08-Sep-16

Ali-Allana college of pharmacy,

Akkalkuwa

1
 08-Sep-16

 INTRODUCTION
 PRINCIPLE
 IMPORTANT DEFINITIONS & RELATIONS
 INSTRUMENTATIONS
 MEASUREMENT OF CONDUCTIVITY
 CONDUCTOMETRIC TITRATIONS
 ADVANTAGES & DISADVANTAGES OF CONDUCTOMETRIC
TITRATIONS
 APPLICATIONS OF CONDUCTOMETRY

2
 08-Sep-16

 Conductivity include measurement of conductivity of solution due to

the mobility of cation and anions toward respective electrode.
 Conductance (C) is inversely proptional to resistance(R) of solution
C=1/R.
 Conductiviy is expressed in unit mhos OR Ohms-1
 standard unit of Conductance is specific conductance(denoted by
K ).

3
 08-Sep-16

INTODUCTION:

 It is defined has as determination or measurement of the

electrical conductance of an electrolyte solution by means of a
conductometer .
 electric conductivity of an electrolyte solution depends on :
1. Type of ions (cations, anions)

2. Concentration of ions
3. Temperature

4. Mobility of ions

4
 08-Sep-16

 PRINCIPLE:
 Based on the conductance of electrical current through electrolyte
solutions similar to metallic conductors

 The electric conductance in accordance with ohms law which

states that “the stength of current(I)passing through
conductor is directly porportional to potential difference(E) &
inversely to resistance(R)”
I =E/R R= resistance
E= potential diffrence
• Resistant depend upon size and composition

5
 08-Sep-16

 Important definitions & relations

 Conductance

 Specific conductance

 Specific resistance

 Molar conductance

 Equivalent conductance

6
 08-Sep-16

 Conductance:(C)
 it implies the ease with which current flows through a conductor, thus
it is is reciprocal to resistance(R)
C=I⁄R

 Specific conductance (K):

The specific conductance of any conductor is the reciprocal of
specific resistance denoted by k
K =1 ⁄ R × 1 ⁄ A

 Specific resistance:(R)
The resistance R of a conductor is directly proportional to its
length(l) and inversely proportional to its area(A)
of cross section.
R∞l⁄A

7
 08-Sep-16

 Equivalent conductance:
specific conductance of the solution containing 1gm equivalent of
an electrolyte when placed between two sufficiently large electrode
which are 1 cm apart.

 Denoted By
λv
 Molecular conductance: (µv)
Conductance of a solution containing 1 gm mole of the electrolyte
when placed between two parallel electrodes which are 1 cm apart.
 Denoted by µv

8
 08-Sep-16

 Rectangular tank with two opposite side madeup of metalic

conductor acting as electrode 1cm apart.
 1cc solution placed in tank give specific conductance of 1cm cube of
solution
 1cc solution contain 1gm equivalent of solute
 Measured conductance is equivalent conductance
 Dilute 1cc of solution to 9cc by water
 Measured conductance is still equivalent conductance
 Measured conductance not equal to specific
conductance 9 cube
The total conductance of solution will be 9 x Kv
Solution diluted to Vcc conductance given by
Kv x v
 Equivalent conductance at any dilution V
 Where v is volume in cc containing 1 gm
Equivalent to electrolyte is
 Equvalent conductance =Kv x V

9
 08-Sep-16

 Conductance increases with dilution

 Conductance depend on number of ion present in solution.
 Degree of ionization of electrolyte increases leads to more ion
production.
 Specific conductance decreases on dilution because number of current
carrying ion or particle decreases in per c.c
 Equvalent and molecular conductance increases on dilution
 On dilution produce more and more electrolyte(degree of ionisation)
 Whole substance has ionised further dilution produce less or no change
in equavelent and molecular conductivities
 Called Equvalent conductance at infinite dilution

10
 08-Sep-16

 Equvalent conductance tends to become maximum as con

decreases and dilution increases
 KCL maximum conductivity reaced at comparatively higher conc
Or lower dilution as compare to CH3COOH

11
 08-Sep-16

 Instrumentation
The instrument used for measurement of
conductance are know as conduct meters
It consists of :
1. Current source
• Alternating current source
2. Conductivity cells
• Wide mouthed cells
• Cell for reactions producing
precipitates
• Dip type cells
3. Electrodes

12
 08-Sep-16

CURRENT SOURCE:
Induction coil
1. Mechanical high frequency AC generator by
Washburn .
2. Vreeland oscillator by Taylor and Acree.
ac with constant frequency 16-
4200cycles/sec
3. Vaccum tube oscillator by Hall & Adams.

13
 08-Sep-16

 Conductivity cells:-
 Made of pyrex or quartz and are fitted with two
platinum electrodes.
 Electrode consist of stout platinum plate (coated
with platinum black) sealed in to glass tube which
passes through ebonite tube
 Should be placed in vessel containing water to
maintain constant temperature
 Types :
1. Wide mouthed cell
2. Cell for reactions producing precipitation
3. Dip type cells

14
 08-Sep-16

 Wide mouthed cell:-

 Measurement of low conductance
 Wide mouthed fitted with an ebonite cover
which has provisions for platinum electrodes
and burettes

15
 08-Sep-16

 Cell for reactions producing ppts:

 Mainly used for ppt reactions
 Also wide mouthed fitted with ebonite cover
which has provisions for burette ,electrode ,
stirrer
 Stirrer may be mechanical or magnetic

16
 08-Sep-16

 Dip type
 Glass tube of cornonig glass are fix copper wire tip
connected to two platinum plate of 1sq.cm
 Fixed at 1 cm apart

17
 08-Sep-16

 Electrodes :
 Platinum sheets, each of 1 cm2 are fixed at
distance of 1 cm
 The surface is coated with platinum black to avoid
polarization effects and increase effective surface
area.
 Platinisation of electrodes is done by coating
solution of 3% chlorplatinic acid and lead acetate
on it to get uniform coating
 Electrodes usage depends on conductivity and
concentration
 If conc is low then electrodes should be largely and
closely packed

18
 08-Sep-16

 Measurement:-
 The instrument used to measure conductance is
called conductance bridge or conductometer
 Classical circuit employed for measurement is
wheatstone bridge
 All other work on this principle
 Various types are:
1. Kohlrausch conductance bridge
2. Direct reading conductance bridge
3. Phillips conductance bridge
4. Mullard’s conductance bridge
5. Pye’s conductance bridge

19
 08-Sep-16

 Kohlrausch conductance bridge:

Head phone is used

 Direct reading conductance bridge:

 In this head phone is replaced by magic eye which is
electronic device

20
 08-Sep-16

 The set up for Measurement :

consists of meter bridge LN attached to standard
resistance R1 & unknown resistance R2
cell is connected to standard resistance to one side ,
meter bridge LN at other. The sliding contact with galvanometer (G)
can be moved on the wire of meter bridge by means of jockey (M) so
that resistance of unknown is balanced with that of standard. When
galvanometer shows null deflection, the resistance of unknown is
measured by following equation:
MN ⁄ ML =R2 ⁄ R1
R2 =MN ⁄ ML × R1
Conductivity cell
Solution

Meter bridge

21
 08-Sep-16

 Hence conductivity of unknown solution:

1 ⁄ R2 =ML ⁄ MN × 1/R1
The measured conductivity (1/R1) is not always
equal to the specific conductivity of solution , because
the physical configuration of platinum electrode i.e,
length and area of electrodes varies from one another .
Hence conductivity of solution is obtained by calculating
a factor called “cell constant”.

22
 08-Sep-16

 Cell constant:
Defined as ratio of distance between the two
electrodes(l) to the area of electrodes(A)
There fore,
θ =1 ⁄ a
We know that
R= ρ l/a
l/a = cell constant
1/R= 1/ρ x 1/cell constant
(observed conductance)C =specific conductance X cell constant
cell constant = observed /specific conductance
C x cell constant = specific conductance

23
 08-Sep-16

 Conductometry filled with N/50 solution of KCL

 Specific conductance found to be 0.002765mhos at 25°c
 Observed conductance can be determined by
 Cell constant= 0.002765/observed conductance

24
 08-Sep-16

 CONDUCTOMETRIC TITRATIONS:
 INTRODUCTION:
 Is process of qualitative chemical analysis in
which conc of sample is determined.Which is
done by adding areagent( titrant ) of known conc
in measured volumes to the sample (anylate )

25
 08-Sep-16

 TYRES OF CONDUCTOMETRIC
TITRATIONS:
 Acid –base or neutral titrations
 Replacement or displacement titrations
 Redox titrations
 Precipitation titrations
 Complexometric titrations
 Non-aqueous titrations

26
 08-Sep-16

1. ACID- BASE OR NEUTRAL TITRATIONS:

 STRONG ACID-STRONG BASE
• EG: HCL vs NaOH
 STRONG ACID-WEAK BASE
• EG: HCL vs NH4OH
 WEAK ACID-STRONG BASE
• EG: CH3COOH vs NaOH
 WEAK ACID -WEAK BASE
• EG: CH3COOH vs NH4OH

27
 08-Sep-16

 Ions Molar conductance

 K+ 73.52
 Na+ 50.11
 Li+ 38.69
 H+ 349.82
 Ag+ 61.92
 Cl- 76.34
 Br- 78.4
 OH- 198

28
 08-Sep-16

 Strong acid strong base:

H+Cl-+ NA+OH- NA+ Cl- +H2O
 Fall in conductance due to replacement of high
conductivity Hydrogen ions by poor conductivity sodium
ions
 Rise in conductance due to increase in hydroxyl ions

29
 08-Sep-16

 Strong acid- weak base:

H+ Cl-+ NH4+ OH- NH4+Cl-
 Fall in conductance due to replacement of hydrogen
by ammonium ions
 Conductance remain constant

30
 08-Sep-16

 Weak acid –Strong base:

CH3COO+H- + Na+ OH- CH3COO+NA- + H2O

 Initial decrease in conductance followed by increase due

to NaOH
 Steep rise due to excess of NaOH

31
 08-Sep-16

 Weak acid- weak base:

 CH3COOH + NH4OH CH3COO- NH4+ + H2O

 Increase in conductance due to excess of CH3COOH

 Constant conductance due to supression of NH4OH by
CH3COOH

32
 08-Sep-16

 [K++ Cl-]+[Ag++No3_]
 not accurate, because of slow precipitation and
adsorption of solute on the precipitate

Increase of
Ag and NO3
Replacement
of cl with NO3

33
 08-Sep-16

 Replacement Titrations
 Titration in which displacement of one ion by other

 Salt of strong acid and weak base vs. strong base

 Ex: ammonium chloride vs. sodium hydroxide
 Salt of strong base and weak acid vs. strong acid
 Eg: sodium acetate vs. hydrochloric acid

34
 08-Sep-16

 a) Salt of strong acid, weak base vs. strong base

 NH4Cl+NaOH→NH4OH+NaCl
 initially plateau because only displacement of
ammonium ion and chloride ion with sodium and
hydroxide ion
250

200

150

100

50

0
0 10 20 30 40 50

35
 08-Sep-16

 b) Salt of strong base and weak acid vs. strong acid

 CH3COONa+HCl→CH3COOH+NaCl
 Gradually increase because of displacement of acetate
ion by chloride ion till end point

250

200

150

100

50

0
0 10 20 30 40 50

36
 08-Sep-16

 Conducted in acid medium

 End point detremined by dicrease in hydrogen ion conc
and dicrease in conductivity
 Titration of ferrous ions with dichromate ions:
400

350 6 Fe2++Cr2O72-+14H+→6Fe3++2Cr3++7H2O
300

250

200

150

100

50

0
0 10 20 30 40 50 60

37
 08-Sep-16

 Complexometric Titration
 Ex.:-KCl vs. Hg(ClO4)2

 Non-aqueous titrations can also be measured using

conductometry.
 Ex:-
 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.

38
 08-Sep-16

 Advantage Of Conductometric Titrations:

 Does not require indicators since change in

conductance is measured by conductometer
 Suitable for coloured solutions
 Since end point is determined by graphical means
accurate results are obtained with minimum error
 Used for analysis of turbid suspensions, weak acids,
weak bases, mix of weak & strong acids

39
 08-Sep-16

 Dis advantages of conductometric

titration:
 Increased level of salts in solution masks the
conductivity changes , in such cases it does not give
accurate results

 Application of conductometric titrations to redox

systems is limited because, high concentrations of
hydronium ions in the solution tends to mask the
changes in conductance

40
 08-Sep-16

Applications :

 Check water pollution in rivers and lakes

 Alkalinity of fresh water
 Salinity of sea water (oceanography)
 Deuterium ion concentration in water- deuterium
mixture
 Food microbiology- for tracing micro organisms
 Tracing antibiotics

41
 08-Sep-16

 Estimate ash content in sugar juices

 Purity of distilled and de - ionised water
can determined
 Solubility of sparingly soluble salts like
AgCl,BaSo4 can be detected
 Determination of atmospheric
so2,etimationof vanillin in vanilla flavour

42
08-Sep-16

43