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Electrochem 3

This document discusses different types of electrodes used in electrochemistry. It describes four main types: [1] metal-metal ion electrodes like the Daniell cell, [2] metal-insoluble metal ion electrodes like the calomel electrode, [3] gas electrodes like the standard hydrogen electrode, and [4] ion selective electrodes like the glass electrode. The document provides examples, representations, reactions, and Nernst equations for each type of electrode. It also discusses some advantages and disadvantages of the standard hydrogen electrode and advantages of the calomel electrode.

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20 views13 pages

Electrochem 3

This document discusses different types of electrodes used in electrochemistry. It describes four main types: [1] metal-metal ion electrodes like the Daniell cell, [2] metal-insoluble metal ion electrodes like the calomel electrode, [3] gas electrodes like the standard hydrogen electrode, and [4] ion selective electrodes like the glass electrode. The document provides examples, representations, reactions, and Nernst equations for each type of electrode. It also discusses some advantages and disadvantages of the standard hydrogen electrode and advantages of the calomel electrode.

Uploaded by

kangirene9705
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Electrochemistry Basics – II

1
Electrodes
• Different types of electrodes
• Reference electrodes - SHE (Primary
Electrode)
• Calomel electrode (Secondary Electrode)
• Glass Electrode
• Single electrode potential -

2
Different types of electrodes
Depending on the nature of materials or its components, Cells are mainly
classified into

1. Metal – Metal Ion electrode

2. Metal – Insoluble Metal Ion Electrode

3. Gas Electrode

4. Ion Selective Electrode (Glass Electrode etc.)

Its descriptions are following,

3
(1) Metal –Metal Ion Electrode
• Eg. Daniell cell, there a metal (eg. Cu) is
immersed in its own ion (CuSO4)
• It is represented by: M/Mn+

• Generally its chemical reaction is represented


by:
M ⇌ Mn+ + ne, and its Nernst equation is:

E = E0 – (RT/nF) ln [Mn+]

4
(2) Metal –Insoluble Metal salt
Electrode
• Eg. Calomel electrode
• Here a metal M, is covered by a layer of sparingly
soluble salt (MX) solution and is dipped into a salt
solution
• Its Cell Representation: M/MX/X-

• Generally its chemical reaction is represented by:


M + X- ⇌ MX + e, and its Nernst equation is:

E = E0 – (RT/nF) ln [ 1/X- ]
5
Diagram of Calomel Electrode

Description: In Calomel electrode liquid mercury is kept in a bottle which is covered


by Calomel (Hg2Cl2). On the top of it saturated solution of KCl is used. This will
produce an EMF of +0.2422 (if we use a saturated solution of KCl) V with respect to 6
Standard Hydrogen Electrode.
Reactions
• When it acts as Anode Cell 2Hg + 2Cl- → Hg2Cl2 + 2e-
( oxidation; Mercury is consumed)

• When it acts as Cathode Cell Hg2Cl2 + 2e- → 2Hg + 2Cl--

( reduction; Hg is produced )

Its Nernst Equation is:

7
(3) Gas Electrode
• Eg. Standard Hydrogen Electrode (SHE)
• In SHE the H2 gas (1 atm pressure) is bubbled
through a Pt foil which is immersed in a 1M
HCl solution.
• It is used as a Primary Reference Electrode
• Arbitrarily its EMF is assumed to be ZERO
E0SHE = 0.0 Volt (by definition)

8
Diagram of SHE

9
(4) Glass Electrode
• It is widely used to measure pH
• It consists of thin walled glass (a doped glass
so it conducts current) which contain Ag metal
covered by AgCl salt (a precipitate).
• Cell Representation:
Ag/AgCl/0.1 M HCl/Glass/H+

10
0.1 M HCl

Its Nernst Equation is:

E G = E0G - 0.0591 [ pH ]
11
Disadvantages of SHE
• In SHE Hydrogen gas is used, which is highly
inflammable
• Experimental set up is difficult
• Maintaining 1 M HCl and 1 atmospheric
pressure of H gas is difficult
• If HCl is not very pure it will poison (catalytic
poison) the Pt surface. It may affect cell
voltage
• Not transportable
12
Advantages of Calomel Electrode
• It is widely used as a secondary standard
electrode
• It will produce a constant voltage of +0.2422V
if we use a saturated solution of KCl and at
standard Temperature
• Easy to set up and easily transportable

13

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