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Basics of Electrochemistry
Basics of Electrochemistry
Basics of Electrochemistry
Application
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Electrochemistry is the use of electricity to:
make chemical measurements
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Electrolytic cell -
Electric current is used to
drive a non- spontaneous
reaction. Voltaic or galvanic cell-
Process is called Spontaneous reaction
electrolysis generates electric current.
Examples: Examples are Daniel’s
cell, fuel cell etc.
1. Electrolysis of fused
salt (Down’s cell ) &
aq.solutions of salts
(Nelson’s cell)
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Electrolytic cell
Non-spontaneous Reactions
DC
Cathode Anode
Reduction - + Oxidation
A Spontaneous Reaction
Pt wire
•Piece of Pt foil in 1M
Solution of HCl H2 gas
•Pure H2 bubbled into
this Solution
•For measurement of Electrode
potential ,concerned electrode Pt foil
is joined with SHE
•Oxidation or reduction may
HCl
takes place depending on the
nature of metal coupled with it.
SHE
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How are measurements
made?
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Line Notation of a Galvanic cell
Anode Cathode
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Electrochemical Series
When elements are arranged in the order of their standard
electrode potentials on the hydrogen scale, the resulting list is
called Electrochemical Series.
Applications
1.Calculation of emf of cells
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Displacement of one metal by another from
compounds.
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Corrosion-A Redox Process
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Corrosion: an undesirable application of spontaneous redox reactions
When iron is exposed to damp air, with both O2 and H2O present, the
half reaction
O2(g) + 4H+(aq) + 4 e- 2H2O(l)
takes place
Fe(s) is first oxidized by O2 to Fe2+
The Fe2+ is then further oxidized to Fe3+
Fe3+ then forms Fe2O3.H2O - rust
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Electrochemical Cells
Consists of two conductors (called electrodes) each immersed in
a suitable electrolyte solution.
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For an electrode measurement,
the cell must consist of:
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AgCl(s) + e- Ag(s) + Cl -
Note that porous plugs can
become clogged.
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The Calomel Electrode
1 - -
Hg2Cl 2 (s) + e Hg(l) + Cl
2
Eo = +0.268V
E(saturated KCl) = +0.241V
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Combination Glass Electrode
solution level
external
reference internal
electrode reference
(porous plug) electrode
potential glass
develops across membrane-
membrane due hydrated
to pH difference constant pH (50 mm thick)
External solution 29
measured voltage
at 25oC:
E = E’ – 0.0591 pH
Experiment:
Measure pH of analyte as titrant is added.
Evaluate pH in the titration of 10.0 mL of 1.0 M HCl
solution with 1.0 M NaOH solution, and plot the
titration curve.
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HCl + NaOH NaCl + H2O
How do we locate the equivalence point?
pH Equivalence point pH
pH = 7
JustpH =7
salt
nkausarjanjua@yahoo.com
nkjanjua@qau.edu.pk
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Key equations in Electrochemical Methods
Ecell = Ecathode – Eanode
ΔGrxn = - nFEcell
if E is positive, G must be negative
-G means reaction is spontaneous in direction
written
ΔGrxn = -RTlnKeq
E = E’ – 0.0591pH
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Consider the following titration. The
goal is to calculate potential vs. Vt.
Ce4+ in HClO4
Fe2+ in HClO4
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