factors affecting conductivity
Cations (o) Anions (o)
H+
Na+
K+
NH4+
Ag+
½Ba2+
Li+
Pb2+
Ca2+
Sr2+
Cu2+
Fe2+
Mg2+
Zn2+
350
50.1
74
73
62
64
38.7
73
59.5
59.46
54
54
35.06
52.8
OH-
Cl-
NO2-
CH3COO-
CH3CH2COO-
½SO42-
Br-
I-
NO3-
ClO4-
ClO3-
BrO3-
IO4-
CH3COO-
198
76
71
41
36
80
78.1
76.8
71.44
67.32
64.58
55.78
54.4
40.9
Molar conductance of various ions at infinite dilution at 25℃
H+ and OH- ions
have by far
the largest equivalent conductances.
H2O has a very low conductivity,
So, acid-base titrations yield the most
clearly defined equivalence points by
conductometry.
Molar conductance of various ions at infinite dilution at 25℃
Solved Example:
Calculate the limiting equivalent
conductance (ionic mobility) of:
1- H2SO4 2- Propionic acid
3- Propionic acid from (Ao) of HCl, sodium
propionate and NaCl.
Solution:
1. Limiting equivalent conductance (ionic
mobility) (Ao) of H2SO4 =
(2 x 350) + (2 x 80) = 860
Molar conductance of various ions at infinite dilution at 25℃
2.(Ao) for propionic acid =
= 350 + 36 = 386
Na-propionate + HCl = NaCl + propionic acid
(85.9) (426) (126.4) (?)
3. (Ao) for propionic acid =
[(Ao) for HCl + (Ao) for Na-propionate - (Ao)
for NaCl] =
= 426 + 85.9 – 126.4 = 385.5
No significant difference between
results in 2 & 3.
Molar conductance of various ions at infinite dilution at 25℃
It can be used for the determination of:-
 Solubility of sparingly soluble salts
 Ionic product of water
 Basicity of organic acids
 Salinity of sea water (oceanographic work)
 Chemical equilibrium in ionic reactions
 Conductometric titration
17
APPLICATIONS OF CONDUCTOMETRY
CONDUCTOMETRIC TITRATIONS
 The determination of end point of a titration by
means of conductivity measurements are known
as conductometric titrations.
18
19
Types of conductometric titrations
 Acid-base titration
 Precipitation titration
 Replacement titration
 Redox (oxidation-reduction) titration
 Complexometric titration
Titration of strong acid
(a) with strong base e.g. HCl with NaOH
(b) with weak base e.g. HCl with NH4OH
20
ACID-BASE TITRATIONS
(c) with strong base e.g. CH3COOH with NaOH
(d) with weak base e.g. CH3COOH with NH4OH
21
Titration of weak acid
[K+ + Cl-] + [Ag+ + No3
_]
22
PRECIPITATION TITRATIONS
A. Salt of strong acid and weak base vs. strong base
Ex: ammonium chloride vs. sodium hydroxide
NH4Cl+NaOH→NH4OH+NaCl
23
REPLACEMENT TITRATIONS
24
B. Salt of strong base and weak acid vs. strong acid
eg. sodium acetate vs. hydrochloric acid
CH3COONa + HCl → CH3COOH + NaCl
REPLACEMENT TITRATIONS
Titration of ferrous ions with dichromate ions:
6 Fe2+ + Cr2O7
2- + 14H+→ 6Fe3+ + 2Cr3+ +7H2O
25
REDOX TITRATION
Eample:- KCl vs. Hg(ClO4)2
 Non-aqueous titrations can also be measured using
conductometry.
Eample:-
a)titration of weak bases vs. perchloric acid in dioxan-
formic acid.
b)Titration of weak organic acids in methanol vs. tetra
methyl ammonium hydroxide in methanol-benzene.
26
COMPLEXOMETRIC TITRATION
 No need of indicator
 Colored or dilute solutions or turbid suspensions can be
used for titrations.
 Temperature is maintained constant throughout the
titration.
 End point can be determined accurately and errors are
minimized as the end point is being determined
graphically.
27
ADVANTAGES OF CONDUCTOMETRIC TITRATIONS
DISADVANTAGES OF CONDUCTOMETRIC TITRATIONS
- non specificity
- interference of high conc. of other electrolytes.
THANKYOU
28

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Conductometry- Pharmaceutical Analysis

  • 2. 2 Introduction Ohm’s law. Conductometric measurements. Factor affecting conductivity. Application of conductometry. 2.Conductometric titration-:  Introduction. Types of conductometric tiration. Advantages of conductometric tiration. 3.Recent devlopement 4.References . Content s
  • 3. Conductometry: is the simplest of the electroanalytical techniques; by Kolthoff in 1929. Conductivity is: “the ability of the medium to carry electric current”. Introduction
  • 4. Conductors are: either metallic (flow of electrons) or electrolytic (movemenmt of ions). Conductance of electricity: migration of positively charged ions towards the cathode and negatively charged ones towards the anode (i.e.) current is carried by all ions present in solution. Conductance depends on the number of ions in solun. Introduction
  • 6. Factors affecting conductance: 1- Temperature: (1C increase in temperature causes 2 % increase in conductance). 2- Nature of ions Size, molecular weight and number of charges. 3- Concentration of ions: As the number of ions increases, the conductance increases. 4- Size of electrodes Conductance is directly proportional to the cross sectional area (A).
  • 7. Specific conductance (K) Conductance is directly proportional to the cross section area A and is inversely proportional to the length of a uniform conductor, Thus, G  A/l so G =KA/L where K is the specific conductance (the conductance when A and L are numerically equal). When unit of A and L is centimeter, K is: “the conductance of a cube of liquid one centimeter on a side” its unit is Ohm-1 Cm-1
  • 8. Equivalent conductance (o ): “It is the conductance of a solution of one-gram equivalent of solute (with no respect of its volume) contained between two electrodes placed 1 cm apart.” Due to the interionic effects, the equivalent conductance (o) is concentration dependant. The value of (o) (equivalent conductance at infinite dilution) is used for comparison purposes.
  • 9. The magnitude of (o) is determined by the charge, size and degree of hydration of the ion. (o) is also known as limiting ionic conductance or ionic mobility. Table 6, shows limiting ionic conductances or ionic mobilities (o) in water at 25C for many ions.
  • 10. 10 Conductivity measurements 1.Electrodes Two parallel platinized Pt. foil electrodes or Pt. black with electrodeposited a porous Pt. film which increases the surface area of the electrodes and further reduces faradaic polarization. 2.Primary standard solutions Primary standard KCl solution ,at 25℃, 7.419g of KCl in 1000g of solution has a specific conductivity of 0.01286Ω-1/cm.
  • 11. 11 3. Conductivity Cell : Avoid the change of temperature during determination 4.Wheat stone bridge : Conductivity Cell and Wheat stone Bridge
  • 12. Factors affecting conductivity:  Size of ions  Temperature  Number of ions  Charge of ions  Specific conductivity:-It is conductivity offered by a substance of 1cm length and 1sq.cm surface area. units are mhos/cm.  Equivalent conductivity:-it is conductivity offered by a solution containing equivalent weight of solute in it. 12 Factors affecting conductivity
  • 13. Cations (o) Anions (o) H+ Na+ K+ NH4+ Ag+ ½Ba2+ Li+ Pb2+ Ca2+ Sr2+ Cu2+ Fe2+ Mg2+ Zn2+ 350 50.1 74 73 62 64 38.7 73 59.5 59.46 54 54 35.06 52.8 OH- Cl- NO2- CH3COO- CH3CH2COO- ½SO42- Br- I- NO3- ClO4- ClO3- BrO3- IO4- CH3COO- 198 76 71 41 36 80 78.1 76.8 71.44 67.32 64.58 55.78 54.4 40.9 Molar conductance of various ions at infinite dilution at 25℃
  • 14. H+ and OH- ions have by far the largest equivalent conductances. H2O has a very low conductivity, So, acid-base titrations yield the most clearly defined equivalence points by conductometry. Molar conductance of various ions at infinite dilution at 25℃
  • 15. Solved Example: Calculate the limiting equivalent conductance (ionic mobility) of: 1- H2SO4 2- Propionic acid 3- Propionic acid from (Ao) of HCl, sodium propionate and NaCl. Solution: 1. Limiting equivalent conductance (ionic mobility) (Ao) of H2SO4 = (2 x 350) + (2 x 80) = 860 Molar conductance of various ions at infinite dilution at 25℃
  • 16. 2.(Ao) for propionic acid = = 350 + 36 = 386 Na-propionate + HCl = NaCl + propionic acid (85.9) (426) (126.4) (?) 3. (Ao) for propionic acid = [(Ao) for HCl + (Ao) for Na-propionate - (Ao) for NaCl] = = 426 + 85.9 – 126.4 = 385.5 No significant difference between results in 2 & 3. Molar conductance of various ions at infinite dilution at 25℃
  • 17. It can be used for the determination of:-  Solubility of sparingly soluble salts  Ionic product of water  Basicity of organic acids  Salinity of sea water (oceanographic work)  Chemical equilibrium in ionic reactions  Conductometric titration 17 APPLICATIONS OF CONDUCTOMETRY
  • 18. CONDUCTOMETRIC TITRATIONS  The determination of end point of a titration by means of conductivity measurements are known as conductometric titrations. 18
  • 19. 19 Types of conductometric titrations  Acid-base titration  Precipitation titration  Replacement titration  Redox (oxidation-reduction) titration  Complexometric titration
  • 20. Titration of strong acid (a) with strong base e.g. HCl with NaOH (b) with weak base e.g. HCl with NH4OH 20 ACID-BASE TITRATIONS
  • 21. (c) with strong base e.g. CH3COOH with NaOH (d) with weak base e.g. CH3COOH with NH4OH 21 Titration of weak acid
  • 22. [K+ + Cl-] + [Ag+ + No3 _] 22 PRECIPITATION TITRATIONS
  • 23. A. Salt of strong acid and weak base vs. strong base Ex: ammonium chloride vs. sodium hydroxide NH4Cl+NaOH→NH4OH+NaCl 23 REPLACEMENT TITRATIONS
  • 24. 24 B. Salt of strong base and weak acid vs. strong acid eg. sodium acetate vs. hydrochloric acid CH3COONa + HCl → CH3COOH + NaCl REPLACEMENT TITRATIONS
  • 25. Titration of ferrous ions with dichromate ions: 6 Fe2+ + Cr2O7 2- + 14H+→ 6Fe3+ + 2Cr3+ +7H2O 25 REDOX TITRATION
  • 26. Eample:- KCl vs. Hg(ClO4)2  Non-aqueous titrations can also be measured using conductometry. Eample:- a)titration of weak bases vs. perchloric acid in dioxan- formic acid. b)Titration of weak organic acids in methanol vs. tetra methyl ammonium hydroxide in methanol-benzene. 26 COMPLEXOMETRIC TITRATION
  • 27.  No need of indicator  Colored or dilute solutions or turbid suspensions can be used for titrations.  Temperature is maintained constant throughout the titration.  End point can be determined accurately and errors are minimized as the end point is being determined graphically. 27 ADVANTAGES OF CONDUCTOMETRIC TITRATIONS DISADVANTAGES OF CONDUCTOMETRIC TITRATIONS - non specificity - interference of high conc. of other electrolytes.