Electrochemistry

Electrochemistry was previously used

for the determination
Of metal traces in aqueous solute
Currently it is used widely to the
structures of organic substances in
non-aqueous media, using different
methods and instruments, such as:
 Electrochemistry was previously used for the
determination
 Of metal traces in aqueous solution
 Currently it is used widely to the structures of
organic substances in non-aqueous media,
using different methods and instruments,
such as:
 * Potentiometry
 * Conductometry
 * Polarography
 * Amperometry
 The basis of analytical application of such
instruments are either:
 * Determination of current
 Or
 * Measuring the resistance developed in a cell under
certain operating conditions.
Electric cell

 Electric cell
 M0 →M+ + e-
 e.g if metal is Cu then the solution will also contain
Cu
 i.e CuSO4
 a-
 The strip becomes more -ve and the solution more
+ve.
 b-
 metal strip becomes more +ve (or less -ve).
 When a metal strip is placed in a solution of
its own, a potential difference will develop
between the metal and solution, by the
tendency of the metal ions to go into solution
anions liberating electrons on the strip.
 This system constitutes a half cell where the
metal strip is called an electrodes and in this
case it is known as an anode).
 Some metals work oppositely, and the
positively charged metal ions in solution
takes electrons from the metal strip and
become neutral atoms depositing on the
electrode.
 M+ + e- → M0
 It is not possible to measure the current
directly between the metal and its solution in
either case, however, when the two half cells
are joined together to form a complete cell,
the potential difference (P.d) created can be
measured.
Salt bridge : - (junction liquid)

 Connection of two half cells is achieved by a

salt bridge which is a junction composed of
KCL in agar gel, that allows the flow of
electrons but does not permit the solutions to
mix.
 By connecting two half cells and considering
one of them as a standard half cell, the
potential of the other half can be measured.
NERNEST'S Equation

 The potential or electro motive force e.m.f of

a half cell or indicator electrode can be
calculated by using the following equation: -
 E= Eо + RT Ln (molar conc.)
 nf
 E= E0 + RT Ln (molar conc)
 nf
 E= potential of the indicator electrode.
 E0 = potential of standard electrode.
 R= Gas constant =8.31 joules/mol/degree
 T=Absolute temperature at
 25°C = 298° K
 n = number of electrons transferred during
reaction or the valency charge of the metal.
 F = faraday number
 = 96493 coloumbs
 Ln = log base c.
 oxidation – reduction reactions the nernest
equation is:
 E= E0 + RT Ln (oxid)
 nf (red)
 if R,T,F and ln is converted to be the log
base 10, are substituted then we get:
 E= E0 +0.0591 x log (molar conc. )
 n
Reference Electrode

 In order to measure the potential of the

indicator electrode, it is necessary to
compare it with a potential of standard
electrode in order to form a complete cell.
 The 2nd half cell serves as standard.
 Theoretically any metal ion system can be
used as a reference electrode, but in practice
this can not be done, since active metals are
subject to chemical attack by the solution and
with some the ionic form is unstable when
exposed to heat, as a result few systems are
used as reference electrodes
(i) Hydrogen electrodes

 They are universal electrodes used as reference.


*Disadvantages: -
 1- In convenient to construct.
 2- Difficult to maintain.
 3- Many solutions that contain oxidizing agents react
with hydrogen gas and alter the PH of the solution
such as KMnO4 , CrO42- , ferric ions and
unsaturated compounds.
 .(b) other substances such as CN, proteins,
hydrogen sulphides may poison the platinum
wire, there by altering the PH.
 3.(c) inconvenience of gas regulation and the
hazard associated with the presence of H2
gas.
 H2(g) 2H+ + 2e-
 .(b) other substances such as CN, proteins,
hydrogen sulphide may poison the platinum
wire, there by altering the PH.
 3.(c) inconvenience of gas regulation and the
hazard associated with the presence of H2
gas.
 H2(g) 2H+ + 2e-
 If a second half is joined to a hydrogen cell to
form a complete cell and by applying ner
nests equation we get: -
 E= E0 + 0.0591 x log c
 n
 for the hydrogen electrode n=2
 E= E0 +0.0591 x log[H+]2
 2
 PH = -log [H+]
 -PH= log [H+]
 E= E0 +0.0591 x log[H+]2
 2
 E= E0 + 2 x 0.0591 x log[H+]
 2
 E = E0 – 0.0591 PH
 E0 for H2 electrode = zero
  E=-0.0591 PH
2) Calomel electrode

 Calomel electrodes are the most widely used

reference electrodes due to:-
 (i) consistency of potential.
 (ii) ease of preparation.
 It consists of pure mercury in contact with
Hg2cl2 (calomel) dipped into solution of KCl.
 The potential of the calomel electrode depends upon
the concentration of Cl- ions in solution.
 Hg2Cl2 +2e- 2Hg + 2Cl-
 The convention used to describe the half cell is
 Hg│Hg2Cl2 │ m KCl ││
 The single line indicates the constituents of the
electrode, and the double line indicates the point
where the electrode joins to a second half cell.
 Apply the Nernest equation: -
 E=E0 – 0.0591 x log (red)
 n (oxid)
 E=E0 –2 x 0.0591 x log [Hg] [Cl-]
 n Hg2Cl2
 [Hg2CL2] & [Hg] are in standard states.
 E=E0 –2 x 0.0591 x log [Cl-]
 2
 E=E0 –0.0591 x log [Cl-]
 From the first equation we notice that the
potential depends on the chlorine ion
concentration.
 E = +0.281V
SILVER- SILVER CHLORIDE
ELECTRODE

 3- Silver-Silver chloride electrode it is more

difficult than the calomel electrode, but is just
as convenient.
 Disadvantage: -
 (i) very sensitive to high solution
concentration.
 (ii) can not measure up to a PH of 8.
Glass electrode

 (Internal standard electrodes)

 Are the most widely used electrodes for the
determination of hydrogen ions.
 They involve ion exchange reactions rather
than electron transfer, they consist of thin
glass membranes of the tip of the electrodes,
which are permeable to hydrogen ions.
 Inside the glass bulb there is a reference
solution used as an internal standard
electrode.
 Ag │AgCl │0.01NHCl │ glass membrane ││
test solution│ where H2 ions are permeable.
 E=K (constant) -0.0591 PH
 Advantage: -
 (i) Rapid in response.
 (ii) Unaffected by oxidizing and reducing
agents.
 (ii) Unaffected by dissolved gases
Hydroquinone Electrode

 * 2HQ → [H+]2+[Q]+2eˉ
 By applying Nernests Eq.:-
 E=E0 –2 x 0.0591 x log [Q] [H+]
 2 [H2Q]
 E=E0 + 0.0591PH
 * Response directly to hydrogen ion activity
as long as the ratio of Q and H2Q remains
constant
 *Advantages:-
 Simple to construct and comes to equilibrium
rapidly. And is less disturbed by poisons and
by oxidizing and reducing agents than is the
hydrogen gas electrode.
 * Disadvantages: -
 (i) Extremely fragile.
 (ii) Should always be stored in distilled water
to prevent hydration.
POTENTIOMETRY
INTRODUCTION

 In potentiometry, the potential of an electrochemical

cell is measured under static conditions because no
current flows while measuring a solution’s potential,
its composition remains unchanged.•
Information on a composition of the sample is
obtained through the potential appearing between
two electrodes.
 The first quantitative potentiometric applications
appeared soon after the formulation of Nernst
equation.• In 1889, the Nernst equation relating an
electrochemical cell’s potential to the concentration
of electroactive species in the cell.•
Potentiometric methods of analysis are based upon
measurements of the potential of electrochemical
cells under conditions of zero current, where the
Nernst equation governs the operation of
potentiometry.
 Nernst equation: Ecell = E0cell - (RT/nF)
QEcell = 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 electrochemicalreaction
(mol)F = Faradays constant, 96500 coulombs/molQ
= reaction quotient
Basic Principles Potentiometer

• A device for measuring the potential of an

electrochemical cell without drawing a current or
altering the cell’s composition. • The potential of an
electrochemical cell is measured under static
conditions. • Because no current, or only a negligible
current flows while measuring a solution’s potential,
its composition remains unchanged. For this reason,
potentiometry is a useful quantitative method.
 Potentiometric measurements: Made by using a
potentiometer to determine the difference in potential
between a indicator electrode and a reference
electrode. Cathode is the sensing electrode. (right
half-cell) Anode is the reference electrode. (left
half-cell) Ecell = Ec ─ EaWhere : Ec is the reduction
potential at the cathode. : Ea is the reduction
potential at the anode.
Potentiometric Electrochemical Cells To
determine difference in potential between
sensing electrode and reference electrode
Separation of the 2 electrodes to prevent the
redox from occurring spontaneously on
surface of one of electrodes Constructed that
one of half cells provided a known reference
potential of other half cell indicates the
analyte concentration
 Salt bridge contain inert electrolyte such as KCl
connects the two half-cells.• The ends of the salt
bridge are fixed with porous frits (to allow the ions of
electrolyte to move freely between the half-cells and
the salt bridge).• This movement of ions in the salt
bridge completes the electrical circuit.• Reference
electrode : left electrode (anode) which undergoes
oxidation.• Sensing electrode : right electrode
(cathode) which undergoes reduction.• When the
potential of an electrochemical cell is measured, the
contribution of the liquid junction potential must be
included; Ecell = Ec ─ Ea Elj
ISE

 Introduction to ion selective electrode (ISE)

The cell consists of both an indicator and reference
electrode.• Since the potential of the reference
electrode is constant, the potential developed at the
indicator electrode that contains information about
the amount of analyte in a sample.• During the
measurement, there is little to no current flow.• An
electrochemical cell for making a potentiometric
measurement with a membrane electrode also
known as an ion-selective electrode{ ISE}
 The selectivity of the ISE is determined by the
composition of the membrane.• Ideally the
membrane allows the uptake of only one specific ion
into it.• The three main components of making a
measurement at an ISE are an inner reference, or
standard solution an outer analyte, or sample,
solution separated by a thin membrane.• The
potential developed at the membrane is the result of
either an ion exchange process or an ion transport
process occurring at each interface between the
membrane and solution.
Reference electrode

 It has a standard potential on its own and its

potential does not change to whichever solution it is
dipped.• Always treated as the left-hand electrode
(anode)
Example of reference electrode: Stadndar
hydrogen electrode (SHE) • Saturated calomel
electrode • Silver-silver chloride electrode
Standard hydrogen electrode

 Defined as the potential that is developed between

H2 gas adsorbed on the Pt metal and H+ of the
solution .• It is used for • determination of electrode
potential of metal electrode system