ELECTROCHEMIS

TRY (2)
CH 3242
Lecture (1)
 Uses of ELECTROCHEMISTRY

 To obtain thermodynamic data about a reaction.

 To generate an unstable intermediate such as a radical ion and study its rate of
decay, the analysis of a solution for trace amounts of metal ions or organic species.

 To understand of the fundamental principles of electrode reactions and the electrical

properties of electrode – solution interfaces.

 In this book the terms and concepts employed in describing electrode reactions are
introduced.
 Electrochemical cells

Oxidation Oxidation
Reduction Reduction
 The electrochemical cells

power
supply power
supply
i i
W.E counter W.E R.E
electrode
R.E
V V
Three –electrode cell Two-electrode cell

In experiments where iRs may be high, a three-electrode

cell is preferable to determine i – E curve.
 3-electrode
electrochemical cell
Working electrode (WE)
• Glassy carbon electrode (GCE)
• Carbon paste electrode
• Carbon steel electrode
• Gold electrode
• Rotating disc electrode (RDE)
• Substrates, e.g. (Ni Foam, Ni Sheet, ITO,
FTO, carbon paper, etc……)
Counter (auxiliary) electrode (CE)
• Usually Pt wire or any substance, which
can conduct current effectively and won't
respond with the bulk solution
• Function: The current produced from the
electrochemical reaction at the working
electrode is balanced by a current flowing in
the opposite direction at the counter electrode

Reference electrode (RE)

• Ag/AgCl (saturated KCl) electrode E°=+ 0.54 V
• Hg/HgO electrode
• Saturated calomel electrode
• Standard hydrogen electrode (SHE) E°=+ 0.00 V
 Electrode reaction
 An electrode reaction is a heterogeneous chemical process involving the transfer
of electrons to or from a surface, generally a metal or a semiconductor.
 The electrode reaction may be an anodic process whereby a species is oxidized by
the loss of electrons to the electrode, the current density for a cathodic process in
positive quantity, e.g

R ⇔ O + ne-
Ce3+ ⇔ Ce4+ + e
 Conversely, the charge transfer may be a cathodic reaction in which a species is
reduced by the gain of electrons from the electrode, the current density for a
cathodic process in negative quantity, e. g.
O + ne- ⇔ R
Fe3+ + e- ⇔ Fe2+
 •The electroactive species may be organic or inorganic, neutral or charged,
species dissolved in solution, the solvent itself, or a film on the electrode surface.
 Electrolysis: It is a chemical decomposition produced by passing an electric
current through a liquid or solution containing ions.

The amount of reduction at the cathode and oxidation at the anode must be equal.

 In the electrochemical cell, ions pass through the solution between the electrodes
and electrons pass through the wire externally interconnecting the electrodes.
 Electron transfer (redox reaction) and energy levels
The illustrated system could represent an aromatic hydrocarbons (e.g. 9,10-dipheny-lanthracene)
in an aprotic solvent (e.g acetonitrile) at a platinum electrode.

 By driving the potential to

more negative values the Electrode Solution Electrode Solution
energy of the electrons is
raised till it reach a level e
Vacant
high enough to occupy MO
vacant orbit of the analyte -
species in the electrolyte
(Reduction process for the
analyte species). Potential
Energy level
 In this case a flow of of electrons
electrons from electrode to +
solution (reduction current)
Occupied
A +e -
A -
MO
  Similarly, the energy of the electrons can lowered by imposing a more positive
potential till it reach a level lower than the occupied molecular orbit, then electron
will transfer from the analyte species to the electrode surface (Oxidation process for
the analyte species).

 Their flow from the Electrode Solution Electrode Solution

solution to the electrode is
an oxidation current Vacant
MO
-
A A+n + ne- Energy level
of electrons
Potential

+
Occupied
MO e-
 The critical potentials at which these processes occur are related to E°
values for the specific chemical substances in system (A / A+ & A / A-)

 When the potential of electrode is moved from its

equilibrium value (zero-current) toward more
negative potentials, the substance which reduce
E° Possible
first is the oxidant of the less negative (or most (Vs. NHE) reduction reaction
positive) E°.
-0.25 Ni+2 + 2e Ni
0 2H+ + 2e H2
+0.15 Sn+4 + 2e Sn+2
+0.77 Fe+3 + e Fe+2

Pt App. potential
1V vs. NHE for zero current
  When the potential of the electrode is moved from zero-current value towards
more positive value, the substance that will be oxidized first is the reductant of
less positive (or most negative) E°.

 Thus, for a Hg electrode immersed in a solution of

Cr+3 & Zn+2 in 1M HCl, the first reduction
process predicted would be the reduction of H+.
E° V
But, this reaction is very slow on Hg, therefore,
the first process actually observed is the reduction
vs. NHE
of Cr+3. -0.76 Zn+2 + 2e Zn

-0.41 Cr+3 + e Cr+2

0 2H+ + 2e H2
Hg
Appl. potential
for zero current
 Types of electrode reactions

Simple electron Metal deposition Gas evolution

transfer

Electron transfer coupled with chemical

Corrosion Oxide film formation reaction ) 2CH2=CH-CN + H2O + 2e 
(CH2-CH2-CN)2
Questions on
lec. 1
1. Explain the pathway of a general electrode reaction.
2. Illustrate the general types of the electrode reactions.

3. In the electrochemical cell, which contains more than two metal ions. When the potential of
electrode is moved from its equilibrium value (zero-current) toward more negative potentials, the
substance which reduce first is the oxidant of the less negative (or most positive) E°.
a) True b) False

.Oxidation reaction produces ……. current .4

a) anodic b) cathodic c) constant d) controlled

5. When the potential of the electrode is moved from zero-current value towards more positive value, the
substance that will be oxidized first is the reductant of ………(a)…… E°. Thus, for a Hg electrode
immersed in a solution of Cr+3 & Zn+2 in 1M HCl, the first reduction process predicted would be the
reduction of ……(b)…... But this reaction is very slow on Hg, therefore, the first process observed is the
reduction of ……(c)………