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CHAPTER IV
ELECTRODES
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There are two electrodes in electrochemical
studies; working electrode (indicator electrode)
and reference electrode.
In practice one always measures the potential
of the working electrode (WE) with respect to
reference electrode (RE)
V
red black
E

working reference
electrode electrode
(WE) (RE)
 Electrode Potentials
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The potential difference developed by the cell may be thought of
as the difference between the potential of WE and RE.
E = Ework - Eref

There is no straightforward way of measuring a single electrode

potential.
What is done is to select one electrode as a standard and define its
potential as zero. The universal accepted standard is the standard
hydrogen electrode (SHE), at which the electrode process is
e-
H+(aq, a=1) H2(g, 105 Pa)
Because this electrode is defined to have zero potential, the
voltmeter is said to measure the electrode potential Ework of the
working electrode.
Ework =E+Eref
 STANDARD HYDROGEN ELECTRODE
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The scheme of the standard hydrogen

electrode:
1. platinized platinum electrode
2. hydrogen blow
3. solution of the acid with activity of H+ =
1 mol dm3
4. hydroseal for prevention of the oxygen
interference
5. reservoir through which the second
half-element of the galvanic cell should
be attached. The connection can be
direct, through a narrow tube to reduce
mixing, or through a salt bridge,
depending on the other electrode and
solution. This creates an ionically
conductive path to the working
electrode of interest.
 Reference Electrodes
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An ideal reference electrode would be one which
maintains a constant potential, Eref, whether we treat it
as an anode or a cathode and irrespective of the
current (if any) that we pass through it. The electrode
process must resist polarization. Moreover, the
electrode should be robust and unaffected by processes
(such as evaporation) that occur when use is
intermittent.
These criteria are best met by saturated calomel
electrode (SCE)
SHE is temperamental and difficult to use. It is
employed only in calibration studies.
 STANDARD CALOMEL ELECTRODE
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The electrode reaction:

Hg2Cl2(s) 2Hg(l) + 2Cl- (aq) Eref vs. SHE = 0.244 V at 298.15 K for
(calomel) e- saturated KCl (to maintain the
activity of Cl- to be constant)
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The potential of saturated SCE has high
temperature coefficient (dEref/dT = 0.67 mV/K).
To overcome this drawback unsaturated SCE (ex.
0.1 M KCl) can be used with Eref = 0.336 V.
Instead of using liquid metal in reference
electrode, an alternative reference electrode,
Ag/AgCl can be used to replace SCE. The process
is AgCl(s) Ag(s) + Cl-(aq)
e-
The potential is 0.199 V at 298.15 K with
saturated KCl. It is almost as stable as SCE.
However this RE can be fabricated very
compactly.
 Silver/Silver Chloride Electrode
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 Standard Electrode Potential
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En E work Eref (1)
o RT a Rr .... o RT a Pp .... (2)
E work ln o Eref ln q
nF aO .... nF aQ ....

Where
ne
oO ... rR .... (3)

Is the electrode reaction in the working electrode, and

ne
qQ ... pP .... (4)

Is the electrode reaction in the reference electrode. However, because

we always select a reference electrode to have constant activities,
there is no point in splitting Eref into a standard potential term and
activity term. Instead we write:
o RT aRr ....
En Ework ln o Eref (5)
nF aO ....
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Alternatively, since En = Ework Eref , hence we can write:

o RT aRr .... (6)

En Ework Eref Ework ln o Eref
nF aO ....
o RT aRr ....
Ework Ework ln o (7)
nF aO ....
This equation is the Nernst equation for a working electrode at
which reaction 3 occurs. Note that when the Nernst equation is written
with negative sign, the products of a reduction appear in the
numerator of the logarithmic term, the oxidized reactants being in the
denominator.
Eowork is the standard electrode potential of the working electrode. The
values are tabulated on standard reduction potential table. Otherwise
we can calculate from:
G o
G o
G o
(8)
E O
product reac tan t

nF nF
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Standard Reduction Potential
 Contoh soal:
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1. A solution is 0.001 M in Cr2O72- and 0.01 M

in Cr3+. If the pH is 2.0, what is the
potential of the half-reaction? Eo = 1.33 V
2. 5 ml of 0.1 M Ce4+ solution is added to 5
ml of 0.3 M Fe2+ solution. Calculate the
potential of a platinum electrode dipping in
the solution.
3. Pt/Fe2+ (0.15 M), Fe3+(0.003M) // MnO4-
(0.02M), Mn2+(0.005 M), H+(1 M)/Pt
What is the cell voltage?
 Pourbaix Diagram
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A concept with a distinguished history is the electrochemical

series of the chemical elements. In this the elements are
arranged in order of the standard electrode potentials of their
redox couples with an aqueous ion.
The more electronegative elements have the most positive Eo
values and therefore occur high in the series, whereas the
electropositive metals are found towards the bottom.
The farther apart two elements are in the electrochemical
series, the more energetic is the reaction between the oxidized
member of the higher element and the reduced member of the
lower element.
For example: 2Ag+(aq) + Mg(s) 2Ag(s) + Mg2+(aq)
occurs violently and to virtual completion, whereas the reaction
Cd2+(aq) + Fe(s) Cd(s) + Fe2+(aq)
between members of couples that are adjacent in the
electrochemical series is mild and incomplete.
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In this diagram of the electrochemical series the formulas

of the two members of each redox couple have been placed
on opposite sides of a horizontal line.
Taking the Ag+(aq)/Ag(s) couple as an example, this
arrangement is intended to suggest the predominance
diagram shown here.

V
1.2
Ag+(aq) predominant
0.8 aAg += 1
0.6226 aAg += 10-3
0.4 Ag (s) predominant

0
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The utility of the electrochemical series is limited because,

depending on the pH, many elements can establish redox couples
in aqueous solution with more than one ion, and also with
nonionic species.
For example:
Zn2+ (aq) + 2e- Zn(s) Eo = -0.7628 V
Zinc metal enters the less familiar redox equilibria:
Zn(OH)2(s) + 2H+ + 2e- Zn(s) + 2H2O(l) Eo = -0.421 V, and
ZnO22- (aq) + 2H2O(l) + 2e- Zn(s) + 4OH-(aq) Eo = -1.215 V
Pourbaix diagram represents E vs. pH.
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From the following data:

Cd2+(aq) + 2e- == Cd(s) Eo = -0.402 V
Cd(OH)2(s) + 2e- == Cd(s) + 2OH- Eo = -0.825 V
Cd(OH)2(aq) + 2H+(aq) == Cd2+(aq) + 2H2O(l) K = 5.01x1013
Construct a Pourbaix diagram for cadmium showing the zones of
predominance of the species Cd(s), Cd2+(s) and Cd(OH)2(s)
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