Larry Brown

Tom Holme

[Link]/chemistry/brown

Chapter 13
Electrochemistry

Technological University of the Philippines - Taguig Campus

Basic Arts and Sciences Department
Chemistry Section
Chapter Objectives
• Describe at least three types of corrosion and identify
chemical reactions responsible for corrosion.

• Define the oxidation and reduction.

• Write and balance half-reactions for simple redox processes.

• Describe the differences between galvanic and electrolytic cells.

• Use standard reduction potentials to calculate cell potentials

under both standard and non-standard conditions .

2
Chapter Objectives
• Use standard reduction potentials to predict the spontaneous
direction of a redox reactions

• Calculate the amount of metal plated, the amount of current

needed, or the time required for an electrolysis process.
• Distinguish between primary and secondary batteries.

• Describe the chemistry of some common battery types and explain

why each type of battery is suitable for a particular application

• Describe at least three common techniques for preventing

corrosion .

3
INTRODUCTION

• Electrochemistry is the branch of chemistry that deals with the

interconversion of electrical energy and chemical energy.

• This conversion takes place in electrochemical cells which are

two types:
I. Galvanic Cells: electricity is produced by means of
spontaneous redox reaction.

CHEMICAL ENERGY ELECTRICAL

ENERGY

II. Electrolytic Cells: electrical energy is used to cause a

non- spontaneous reaction to occur.

ELECTRICAL ENERGY CHEMICAL 4

Oxidation-Reduction Reactions

• Reactions that transfer electrons between reactants are

known as oxidation-reduction or redox reactions.
• Oxidation is the loss of electrons from some chemical
species.
• Reduction is the gain of electrons to some chemical
species.

• When copper wire is placed in a silver nitrate solution, a redox

reaction occurs.
• A reaction is observed to occur because the solution
changes color and crystals form on the surface of the
copper wire.

5
Oxidation-Reduction and Half-Reactions

• When a clean copper wire is placed into a colorless solution

of silver nitrate, it is quickly apparent that a chemical reaction
occurs.
6
Oxidation-Reduction and Half-Reactions

• The solution’s blue color is indicative of Cu2+ ions in solution.

• Cu2+ is formed when a copper atom loses two electrons.
• The copper metal is oxidized.

Cu(s)  Cu2+(aq) + 2e

• The crystals forming on the surface of the copper wire are
silver metal.
• Silver is formed when a silver cation gains an electron.
• The silver cation is reduced.

Ag+(aq) + 1e  Ag(s)

7
Oxidation-Reduction and Half-Reactions

• For the reaction between silver cation and copper metal, two
half-reactions are written.
• One for the oxidation of copper and one for the reduction
of silver.
• Neither half-reaction can occur without the other.

• The half-reactions as written indicate that Ag+ only accepts

one electron whereas Cu loses two electrons.
• The electron transfer must balance, so the reduction half-
reaction is multiplied by 2.

Cu(s)  Cu2+(aq) + 2e

2Ag + (aq) + 2e  
8
Oxidation-Reduction and Half-Reactions

• Add the two half-reactions together, the electrons cancel out,

leaving the net ionic equation for the redox reaction.

Cu(s)  Cu2+(aq) + 2e

2Ag + (aq) + 2e  
2Ag(s)
Cu(s) + 2Ag+(aq)

Cu2+(aq) + 2Ag(s)

9
Oxidation-Reduction and Half-Reactions

• The species undergoing oxidation is referred to as a reducing

agent.
• The Cu was oxidized and is the reducing agent.
• The Cu facilitated the reduction of Ag+ by losing electrons.

• The species undergoing reduction is referred to as an

oxidizing agent.
• The Ag+ was reduced and is the oxidizing agent.
• The Ag+ facilitated the oxidation of Cu by gaining
electrons.

1
Problem 13.5
• Prob. 13.5. For the following oxidaton-reduction reactions,
identify the half reactions and label them as oxidation or reduction.

(a) Cu(s) + Ni2+(aq) Ni(s) + Cu2+(aq)

oxidation rxn: Cu(s) Cu2+(aq) +
2e- reduction rxn: Ni2+(aq) +
2e- Ni(s)
Cu is oxidized and Cu is reducing agent
Ni is reduced and Ni2+ is oxidizing agent
(b) 2 Fe3+ (aq) + 3 Ba (s) 3 Ba2+ (aq) + 2
oxidation rxn: Ba(s) Fe (s) Ba2+(aq) +
reduction rxn: Fe3+(aq) + 2e
Fe(s)
-

3e-
Ba is oxidized and Ba is reducing agent
Fe is reduced and Fe3+ is oxidizing agent
11
Building a Galvanic Cell
• A galvanic cell is any electrochemical cell in which a spontaneous
chemical reaction can be used to generate an electric current.

• To harness electricity from a galvanic cell, each half-reaction is

prepared separately in half-cells.
• Cu metal immersed in Cu2+ solution is one half-cell.
• Ag metal immersed in Ag+ solution is the second half-cell.

• Current flows by the migration of ions in solution.

• To transfer current between the half-cells, a salt bridge is
used.
• The salt bridge contains a strong electrolyte that allows either
cations or anions to migrate into the solution where they are
needed to maintain charge neutrality.
• A metal wire cannot transport ions and cannot be used. 12
Building a Galvanic Cell

• A salt bridge is crucial to a galvanic cell. The salt bridge

allows ions to flow between each half-cell, completing the
circuit. 13
Terminology for Galvanic Cells

• Electrodes are the electrically conducting sites at which either

oxidation or reduction occurs.
• The electrode where oxidation occurs is the anode.
• The electrode where reduction occurs is the cathode.

• Cell notation - a shorthand notation for the specific chemistry

of an electrochemical cell.
• Cell notation lists the metals and ions involved in the
reaction.
• A vertical line, |, denotes a phase boundary.
• A double vertical line, ||, denotes a salt bridge.
• The anode is written on the left, the cathode on the
right.
14
Terminology for Galvanic Cells
• General form of cell notation

anode | anode electrolyte || cathode electrolyte |

cathode

• For the previous example of copper and silver

Cu(s) | Cu2+(aq) (1 M) || Ag+(aq) (1 M) | Ag

• An electrochemical cell is at its standard state when the

electrolyte concentrations are 1 M.

• For half-cells that generate or consume a gas, a partial

pressure of 1 atm is required for the standard state. 15
Problem 13.11

• Prob 13.11. The following oxidation-reduction reactions are

used in electrochemical cells. Write them using cell notation.

(a) Ni (s) + 2 Ag+(aq)(0.50 M) 2 Ag (s) + Ni2+(aq)(0.20 M)

oxidation rxn: Ni (s) Ni2+(aq)
+ 2e- reduction rxn: Ag+(aq) +
e- Ag(s)

Ni(s) | Ni2+ (aq) (0.20 M) || Ag+ (aq) (0.50 M) |

Ag

16
Problem 13.12

• Prob 13.12. Write a balanced chemical equation for the overall

cell reaction represented as

(a) Ag(s) | Ag+ (aq) || Sn 4+(aq), Sn 2+(aq) |

Pt(s)
oxidation rxn: Ag (s) Ag+ e-
(aq) + reduction rxn: Sn4+(aq) + Sn2+(aq)
2e-
Sn4+(aq) + 2 Ag (s) 2 Ag+ (s) + Sn2+(aq)

17
Cell Potentials

• The build up of charge on the electrode means there is

potential for electrical work.
• This potential is the cell potential, or electromotive force
(EMF).

• EMF is related to the maximum work obtainable from an

electrochemical cell.
• wmax = qE
• q is the charge, E is the cell potential.

• A voltmeter measures the size of the electrical potential and

also its polarity - the locations of the negative charge
(negative pole) and the positive charge (positive pole).
18
Measuring Cell Potential

• When a voltmeter is connected to the previously described

copper/silver cell, a potential of 0.462 V is measured.

• Connecting the copper half-cell to a reducing iron(III)/iron(II)

half-cell, a cell potential of 0.434 V is measured.

• Connecting the iron(III)/iron(II) half-cell to the silver half-cell

results in a cell potential of 0.028.

19
Measuring Cell Potential

• Measurement of standard cell voltages for various

combinations of the same half-reactions suggests that a
characteristic potential can be associated with a particular
half-reaction. 19
Measuring Cell Potential

• The standard hydrogen electrode

(SHE) is the choice for the standard
component in cell potential
measurements.
• The cell is constructed of a platinum
wire or foil as the electrode.
• The electrode is immersed in a
1 M HCl solution through which
H2 gas with a pressure of 1 atm
is bubbled.

• The SHE has been chosen as the

reference point for the scale of
standard reduction potentials, and
assigned a potential of exactly zero
volts.
21
Measuring Cell Potential

• For the Standard Hydrogen Electrode

• The half-reaction for the SHE is: 2 H+(aq) + 2 e–  H2(g).

• The half-cell notation is: Pt(s) | H2(g, 1 atm) | H+ (1 M).

• The half-cell is assigned a potential of exactly zero volts.

• The cell potential is attributed to the other half-reaction.

22
Standard Reduction Potentials

• To compare the oxidation-reduction trends of species used in

electrochemistry, all half-cell potentials are written as
reductions.

• A table of standard reduction potentials lists the potential

of any half-reaction when connected to a SHE.

• All materials are 1 M for aqueous species and 1 atm

partial pressure for gases.

23
Standard Reduction Potentials

• Standard reduction potentials for several half-reactions

involved in the cells discussed in the text.
24
Standard Reduction Potentials

• Although the half-reactions are listed as reductions in the

table, one half-reaction in any electrochemical cell must be an
oxidation and, therefore, reversed from what appears in the
table.

• The cell potential sign must be changed when writing the

half-reaction as an oxidation.

• Some half-reactions have positive potentials, whereas others

have negative potentials.

25
Standard Reduction Potentials

• The tendency for the chemicals involved in a half-reaction to

be an oxidation or reduction depends on the value of the
reduction potential.

• A large, positive value for the standard reduction potential

implies the substance is reduced readily and a good
oxidizing agent.

• A large, negative value for the standard reduction potential

implies the substance is oxidized readily and a good
reducing agent.

26
Standard Reduction Potentials

• For a galvanic cell,

• The half-reaction with the more positive reduction potential
will be the cathode.
• The half-reaction with the more negative reduction potential
will be the anode.

• The standard reduction potential for any pair of half-reactions,

Eo cell
, is calculated from the standard reduction potentials for
the cathode and anode.
Eo = Eo + Eo
cell red
ox

• Eo red is the standard reduction potential for the cathode

and Eo ox is the standard reduction potential for the anode.

27
Standard Reduction Potentials

• For standard reduction potentials arranged horizontally, the

anode and cathode for a galvanic cell can easily be
determined. The reduction potential furthest to the left is
the anode.

28
Problem 13.20
• Prob 13.20. Four voltaic cell are set up. In each, one half contains a
standard hydrogen electrode. The second half cell is one of the following:
Cr3+ (aq) | Cr(s) , Fe2+ (aq) | Fe(s) , Cu2+ (aq) | Cu (s) , Mg2+ (aq) | Mg (s)
(a) In which of the voltaic cell does the hydrogen electrode serve as the
cathode ?
(b) Which voltaic cell produces the highest voltage? Which produces the
lowest ?

(a) For hydrogen to serve as Cathode Eored ( H+| H2) > Eored ( X)
since Eored ( Cr3+ | Cr) , Eored ( Fe2+ | Fe) , Eored ( Mg2+ | Mg) < Eored ( H+| H2)
Hydrogen will be cathode (reduced) and others will be anode (oxidized)
(b) Eocell + Eoox
= Eored
= Eored ( H+| H2) + Eoox ( Mg | Mg2+) = 0.00 + (+2.37) = 2.37 V the highest
E o
cell
= Eored ( H+| H2) + Eoox ( Cr | Cr2+) = 0.00 + (+0.74) = 0.74 V
Eocell = Eo ( H+| H ) + Eo ( Fe | Fe3+) = 0.00 + (+0.41) = 0.41 V
red 2 ox

Eocell = E red ( Cu | Cu) + E ox (H2 | H ) = 0.337 + 0.00 = 0.337 V the lowest

o 2+ o +
29
 Problem 13.24
• Prob 13.24. Consider for the reduction of the following metal ions to the
metal:

Sn2+ (aq) , Au+(aq), Zn2+ (aq) , Co2+ (aq) , Ag+(aq), Cu2+ (aq)
Among
a. Whichthe metal
metal ionions andweakest
is the metals that makeagent?
oxidizing up these half reactions: ( Zn2+ | Zn) = - 0.763 V
Eo red
b. Which metal ion is the strongest oxidizing agent? Eo red ( Co2+ | Co) = - 0.28 V
c. Which metal is the strongest reducing agent? Eo red ( Sn2+ | Sn) = - 0.14 V
Eo red ( Cu2+ | Cu) = + 0.337V
d. Which metal is the weakest reducing agent?
Eo red ( Ag+ | Ag) = + 0.799
e. Will Sn(s) reduce Cu2+ (aq) to Cu(s)? Eored V ( Au+| Au) = + 1.68 V
f. Will Ag(s) reduce Co2+ (aq) to Co(s)? --------------------------------------------
g. Which metal ions in the list can be reduced by --------------------------------------------
( Au | Au ) = - 1.68 V
Sn(s)? Eo ox +

Eo ox ( Ag | Ag ) = - 0.799
+
h. What metals can be oxidized by Ag+(aq)?
Eo ox V
ANSWERS Eoox ( Sn
Cu | Sn 2+) = +
Cu2+ 0.14
- 0.337V
a. With the lowest E red value Zn is the weakest oxidizing agent.
Eo ox V
( Co | Co ) = + 0.28 V
o 2+ 2+

b. With the highest Eored value Au+ is the strongest oxidizing agent. Eo ox ( Zn | Zn ) = + 0.763 V
2+

c. With the highest Eo value Zn is the strongest reducing agent.

ox
d. With the lowest Eo value Au is the weakest reducing agent.
ox
e. Yes, since Eo ( Cu2+ | Cu) > Eo ( Sn2+ | Sn) , Sn will reduce Cu2+ to Cu.
red red
f. No, since Eo ( Co2+ | Co) < Eo ( Ag+ | Ag) , Ag will not reduce Co2+ to Co.
red red
h. Except Au (Eo ( Au+ | Au) > Eo ( Ag+ | Ag)) , all other metals; Zn, Co, Sn, Cu will be oxidized by Ag
+.
red red
30
 Problem 13.25 & 26
• Prob 13.25. Calculate cell potentials of the following
cells:
a. Ga(s) | Ga3+(aq) ║ Ag+(aq) | Ag(s)
Eo +
red ( Ag | Ag) = + 0.799 V
E red ( Ga | Ga) = - 0.53 V
o 3+ Eo 3+
oxidation half-rxn : Ga(s) Ga (aq) + 3e
3+ -
ox ( Ga | Ga )=+
0.53 V
reduction half-rxn : Ag+(aq) + e- Ag(s) Eo +
Eo red ( Ag | Ag) = + 0.799 V
+ Eo
ox

==E0.799+ 0.53
o
cell red
Eo = 1.33 V
cell

• Prob 13.26. Calculate cell potentials of the following

cells:
b. Pt | Fe2+ (aq), Fe3+(aq) ║ MnO4 (aq), H (aq) , Mn
(aq) | Pt -
+
2+
E red (Fe | Fe ) = + 0.771 V 3+ Eo 2+ 3+
oxidation
o half-rxn : 3+ Fe2+2+(aq) Fe (aq) + ox (Fe| Fe ) = - 0.771
e-
E red (MnO4 | Mn MnO4 -(aq) ) = +1.507
8 H (aq)
V + 5e V Eo - 2+
reduction half-rxn : - Mn 2+ (aq) + +H2O red (MnO4 | Mn )=
o 2+ +
-
Eo o +E o 1.507 V
ox
= - 0.771+ 1.507
Eo = 0.736 V
cell

31
Nonstandard Conditions

• The cell potential at nonstandard conditions is calculated using the

Nernst equation.

E 
0.0591 log
Eo n
Q and n is the number of electrons transferred
• Q is the reaction quotient,
in the reaction.

• For rxn; aA + bB cC + dD

C  D 
c d

Q 
 A  B 
a b

• In Q calculations only concentration of (aq) state and partial

pressure of (g) state included.

32
Problem 13.29
• Prob.13.29. Calculate the cell potentials of the following cells at 25
oC.

a. 2 Ag+ (aq) (0.50M) + Ni(s) 2 Ag(s) + Ni2+(aq)

E   0.0591 log
(0.20M)

Eo n
oxidation half-rxn
Q : Ni(s) Ni 2+(aq) + 2e- Eoox ( Ni | Ni2+) = + 0.25 V
reduction half-rxn : Ag+(aq) + e- Ag(s) Eored ( Ag+ | Ag) = + 0.799 V
+ Eoox
E cell =
o
= 0.799 + 0.25 = 1.049 V
Eored


 Ni 2 
0 . 2 0  
1

0.8
Q n= 2
 A g

1 
0 . 5 0 
2

 2

E  Eo 
0.0591 log Q  1.049  (0.0591) log(0.8) 
1.052V
n 2
33
Electrolytic Cells

Electrolytic Cells: electrical energy is used to cause a non-spontaneous

reaction to occur.

• Electrolysis is the process of passing an electric current through an

ionic solution or molten salt to produce a chemical reaction.

• Electrolytic cells are divided into two categories based on the nature
of the electrodes used.

• Passive electrolysis: the electrodes are chemically inert materials

that simply provide a path for electrons.

• Active electrolysis: the electrodes are part of the electrolytic

reaction. 34
Electrolysis

• Electrolysis changes the polarity of the electrodes in a system.

• For reduction, electrons are forced to the cathode. The
cathode becomes the negative electrode.
• For oxidation, electrons are pulled from the anode. The
anode becomes the positive electrode.
• In electrolysis, an
external source of
current drives a redox
reaction that would
otherwise not be
spontaneous.

The flow of ions

through the solution
completes the circuit. 35
Electroplating
• The process of depositing a thin coat of metal on another metal by
using electrolysis is electroplating.
• In some cases, the thin coating is cosmetic, or to provide some
vital functionality for the coated piece, such as corrosion
resistance or desirable conductive properties.

• Silver is plated onto electrical devices because silver is a good

conductor and resistant to corrosion.
• Ag+ (aq) + e- Ag(s) Rxn occur at
cathode.
• To collect 1 mol of Ag 1mol of e- is required

• Metal ions reduce at the surface of cathode;

• M+x(aq) + Xe- M (s)
• 1 mol M = X mol e-
36
Electrolysis and Stoichiometry

• For electroplating, it can be vitally important to use carefully

controlled amounts of materials.

• Controlling the flow of electrons (current) in an

electroplating operation provides a method to accurately
limit the amount of material deposited.

• Electroplating is often used to prevent galvanic corrosion

in an electrical apparatus in places where different metals
come into contact with one another.

37
Current and Charge

• When current is measured in an electric circuit, the

observation is the flow of charge for a period of time.

• The unit of current, the ampere (A), is defined as one

coulomb per second: 1 A = 1 C s-1.

• If a known current flows through a circuit for a known time,

the charge can be easily calculated.

Charge = current 
time
QIt
38
Current and Charge

• Using Faraday’s constant, F = 96,485 C mol-1 and the

calculated charge, the number of moles of electrons that pass
through the circuit can be calculated.

• If the number of electrons required to reduce each metal

cation is known, the number of moles of material plated can
be calculated.

• Electricity use is often measured in terms of power. The SI

unit for power is the watt (1 watt = 1 J s-1)
• Electrical utilities normally determine consumption in kilowatt-
hours, kWh (1 kWh = 3.60  106 J)

39
Calculations Using Masses of Substances in Electrolysis

• A knowledge of current, how long the current flows,

stoichiometry, and the number of electrons required to reduce
a metal cation are used to answer the following questions.

• How much material is plated given a specific current for an

allotted time or electrical energy expenditure?

• How long must a given current to pass through the cell to

yield a desired mass of plated material?

40
Example Problem 13.75

• Prob.13.75. If current of 15 A is run through an electrolysis cell

for
2.0 hours, how many moles of electrons have moved?

Charge = Current x time

Q = 15 x (2.0 x 3600) = 1.08 x105 C

1 mol e- = 96,500 C
96,500 C 1 mol e-
1.08 x105 C X = 1.12 mol e-

41
Example Problem 13.79
• Prob.13.79. In a copper plating experiment in which copper
metal is deposited from copper(II) ion solution, the system is run
for 2.6 hours at a current of 12.0 A. What mass of copper
depozited?

copper(II)
Cu2+(aq) +ion
2e-solution Cu(s) Cu2+(aq)

Charge = Current x time = 12.0 x (2.6 x 3600) = 1.12 x105 C

96,500 C 1 mol e-
1.12 x105 C X = 1.16 mol e-
2 mol e- : 1mol Cu
1.16 mol e- X
= 0.58 mol
Cu = 0.58 42