Dr. P. G.

Umape
Pune Institute of Computer
Technology
• What is Conductivity?
“It is the ability of the medium to carry electric current”.

Conductors are either metallic (flow of electrons) or

electrolytic (movement of ions). - +

• Electrolytic Conductance
“Conductivity shown by an
electrolytic Solution, when +
- +
-
potential difference applied - + -
+

between two electrodes - - +

+
(Cathode and Anode) due to
migration of ions”. Cathode Anode
The cations move towards cathode, anion move towards anode.

In case of electrolytic conductivity not only electrical charge is

transferred but also there is a mass transfer on the electrode.

Solution of Electrolyte also obey ohm’s Law

It state that Current flowing through electrolytic solution increases

directly with applied voltage and inversely with resistance offered by
solution.

In electrochemistry conductance is preferably used

V
terminology, instead of resistance I
R
Conductance is the ease with which current flows through an
electrolytic solution and it is reciprocal of 1
I 
resistance having unit ohm-1 or mho R
Specific Conductance
As resistance of any uniform conductor is directly proportional to
its length and inversely to cross sectional area
A
l 
R
l  R   
A  A l
• Where ρ is called as Specific resistance
Specific Conductance
• It is the resistance offered by a conducting medium having
length 1cm and cross-sectional area 1 cm2

• Reciprocal of specific resistance is called as specific

conductance,

• Hence Conductance of a 1 cm3 of a solution is Specific

Unit of Specific conductance
conductance denoted by k (Kappa) will be ohm-1cm-1 or Sm-1
1
k 

l 1
k   l is called as cell
A R
l A constant
Conductance
k  
A of solution
Equivalent Conductance (ᴧ)
• Conductance offered by all the ions produced by 1 gm equivalent of
an electrolytic solution
• If v is the volume of solution containing 1 gm equivalent of
electrolyte and k is the specific conductance then
  kV
• If C is the concentration of gm equivalent solution (Normality)
• Then
1000 Unit of Equivalent
V
C Conductance (ᴧ) is
k  1000
  ohm-1 cm2 per equivalent
C
• Molar Conductance (µ)
Conductance offered by all the ions produced by 1 gm mole of
an electrolytic solution.

k  1000
  kV 
M

Unit of molar Conductance (ᴧ) is ohm-1 cm2 per mole

Definition: It is a cell which is used to measure conductivity of a
electrolytic solution.
• The conductivity cell are of various shapes and size.
Construction and working:
• It is made-up of a pyrex glass.
• Provided with ebonite cover.
• The ebonite cover is fitted with a pair of platinum electrode fused
in glass tube, so as to avoid change in distance btween two
electrodes.
• The platinum electodes are connected to A. C. supply.
A.C. Battery

Ebonite cover
Pyrex glass tube

Test solution
Glass tubes

Pt electrode
Construction and working:

• While evaluating the conductivity of a solution the cell is

immersed in the test solution and an A.C. voltage is applied.

• The ions present in the solution migrates towards the

respective electrode, which determine the conductance of
given solution.

• The conductivity of the solution depends on number of ions,

size and charge of the ions.
• What is conductance

Definitions formula and units for

• Specific conductance

• Equivalent conductance

• Molar conductance

• Cell constant

• Conductivity cell diagram, construction and working

 Variable condenser

• Measurement of conductance of an electrolytic solution is

nothing but measuring the resistance of the electrolytic
solution.
• It can be carried out by Wheatstone bridge method
• In Wheatstone bridge method “C” is a cell containing

electrolytic solution of which conductance is to be measured.

• “Rc” is the resistance offered by the cell.

• “S” is the source of A.C.

• “Rs” is a resistance box by which resistance can be varied.

• “G” is the galvanometer

• “AB” is a uniform resistance wire

• “X” is a point of contact

• When conductance of a cell is to be measured, resistance of

the cell is measured directly and converted to conductance .

• Here specific resistance is set by resistance box and point of

contact “X” is moved along uniform resistance wire AB.

• When null deflection is observed in galvanometer the

resistance in the arms of bridge is related by given formula

Rc AX
 Where Rc is the resistance of cell

Rs BX The conductance of cell is reciprocal of resistance

Ʌo

Strong electrolyte
Ʌo
Moderately Strong
electrolyte

Weak electrolyte

C
• Specific conductance of an electrolyte increases with the
concentration.

• As the concentration increases number of ions per ml increases

sharply for strong and moderately strong electrolyte.

• For weak electrolyte the increase in specific conductance with

dilution is very gradual, as it has small degree of dissociation and
weak ionisation.

• Though concentration increases but number of ions per ml for weak

electrolyte increases slightly.
• In case of equivalent conductance, for strong and moderately
strong electrolyte the equivalent conductance increases sharply
with dilution.

• As the dilution increases number of ions increases and equivalent

conductance increases.

• For strong electrolyte as dilution increases number of ions remains

same but the inter ionic interactions goes on decreasing.

• At infinite dilution the ions are far away from each other, that
makes inter ionic interactions become nil and the ion behave as an
independent ion and the equivalent conductance increases.
• For weak electrolyte as the dilution increases, the ionisation of the
electrolyte increases and ultimately number of ions increases.

• Hence the equivalent conductance gradually increases for weak

electrolyte.

• When the dilution reaches to infinite dilution range, there is a

tangential increase in equivalent conductance for a waek
electrolyte

• Because at infinite dilution the weak electrolyte behave as a strong

electrolyte
• Hence the graph of the electrolyte concentration verses
equivalent conductance will decide the nature of electrolyte

• The equivalent conductance for strong and moderately strong

electrolyte show a linear increment.

• While weak electrolyte shows gradual increment and at

infinite dilution tangential increment.

• Hence the equivalent conductance at infinite dilution for

strong and moderately strong electrolyte can be determined,
while for weak electrolyte it is difficult to determine.
• Finally, the maximum equivalent conductance observed for an
electrolyte at infinite dilution is called as equivalent
conductance at infinite dilution and is denoted as Ʌo

• Kohlrausch’s law is used to determine the equivalent

conductance at infinite dilution
At infinite dilution each ion migrates independently of its co-ion
and contributes a definite share to total equivalent conductance
of the electrolyte.

o=o++ o-

λo= equivalent conductance at infinite dilution

λo+ = equivalent conductance of positive ion at infinite dilution

λo- = equivalent conductance of negative ion at infinite dilution

 Dr. P. G. Umape
Pune Institute of Computer
Technology
• Conductometry is a method of analysis based on measuring
the conductivity of ionic solutions caused by the mobility of
ions toward respective electrodes in the presence of an electric
field.

• Conductivity is measured by using a conductometer (or

conductivity probe).

• Conductometric titration: The determination of an end point

or equivalence point of a titration by means of conductivity
measurements is know as conductometric titration. Here the
conductivity depends upon number and mobility of ions
present in electrolytic solutions.
• Following are the different conductometric titrations

 Acid-base titration

 Precipitation titration

 Replacement titration

 Redox (oxidation-reduction) titration

 Complexometric titration
Factors affecting conductivity of an electrolytic solution
• Number of ions per ml: Greater the number of ions per ml in the
solution , greater is the specific resistance. At higher
concentration number of ions per ml is higher.
• Concentration: at higher concentration the number of ions
available for conductance is less due to low dissociation. Hence
specific conductance is slightly lesser than expected. In other
words decrease in concentration leads to increased equivalence
conductance although specific conductance lowers. It is due to
increased number of ions.
Factors affecting conductivity of an electrolytic solution
• Mobility of ions: Small size ions have high mobility and high
conducting ability.

• Charge on ion: Higher the charge on an ion greater is the

conducting ability

• Temperature: At higher temperature kinetic energy of ions is

more, viscosity of water is lesser and ionic interactions are lesses
hence high conductivity.
Consider titration of HCl with NaOH
Na+ + -OH + H++ Cl- Na+ + Cl- + H2O
Strong acid VS Strong Base Titration
(HCl with NaOH)
• In this titration HCl is taken in conical flask and burette is
filled with standard NaOH solution.
• Initially the conductance is high due to the presence of
highly mobile hydrogen ions.
• When the base is added, the conductance falls due to the
replacement of high mobile hydrogen ions by the added
low mobile cation (Na+).
Strong acid VS Strong Base Titration
• As H+ ions react with OH− ions to form water molecule. This
decrease in the conductance.
• This decrease in the conductance continues till the
equivalence point.
• At the equivalence point, the solution contains only NaCl.
• After the equivalence point excess NaOH is added and hence
the conductance increases.
• It is due to the large conductivity of OH- ions.
Strong acid VS Strong Base Titration
• In the figure AB curve indicates decrease in conductance due
to addition of NaOH, point B indicates equivalence point.
• while Curve BC indicates increase in conductance due to
addition of excess NaOH after neutralization.
• Hence by knowing equivalence point strength of acid/base
can be calculated by using formula,
N1V1 = N2V2
Consider titration of acetic acid with NaOH

CH3COOH+ Na+ + -OH CH3COO- + Na++ H2O

Weak acid VS Strong Base Titration

CH3COOH with NaOH

• Here the acid is taken in flask and base is taken in burette

• Initially the conductance is low due to the feeble ionization of

acetic acid.

• On the addition of base, the conductance decreases due to

the replacement of H+ by Na+, as well formation of CH3COONa
which dissociate and suppresses the dissociation of acetic acid
due to common ion effect.
Weak acid VS Strong Base Titration

• After that addition of NaOH the conductance increases

• Here un-dissociated CH3COOH is neutralised by NaOH to form

CH3COONa.

• The CH3COONa is strong electrolyte and leads to increased

conductivity.

• This increment will continue till equivalence point.

• After equivalence point excess of NaOH is added which is

strong electrolyte, this leads to sharp rise in conductivty.
Weak acid-Strong Base Titration:
• In the graph point A to B shows neutralisation of acetic acid by

sodium hydroxide.

• Here initially conductance decreases and then steadily

increases.

• Point B indicates equivalent point, where all the acid

molecules are completely neutralised by base and only
sodium acetate exist in dissociated form.

• From point B to point C there is sharp rise in conductance due

to addition of Strong electrolyte NaOH.
Consider titration of Strong acid HCl with weak base NH4OH
H+ + Cl- + NH4OH H2O + NH4+ +Cl-
Strong Acid VS Weak Base
HCl with NH4OH
• In this titration weak base NH4OH is taken in flask, while
Strong acid HCl is taken in burette .
• The weak base have low dissociation constant and dissociates
into NH4+ and –OH, hence initial conductance is low.
• On addition of HCl, the neutralisation of base takes place to
form NH4Cl and H2O.
• As NH4Cl is a strong electrolyte it dissociate to give NH4+ and
Cl- but both have low mobility due to large size hence
conductance increases but slowly.
Strong Acid VS Weak Base

HCl with NH4OH

• The slow increase in conductance takes place till equivalence

point.

• At equivalence point all the base molecules are neutralised by

acid, here conductance is only due to NH4+ and Cl-

• After equivalence point there is sharp increase in conductance

due to addition of strong acid HCl.
Strong Acid VS Weak Base

HCl with NH4OH

• In the graph the point A to point B indicates slow increase in

conductance due to addition of strong acid (HCl) to weak base
NH4OH leading to formation of NH4Cl.

• Point B indicate equivalence point and conductance is due to

presence of NH4+ and Cl-

• The sharp increase in conductivity indicated by line B to C is

due to addition of excess of acid after neutralisation.
Consider weak acid CH3COOH and weak base NH4OH

CH3COOH+NH4OH CH3COO- + NH4++ H2O

Weak Acid VS Weak Base

CH3COOH with NH4OH

• In case of weak acid, weak base titration weak base is taken in

flask while weak acid is taken in burette.

• As the base (NH4OH )is weak it has low dissociation and hence
less number of ions and shows low conductivity.

• On addition of weak acid (CH3COOH ) the neutralisation takes

place and a strong electrolyte (CH3COONH4 ) is formed along
with H2O.
Weak Acid VS Weak Base

CH3COOH with NH4OH

• The CH3COONH4 is a strong electrolyte and dissociates

completely to CH3COO- and NH4+ but the ions are bulky hence
the conductance increases but slowly.

• At equivalence point the conductance is due to CH3COO- and

NH4+ indicating complete neutralization of base.

• After neutralization excess acid is added, but the acid is weak

and dissociated is negligible hence the conductance remains
constant or increases very slowly.
• What is conductometry?

• What is Conductometric titration?

• SA-SB titration

• WA-SB titration

• SA-WB titration

• WA-WB titration
Weak Acid VS Weak Base

CH3COOH with NH4OH

• In the graph line AB indicate slow rise in conductivity due to

neutralization of weak base and formation of strong
electrolyte.

• Point B indicate neutralisation of base i.e. equivalence point.

• The line BC which is parallel to X axis indicate no incresae in

conductance and is due to addition of weak acid.
 Dr. P. G. Umape
PUNE INSTITUTE OF
COMPUTER TECHNOLOGY
• pH is the scale to measure H+ ion concentration in an aqueous
solution, pH of an aqueous solution can very between 0-14

• Mathematically it is expressed as pH = -log[H+]

• The analyser which measures pH of a solution is called as pH

meter.

• The technique which measure the pH of a solution is called as

pH metry.

• Glass electrode is used to measure the pH of a solution.

• It is an aqueous solution of either weak acid and its salt with
strong base or weak base and its salt with strong acid, which
resist the change in pH of a solution in which it is added, even
if small quantity of an acid or base is added in it.

• Buffers are of two types

1. Acidic buffer: It is a mixture of weak acid and its salt with strong
base e.g. CH3COOH + CH3CONa.

2. Basic buffer : It is a mixture of weak base and its salt with strong acid
e.g. NH4OH + NH4Cl.
Henderson equation
• It is used to prepare buffer of specific pH or pH of a buffer
solution can be calculated by using Henderson equation.
[Salt]
pH of acidic buffer = pKa + log
[Weak acid ]
[Salt]
pOH of basic buffer = pKb + log
[Weak base]

• Where pKa and pKb are the negative log10 of the dissociation
constant of weak acid and weak base
Principle: When two solutions of
different H+ ion concentration are
Rubber cap
separated by a thin glass membrane
then potential difference developed on
inner and outer surface of the
membrane is proportional to the Glass tube

difference in H+ ion concentration of two Pt or Ag/AgCl wire

membrane i.e. pH of outer solution.

0.1 N HCl
Thin walled
Glass bulb
Construction:

 It consists of a glass tube.

 At the end of this glass tube a special glass bulb is attached.

 This glass bulb is having characteristic to exchange H+ ions

with Na+ ions present in glass.

 The glass bulb is filled with 0.1 M HCl solution as internal

reference Solution.

 A Pt wire or Silver wire coated with AgCl is Immersed in the

inner solution and externally connected to Potentiometer.
Construction:

 The glass tube is sealed with rubber cap, so as to maintain

concentration of reference solution constant.

 Glass electrode is represented as follows

Pt,0.1M HCl Glass

 Potential on glass electrode is given as

EG = EG o + 0.0591 pH

 Where EG o is the potential of glass electrode in a solution of

known pH
 In order to determine the pH of solution, glass electrode is
coupled with a reference electrode (Calomel electrode).

 These coupled electrodes are dipped into solution of a

unknown pH and the cell formed is represented as

Pt| Hg,Hg2Cl2 | Cl- || Test Solution || Glass electrode

 EMF of the cell is measured as

E cell = Ecal – EG = 0.2422 – (EG o + 0.0591 pH)

 Where EG o is the potential of glass electrode in a solution of
known pH

Advantages:
• It is simple to use
• Results are accurate and quick
• Equilibrium is easily attained
• Electrodes do not get poisoned easily
Advantages:
• It can be used in strong oxidizing and reducing solutions
• H+ ions can be determined in presence of other ions
• Turbid, colloidal or colored solutions can be analyzed
• It is portable and compact
Disadvantages:
• Glass membrane is fragile
• Frequent calibration is required
• Non aqueous solutions does not give accurate results
1. Definition of pH and PH metry
2. Definition of buffer and types of buffer
3. Henderson equation to calculate pH of buffer
4. Glass electrode principle, construction and working with
diagram.
 Dr. P. G. Umape
PUNE INSTITUTE OF COMPUTER
TECHNOLOGY
• These are the methods of analysis, which analyses the analyte sample
by measuring the potential and/or current of the sample using
electrochemical cell.
• The electrochemical cell is a device, that converts the chemical energy
is converted into electrical energy.
• The electrochemical cell consists of one anode and a cathode, which
are in contact with an electrolytic solution.
• Anode is an electrode where oxidation occurs, while at cathode
reduction occurs.
• This oxidation and reduction reaction of chemical species present in an
electrolytic solution, is responsible for production of electrical energy.
The electrochemical cell can be represented as

Anode ion ion cathode

For example, Daniel cell

Zn Zn++ Cu++ Cu

The anodic and cathodic reaction occurring in Daniel cell is

At anode: Zn(S) Zn++(aq) + 2e-

At cathode: Cu++(aq) + 2e- Cu (S)

Total cell reaction: Zn(S) + Cu++(aq) Zn++(aq) + Cu (S)

Nernst equation:
The Nernst equation relates the reduction potential of an
electrochemical cell (half or full cell reaction) to the standard
electrode potential, temperature and activities of the chemical
species undergoing reduction and oxidation.

Considering the electrode potential of the electrodes EMF of cell

is given by

Ecell = Ecathode - Eanode

At 25 oC the Nernst equation for potential of reduction electrode

is
0.0591
E = E - 𝑛 log[M+n]
o
If Eo is standard reduction potential then the potential of
electrode, when concentration is not unit is given by
𝑅𝑇 [𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑠𝑡𝑎𝑡𝑒]
E = Eo- 𝑛𝐹 log[𝑜𝑥𝑖𝑑𝑖𝑠𝑒𝑑 𝑠𝑡𝑎𝑡𝑒]

By substituting the values of R =0.082 and F = 96500 coulombs at

25 oC we get
0.0591 [𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑠𝑡𝑎𝑡𝑒]
E = Eo- 𝑛
log [𝑜𝑥𝑖𝑑𝑖𝑠𝑒𝑑 𝑠𝑡𝑎𝑡𝑒]

Or
0.0591 [𝑜𝑥𝑖𝑑𝑖𝑠𝑒𝑑 𝑠𝑡𝑎𝑡𝑒]
E = Eo+ 𝑛
log [𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑠𝑡𝑎𝑡𝑒]
Reference electrode:
The electrode which produces stable and reproducible potential
irrespective of the type and concentration of solution in which it
is immersed.
The reference electrode completes the cell by acting as a half cell
and provide stable electrode potential, against which indicator
electrode is compared and measured.
e.g. calomel electrode, standard hydrogen electrode, silver-silver
chloride electrode, Copper-Copper sulphate electrode etc.

Indicator electrode:
The electrode of which electrode potential varies with type and
concentration of solution in which it is immersed.
Indicator electrode is used to analyse the analyte sample based
on potential or conductivity shown by the electrode when in
contact with analyte sample.
Construction:
• It consists of a narrow glass tube with tapering lower end and
the bottom of end is porous.
• The bottom of glass tube is filled with liquid Mercury.
• Above the liquid Mercury paste of Hg-Hg2Cl2 is placed and
the electrode is filled with KCl solution.
• In order to make optical contact with outer circuit a platinum
wire is deep in liquid Mercury.
• In some calomel electrodes side tube filled with gel is
provided, which will act as salt bridge for making electrical
contact.
Calomel electrode is represented by
Pt, Hg Hg2Cl2 Cl-
Cell Reactions:
2 Hg + 2 Cl- Hg2Cl2 + 2e- (If Calomel electrode acts as an anode)
Hg2Cl2 + 2e- 2 Hg + 2 Cl- (If Calomel electrode acts as a cathode)

The reduction potential of the calomel electrode is given by

E = Eo- 0.0591log10[Cl-]
When Calomel electrode is connected to standard hydrogen
electrode, the EMF of cell is equal to potential of Calomel
electrode
The potential of Calomel electrode depends on the
concentration of KCl solution inside the Calomel electrode.
In other words potential of Calomel electrode depends on
concentration of Cl-

Concentration
Saturated KCl 1M KCl O.1 M KCl
of KCl

Eo of Calomel 0.2422 V 0.281 V 0.3334 V

Demerits of Calomel electrode:

• It cannot be used above 50 oC as Hg2Cl2 decomposes.
• Both Hg and Hg2Cl2 are poisonous
Standardization/Calibration process:
1. Activate the glass electrode and connect to the pH meter.
2. Connect the pH meter to electrical supply and switch on the
pH meter.
3. Clean the glass electrode by distilled water
4. Immerse the glass electrode in a solution of known pH
(Buffer solution of pH 4/10).
5. Adjust the temperature to 20 0C by temperature knob
provided with pH meter.
Standardization/Calibration process:
6. Once the temperature is achieved, check the pH on pH
display.
7. If the pH in the display is deviating from the pH value of
buffer solution.
8. Adjust the standardization knob to the pH value of buffer.
9. Now the pH meter is said to be standardized.
10. Do not disturb the standardization knob throughout the pH
analysis.
11. After use of glass electrode keep it in the distilled water to
keep it hydrated.
Strong Acid- Strong Base pH metric titration
• Consider a strong acid HCl and strong base NaOH
• Strong acid is taken in flask while strong base is taken in
burette
• As both are strong acid and strong base they undergoes
complete dissociation
The net reaction during the titration is as follows
Na+ + -OH + H+ + Cl- Na+ + Cl- + H2O
Strong Acid- Strong Base pH metric titration

• Consider strong acid (HCl) and strong base (NaOH)

conductometric titration.
Strong Acid- Strong Base pH metric titration
• Procedure:
• Take V1 ml of acid in a conical flask of unknown concentration
• Fill the burette with N2 normal NaOH and titrate.
• Check the pH of Solution after addition of 0.5 ml of NaOH
each time.
• Initially pH rises gradually upto pH 4 after that a sudden rise
in pH is observed upto pH 10, near equivalence point.
• After that gradual rise in pH takes place by continuing the
addition of NaOH addition.
Strong Acid- Strong Base pH metric titration
• The equivalence point of the titration is 7.
From the graph
• The V2 is the volume of NaOH required at equivalence point.
• If V1 is volume of acid taken for titration, V2 is the burette
reading and N2 is the normality of NaOH, then Normality of

HCl (N1) can be calculated as

N1V1 = N2V2
1. How to activate glass electrode?
2. Why activation of glass electrode is needed?
3. How to standardise pH meter?
4. SA-SB pH metric titration