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Chapter 16

Electron Transfer Reactions


and Electrochemistry

Copyright 2015 by Nelson Education Limited

Electron Transfer Reactions and


Electrochemistry

Copyright 2015 by Nelson Education Limited

Artificial Leaves: Personal Energy


Sources for Everyone?
Photosynthesis: Natures Way of Harvesting Solar Energy
Sustainable life on this planet would not be possible
without ways of harvesting solar energy.
The generalized process of photosynthesis is:
photons
6 CO2(g) + 6 H2O()
C6H12O2(aq) + 6 O2(aq)
In actuality, it is a complex sequence of chemical
reactions that happen in a coordinated manner. To
produce a sugar, plants require nearly 30 proteins!
Respiration converts sugars to energy, water, and CO2(g).
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Artificial Leaves: Personal Energy


Sources for Everyone?

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Artificial Leaves: Personal Energy


Sources for Everyone?
The Challenge for Chemists
More than 100 years ago, Giacomo Ciamician posed a
challenge for chemists to fix the solar energy through
suitable photochemical reactions with new compounds
that master the photochemical process that hitherto
have been the guarded secret of plants.
Plants are only about 1% efficient in harnessing solar
energy by photosynthesis.
There are many challenges to chemists and engineers in
the quest to develop an artificial leaf.
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Artificial Leaves: Personal Energy


Sources for Everyone?
Progress Toward an Artificial Leaf
The most basic chemistry-based
method uses photovoltaic solar
panels to decompose dilute salt
solutions by electrolysis.

Anode: 2 H2O() O2(g) + 4 H+(aq) + 4 e


Cathode: 4 H+(aq) + 4 e(aq)
2 H2(g)
2 H2O()

O2(g) + 2 H2(g)
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Oxidation-Reduction Reactions
SUMMARY:
Oxidation and reduction occur simultaneously when
electrons are transferred from one species to another.
The species that gains electrons is said to be reduced.
The species that loses electrons is said to be oxidized.
The species which gains e's is the oxidizing agent.
The species which loses e's is the reducing agent.

e16.2 Watch an animation of oxidation and reduction


processes at a molecular level.
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OIL RIG

Oxidation-Reduction Reactions

Ag+(aq) gains electrons and is reduced to Ag(s).


Cu(s) loses two electrons and is oxidized to Cu2+ (aq).
The reaction can be imagined to consist of two
components, called half-reactions:
Oxidation: Cu(s)
Cu2+(aq) + 2 e
Reduction: 2 Ag+(aq) + 2 e
Ag(s)
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Oxidation-Reduction Reactions
The oxidation state measures the degree of
oxidation of an element in a compound,
compared with when that element is pure and
uncombined.
Oxidation leads to an increase in the oxidation state of
an element in the compound (more +ve).
Reduction leads to a decrease in the oxidation state of
an element in the compound (more -ve).
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Oxidation-Reduction Reactions
Guidelines:
The oxidation state of each atom in a pure element is zero.
For a monatomic ion, the oxidation state is its charge.
The sum of oxidation states in an ion is equal to its charge.
In a molecule, the sum is zero.
In all of its compounds and ions, F is in oxidation state 1.
In most compounds and ions, H is in oxidation state +1.
In most compounds, O is in oxidation state 2.

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e16.4 Work through a tutorial on assigning oxidation states.

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Oxidation-Reduction Reactions
Recognizing Oxidation and Reduction

Compare the oxidation state of each element in the


products to those same elements in the reactants.

Like O2, the halogens (F2, Cl2, Br2, I2) are always oxidizing
agents when reacting with metals and non-metals.
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Oxidation-Reduction Reactions
EXAMPLES:
Sodium-chlorine reaction.
Sodium metal reduces chlorine gas;
chlorine gas oxidizes sodium metal.

The thermite reaction.


Aluminum reduces iron (III) oxide to
iron metal in a highly exothemic
reaction.
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Oxidation-Reduction Reactions
EXAMPLE: Copper and Nitric acid
reaction
Copper reacts vigorously with NO3(aq)
ions in concentrated nitric acid
solution. NO3(aq) ions are reduced to
the brown gas NO2(g), and Cu(s) is
oxidized to blue-green Cu2+(aq) ions.

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e16.5 Compare the reactions of copper and zinc metals with nitric
acid solutions.

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Oxidation-Reduction Reactions
Oxidation-Reduction Reactions as Competition
Oxidation-reduction reactions can be regarded as the
result of competition between species for electrons:
the winner is reduced, and oxidizes the other species.
The outcome of competition determines the direction
of spontaneous reaction: the direction of reaction that
takes the reaction mixture toward equilibrium.
The ability of a species to compete for electrons is
ranked on a scale of reduction potentials.
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Voltaic Cells: Electricity From


Chemical Change
Electrochemistry is a field of study about the
interaction between electricity and chemistry.
There are two types of electrochemical cells,
used in industry and in the laboratory:
Voltaic cells (or galvanic cells) direct the transfer of
electrons in a spontaneous redox reaction from one
compartment of the cell, through a conductor, to
another compartment. The two compartments are
called half-cells.
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Voltaic Cells: Electricity From


Chemical Change
An electrolysis cell (or electrolytic cell), is an
electrochemical cell where a voltage is applied so that
electrons are forced to flow in the reverse-normal
direction, leading to a non-spontaneous redox reaction to
occur. This forced non-spontaneous process is called
electrolysis.

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Almost all chemical energy is just


stored electrical energy
(Chemical reaction involve breaking and reforming chemical bonds, which are made of pairs of
electrons, and since electrons are electrically charged, these chemical reactions are associated
with changes in energy, mostly electrical energy, measured by G.)

Voltaic Cells: Electricity from


Chemical Change
The electrode where oxidation occurs is called
the anode
The electrode where reduction occurs is called
the cathode.

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Voltaic Cells: Electricity from


Chemical Change

One half-cell contains copper metal in a solution of Cu2+(aq) ions;


the other has silver metal in a solution of Ag+(aq) ions.
Electrons flow through the external circuit from the half cell where
Cu(s) is oxidized (the anode) to the half-cell where Ag+(aq) ions are
reduced (the cathode).
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Voltaic Cells: Electricity from


Chemical Change

In the salt bridge, which contains aqueous NaNO3 solution, negative


NO3 (aq) ions migrate toward the anode, and positive Na+ (aq) ions
migrate toward the cathode.
In battery-operated devices, the voltmeter is replaced by devices
that operate by using electrical energy.
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Voltaic Cells: Electricity from


Chemical Change
Summary of Voltaic Cell Processes and Terms
The electrons transferred during a spontaneous
reaction are harnessed as an electrical current
electrons move from the anode, the site of oxidation,
through the external circuit to the cathode, the site of
reduction.
Charge balance in each half-cell is achieved by
migration of ions through the salt bridge (internal
circuit). Anions move toward the anode, and cations
move toward the cathode.
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Voltaic Cells: Electricity from


Chemical Change
Summary of Voltaic Cell Processes and Terms

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e16.8 Examine the components of a voltaic cell.

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Voltaic Cells: Electricity from


Chemical Change
Voltaic Cells with Inert Electrodes
Inert electrodes are made of
conducting materials that are too
unreactive to be oxidized or reduced
e.g. like platinum.
If the components of a half-cell are
gases, liquids, or dissolved species,
electrons can be transferred to or
from the external circuit through
inert electrodes.
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Voltaic Cells: Electricity from


Chemical Change

This cell has Fe3+(aq) ions and Fe2+(aq) ions, in the


cathode compartment, and H2(g) and H+(aq) ions in the
anode compartment.
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Voltaic Cells: Electricity from


Chemical Change
Electrochemical Cell Conventions

The convention for representing isolated half-cells places


the oxidized species on the left.
A vertical line represents a boundary between phases.
For cells, if the identity of the anode is known, it is
written on the left with order of species reversed.
Double vertical lines represent the salt bridge.
Cu(s) Cu2+(aq, 1.0 mol L1) Ag+(aq, 1.0 mol L1) Ag(s)
Pt H2(g, 1.0 bar) H+(aq, 1.0 mol L1) Fe3+(aq, 1.0 mol L1), Fe2+(aq, 1.0 mol L1) Pt

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Voltaic Cells: Electricity from


Chemical Change
The batteries that we depend on as portable
energy sources in our everyday lives are voltaic
cells.
A voltaic cell must have a large mass of reactants
to produce current over a prolonged period.
A voltaic cell that can be recharged and is
reusable is attractive because it reduces waste
and is cheaper (especially when taking recycling
or disposal costs into account).
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Voltaic Cells: Electricity from


Chemical Change
Primary batteries cannot be returned to their
original state by recharging, so when the
reactants are consumed, these batteries are
dead and are discarded.
With secondary batteries (also called storage
batteries or rechargeable batteries), the
reactions can be reversed, and the batteries can
be reused.
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Cell emf, and Half-Cell Reduction


Potentials
Cell emf, Competition for Electrons
The applied potential required to stop electron flow is called
the cell electromotive force, or cell emf or cell voltage (Ecell).
It is a measure of the difference between the abilities of
species in the half-cells to compete for electrons.

EXAMPLE:
Zn(s) Zn2+(aq, 1.0 mol L1) Cu2+(aq, 1.0 mol L1) Cu(s)
The cell above has Ecell = 1.10 V. This means that the cathode
half cell potential is 1.10 V greater than the anode half cell
potential.
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Cell emf, and Half-Cell Reduction


Potentials
For purposes of comparison, we measure cell
emf values under standard conditions, meaning:
Solutes in aqueous solution have a concentration of
1.0 mol L1.
Gaseous substances have a pressure of 1.0 bar.
Solids and liquids (not solutions) are pure.

The standard cell emf (Ecell) is the cell emf


measured under these standard states.
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Cell emf, and Half-Cell Reduction


Potentials
Half-Cell Reduction Potentials
The cell emf is a quantitative measure of the difference
in potentials of half-cells to attract electrons:
Ecell = Ecathode Eanode
Ecathode and Eanode are half-cell reduction potentials or
electrode potentials (Ehalf-cell)
The reference or standard half-cell is the standard
hydrogen electrode (SHE), which is arbitrarily assigned a
value of 0 V. Everything is measured relative to it.
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Cell emf, and Half-Cell Reduction


Potentials

This cell is constructed from a standard hydrogen


electrode and a Zn2+(aq) | Zn(s) half-cell.
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Cell emf, and Half-Cell Reduction


Potentials
In the preceding cell we can determine
The direction of the redox reaction
The direction of electron flow in the external
circuit
The relative oxidizing and reducing abilities of
cell reagents
Quantitative estimates of half-cell reduction
potentials
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Cell emf, and Half-Cell Reduction


Potentials
A Potential Ladder for Reduction Half-reactions:

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Cell emf, and Half-Cell Reduction


Potentials
Standard Half-Cell Reduction Potentials
Ehalf-cell depends on concentrations of reaction species.
When all species are in their standard states, the halfcell reduction potential is called the standard halfcell reduction potential (Ehalf-cell).

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Cell emf, and Half-Cell Reduction


Potentials

For any cell, the standard cell emf can be


calculated from the standard half-cell reduction
potentials
Eocell = Eocathode Eoanode

Table 16.1 Standard Half-Cell Reduction Potentials


Any half-cell may be either the cathode or anode,
depending on which cell is joined to it. All are written in
the direction of reduction.
The half-cell higher in the table is the cathode.
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e16.10 Compare E values in acidic and basic conditions.


e16.11 Use standard reduction potentials to calculate standard cell
emf.

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Cell emf, and Half-Cell Reduction


Potentials
Relative Oxidizing and Reducing Abilities,
Predicting Spontaneous Reactions
The more positive the value of Ehalf-cell, the better the
oxidizing ability of the ion or compound on the left side
of the half-reaction i.e. the more likely it is reduced.
The more negative the value of Ehalf-cell, the less likely
the half-reaction will occur as a reduction, and the
more likely the reverse half-reaction will occur (as an
oxidation).
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Cell emf, and Half-Cell Reduction


Potentials
The spontaneous reaction is the one between any
species on the left of a upper half-equation in the with
any species on the right of a lower half-equation in the
table of reduction potentials.

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Voltaic Cells under Non-standard


Conditions
Dependence of Cell emf on Concentrations
When the species in a voltaic cell are not in their
standard states, cell emf can be calculated using the
Nernst equation:
E cell =E

o cell

RT
0 . 0257 V
o

ln Q=E
nF
n
cell

at 25 o C

Q is the reaction quotient for the overall reaction.


n is the number of electrons in the overall reaction,
coming from the balanced half-reactions
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e16.13 Use graphs to visualize the relationships expressed by the


Nernst equation.
e16.14 Read about Michael Faradays contributions to
electrochemistry.
e16.15 Calculate the cell potential under non-standard conditions at
25C.

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Voltaic Cells under Non-standard


Conditions
pH Meters and Ion-Selective Electrodes
The Nernst equation can be used to determine an
unknown concentration by using a measured cell
potential, using a pH meter.
The electrodes used to measure ion concentrations are
known as ion-selective electrodes.
The readout from pH meters is calibrated, on the basis
of the Nernst equation, to read the concentration of the
ion directly.
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Voltaic Cells under Non-standard


Conditions

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Voltaic Cells under Non-standard


Conditions
pH-Dependence of Oxidizing Power of Oxoanions
A nitric acid solution will oxidize and dissolve metallic
copper, but copper nitrate solution will not.
When the half-equation for a reduction process involves
H+(aq) ions (i.e., acidic solutions), the half-cell reduction
potential depends on the concentration of these ions,
or pH, in accordance with the Nernst equation.
The lower the pH of solution, the more powerful
oxoanions are as oxidizing agents.
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Standard Cell emf and Equilibrium


Constant
Relationship between the standard cell emf and
the equilibrium constant for the overall cell
reaction:
ocell

nFE
ln K=
RT

o cell

nE
=
0 . 0257 V

at 25 o C

This relationship can be used to determine


equilibrium constants for cell reactions, using
standard cell emf values calculated from
standard reduction potentials in Table 16.1.
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Standard Cell emf and Equilibrium


Constant
EXAMPLE: Calculate the equilibrium constant at 25C
for the following reaction:
Fe(s) + Cd2+(aq)
Reduction: Cd2+(aq) + 2 e
Oxidation: Fe2+(aq) + 2 e

Fe2+(aq) + Cd(s)
Cd(s) E = 0.40 V
Fe(s) E = 0.44 V

Ecell = Ecathode Eanode = 0.40 V ( 0.44 V) = +0.04 V


ocell

o cell

( 2 ) ( 0 . 04 V )
nFE
nE
ln K=
=
=
=3 .1
RT
0 . 0257 V 0 . 0257 V
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K = 22
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Electrolysis: Chemical Change Using


Electrical Energy
During electrolysis, reactions are forced to go in
the non-spontaneous direction by application of
electrical energy to reagents in an
electrochemical cell called an electrolysis cell.
Electrolysis is widely used in the refining of
metals (such as aluminum and copper) and in the
production of substances such as chlorine gas.

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Electrolysis: Chemical Change Using


Electrical Energy
Electrolysis of
water produces
hydrogen and
oxygen gases.

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Electrolysis: Chemical Change Using


Electrical Energy
Electroplating adds a layer of
metal to the surface of an object.
It can be used to protect the
object from corrosion or to
improve its physical appearance.
The procedure uses an
electrolysis cell, set up with the
object to be plated as the
cathode.
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Electrolysis: Chemical Change Using


Electrical Energy
Electrolysis of Molten Salts

During the electrolysis of molten salts, when the applied


emf is sufficiently high, the cation of the salt is reduced
at the cathode, and the anion is oxidized at the anode.
These are the only possible reactions.

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Electrolysis: Chemical Change Using


Electrical Energy
EXAMPLE:
The production
of sodium and
chlorine by the
electrolysis of
molten NaCl.

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Electrolysis: Chemical Change Using


Electrical Energy
Electrolysis of Aqueous Solutions
Electrolysis of aqueous solutions is more complicated
than in molten salts, due to the presence of water.
The processes at each electrode are competitions
between water molecules and aquated ions to grab
electrons at the cathode, or lose electrons at the anode.
EXAMPLE:
Consider the electrolysis of a sodium iodide solution:
2 H2O() + 2 e
H2 (g) + 2 OH(aq) E = 0.41 V
Na+(aq) + e
Na(s)
E = 2.71 V
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Electrolysis: Chemical Change Using


Electrical Energy
An aqueous NaI solution is
electrolyzed, using an
external source of electricity.
A drop of phenolphthalein
has been added to the
solution so that the
formation of OH(aq) can be
detected (by the red colour).
Iodine forms at the anode,
and H2(g) and OH(aq) ions
form at the cathode.
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Electrolysis: Chemical Change Using


Electrical Energy
Electrolysis of an aqueous tin(II) chloride solution. Tin
metal is produced by reduction of Sn2+(aq) ions at the
cathode. Chlorine gas is formed at the anode by oxidation
of Cl(aq) ions, even though the potential for the oxidation
of Cl(aq) ions is less than that for the oxidation of water.

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Electrolysis: Chemical Change


Using Electrical Energy
Electrolysis of Aqueous Solutions

When large currents are applied in industrial


situations, the production of gaseous products may
involve application of an overvoltage and the
substances produced may be different from those
predicted by use of the table of standard reduction
potentials.
Overvoltage is the amount by which the applied emf
must be greater than predicted by the table of
standard reduction potentials, to allow this to happen.
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e16.17 Examine the processes involved in the electrolysis of water.

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Corrosion of Iron
Corrosion is the deterioration of metals resulting
from oxidation in the presence of air and water.
It is an electrochemical process and the product
is a hydrated iron oxide (rust).

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Corrosion of Iron
Corrosion is an electrochemical process in which
iron is oxidized at an anodic region and water is
reduced at a cathodic region.

e16.18 Examine the processes involved in the rusting of iron.


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Corrosion of Iron
Acceleration of the Rate of Corrosion
Contact with salty water reduces the resistance to ion
migration.
Deformation of the iron makes it more reactive.
Acidic Conditions increase the reduction potential of the
cathode half-reaction.
Contact with a more noble metal forms a voltaic cell
with iron as the anode.
Differential aeration creates a cell, with anode in the
region of lower oxygen pressure.
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Corrosion of Iron
Protection against Corrosion of Iron
Use of sacrificial anodes, which are preferentially
oxidized.
An applied electric potential can render the iron the
cathode.
Prevent contact with air through use of paint, sacrificial
metal coatings, or coatings of less-reactive metals.
Corrosion inhibitors form a protective film on the
surface of the iron.
Use of corrosion-resistant alloys such as stainless steel.
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