Electrochemistry

Electrical energy Chemical energy

into electrical
into chemical

Voltaic cells or Galvanic

Electrolytic cells cells. (Spontaneous)
(non spontaneous)
Electrode
potential and Types of cells
Electrochemical
series
Primary
Electrolytic conduction Secondary

Application
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Electrochemistry is the use of electricity to:
 make chemical measurements

 drive chemical reactions

A galvanic cell uses a spontaneous chemical

reaction to generate electricity
One reactant must be oxidized, i.e., lose an
electron(s)
One reactant must be reduced, i.e., gain an
electron(s)

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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

Na+ + e- Na Na+ Cl-

2Cl- Cl2 +2e-

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 Voltaic cell or Galvanic cells
Voltmeter
cathode
Zn
+ Salt Bridge -
Cu
Anion Anode
movement
Zn2+
Cu2+
Cation
movement

A Spontaneous Reaction

Zn(s)+Cu2+ Zn2+ + Cu (s)

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Materials:- a lemon, a strip of copper, a strip of zinc, a voltmeter,
two cables with alligator clips,
a thermometer or clock with an LCD display
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 Electrode potential

When a metal rod is placed

in a solution of its own ions,
there are two tendencies,
M atom may dissolve as +ve
ions leaving electrons on rod . -
 The M+ in solution may take - Zn2+
Zn 2+
up electrons from metal & get -2 Zn2+
discharged as atoms giving
Zn2+ Zn2+
+ve charge to the metal Zn2+
The potential difference set
up between the solution & the
metal is called single electrode M M + + e-
potential. 10
 Standard hydrogen electrode

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

Zn Zn2+ (1.0 M) Cu2+ (1.0 M) Cu

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

2.Prediction of the feasibility of a chemical reaction

3.Relative chemical reactivity

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 1.EMF of Cell
In a galvanic cell, the electrode with more positive red.potential in the
Electrochemical series, will act as a cathode; the other electrode will
act as an anode.

Zn (s) Zn2+ (aq) + 2e- Cu2+(aq) + 2e- Cu (s)

The larger the difference between the oxidizing and

reducing strengths, the larger is the cell potential Eocell = Eooxid + Eo
red

2.Relative chemical reactivity

Large positive value in Electrochemical series,
the greater is the oxidizing power

3.Prediction of the feasibility of a chemical reaction

If Eocell is positive, the process is energetically feasible.

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 Displacement of one metal by another from
compounds.

M + HCl H2 +MCl An element that is

One element is pushing out more easily oxidized
another by means of redox will displace the one
reaction.
that is less easily
In this reaction metal is oxidized.
displacing hydrogen from
acid (M is more active Relative ease of
than H2) oxidation of two
Active means easily metals can be
oxidized. established.

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 Corrosion-A Redox Process

O2-free water O2 dissolved

In water

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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.

For electricity to flow:

1) The electrodes must be connected externally by means of a
(metal) conductor.

2) The two electrolyte solutions are in contact to permit

movement of ions from one to the other.

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For an electrode measurement,
the cell must consist of:

Reference Indicator electrode

electrode  Potential depends
 Maintains a fixed on concentration of
constant potential electroactive
 Composition must species
not change  For glass electrode,
 Common references the electroactive
 Calomel
species is H+
 Silver chloride

Must have two electrodes!

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 The Reference Electrode

Most commonly, the reference electrode is the

silver/silver chloride electrode. The
potential is based on the following equilibrium:
AgCl(s) + e Ag(s) + Cl-(aq)
The half cell is:
Ag|[AgCl(Sat'd),KCl(xM)]

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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

depends on internal reference

electrode and glass membrane
behavior, which changes with time

Must calibrate with a buffer!

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 Potentiometric Titration

How does the pH change during an acid-base

neutralization reaction?

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

Volume of titrant (mL NaOH)

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 HCl + NaOH  NaCl + H2O
What is present at various points?
xs NaOH & salt
pH

JustpH =7
salt

Just acid Both acid & salt

Volume of titrant (mL NaOH)

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 Thank you
Dr. Naveed Kausar Janjua, Assistant Professor,
Physical Chemistry, Chemistry Department,
Quaid-i-Azam University, Islamabad, Pakistan

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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