Electrochemistry

Chemistry 4th Edition

McMurry/Fay
Dr. Syed Mazhar Shah
UET RCET, Gujranwala.
 Redox Reactions 01

Prentice Hall ©2004 Chapter 18 Slide 2

 Redox Reactions 01

Redox reaction are those involving the oxidation

and reduction of species.

OIL – Oxidation Is Loss of electrons.

RIG – Reduction Is Gain of electrons.

Oxidation and reduction must occur together.

They cannot exist alone.
Prentice Hall ©2004 Chapter 18 Slide 3
 Redox Reactions 02

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 Redox Reactions 02

• Oxidation Half-Reaction: Zn(s)  Zn2+(aq) + 2 e–.

• The Zn loses two electrons to form Zn2+.

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 Redox Reactions 03

• Reduction Half-Reaction: Cu2+(aq) + 2 e–  Cu(s)

• The Cu2+ gains two electrons to form copper.

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 Redox Reactions 04

• Overall: Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)

Prentice Hall ©2004 Chapter 18 Slide 7

 Electrochemical Cells 01

• Electrodes: are usually metal strips/wires

connected by an electrically conducting wire.
• Salt Bridge: is a U-shaped tube that contains a gel
permeated with a solution of an inert electrolyte.
• Anode: is the electrode where oxidation takes
place.
• Cathode: is the electrode where reduction takes
place.

Prentice Hall ©2004 Chapter 18 Slide 8

 Electrochemical Cells 02

• Convention for expressing the cell:

Anode Half-Cell || Cathode Half-Cell
Electrode | Anode Soln || Cathode Soln | Electrode
Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)
Pt(s) | H2 (1 atm) | H+ (1 M) || Fe3+(aq), Fe2+(aq) | Pt(s)

• Electrons flow from anode to cathode. Anode is

placed on left by convention.
Prentice Hall ©2004 Chapter 18 Slide 9
 Electrochemical Cells 03

• The standard potential of any galvanic cell is the

sum of the standard half-cell potentials for the
oxidation and reduction half-cells.

E°cell = E°oxidation + E°reduction

• Standard half-cell potentials are always quoted as a
reduction process. The sign must be changed for
the oxidation process.
Prentice Hall ©2004 Chapter 18 Slide 10
 Electrochemical Cells 04

• The standard half-cell potentials are determined

from the difference between two electrodes.
• The reference point is called the standard hydrogen
electrode (S.H.E.) and consists of a platinum
electrode in contact with H2 gas (1 atm) and
aqueous H+ ions (1 M).
• The standard hydrogen electrode is assigned an
arbitrary value of exactly 0.00 V.

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 Electrochemical Cells 05

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 Electrochemical Cells 06

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 Electrochemical Cells 07

• When selecting two half-cell reactions the more

negative value will form the oxidation half-cell.

• Consider the reaction between zinc and silver:

Ag+(aq) + e–  Ag(s) E° = 0.80 V
Zn2+(aq) + 2 e–  Zn(s) E° = – 0.76 V

• Therefore, zinc forms the oxidation half-cell:

Zn(s)  Zn2+(aq) + 2 e– E° = – (–0.76 V)

Prentice Hall ©2004 Chapter 18 Slide 14

 Electrochemical Cells 08

• What is the standard emf of an electrochemical cell

made of a Cd electrode in a 1.0 M Cd(NO3)2
solution and a Cr electrode in a 1.0 M Cr(NO3)2
solution?

• What is the standard emf of an electrochemical cell

made of a Mg electrode in a 1.0 M Mg(NO3)2
solution and a Ag electrode in a 1.0 M AgNO3
solution?
Prentice Hall ©2004 Chapter 18 Slide 15
 Spontaneity of a Reaction 01

• The value of E˚cell is related to the thermodynamic

quantities of ∆G˚ and K.

• The value of E˚cell is related to ∆G˚ by:

∆G˚ = –nFE˚cell

• The value of K is related to ∆G˚ by:

∆G˚ = –RT ln K

Prentice Hall ©2004 Chapter 18 Slide 16

 Spontaneity of a Reaction 02

• These are combined:

–nFE˚cell = –RT ln K

• and rearranged at 25°C to give:

E˚cell = (0.0257n) ln K
or E˚cell = (0.0592n) log K

• (Units = volts, n = moles, F = 96,500 coulombs)

Prentice Hall ©2004 Chapter 18 Slide 17

 Spontaneity of a Reaction 03

• Calculate the standard free energy change (∆G˚) and

the equilibrium constant (K) for the following
reactions at 25°C:

1. Sn(s) + 2 Cu2+(aq) æ Sn2+(aq) + 2 Cu+(aq)

2. Fe2+(aq) + 2 Ag(s) æ Fe(s) + 2 Ag+(aq)

3. 4 Fe2+(aq) + O2(g) + 4 H+(aq)  4 Fe3+(aq) + 2 H2O(l)

Prentice Hall ©2004 Chapter 18 Slide 18

 The Nernst Equation 01

• Cell potentials can be modified by temperature and

composition changes according to the equation:

∆G = ∆G° + RT lnQ

 –nFE = –nFE° + RT lnQ

• Giving:

Prentice Hall ©2004 Chapter 18 Slide 19

 The Nernst Equation 03

• Consider the reaction of metallic zinc with

hydrochloric acid. Calculate the cell potential at
25°C when [H+] = 1.0 M, [Zn2+] = 0.0010 M, and
PH2 = 0.10 atm.

• Consider the reaction of metallic copper with

iron(III) to give copper(II) and iron(II). What is the
potential of a cell when [Fe3+] = 0.0001 M, [Cu2+] =
0.25 M, and [Fe2+] = 0.20 M?
Prentice Hall ©2004 Chapter 18 Slide 20
 The Nernst Equation 04

• A particularly important use of the Nernst equation

is in the electrochemical determination of pH.

Pt | H2 (1 atm) | H+ (? M) || Reference Cathode

Ecell = EH2  H+ + Eref
• The Nernst equation can be applied to the
half-reaction:
H2(g)  2 H+(aq) + 2 e–

Prentice Hall ©2004 Chapter 18 Slide 21

 The Nernst Equation 05

• For the half-reaction: H2(g)  2 H+(aq) + 2 e–

• E° = 0 V for this reaction (standard hydrogen

electrode). PH2 is 1 atm.

Prentice Hall ©2004 Chapter 18 Slide 22

 The Nernst Equation 07

• The overall potential is given by:

• Which rearranges to give an equation for the

determination of pH:

Prentice Hall ©2004 Chapter 18 Slide 23

 The Nernst Equation 08

• A higher cell potential indicates a higher pH,

therefore we can measure pH by measuring Ecell.
• A glass electrode (Ag/AgCl wire in dilute HCl) with a
calomel reference is the most common
arrangement.
Glass: Ag(s) + Cl–(aq)  AgCl(s) + e– E° = –0.22 V

Calomel: Hg2Cl2(s) + 2 e–  2 Hg(l) + 2 Cl–(aq) E° = 0.28 V

Prentice Hall ©2004 Chapter 18 Slide 24

 The Nernst Equation 09

• The glass pH probe is constructed as follows:

Ag(s) | AgCl(s) | HCl(aq) | glass | H+(aq) || reference

•The difference in [H+] from one side of the glass

membrane to the other causes a potential to develop,
which adds to the measured Ecell.

Prentice Hall ©2004 Chapter 18 Slide 25

 The Nernst Equation 10

• The following cell has a potential of 0.55 V at 25°C:

Pt(s) | H2 (1 atm) | H+ (? M) || Cl– (1 M) | Hg2Cl2(s) | Hg(l)

• What is the pH of the solution at the anode?

• The following cell has a potential of 0.28 V at 25°C:

Pt(s) | H2 (1 atm) | H+ (? M) || Pb2+ (1 M) | Pb(s)

• What is the pH of the solution at the anode?

Prentice Hall ©2004 Chapter 18 Slide 26

 Batteries 01

• Batteries are the most important practical

application of galvanic cells.

• Single-cell batteries consist of one galvanic cell.

• Multicell batteries consist of several galvanic cells

linked in series to obtain the desired voltage.

Prentice Hall ©2004 Chapter 18 Slide 27

 Batteries 02

• Lead Storage Battery: A typical 12 volt battery

consists of six individual cells connected in series.
• Anode: Lead grid packed with spongy lead.
Pb(s) + HSO4–(aq)  PbSO4(s) + H+(aq) + 2 e–

Cathode: Lead grid packed with lead oxide.

PbO2(s) + 3 H+(aq) + HSO4–(aq) + 2 e–  PbSO4(s) + 2 H2O(l)

Electrolyte: 38% by mass sulfuric acid.

Cell Potential: 1.924 V

Prentice Hall ©2004 Chapter 18 Slide 28

 Batteries 03

• Zinc Dry-Cell: Also called a Leclanché cell, uses a

viscous paste rather than a liquid solution.
Anode: Zinc metal can on outside of cell.
Zn(s)  Zn2+(aq) + 2 e–
• Cathode: MnO2 and carbon black paste on graphite.
•2 MnO2(s) + 2 NH4+(aq) + 2 e–  Mn2O3(s) + 2 NH3(aq) +
2 H2O(l)
• Electrolyte: NH4Cl and ZnCl2 paste.
• Cell Potential: 1.5 V but deteriorates to 0.8 V with use.
Prentice Hall ©2004 Chapter 18 Slide 29
 Batteries 04

• Alkaline Dry-Cell: Modified Leclanché cell which

replaces NH4Cl with NaOH or KOH.
Anode: Zinc metal can on outside of cell.
Zn(s) + 2 OH–(aq)  ZnO(s) + H2O(l) + 2 e–
Cathode: MnO2 and carbon black paste on graphite.
2 MnO2(s) + H2O(l) + 2 e–  Mn2O3(s) + 2 OH–(aq)
Electrolyte: NaOH or KOH, and Zn(OH)2 paste.
Cell Potential: 1.5 V but longer lasting, higher power,
and more stable current and voltage.
Prentice Hall ©2004 Chapter 18 Slide 30
 Batteries 05

• Mercury Dry-Cell: Modified Leclanché cell which

replaces MnO2 with HgO and uses a steel cathode.
Anode: Zinc metal can on outside of cell.
Zn(s) + 2 OH–(aq)  ZnO(s) + H2O(l) + 2 e–
Cathode: HgO in contact with steel.
2 HgO (s) + H2O(l) + 2 e–  Hg(l) + 2 OH–(aq)
Electrolyte: KOH, and Zn(OH)2 paste.
Cell Potential: 1.3 V with small size, longer lasting,
and stable current and voltage.
Prentice Hall ©2004 Chapter 18 Slide 31
 Batteries 06

• Nickel–Cadmium Battery: Modified Leclanché cell

which is rechargeable.
Anode: Cadmium metal.
Cd(s) + 2 OH–(aq)  Cd(OH)2(s) + 2 e–

Cathode: Nickel(III) compound on nickel metal.

NiO(OH) (s) + H2O(l) + e–  Ni(OH)2(s) + OH–(aq)

Electrolyte: Nickel oxyhydroxide, NiO(OH).

Cell Potential: 1.30 V

Prentice Hall ©2004 Chapter 18 Slide 32

 Batteries 07

• Nickel–Metal–Hydride
(NiMH):
• Replaces toxic Cd anode with
a hydrogen atom impregnated
ZrNi2 metal alloy.

• During oxidation at the anode,

hydrogen atoms are released
as H2O.

• Recharging reverses this

reaction.

Prentice Hall ©2004 Chapter 18 Slide 33

 Batteries 08

• Lithium Ion (Li–ion): The newest rechargeable

battery is based on the migration of Li+ ions.
•Anode: Li metal, or Li atom impregnated graphite.
Li(s)  Li+ + e–
Cathode: Metal oxide or sulfide that can accept Li+.
MnO2(s) + Li+(aq) + e–  LiMnO2(s)
Electrolyte: Lithium-containing salt such as LiClO4, in
organic solvent. Solid state polymers can also be used.
Cell Potential: 3.0 V
Prentice Hall ©2004 Chapter 18 Slide 34
 Batteries 09

• Fuel Cell: Uses externally fed CH4 or H2, which

react to form water. Most common is H2.
• Anode: Porous carbon containing metallic catalysts.
2 H2(s) + 4 OH–(aq)  4 H2O(l) + 4 e–

Cathode: Porous carbon containing metallic catalysts.

O2(s) + 2 H2O(l) + 4 e–  4 OH–(aq)
Electrolyte: Hot aqueous KOH solution.
Cell Potential: 1.23 V, but is only 40% of cell capacity.
Prentice Hall ©2004 Chapter 18 Slide 35
 Batteries 10

• Fuel cells are not batteries

because they are not self-
contained.

• Fuel cells typically have

about 40% conversion to
electricity; the remainder is
lost as heat.

• Excess heat can be used to

drive turbine generators.

Prentice Hall ©2004 Chapter 18 Slide 36

 Corrosion 01

• Corrosion is the oxidative deterioration of metal.

• 25% of steel produced in USA goes to replace steel

structures and products destroyed by corrosion.

• Rusting of iron requires the presence of BOTH

oxygen and water.

• Rusting results from tiny galvanic cells formed by

water droplets.
Prentice Hall ©2004 Chapter 18 Slide 37
 Corrosion 02

Oxidation: Fe(s)  Fe2+(aq) + 2 e–

Reduction: O2(g) + 4 H+(aq) + 4 e–  2 H2O(l)
Overall: 2 Fe(s) + O2(g) + 4 H+(aq)  2 Fe2+(aq) + 2 H2O(l)
Prentice Hall ©2004 Chapter 18 Slide 38
 Corrosion 03

• Galvanizing: is the coating of iron with zinc. Zinc is

more easily oxidized than iron, which protects and
reverses oxidation of the iron.

• Cathodic Protection: is the protection of a metal

from corrosion by connecting it to a metal (a
sacrificial anode) that is more easily oxidized.

• All that is required is an electrical connection to the

sacrificial anode (usually magnesium or zinc).
Prentice Hall ©2004 Chapter 18 Slide 39
 Corrosion 04

• Cathodic Protection with Zinc Layer

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 Corrosion 05

• Cathodic Protection with Magnesium Anode

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 Electrolysis 01

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 Electrolysis 01

• Electrolysis: is the process in which electrical

energy is used to drive a nonspontaneous chemical
reaction.

• An electrolytic cell is an apparatus for carrying out

electrolysis.

• Processes in an electrolytic cell are the reverse of

those in a galvanic cell.

Prentice Hall ©2004 Chapter 18 Slide 43

 Electrolysis 05

• Electrolysis of Water: Requires an electrolyte

species, that is less easily oxidized and reduced
than water, to carry the current.

• Anode: Water is oxidized to oxygen gas.

2 H2O(l)  O2(g) + 4 H+(aq) + 4 e–

• Cathode: Water is reduced to hydrogen gas.

4 H2O(l) + 4 e–  2 H2(g) + 4 OH–(aq)
Prentice Hall ©2004 Chapter 18 Slide 44
 Electrolysis 02

•Electrolysis
ElectrolysisofofAqueous
Molten Sodium
SodiumChloride:
Chloride: uses
different processes to molten sodium chloride.
Based on cell potentials, water (–0.83 V) would be
preferentially reduced over sodium ions (–2.71 V).
Based on cell potentials, water (+1.23 V) should be
preferentially oxidized over chloride ions (+1.36 V).
The observed product at the anode is Cl2, not O2,
because of a phenomenon called overvoltage.

Prentice Hall ©2004 Chapter 18 Slide 45

 Electrolysis 04

• Overvoltage: Additional voltage needed to

maintain the rate of electron transfer at the
electrode–solution interface.

• Overvoltage is required when a half-reaction has a

significant activation energy, and so a slow rate.

• Overvoltage for formation of O2 or H2 is much

greater than for formation of Cl2.

Prentice Hall ©2004 Chapter 18 Slide 46

 Electrolysis 07

• Quantitative Electrolysis: The amount of

substance produced at an electrode by
electrolysis depends on the quantity of charge
passed through the cell.
• Reduction of 1 mol of sodium ions requires 1 mol
of electrons to pass through the system.
• The charge on 1 mol of electrons is 96,500
coulombs.
Prentice Hall ©2004 Chapter 18 Slide 47
 Electrolysis 08

• To determine the moles of electrons passed, we

measure the current and time that the current flows:
Charge (C) = Current (A) x Time (s)
• Because the charge on 1 mol of e– is 96,500 C, the
number of moles of e– passed through the cell is:

Prentice Hall ©2004 Chapter 18 Slide 48

 Electrolysis 09

• A constant current of 30.0 A is passed through an

aqueous solution of NaCl for a time of 1.00 hour.
How many grams of Na and how many liters of Cl2
gas at STP are produced?

• How many amperes must be passed through a

Downs cell to produce sodium metal at a rate of
30.0 kg/hour?
Prentice Hall ©2004 Chapter 18 Slide 49
 Electrolysis Applications 01

• Manufacture of Sodium (Downs Cell):

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 Electrolysis Applications 02

• Manufacture of Cl2 and NaOH (Chlor–Alkali):

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 Electrolysis Applications 03

• Manufacture of Aluminum (Hall–Heroult):

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 Electrolysis Applications 04

• Electrorefining and Electroplating:

Prentice Hall ©2004 Chapter 18 Slide 53