MS617 Solid State Electrochemistry

Chap. 1 Thermodynamics of Electrochemical Cells

2020. 3. 16.

EunAe Cho

Department of Materials Science and Engineering

Korea Advanced Institute of Science and Technology (KAIST)

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Contents
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1. Electrochemical Cell
2. Electrode Potential
3. Electrochemical Cell EMF (electromotive force)
4. Nernst Equation

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What is Electrochemistry?
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Electrochemistry = Electricity + Chemistry

• Deals with the interaction between chemical reaction and electricity.

- Certain chemical reactions can create electricity. Fuel Cell, Battery discharging
- Electricity can make certain chemical reaction happen
that wouldn’t happen otherwise. Electrolysis, Battery charging

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Atomic Structure and Chemical Reaction
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Atomic structure

Proton
Neutron
Electron

Chemical reaction

- Electrons move between atoms

- Oxidation: an atom or ion loses one or more electrons
Energy Conversion & - Reduction: an atom or ion gains one or more electrons
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Electricity
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Electricity
- Flow of electrons e-

e- e-
ion
e- e- e-

- Flow of charge: electron/hole, ion

Electrical conductors H2SO4 solution

Electrical insulators
Materials
Electronic conductors: metals, semiconductors etc.
Electrical conductors

Ionic conductors: electrolyte, molten salt etc.

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Interaction between Chemical Reaction and Electricity
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Chemical reaction

Electricity
- Flow of charge

e- e- e- e- e-

- Electricity can make certain chemical reaction

- Certain chemical reactions can create electricity. happen that wouldn’t happen otherwise.

e- e-
A B A e- B C D C e- + Battery - e- D

won't normally happen

Galvanic Cell Electrolytic Cell

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Electrochemical Cells
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Electrochemical Cells
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2H+ + 2e- à H2(g)

ion e-
Zn à Zn2+ + 2e-

HCl solution

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Charge Neutrality
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Consider what happens when Zn is placed in dilute HCl solution :

Zn + HCl g ZnCl2 + H2 : Cl- is not involved in the reaction.

Zn + 2H+ g Zn2+ + H2 (1)
Reaction (1) can be separated into half cell reactions :

Zn g Zn2+ + 2e- .............anodic or oxidation reaction : (2)

2H+ + 2e- g H2 ...............cathodic or reduction reaction : (3)
During electrochemical reaction, the rate of oxidation equals the rate of reduction.

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Electrochemical Cells
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Chemical reaction

- Oxidation: an atom or ion loses one or more electrons

- Reduction: an atom or ion gains one or more electrons

Electrochemical reaction

® Electrode : An interface between a metal and a solution

across which a charge transfer occurs by an
electrochemical reaction.
H+ H+
e e • Anode : the electrode on which an anodic
e H+ H+ e oxidation reaction occurs. H2 à 2H+ + 2e-
H
H e H+ H+ e • Cathode : the electrode on which a cathodic
reduction reaction occurs. ½O2 + 2H+ + 2e- à H2O
e e (½O2 + 2e- à O2-)
HH H+ H+

Anode Electrolyte Cathode ® Electrolyte : an ionic conductor.

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Electrolytic vs. Galvanic Cell
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2H2O 2H2 + O2 2H2 + O2 2H2O

Electricity Electricity

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Galvanic Cell (or Voltaic Cell)
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Spontaneous Reactions.
- Chemical reactions create electricity.
e Electron Flow
e
Anode Cathode
Zn Porous barrier Cu Zn Porous barrier Cu
Zn Cu Zn Cu

e
e e
e
Cu

Cu2+
Zn2+ Zn2+ Cu2+
ZnSO4 (aq) CuSO4 (aq) ZnSO4 (aq) CuSO4 (aq)

e- e-
Electrode
Zn Cu2+ Zn2+ Cu
- Anode: oxidation, loss of electrons
Cu has the stronger pull for electrons than Zn. - Cathode: reduction, gain electrons
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Galvanic Cell (or Voltaic Cell)
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Devices that use a chemical reaction to generate electricity.

Electron Flow
ee
e
Salt Bridge Cu
Zn
Weaker pull Stronger pull
Anodic compartment for electrons for electrons Cathodic compartment
ee ee
Oxidation occurs Reduction occurs
Cu
Zn(s) ® Zn2+(aq)+2e- SO42- Cu2+(aq)+2e- ® Cu(s)
2+ SO42-
Zn2+ Zn Cu2+

ZnSO4 (aq) CuSO4 (aq)

Which one has the stronger pull for electrons?

• Neutral atoms make up solid metal.
• Metal ions can usually dissolve in water.

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Galvanic Cell: Cell Notation
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Half cell reactions

Electron Flow
ee Oxidation at anode Zn(s) ® Zn2+(aq)+2e-
e
Salt Bridge
Zn Cu Reduction at cathode Cu2+(aq)+2e- ® Cu(s)

ee ee
Cell reactions Zn(s) + Cu2+(aq) ® Zn2+(aq) + Cu(s)
Cu
SO42-
Cell Notation
Zn2+ SO42-
Zn2+ Cu 2+
Left: oxidation (anode)
ZnSO4 (aq) CuSO4 (aq)
Right: reduction (cathode)

Zn(s)½Zn2+(aq) || Cu2+(aq)½Cu(s)

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Salt Bridge
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If no salt bridge were present, the solution in one half cell

would accumulate negative charge and the solution in the
other half cell would accumulate positive charge as the
reaction proceeded, resulting in potential difference in the
solutions (or quickly preventing further reaction, and hence
production of electricity in Galvanic cell).

The electrolyte in a salt bridge

1. does not react with any of the chemicals used in the cell
2. the anion and cation have similar conductivity, and hence
similar migratory speed.

Usually KCl or NaCl is used.

Conductivity µ concentration of the electrolyte

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Electrolytic Cell
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- Electricity can make certain chemical reaction happen that wouldn’t happen otherwise (Electrolysis).

2H2O 2H2 + O2 2H2O 2H2 + O2

Electricity
e-

O2- H+ + -

Which one has the stronger pull for electrons?

Not a spontaneous Reaction.

O2- e- + Battery - e- H+
Electrons pulled from oxygen. Electrons pushed to hydrogen.
Oxygen is oxidized. Hydrogen is reduced.

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Electrolysis: H2O
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Half cell reactions

Oxidation at anode 2H2O ® O2(g) + 4H+ + 4e-

Reduction at cathode 2H2O + 2e- ® H2 + 2OH-

Cell reactions 2H2O + 2e- ® H2 + 2OH-

H H+
H+ H+
O2-
O2- H O2-

H+

+ 2- H+ H+
H O O

+ O H+ H+
H

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Electrolysis: NaCl
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A process where electricity is used to make a chemical reaction happen

that wouldn’t happen otherwise.

2NaCl ® 2Na + Cl2

Half cell reactions

Oxidation at anode 2Cl-(l) ® Cl2(g) + 2e-

Reduction at cathode 2Na2+(l) + 2e- ® 2Na(l)

Cell reactions 2NaCl(l) ® 2Na(l) + Cl2(g)

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Summary
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• Electrochemistry deals with the interaction between chemical reaction and electricity.

- Certain chemical reactions can create electricity.

- Electricity can make certain chemical reaction happen that wouldn’t happen otherwise.

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