Reference Electrode:

Reference electrodes is an electrode which has a stable and known electrode potential with reference to which
the electrode potential of any other electrode can be determined.
By knowing the potential of one electrode and EMF of a galvanic cell, potential of other electrode can be
determined using the formula: Ecell = Ecathode – Eanode
Criteria:
i. Potential should be known under the conditions of utility.
ii. It should show minimum variation with respect to temperature.

Types:
I. Primary reference electrode:
Standard hydrogen electrode (SHE) is the only primary reference electrode (gas
electrode).
Represented as Pt/H2(g)(1 atm) / HCl(1M)
The potential of SHE is taken as zero by convention. Therefore, potential values
of all other electrodes are expressed w.r.t. this electrode.
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 Advantages of SHE:
a) It can be used over the entire range of pH
b) It exhibits no salt error and highly accurate.
c) It has negligible electric leakage errors.

Construction and maintenance is difficult since it’s a gas electrode.

Limitati
ons of Pt metal used in the electrode is easily poisoned by any impurity
present in the system.
SHE: Cannot be used in the presence of oxidizing agents like nitrates, H2S,
chlorides, etc. as they poison Pt.
Difficulty in maintaining pressure at 1 atm under normal laboratory
condition.

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II. Secondary reference electrode
These are the electrodes whose potential is measured w.r.t. SHE and then can be used as reference electrode for
measuring potentials of other electrodes.
Eg: Calomel electrode, silver-silver chloride electrode

Construction:
• Calomel electrode is a metal-metal salt ion electrode.
• The electrode consists of a narrow glass tube with two side tubes.
• A little Hg is placed at the bottom of the glass tube followed by a layer of
Hg2Cl2 (Mercurous chloride or calomel) and paste of Hg.
• The remaining part of the glass tube is filled with KCl solution of definite
concentration.
• The thin glass tube with a platinum wire is then inserted, taking care that
the platinum wire dips into mercury.

Representation:
Hg|Hg2Cl2|KCl(sat)
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Working Principle:
The calomel electrode can act as anode or cathode depending on the nature of another electrode of the cell.

As anode: As cathode:
2Hg Hg2+ + 2e- Hg2Cl2 Hg2+ + 2Cl-
Hg2+ + 2Cl- Hg2Cl2 Hg2+ + 2e- 2Hg
2Hg + 2Cl- Hg2Cl2 + 2e-
Hg2Cl2 + 2e- 2Hg + 2Cl-

Electrode Potential of calomel electrode is given by:

ECE = EoCE -0.0598 log [Cl-] at 298 K

• Calomel electrode is reversible with respect to Cl- ions

• Potential value of calomel electrode decreases with increase in concentration of KCl as fallows.

Name Decinormal CE Normal CE Saturated CE

Conc of KCl 0.1 N 1.0 N Saturated
Potential of 0.3335 0.281 0.242
CE in V
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 Example: Measurement of electrode potential(Zinc) using Calomel electrode:

Ecell is measured using a potentiometer:

Ecell = Ecathode – Eanode

= ESCE – EZn2+/Zn
EZn2+/Zn = ESCE – Ecell
ESCE = 0.2422 V
Therefor, EZn2+/Zn = 0.2422 V – Ecell

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Advantages: Disadvantages:
a) Easy to set up and operate. a) Calomel electrode should not be used at above 50
b) Potential values do not vary much with variation in oC because the mercurous chloride breaks down
temperature. yielding unstable readings.
c) Not poisoned by oxidizing impurities. b) Since mercury is toxic, this electrode losing its
d) They are calibrated with respect to SHE. popularity.

Application:
• Used as a reference electrode in PH meter.
• Used to measure the potential of any other electrode.

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Ion selective electrode:
Ion selective electrodes are the electrode that generates
potential in response to the presence of a specific ion in solution
while neglecting others.
These electrode are sensitive to univalent cations K+, Na+,
and H+ ions, depending upon the composition of glass membrane.
The conc of 10-6 can be measured using these electrode. The Cell representation
potential is determined by the relative concentration of an analyte External Solution Internal Internal

Membrane
reference to be analyzed standard reference
on each side of the membrane. electrode (analyte)
solution electrode
[Mn+] = C2 [Mn+] = C1
Glass Electrode : Principle.

Glass electrode is pH sensitive electrode which can selectively detect and measures H+ ions in a system. Thus, it is
widely used for pH measurements. A glass electrode is a type of ion selective electrode where a thin bulb shape glass
membrane is used as a sensing material. It is sensitive to hydrogen ions in the solution. When a thin glass membrane separates
two electrolytes, a potential is developed across the membrane is related to the activities of the ions of the interest in std
(inside)and analyte (outside) solution.
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Construction:
Glass electrode consists of a long glass tube
with a thin-walled glass bulb(0.03-0.1 mm) at one end.
It is made up of special glass of low melting point and
silicate corning glass 22% Na2O, 6% CaO and 72%
SiO2.

The bulb is filled with 0.1M HCl. Ag/AgCl

electrode (internal reference electrode) is placed in the
solution provides an electrical contact. The bulb of the
glass electrode is dipped into any solution containing
hydrogen ions.

If there is a difference in H⁺ ion concentration

between the solution inside and outside the glass Glass electrode can be represented as
membrane, a potential will develop across the glass
membrane. Ag│ AgCl │ 0.1 M HCl │ Glass membrane

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 Working :
When the glass electrode is dipped in the test solution (xM), ion exchange
reaction takes place between the Na+ ions of the glass membrane and H+ ions
from the solution. The ion-exchange reaction can be written as

Glass
membrane
Test solution 0.1 M HCl Ag/AgCl
Unknown [H+]= C2 C1= 0.1 M Internal Ref Electrode
Eb= E2-E1

Test solution whose conc is C2 and its electrode potential is E2, internal reference solution whose conc is C1and
electrode potential is E1. The exchange of ions form inner and outer membrane gives rise to boundary potential (Eb).

Eb = L – 0.0591 pH

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 The potential of glass electrode depends on three components.
i) Boundary potential Eb
ii) Asymmetric potential Easy
iii) Potential of internal reference electrode Ag/AgCl electrode, i.e, EAg/AgCl

EG = Eb + EAg/AgCl + Easy

WKT Eb = L – 0.0591 pH

EG = L – 0.0591 pH + EAg/AgCl + Easy

EG = EOG – 0.0591 pH

Where EOG is a constant = L + EAg/AgCl + Easy

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 Determination of pH using glass electrode:
To determine the pH of the given solution, a galvanic cell is constructed by combining glass electrode (indicator electrode)
with a reference electrode such as a saturated calomel electrode. The whole cell is dipped in a test solution whose pH is to be
determined. The emf is measured by using potentiometer.

The emf of the cell is given by

Ecell = Ecathode - Eanode

Ecell = EG - ESCE

o
Ecell = E G – 0.0591 pH - ESCE

o
pH = E G – Ecell – 0.244
0.0591
Cell representation:
Hg/ Hg2Cl2/Cl- /Solution of unknown pH /glass /0.1M HCl /AgCl/Ag
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Advantages of Glass Electrode:

• It is portable and compact

• Even in very dilute solutions, it gives accurate result
• It can be used in the presence of viscous biological fluids
• Environmental analysis
• Measurement of soil pH level by glass electrode is an important process to observe soil acidity
Limitations of Glass Electrode:

• It should be handled with care as the glass membrane is thin and fragile
• Fluoride ions in the sample attack the glass surface and alter the composition of the membrane
• It shows alkaline error when the solution pH is 11 or more. Above this pH, it shows selectivity
towards not only H+ ions but also Na + ions of the alkali. This problem can be greatly reduced
by replacing sodium oxide of glass by lithium oxide.

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