Electrochemical method of Analysis
Electrochemical methods of analysis are physico-
chemical methods, which deal with electrical
quantity or property of a solution of the substance
to be analyzed qualitatively or quantitatively.
Advantages of electrochemical methods of analysis
1- Shorten time required for analysis.
2- Can be used when the classical methods of analysis can't be
applied, e.g. in case of colored, turbid, very dilute solutions and when
there is no suitable indicator.
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Electrochemical methods of analysis
Potentiometry depends on measuring of voltage between two electrodes.
electron transfer occurs where redox reactions take place at the electrodes
surfaces ( Galvanic cell).
Voltammetry (Polarography):
Depends on measuring the current produced when a voltage is applied (electrolytic
cell). Redox reaction takes place on the electrode surface.
Conductometry and electrophoresis:
Depend on the movement of ions in an electric field leading to conductance of
electricity without occurrence of redox reaction at the electrode (inert) surface (i.e.
no electron transfer).
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Ampere: It is a measure of the number of charges
unit of current flowing through a conductor/ second.
strength
Ohm: It is that resistance through which a potential
unit of electrical difference of one volt will produce a current
resistance (R) of one ampere
Volt (V) : unit of It is the potential required to produce a
potential current flow of one ampere through
difference resistance of one ohm
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Some electrochemical, definitions and units
• What is the relation between I, V & R ?
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V V
R or I
I R
Where:
I : is the intensity (strength) of electric current
V : is the potential difference.
R : is the resistance
From Ohm's law:
IV I 1
R
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Conductometry :
1- Metallic conductance
2- Electrolyte conductance
Electric Current pass through metallic conductors, e.g iron wire or
copper wire in the form of electron flow.
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Electrolyte conductance
Conductance is the ability
of electrolyte solution to
carry the electric current
But conduction of electricity through an
electrolytic solution involves migration of
cations towards cathode and anions
toward anode, i.e current is carried by all
ions present in solution.
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Conductance:
1- Measure conductance
2- NO electrons transfer , only movement of ions
Conductance (G) of a solution is a reciprocal of its
resistance
𝟏
G =
𝑹
(G = conductance & R = resistance)
Unit of resistance = ohm
Unit of Conductance = ohm-1 or seimen.
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1) Nature of ions
The velocity by which ions move towards the electrode carrying the
electric current, varies according to their nature (i.e charge, size and
hydration).
Velocity of ions charge
1
size
Al3+ Mg2+ Na+
1
hydration
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2) Concentration of ions
Conductance has a direct relation with concentration of ions.
i.e conductance is directly proportional to the number of ions.
𝑪
Strong electrolyte, may be incompletely
dissociated due to interionic attractive
forces. . 12
• So we deal with activity rather than concentration
At infinite dilution, where interionic attraction is negligible, activity of ions (a)
equals concentration (c)
i.e a=C or a/C = 1
The ratio of a / c is known as activity coefficient (Fa).
As concentration of solution is increased, the ratio of a/c becomes less
than unity.
Conductometric determinations must be carried out on dilute
solution, where each ion behave independently and activity
equals concentration 13
3) Temperature
Conductance is increased by increase of temperature, as
viscosity and hydration are decreased.
An increase of temperature by 1°C is accompanied by 2% increase
in conductance, conductometric determinations must be carried
out under thermostatically controlled conditions
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4) The size of the electrodes.
Conductometric measurements
are carried out in a conductance
cell, which consists of two parallel
sheets of pt. as inert electrodes.
The conductance of electrolyte (G) is directly proportional to surface area of
electrode (A) and inversely proportional to the distance between the two
electrodes (L).
i.e. G A G 1 G A
L L
or G = K. A
L
K: is proportionality constant, known as specific conductance or conductivity
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It is the conductance when L is unity (1cm) and A is unity (1cm2).
or it is the conductance of a cubic centimeter of liquid (1cm3)
K = G. L = 1 ohm-1 . cm-1
A ohm. cm
K : is constant for specific solution, but it is changed with concentration,
temperature and change in cell constant
L is known as cell constant, it is determined for each cell using solutions
A of known conductivity.
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)
It is the conductance of one gm equivalent of solute contained between
two electrodes spaced one cm apart.
Equivalent conductance () = K x 1000 C = concentration in
C gm equivalent / liter.
• λ expresses the ability of 1 g equivalent of
a substance to conduct electric current.
From the previous equation, equivalent
conductance is inversely proportional with
concentration, until it reaches a constant
limiting value at infinite dilution which is known
as limiting equivalent conductance () or
mobility, which is characteristic C
for each substance.
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Mobility: (the average velocity of a carrier due to an applied
electric field of unit strength
The mobility of some electrolytes :(at 25oC)
H+ = 350
Na+ = 42.6
Ag+ = 62
Ba2+ = 64
OH- = 198
Cl- = 76
CH3COO- = 41
SO42- = 80
K+ = 74
NH4+ = 73
NO3- = 71
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1) Direct conductometry:
This method is used in industry for:
1. Checking purity of distilled water or
other chemicals.
2. Determination of some physical
constants e.g ionization constant.
In this method, a calibration curve is
constructed by plotting the
conductance of a series prepared
from extra pure grade of the
substance to be analyzed versus
concentration.
The conductance of the sample is measured
and then its concentration is obtained from Concentration
the calibration curve.
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2) Indirect conductometry (Conductometric titrations)
• A conductometric titration involves
measurement of the conductance after
successive addition of titrant.
• The end point is obtained from a plot of
conductance against mls. of titrant. ml of titrant
The most important advantages of this method are:
a) It can be used for determination of turbid and highly colored
solutions.
b) It can be used for determination of very dilute solutions.
c) It can be used, when reaction is not complete and when there
is no suitable indicator e.g during weak acid, weak base titration.
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1. The titrant used must be at least 10 times concentrated as the
solution to be titrated e.g titration of 0.01 N HCl should be against
0.1 N NaOH. By this way, we can minimize decrease in
conductance due to dilution. However a correction factor must be
used to compensate for this dilution.
Correction factor = vi vt
vi
Where:
vi = initial volume of the titrated solution. vt = volume of titrant added.
2. The method is not suitable for detection of end point
of redox reactions as there is no electron transfer at
electrode surface during conductometric
determinations.
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Acid –Base titration
Strong acid (HCl) versus strong standard base
(NaOH)
Initial ↑G due to H+ + Cl- + Na++ OH- Na+ + Cl- + H2O
the high mobility
of H+ Na+ OH-
G’ decrease due to
Corrected Conductance (G’)
OH- OH- OH- OH-
H+↓, ↑Na+
H+ is Replaced by
Na+ Na+ Na+ Na+
low mobility Na+ G increase due to
OH-↑ and Na+↑
H+ H+ H+ H+
Cl- Cl- Cl- Cl-
H2 O H2 O
End Point H2 O
H2 O
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Volume of titrant (mLs)
1) Acid - base titration
a) strong acid strong base e.g HCl NaOH
HCl + NaOH NaCl + H2O
H+ + Cl- + Na++ OH- Na+ + Cl- + H2O
NaOH
Xss
H+ +100
Cl- ml+of Na+ + OH-
HCl OH-
Na ++Cl- + H2O
E.P mL of titrant
1) Acid - base titration
a) strong acid strong base e.g HCl NaOH
HCl + NaOH NaCl+H2O
H+ + Cl- + Na++ OH- Na+ + Cl- + H2O
First, H+ present in the acid sample causes high
conductance. By addition of NaOH, OH- will consume
H+ forming H2O, which doesn’t conduct electricity,
therefore conductance will be decreased during the
progress of the reaction although H+ is replaced by Na+
(as H+ has higher mobility (349.8) if compared with
mobility of Na+ (50.1).
ml NaOH
After complete reaction excess NaOH added will give free OH- as
well as Na+, therefore conductance is increased
Acid –Base titration
weak acid (CH3COOH) versus strong standard base (NaOH)
Buffer action due
G increase due to
Corrected Conductance (G’)
HAC/NaAC
OH-↑ and Na+↑ OH- OH-
Na+ Na+
Initial low G
due to the
weakly ionized
HAC
H+
HAC HAC
Initially G↓ Due End Point Ac-
to H+↓&Na+↑ HAC
Volume of titrant (mLs) H2O
b) Weak acid strong base (e.g CH3COOH NaOH)
CH3COOH+NaOH CH3COONa+H2O
Before titration low initial conductance is observed
due to low [H+] obtained during dissociation of the
weak acid CH3COOH.
During titration slight decrease of potential
due to consumption of initial H+, during
progress of titration, then slight increase in
conductance due to the presence of CH3COO-
& Na+ and nearly constant (H+) due to the buffer
action of the produced CH3COONa and the
remaining CH3COOH.
After complete reaction excess NaOH will lead to
increase in conductance due to increasing of Na+ and OH-
after the end point
e.g HCl/CH3COOH mixture
The same principles of (a) & (b) can be considered during titration of the
mixture NaOH.
preciptimetric titration
Sodium chloride (NaCl) versus strong standard AgNO3
Ag+ NO3-
+
Ag+ Ag+ Ag+ Ag
Corrected Conductance (G’)
- - NO3-
NO3- NO3 NO3
G increase due
Cl-↓ & NO3-↑ to
Both have almost Ag-+↑ and NO3-
the same ↑
mobility
Cl- Cl- Cl- Cl-
Na+ Na+ Na+ Na+
End Point AgCl AgCl
AgCl AgCl
Volume of titrant (mLs)
2) Precipitation titration
a) Titration of NaCl AgNO3
NaCl + AgNO3 AgCl + NaNO3
Na+ + Cl- + Ag+ + NO3- AgCl + Na+ + NO3-
During titration of NaCl against AgNO3, Ag+
precipitate Cl- as AgCl and NO3- replace Cl- in the
medium.
During titration : As mobility of NO3- (71.5) is nearly equals that of Cl- (76.3) we
observe nearly no change in conductance.
After complete precipitation of Cl-, excess Ag+ (61.9) and NO3- (71.5) will
increase conductance of solution.
Best wishes
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