Corrosion Engineering

Lecture 8
CHE 311
Reference Electrodes

Introduction:
 A stable and reliable reference electrode is a critical component of most
electrochemical test methods. It is used with an electrometer to measure the
electrochemical potential of a metal surface in a given environment. When a stable
reference electrode is used, any changes in potential can be related to changes at
the metal surface of interest. The requirements of a reference electrode are the
following:

 A reproducible potential for the reference electrode itself.

 A stable (unchanging) potential of the reference electrode.
 A convenient and durable construction.
Reference Electrodes
 Several reference electrode systems meet these requirements, and they are used in
a broad range of electrochemical test techniques in laboratory and field
applications. The selection of a particular reference electrode depends on the given
application. Factors that influence selection are the required degrees of accuracy,
durability, and ruggedness, and the properties of the specific corrosive environment.
The common reference electrodes are:

 Calomel reference electrode

 Silver /silver chloride reference electrode
 Cooper / cooper sulfate reference electrode
Reference Electrodes
 These reference electrodes contain solution at certain concentration to produce the
required potentials. The reference electrodes can be used in conjunction with a
potential measuring device (electrometer or high impedance voltmeter) to measure
the potential of the metal electrode of interest.
Calomel Reference Electrode (CRE)
 Calomel is an old name for the compound
mercury (I) chloride (Hg2Cl2).
 One common design of the CRE is shown in
the figure. The abbreviation of this
electrode is CE.
 Potassium chloride (KCl) solution is used in
the CE at a desired concentration (e.g.
saturated, 1 M, or 0.1 M solutions). The
function of these porous plugs is to allow
the free passage of ions which are the cause
of flow of current. The contact between the
mercury and the calomel allows limited
amount of Hg+ to go to KCl solution. The
potential of this electrode is develop due to
the presence of Hg2/Hg couple. The activity
of mercurous ions depends on the ion
concentration of KCl solution.
Potentials of Calomel Electrodes (CE).
 The common concentrations of KCl solution In the CE are
 Hg/Hg2Cl2/ Sat. KCl (SCE).
 Hg/Hg2 Cl2/ 1 M KCl (MCE)
 Hg/Hg2Cl2 / 0.1 M KCl (0.1MCE).
 Nernst equation can be used to find the potential of each half cell.
 The potential values are listed in Table 1.
 The calomel electrode is widely used as a reference electrode in research,
industry, and pH measurements.
Silvers/silver chloride electrode (SSCE)
 This electrode is basically made with a silver
wire, the end of which is coated with a thin
layer of silver chloride AgCl as its name
implies. KCl solution is used with the SSCE of
desired concentration. The figure is one
demonstration for the design of SSCE. The
potential in this electrode is developed due to
the activity of Ag+ ions in equilibrium with CL-
ions. The abbreviation of this electrode is
SSCE.
Potential of SSCE electrodes
 The half cells of SSCE’s, using different KCl concentrations are Ag/AgCl (Sat.),
Ag/AgCl(IM), and Ag/AgCl (0.1M).
 The half cell reactions for SSCE are: AgCl Ag   CI-

Ag   e- Ag

 The overall reaction is Ag  Cl- Ag Cl + e 

 Applying Nernst equation, the value of  SHE is a function of KCl solution:

  SHE = 0.2224 – 0.0592 log aCl-
 The common concentrations of KCl solution for SSCE are (sat. KCl), (1MKCl), and
(0.1MKCl). The SSCE is Suitable for use in seawater and salty water environments
Copper/ copper Sulphate Electrode (CCSE)
 The electrode consists of a small glass or plastic tube, its lower end is sealed
with porous plug. Small amount of copper sulphate crystals are added, on top of
it, saturated copper sulphate solution is added. A copper rod is immersed in
solution. A connecting wire is hocked to the copper rod. The top of the tube is
sealed. The figure is one possible designs for such an electrode.
Potential of CCSE electrodes
 Cu | CuSO4 | CuSO4 sol.
 The half cell reaction is
 Cu2+ + 2e  Cu
 Nernst equation can be used to find the potential of each half cell.
 The accepted potential of sat. CCSE is 0.318 volts at 25oC.The potential values are
listed in Table 1. Table 2 shows some application of the SHE and the reference
electrodes.
Potential of reference electrodes (Table 1)
  Reference electrode potentials versus Temperature
Name of RE Abbreviation
SHE variation mV/°C
 
1 Saturated Calomel electrode SCE 0.242 - 0.76
 
2 1M calomel MCE 0.280 - 0.24
 
3 0.1Mcalomel 0.1 MCE 0.334 - 0.07
 
4 Saturated silver/silver chloride SSCE 0.197 - 0.6
 
5 1M silver/silver chloride MSSCE 0.2353 - 0.6
 
6 0.1M silver/silver chloride 0.1MSSCE 0.288 - 0.65
 
7 Silver/silver chloride(seawater) SWSSCE ~ 0.25  

 
8 Saturated copper/copper sulfate SCCSE 0.318 + 0.7

9 Copper/copper sulfate(seawater) SWCCSE ~ 0.3  

Mercury/mercurous sulfate
10   0.615  
Hg/Hg2SO4 *
Mercury/mercuric oxide
11   0.098  
Hg/HgO ** in 1M NaOH
Mercurous sulfate
12   0.68  
Hg/Hg2SO4/sat H2SO4
Applications of SHE and reference
electrodes (Table 2)

# Electrode Application

1 SHE Suitable to measure the standard electrode potentials of different

materials.

2 SCE Suitable as a reference electrode in research and pH measurements.

3 Ag/AgCl Suitable for use in seawater and salty water environments.

4 Cu//CuSO4 Suitable for use in soil with cathodic protection.

The reference electrode potentials shown in Table 2 are calculated by using

Nernst equation (Will be discussed later).
Electrochemical application of
reference electrodes
 Most of the electrochemical measurements use a three electrode cell
(electrochemical cell); one of them is the reference electrode (such as SCE or
Ag/AgCl). The other two electrodes are the working electrode (the metal under
the test, and it the anode) and the auxiliary electrode (such as Pt or glassy
carbon). The photos in the Appendix are samples for the three electrode cell.
Examples of electrochemical measurements are:
 Potential measurement
 Current measurement
 Resistivity measurement
 Polarization curves
 Linear polarization.
 Frequency response (alternating-current impedance)
 The instrument used to run electrochemical measurements is the Potentiostat /
Galvanostat.
Example 1:
 The potential of a test metal (M) is measured to be (- 0.215 V) against Hg/Hg2SO4
reference electrode. Calculate the potential the of M electrode versus:
 a) SHE b) SCE
 Solution: a)

v.s.SHE  0.615  (0.215) = +0.4 V

 b)

v.s.ref  v.s.SHE  ref v.s.SHE

v.s.ref  0.4  0.242 = 0.158 V

Example 2:
 The potential of a cathode at which H+ discharges is (-0.9) V at 0.01A/cm2 against
0.1M Ag/AgCl reference electrode at 25 C. What is the potential against SCE?
 Solution:

(0.9)    0.288
v.s.SHE

v.s.SHE  (-0.9)) + 0.288 = - 0.612 V

 Reapply Eqn.1:

v.s.ref   0.612  0.242  - 0.854 V