Corrosion Engineering

Lecture 7
CHE 311

1
Standard Electrodes and Reference
Electrodes
Introduction:
 The electrode potential represents a free energy level, but not a potential
difference. Electrode potential is a quantity of unknown absolute value and can’t be
measured. In practice potential difference are measured using a galvanic cell which
consist of the following elements:
 a) The electrode in question (test electrode).
 b) Standard electrode, e.g. standard hydrogen electrode (SHE).
 c) Special solution at a fixed concentration and temperature.
 d) A measuring device such as a potentiometer, to measure the potential.

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Standard Electrode

 Question: What is a standard

electrode?
 Answer: It is an electrode that has an
accurately known potential. It is at
equilibrium with its salt at STP.
 One of the common standard
electrodes is the standard hydrogen
electrode (SHE). It is made from
inert electrode of platinum (Pt),
immersed in a solution in which the
concentration of the hydrogen ions
(H+) is exactly 1M (unit activity).
Hydrogen gas at exactly 1 bar
pressure and 298K is passed over the
Pt electrode as in the figure to keep
the solution saturated at the
electrode site with respect to the 3

gas.
Fig 1: Standard Hydrogen Electrode
What is happening?

 As the hydrogen gas flows over the porous platinum, an equilibrium is set up
between hydrogen molecules and hydrogen ions in solution. The reaction is catalyzed
by the platinum.


 This is the equilibrium that we are going to compare all the others with.
 Standard conditions
 The conditions must be standardized so that you can make fair comparisons.
 The hydrogen pressure is 1 bar (100 kPa).
 The temperature is 298 K (25°C).
 All ion concentrations are taken as being 1 mol/dm3

4
Using the standard hydrogen electrode
 The standard hydrogen electrode Potentiometer
is attached to the electrode
system you are investigating - for
example, a piece of magnesium in
a solution containing magnesium
ions
 a) The electrode in question
(test electrode).
 b) Standard electrode, e.g.
standard hydrogen electrode
(SHE).
 c) Special solution at a fixed
concentration and temperature.
 d) A measuring device such as a
potentiometer, to measure the
potential.
Fig 2: Set-up to measure standard
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electrode potential
Standard Electrodes

Cells and half cells:

 The whole of this set-up is described as a cell. It is a simple system which generates
a voltage. Each of the two beakers and their contents are described as half cells.

The salt bridge:

 The salt bridge is included to complete the electrical circuit but without
interference to the redox reaction of the cell. It is just a glass tube filled with an
agar-agar. The ends are "stoppered". This stops the mixing of the contents of the salt
bridge with the contents of the two beakers.
 The electrolyte in the salt bridge is chosen so that it doesn't react with the contents
of either beaker

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Standard Electrodes

What happens ?
 These two equilibria are set up on the two electrodes (the magnesium and the
porous platinum):


 Magnesium has a much greater tendency to form its ions than hydrogen does. The
position of the magnesium equilibrium will be well to the left of that of the hydrogen
equilibrium.
 That means that there will be a much greater build-up of electrons on the piece of
magnesium than on the platinum.

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Electromotive Force (e.m.f.) Series

 Electromotive force (emf)

 The energy per unit charge that is converted reversibly from chemical, mechanical, or
other forms of energy into electrical energy in a battery or dynamo.

 Electromotive force (emf)

 Electric potential or voltage. Electromotive force is not really a force, but a measure of
how much work would be done by moving an electric charge.

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Electromotive Force (e.m.f.) Series

 Active state
 A state of metal tens to corrode (opposite to noble or passive). Also referring to negative
direction of electrode potential, e.g., metals with more negative potentials are referred to
as active or anodic metals.

 Noble state
 A state of a metal tends not to corrode (opposite to (active). Also referring to positive
direction of electrode potential, e.g., noble metal is a metal which is not active and has
more positive potential.

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Defining standard electrode potential
(standard redox potential)
 The values that we have just quoted for the two cells are actually the standard
electrode potentials of the Mg2+ / Mg system.
 The emf measured when a metal / metal ion electrode is coupled to a hydrogen
electrode under standard conditions is known as the standard electrode potential of
that metal / metal ion combination.
 By convention, the hydrogen electrode is always written as the left-hand electrode
of the cell. That means that the sign of the voltage quoted always gives you the sign
of the metal electrode.
 Standard electrode potential for a metal is given the symbol  o .The emf of a cell
measured under standard conditions is given the symbol o
cell

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Electromotive Force (e.m.f.) Series

 The electromotive force series is an orderly arrangement of the standard reduction

potentials (  0 ) for all metals measured against SHE (Fig. 1) in a cell shown by Fig. 2.
It ranks the values of  in decreasing order from the most positive value down to
0

the most negative value (according to IUPAC) convention. In other words it ranks the
metals in decreasing order from the most corrosion resistance (more noble) down to
the most active (less noble) metals.
 Table 1 is a demonstrations of the (e.m.f.) series. We notice from the above sign
convection that positive potentials are assigned to metals which are cathodic to
hydrogen such as copper and gold, and negative potentials are assigned to metals
which are anodic to hydrogen such as iron and zinc.

 The (e.m.f.) are thermodynamic data and will help to find the tendency and
spontaneity of the overall cell reaction. Here the equilibrium potential difference
between two metals is determined by taking the absolute difference between their
standard (e.m.f.) potentials
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Electromotive Force (e.m.f.) Series

Table 1: electromotive force series 12

Example
Electromotive Force
 Example: Use the e.m.f. series to test if silver will corrode in
cupric sulfate solution

 o  cu
  
cell Ag
 0.337 - 0.8
 - 0.463 V.

0
 In this case corrosion of silver is not possible in cupric sulfate solution since ( G ) is
positive.
o
G 0 = - nFcell

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Galvanic Series
 The electromotive force (e.m.f.) series is developed for pure metals under standard
conditions. The (e.m.f.) series does not include alloys and the passive state. The
(e.m.f.) series is only used for qualitative and approximate estimation of galvanic
action between two metals.
 In real corrosion systems, equilibrium between metals and their ions rarely occurs. A
more practical series is the galvanic series which ranks metals and alloys in a relative
order of nobility (or activity). Moreover, the galvanic series includes the state of
passivity. Since the media is a non-standard one, an individual galvanic series must
be developed for any particular media. A peculiar feature of a galvanic series is the
grouping of metals and alloys which have similar composition. This implies that there
is little danger of galvanic corrosion when two metals or alloys in one group are
coupled to each other

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Galvanic Series
 Table 2 is a galvanic series for metals and alloys in stagnant seawater. This table is
based on potential measurement and galvanic corrosion tests using clean seawater.
The observations that can be noticed in these tables are:

 1. The relative ranking from the most nobility to the most activity of the metals and alloys.
 2. The galvanic grouping feature.
 3. The passive and active positions of some alloys. For example, the 18-8 stainless steel
when passive behaves galvanically like silver (or noble) and when active behaves like zinc
(active).
 4. Galvanic series should be used with precaution by design engineers when selecting
materials for equipment since some alloys possess two positions in the same series.

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Galvanic Series

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Table 2: Galvanic series of selected metals and alloys in stagnant seawater (Active or anode at top, noble or cathode at
bottom)