REFERENCE ELECTRODES

Reference electrode is used for measuring the potentials of

other electrodes.
Easy to use and maintain Stable potential over time and
therefore used to measure the potential of other
electrodes.

Measurement of potential using reference electrode

Hydrogen Electrode
The hydrogen electrode can be used as a reference
electrode but it is cumber-some, even in the laboratory.

Other common reference electrodes:

Silver-silver chloride
Calomel
Copper-copper sulfate
 Normal hydrogen electrode (N.H.E.)

Electrode reaction: 2H+ + 2e H2

Nernst equation:

E25oC = Eo - 0.059/n log H2 / [H+]2

Salt
bridge
E25oC = Eo + 0.059 log [H+] (gas conc is
considered as 1)
E [H+] in N.H.E [H+] = 1 , log 1 is zero
platinum
So E25oC = E = zero
o
coated with
Pt black
[H+] = 1 M
 HYDROGEN ELECTRODE
Hydrogen electrode is used as a reference
electrode for potential measurements.
The electrode consists of a platinum wire
immersed in a solution containing hydrogen ions
and saturated with hydrogen gas.
The potential of hydrogen electrode is assumed to
be zero at all temperatures
Disadvantages: It is difficult to keep H2 gas at one
atmosphere during all determinations:
it needs periodical re-
plating of platinum sheet.
 SILVER-SILVER CHLORIDE ELECTRODE
This electrode is composed of a silver wire coated with silver chloride
and immersed in a solution of chloride ions
Electrode reaction: AgCl + e Ag + Cl-
Nernst equation:

EAg/AgCl = Eo + RT . ln aAgCl
nF aAg. aCl-

aAg. = 1, aAgCl = 1

EAg/AgCl = 0.224 0.059 log aCl-

Values of Ag/AgCl electrode potential in
different HCl concentrations
Concentration (M)` Electrode potential (volts)

0.1 0.28

0.01 0.34

0.001 0.40
 CALOMEL ELECTRODE
The most commonly used reference electrode. It has a
constant and reproducible potential.
The electrode basically consists of a platinum wire
dipped into pure mercury which rests in a paste of
mercurous chloride and mercury.
The paste is in contact with a solution of potassium
chloride which acts as a salt bridge to the other half of
the cell.
The most commonly used concentrations of KCl are 0.1
N, 1.0 N and 3.5 N and saturated KCl.
The potential of electrode at 25C is 0.241 V in saturated
KCl solution.
Calomel Electrode

Electrode reaction : Hg2Cl2 + 2e 2Hg + 2Cl-

Hg2Cl2 and H2 Activity = 1

E Calomel = Eo + RT . ln 1
2F aCl-

= Eo - 0.059 . log aCl-

2
= 0.267 log aCl-
Saturated calomel reference electrode
COPPER - COPPER SULFATE ELECTRODE

Fig. Copper copper sulfate reference

electrode in contact with earth
 This reference electrode is mainly used in cathodic
protection measurements, such as the measurement of
pipe-to-soil potential.
It has a lower accuracy than other electrodes used for
laboratory work.
It consists of copper metal placed in a solution
containing copper sulfate and copper sulphate crystals
placed in a non-conducting holder with a porous plug.
The copper sulphate crystals maintain the solution at a
fixed ion concentration.
Necessary contact with the earth is made through the
porous plug. It is easily recharged when it becomes
contaminated.
The potential of Copper / copper sulphate reference
electrode is 0.30 Volts vs SHE.
Electrode reaction :

Cu2+ + 2e Cu

ECu2+/ Cu = Eo + 0.059 . log aCu2+

2
= 0.34 + 0.059 . log 0.051
2

= 0.30 Volts

(for saturated copper sulphate activity = 0.051)

Portable Copper-Copper Sulfate Reference Electrodes
A stationary copper-copper sulfate reference electrode is used for installation
underground.

Stationary reference electrodes

 EMF SERIES

EMF series is an orderly listing of standard

half-cell electrode potentials of pure metals.
The standard potential (Eo) of various pure
metals are measured at a temperature of
25oC, in a solution of 1 molar concentration of
the metal ions.
Standard Electrochemical Series for Some Common Metals

17
CHARACTERISTICS OF EMF SERIES
Metals with large positive potentials are called 'noble' metals
because they do not dissolve easily. Examples are copper, silver,
gold, etc. The potential of a noble metal is preceded by a
positive (+) sign.
The electrode potentials are thermodynamic quantities and have
little relevance to potential of metals in solution encountered in
service.
The emf series lists only the electrode potentials of metals and
not alloys. Alloys are not considered in the emf series.
Na, Mg, Al, Zn are called 'active metals'
From the standard emf series of metals, it is possible to predict
whether a particular metal will spontaneously dissolve.
It gives an indication of how active the metal
LIMITATIONS OF EMF SERIES
The emf series lists only pure metals which have only a
limited use in engineering applications. Alloys are of
major interest to engineers rather than pure metals.
The electrode potential has little relevance to potentials of
metals in solutions, in which the potential of interest is the
corrosion potential and not the electrode potential of the
metal.
EMF series predicts the tendency to corrode but it cannot
predict whether corrosion would actually take place. For
instance, on the basis of some negative potential, iron
shows tendency to corrode, however, if it develops a
passive film in some environment it would not corrode.
GALVANIC SERIES

Galvanic series is a table of metals and

alloys arranged according to their relative
corrosion potential in a given
environment.
 GALVANIC POTENTIAL SERIES FOR METALS IN SEAWATER V vs. SCE

More Active Magnesium -1.48

Zinc - 1.03
Aluminium - 0.79
Wrought iron and carbon steel -0.61
Cast Iron -0.61
Stainless Steel Type 400 AISI (17% Cr) -0.57
Stainless Steel type 304 AISI (18% Gr, 18% Ni) -0.53
Less Active Rolled brass -0.40
Copper -0.36
Aluminium brass -0.32
Nickel -0.20
Titanium -0.15
Silver -0.13
Graphite 0.25
Platinum 0.26

The series was generated by measuring the stable potential between the metal
and a saturated calomel electrode (SCE) in a seawater. This potential is
referred to as a corrosion potential or an open circuit potential. The galvanic
series provides an indication of the relative reactivity of the different metals.