Unit II

Electro analytical techniques

 REPRESENTATION OF A CELL
Let us illustrate the convention taking the example of Daniel cell.
(i) Anodic half -cell is written on left and cathodic half- cell on right hand
side.
Zn(s) | ZnSO4 (sol) || CuSO4 (sol) |Cu (s)
(ii) Two half cells are separated by double vertical lines: Double vertical
lines indicate salt bridge or any type of porous partition.
Zn-| ZnSO4 (aq.) || CuSO4 (aq.) | Cu+
(iii) EMF (electromotive force) may be written on the right hand side of
the cell.
(iv) Single vertical lines indicate the phase separation between electrode
and electrolyte solution.
Zn|Zn2+||Cu2+|Cu
(v) Invert electrodes are represented in the bracket
Zn|ZnSO4||H+|H2, Pt
The Nernst Equation

E cell = E 0 cell - (RT/nF) lnQ

Ecell = cell potential under nonstandard conditions (V)

Ecell = cell potential under nonstandard conditions (V)
E0cell = cell potential under standard conditions
R = gas constant, which is 8.31 (volt-coulomb)/(mol-K)
T = temperature (K)
n = number of moles of electrons exchanged in the electrochemical
reaction (mol)
F = Faraday's constant, 96500 coulombs/mol
Q = reaction quotient, which is the equilibrium expression with
initial concentrations rather than equilibrium concentrations
 Types of Electrodes

 Reference electrodes
 Indicator electrode
 Reference electrodes

A) Primary reference electrode

e.g. Hydrogen electrode
B) Secondary reference electrode
e.g. Calomel electrode, silver-silver chloride
electrode, mercury-mercury sulphate electrode,
mercuric oxide electrode, glass electrode,
quinhydrone electrode.
 Secondary Reference Electrode

Calomel Electrode:
Principle: The potential of the calomel electrode depends
upon the concentration of KCl. If KCl solution is saturated,
then its potential is0.2415V and such electrode is called
saturated calomel electrode(SCE).
If KCl solution is 1N,then its potential is 0.280V and such
electrode is called normal calomel electrode(NCE).If KCl
solution is0.1N,then its potential is 0.3338V and such electrode
is called decinormal calomel electrode.(DNCE).
Representation of calomel electrode:
Hg|Hg2Cl2.KCl(xM)
 Reactions:-

At Anode :- 2Hg → 2Hg+ + 2e-

At cathode: 2Hg+ + 2Cl- + 2e- → Hg2Cl2
------------------------------------------
2Hg + 2Cl- → Hg2Cl2

Fig: Calomel electrode

 Indicator Electrode (Glass Electrode)

The glass electrode consists of a very thin walled glass bulb,

made from a low melting glass having high electrical
conductivity, blown at the end of a glass tube as shown in fig.
The bulb contains 1M HCl solution sealed into glass tube is a
silver wire coated with silver chloride at its lower end. The lower
end of the silver wire dips into the HCl, forming silver-silver
chloride electrode.
When glass electrode is placed in a solution the potential
develops across the glass membrane as a result of a concentration
difference of H+ ions on the two side of the membrane. The
potential of a glass electrode is determined using standard
calomel electrode as shown in fig (a) & (b).
Fig (a): Indicator electrode Fig (b):Glass electrode connect calomel electrode
 Ion selective electrodes
An ion selective electrode measures the potential of a
specific ion in solution against a stable reference electrode of
constant potential. The potential difference depends upon the
activity of the specific ion in solution.

There are two main types of membrane material:

Solid crystal matrix -a single crystal or a polycrystalline
compressed pellet.
Ion carrier - a complex organic molecule impregnated into a
plastic, PVC. or rubber film which acts as an ion carrier.
Types of Ion selective electrodes

 Glass membrane
 Liquid membrane
 Solid-state
 Gas sensing
 Reference:
 Combination
 Ion-exchange resin membranes
 Enzyme electrodes
CONDUCTOMETRY

Principle
The ability of any ion to transport charge
depends on the mobility of the ion, mobility of ion is
affected by factors like the charge on ion, size and
mass of ion and extent of solvation.
Important laws, used in conductometry
Ohm’s Law : It is written as, I α E
Unit = Ω(ohm).

Conductance (c): It is written as C = 1/R,
Unit = ohm or mho (ohm-1)

Specific resistance (ρ): It is written as R α l/a or R=ρ.l/a
Unit = ρ is ohm.cm

Specific conductance (k):  It is written as K =C.l/a
Unit = mho.cm-1

Cell constant: It is written as K = C.(l/a)
Unit= cm-1

Equivalent conductance (λv): λv = K x 1000/C
Unit = λv = ohm-1.cm2.gm-equiv-1
Molar conductance (µ): µ = K x 1000/Molarity
µ=µ
Effect of dilution on conductivity:-

 The conductivity of solution increases on dilution.

 The specific conductivity decreases on dilution (as
number of ions decreases w.r.t. to volume).
 The equivalent and molar conductivities increase with
dilution.
 The equivalent and molar conductivities tend to
acquire maximum value with increasing dilution.
[Maximum at dilution]
 Variation of molar conductance with concentration
Effect of temperature on conductivity :-
The conductance of the solution increases with
increase in temperature due to,
 Increase in the velocity of ions.
 Decrease in the viscosity of the medium.
 Decrease in the interaction between the ions.

Kohlarusch’s Law:-
The equivalent conductance of an electrolyte
at infinite dilution is equal to the sum of the
equivalent conductance of the component ions.
Mathematically it is written as, λ∞ =λ anion + λ cation
Method:
Determination of specific conductivity:
The observed conductivity of solution is then
calculated by applying the following formula:

Thus AH and BH are measured on graduated scale and R in

ohms from resistance box.
Determination of cell constant :-
It is calculated by following formula,
Application of Kohlarusch’s Law :-

 Calculation of molar conductivity at infinite dilution

for weak electrolytes:
 Calculation of degree of dissociation:
 Calculation of dissociation constant for a weak
electrolyte:
 Calculation of solubility of sparingly soluble salt:
Conductometric titrations:

Principle :- The principle involved is that electrical

conductance depends upon number and mobility of
ions in the solutions.
  Types of Conductometric Titrations:


Titration of strong acid (HCl) with strong base (NaOH):

HCl + NaOH → NaCl + H2O

 
 Titration of a weak acid (CH3COOH) and a strong base
(NaOH) :-
CH3COOH + NaOH → CH3COO-Na+ + H2O
 Titration of mixture of a strong acid and weak
acid with as strong base:
 Strong Acid with a Weak Base, e.g. HCl Vs
NH4OH:
 Weak Acid with a Weak Base: 
Precipitation titration:
Advantage of conductometric titrations:-
 
 This method can be used with very diluted solutions
 This method can be used with colored or turbid
solutions in which end point can not be visible.
 This method can be used in which there is no suitable
indicator is found to work satisfactorily can be
successfully titrated by this method.
 It has many applications, i.e. it can be used for weak
acid and weak bases, redox, precipitation, or complex
titrations
 More accurate results are obtained because the end
point is determined graphically.
pH Metry :-
The concept of pH was first introduced by Danish
chemist Sorensen. The equation that defines pH is given
as follows:
pH= -log[H+]
which is read as: the pH is equal to minus the log of
the H+ concentration.
For example :-
H+ concentration is very low, lets say about
0.0000001M, then the pH is,
pH= -log[.0000001] which is the same as -log[1 X 10-7]
The term log [1 X 10-7] = -7
- (-7) = 7
Types of Buffer solutions :

 Acidic buffer:
Acidic buffer solution contains equimolar quantities of a weak
acid and its salt with strong base. For example: acetic acid,
CH3COOH and sodium acetate I.e. CH3COONa. A solution
containing equimolar quantities of acetic acid and sodium acetate
maintains its pH value around 4.74.
 Basic buffer:
Basic buffer solution contains equimolar quantities of a weak
base and its salt with strong acid. For example: ammonium
hydroxide i.e. NH4OH and ammonium chloride I.e. NH4Cl. A
solution containing equimolar quantities of ammonium hydroxide
and ammonium chloride maintains its pH value around 9.25.
pH metric Titrations:-
 Titration of Mixture of Acids (HCl + H3PO4 ) against
strong base (NaOH) :-
Principle:
That titration where the end point is measure
by change in pH is known as pH metric titration. On
addition of NaOH in mixture of HCl-H3PO4 following
reactions will occur:
HCl +NaOH→H2O+NaCl
H3PO4 + NaOH→ H2PO4-+ H2O + Na+
H2PO4- + NaOH→ HPO4-2+ H2O +Na+
HPO4- + NaOH→ PO4-3 + H2O +Na+
 
 Titration Curve:-
 
Potentiometry :

Potentiometry is a method used in

electroanalytical chemistry, usually to find the
concentration of a solute in solution.

Types of Potentiometry Titratons :-

 Acid base titration

 Oxidation-reduction titration
 Precipitation titration
.=
=

Potentiometric Titrations:-
The reaction involved, during titration are:
Ce+4 + Fe+2 → Ce+3 + Fe+3
Oxidation : Fe+2 → Fe+3 + e-1(E01= 0.75V)
Reduction : Ce+4 + e-1 → Ce+3(E02 = 1.45V)
Net Reaction : Ce+4 + Fe+2 → Fe+3 + Ce+3

At Initial Stage :-
E1 = Eo1+0.059/n log [Fe3+ ] / [Fe 2+ ]
At Equivalence point :-
 Eeq.pt. = == = 1.1 volts
After Equivalence point :-
E2 = Eo2 + 0.059/n log [ Ce4+ ] / [Ce3+]
 
Graph :-
1.8

1.6

1.4
E, volts

1.2

1.0

0.8

0.6
0 20 40 60 80 100 120 140 160 180 200
mL Ce4+
UV-Visible Spectroscopy :-

Regions of the spectrum:

The types of electromagnetic radiation are broadly
classified into the following classes:
 Gamma radiation
 Ultraviolet radiation
 Visible radiation
 Infrared radiation
 Microwave radiation
 Radio waves
Principle of UV spectroscopy :-
Lambert’s Law :-
Mathematically, the law can be written as,
Integrating within limits,

Statement :-The intensity of transmitted light (It)

decreases exponentially as the thickness of absorbing
medium increases, for a fixed concentration
Beer’s Law :-
Mathematically, the law can be written as,

Integrating within limits

Statement :-
Beer’s law can be stated as, the intensity of
transmitted light decreases exponentially with
increase of concentration, for a fixed path length of
solution.
Combined Lambert-Beer’s Law :
Statement :-
Lambert-Beer’s law can be stated as “absorption of a
light by solution is directly proportional to the
concentration of solution and the path length”.
Terms in UV-Visible Spectrophotometry :-
 Chromophore :-
The part of a molecule responsible for imparting color,
are called as chromospheres.
e.g. NO2, N=O, C=O, C=N, C≡N, C=C, C=S, etc
 Auxochrome: -
The functional groups attached to achromophore
which modifies the ability of the chromophore to absorb
light, altering the wavelength or intensity of absorption.

 Bathochromic Shift (Red Shift):
When absorption maxima (λmax) of a compound
shifts to longer wavelength, it is known as
bathochromic shift or red shift.
e.g. An auxochrome group like –OH, -OCH3 causes
absorption of compound at longer wavelength
 Hypsochromic Shift (Blue Shift):
When absorption maxima (λmax) of a
compound shifts to shorter wavelength, it is known as
hypsochromic shift or blue shift.•
E.g; Aniline shows blue shift in acidic medium, it loses
conjugation
 Hyperchromic Effect:
When absorption intensity (ε) of a compound is increased,
it is known as hyperchromic shift.

. Hypochromic Effect:
When absorption intensity (ε) of a compound is decreased, it is known as
hypochromic shift. CH3 Naphthalene 2-methyl naphthalene ε = 19000 ε =

10250 Shifts and Effects Hyperchromic shift Blue RedAbsorbance ( A ) shift

 Types of electronic Transitions :


σ →σ* transition

n →π* transition


n →σ* transition


π →π* transition

The order of energy required for electronic transition is:

σ →σ* > σ →π* > π →σ* > n → σ* > π → π* > n → π*
. Fig. (a) : Single beam UV/visible spectrophotometer

I trumentation UV-Visible spectroscopy :-

Fig.(b): Double beam UV/VIS spectrophotometer

UV-Visible spectrometers are composed of four basic
parts:
 The light source :- , .
The rotating discs 
 The sample and reference cells
 The detector and computer
 The chart recorder :-
Applications of UV-Visible Spectroscopy:-

 Qualitative analysis of organic compounds

 Detection of impurities in the organic compounds
 Quantitative analysis: This is based upon Beer’s law
i.e. A ∝ C
 Chemical kinetics:
 Structural information
 Dissociation constants of weak acid or weak base :