C

H
E
M
1
CHEM 101-GENERAL CHEMISTRY
CHAPTER 13
ELECTROCHEMISTRY
0
1
INSTR : FİLİZ ALSHANABLEH
CHAPTER 13
ELECTROCHEMISTRY

• Oxidation – Reduction Reactions

• Galvanic Cells
• Cell Potentials
• Cell Potentials and Equilibrium
• Batteries
• Electrolysis
• Electrolysis and Stoichiometry

2
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 ENERGY

3
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.

4
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.
5
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 2+ (aq) + 2e −
Cu(s) 
• 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)

6
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 2+ (aq) + 2e −
Cu(s) 
2Ag + (aq) + 2e − 
→ 2Ag(s)
7
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 2+ (aq) + 2e −
Cu(s) 
2Ag + (aq) + 2e − 
→ 2Ag(s)
Cu(s) + 2Ag (aq) 
+
→ Cu (aq) + 2Ag(s)
2+

8
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.

9
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 Fe (s)

oxidation rxn: Ba(s) Ba2+(aq) + 2e-
reduction rxn: Fe3+(aq) + 3e- Fe(s)
Ba is oxidized and Ba is reducing agent
Fe is reduced and Fe3+ is oxidizing agent
10
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.
11
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.
12
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.

13
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) | Cu 2+ (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.
14
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) | Ni 2+ (aq) (0.20 M) || Ag + (aq) (0.50 M) | Ag

15
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+(aq) + e-

reduction rxn: Sn4+(aq) + 2e- Sn2+(aq)

Sn4+(aq) + 2 Ag (s) 2 Ag+ (s) + Sn2+(aq)

16
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).
17
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.

18
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.
20
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.

21
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.

22
Standard Reduction Potentials

• Standard reduction potentials for several half-reactions

involved in the cells discussed in the text.
23
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.

24
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.

25
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,

Eocell, is calculated from the standard reduction potentials for
the cathode and anode.
Eocell = Eored + Eoox

• Eored is the standard reduction potential for the cathode

and Eoox is the standard reduction potential for the anode.

26
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.

27
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 = Eored + Eoox
Eocell = Eored ( H+| H2) + Eoox ( Mg | Mg2+) = 0.00 + (+2.37) = 2.37 V the highest
Eocell = Eored ( H+| H2) + Eoox ( Cr | Cr2+) = 0.00 + (+0.74) = 0.74 V
Eocell = Eored ( H+| H2) + Eoox ( Fe | Fe3+) = 0.00 + (+0.41) = 0.41 V
Eocell = Eored ( Cu2+| Cu) + Eoox (H2 | H+) = 0.337 + 0.00 = 0.337 V the lowest
28
 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 the metal ions and metals that make up these half reactions:
a. Which metal ion is the weakest oxidizing agent? Eored ( Zn2+ | Zn) = - 0.763 V
b. Which metal ion is the strongest oxidizing agent? Eored ( Co2+ | Co) = - 0.28 V
c. Which metal is the strongest reducing agent? Eored ( Sn2+ | Sn) = - 0.14 V
Eored ( Cu2+ | Cu) = + 0.337V
d. Which metal is the weakest reducing agent?
Eored ( Ag+ | Ag) = + 0.799 V
e. Will Sn(s) reduce Cu2+ (aq) to Cu(s)? Eored ( 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 Sn(s)? --------------------------------------------
h. What metals can be oxidized by Ag+(aq)? Eoox ( Au | Au +) = - 1.68 V
Eoox ( Ag | Ag +) = - 0.799 V
Eoox ( Cu | Cu2+) = - 0.337V
ANSWERS Eoox ( Sn | Sn2+) = + 0.14 V
a. With the lowest Eored value Zn2+ is the weakest oxidizing agent. Eoox ( Co | Co2+) = + 0.28 V
b. With the highest Eored value Au+ is the strongest oxidizing agent. Eoox ( Zn | Zn2+) = + 0.763 V
c. With the highest Eoox value Zn is the strongest reducing agent.
d. With the lowest Eoox value Au is the weakest reducing agent.
e. Yes, since Eored ( Cu2+ | Cu) > Eored ( Sn2+ | Sn) , Sn will reduce Cu2+ to Cu.
f. No, since Eored ( Co2+ | Co) < Eored ( Ag+ | Ag) , Ag will not reduce Co2+ to Co.
h. Except Au (Eored ( Au+ | Au) > Eored ( Ag+ | Ag)) , all other metals; Zn, Co, Sn, Cu will be oxidized by Ag +.

29
 Problem 13.25 & 26
• Prob 13.25. Calculate cell potentials of the following cells:
a. Ga(s) | Ga3+(aq) ║ Ag+(aq) | Ag(s)
Eored ( Ag+ | Ag) = + 0.799 V
Eored ( Ga3+ | Ga) = - 0.53 V
oxidation half-rxn : Ga(s) Ga3+(aq) + 3e- Eoox ( Ga | Ga3+) = + 0.53 V
reduction half-rxn : Ag+(aq) + e- Ag(s) Eored ( Ag+ | Ag) = + 0.799 V
Eocell = Eored + Eoox
= 0.799+ 0.53
Eocell = 1.33 V

• Prob 13.26. Calculate cell potentials of the following cells:

b. Pt | Fe2+ (aq), Fe3+(aq) ║ MnO4- (aq), H+ (aq) , Mn 2+ (aq) | Pt
Eored (Fe3+ | Fe2+ ) = + 0.771 V
Eored (MnO4- | Mn 2+ ) = 1.507 V
oxidation half-rxn : Fe2+ (aq) Fe3+(aq) + e- Eoox (Fe2+ | Fe3+ ) = - 0.771 V
reduction half-rxn : MnO4- (aq) + 8 H+ (aq) + 5e- Mn 2+ (aq) + +H2O Eored (MnO4- | Mn 2+ ) = 1.507 V
Eocell = Eored + Eoox
= - 0.771+ 1.507
Eocell = 0.736 V

30
Nonstandard Conditions

• The cell potential at nonstandard conditions is calculated using the Nernst

equation.

E=E o
−
(0.0591)
log Q
n
• Q is the reaction quotient, and n is the number of electrons transferred
in the reaction.

• For rxn; aA + bB cC + dD

Q=
[C ] [D ]
c d

[A]a [B ]b
• In Q calculations only concentration of (aq) state and partial pressure
of (g) state included.

31
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) (0.20M)

E=E o
−
(0.0591)
log Q
n
oxidation half-rxn : 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
Eocell = Eored + Eoox
= 0.799 + 0.25 = 1.049 V

Q=
[Ni ] 2+ 1
=
[0.20]1 = 0.8
[Ag ] + 2
[0.50]2 n= 2

E = Eo −
(0.0591) log Q = 1.049 − (0.0591) log(0.8) = 1.052V
n 2

32
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. 33
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.
34
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-
35
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.

36
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

37
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)

38
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?

39
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-

40
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) ion solution Cu2+(aq)

Cu2+(aq) + 2e- Cu(s)

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 (63.55) = 37.0 g Cu

41