Chemistry, The Central Science6 10th edition

Theodore L. Brown; H. Eugene LeMay6 Jr.; and Bruce E. Bursten

Chapter 20
Electrochemistry

John D. Bookstaver
St. Charles Community College
St. Peters6 MO |

 

0 20066 Prentice Hall6 Inc.

Electrochemical Reactions

In electrochemical reactions6 electrons

are transferred from one species to
another.

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Oxidation Numbers

In order to keep
track of what loses
electrons and what
gains them6 we
assign oxidation
numbers.

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 Oxidation and Reduction

‡ A species is oxidized when it loses electrons.

6 Here6 zinc loses two electrons to go from neutral
zinc metal to the Zn2+ ion.

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 Oxidation and Reduction

‡ A species is reduced when it gains electrons.

6 Here6 each of the H+ gains an electron and they
combine to form H2.

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 Oxidation and Reduction

‡ What is reduced is the oxidizing agent.

6 H+ oxidizes Zn by taking electrons from it.
‡ What is oxidized is the reducing agent.
6 Zn reduces H+ by giving it electrons.
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Assigning Oxidation Numbers

1. Elements in their elemental form have

an oxidation number of 0.
2. The oxidation number of a monatomic
ion is the same as its charge.

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Assigning Oxidation Numbers

3. Nonmetals tend to have negative
oxidation numbers6 although some are
positive in certain compounds or ions.
6 Oxygen has an oxidation number of í26
except in the peroxide ion in which it has
an oxidation number of í1.
6 Hydrogen is í1 when bonded to a metal6
+1 when bonded to a nonmetal.

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Assigning Oxidation Numbers

3. Nonmetals tend to have negative
oxidation numbers6 although some are
positive in certain compounds or ions.
6 Úluorine always has an oxidation number
of í1.
6 The other halogens have an oxidation
number of í1 when they are negative;
they can have positive oxidation
numbers6 however6 most notably in
oxyanions.
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Assigning Oxidation Numbers

4. The sum of the oxidation numbers in a
neutral compound is 0.
5. The sum of the oxidation numbers in a
polyatomic ion is the charge on the
ion.

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Balancing Oxidation-Reduction
Equations
Perhaps the easiest way to balance the
equation of an oxidation-reduction
reaction is via the half-reaction method.

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Balancing Oxidation-Reduction
Equations
This involves treating (on paper only) the
oxidation and reduction as two separate
processes6 balancing these half reactions6
and then combining them to attain the
balanced equation for the overall reaction.

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 Half-Reaction Method

1. Assign oxidation numbers to

determine what is oxidized and what is
reduced.
2. Write the oxidation and reduction half-
reactions.

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 Half-Reaction Method

3. Balance each half-reaction.

a. Balance elements other than H and O.
b. Balance O by adding H2O.
c. Balance H by adding H+.
d. Balance charge by adding electrons.
4. Multiply the half-reactions by integers
so that the electrons gained and lost
are the same.
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 Half-Reaction Method

5. Add the half-reactions6 subtracting

things that appear on both sides.
6. Make sure the equation is balanced
according to mass.
7. Make sure the equation is balanced
according to charge.

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 Half-Reaction Method

Consider the reaction between MnO4í and C2O42í :

MnO4í(aq) + C2O42í(aq) ‰‰ Mn2+(aq) + CO2(aq)

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 Half-Reaction Method

Úirst6 we assign oxidation numbers.

+7 +3 +2 +4

MnO4í + C2O42- ‰‰ Mn2+ + CO2

Since the manganese goes from +7 to +26 it is reduced.
Since the carbon goes from +3 to +46 it is oxidized.
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 Oxidation Half-Reaction

C2O42í ‰‰ CO2

To balance the carbon6 we add a

coefficient of 2:

C2O42í ‰‰ 2 CO2

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 Oxidation Half-Reaction

C2O42í ‰‰ 2 CO2

The oxygen is now balanced as well.

To balance the charge6 we must add 2
electrons to the right side.

C2O42í ‰‰ 2 CO2 + 2 eí
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 Reduction Half-Reaction

MnO4í ‰‰ Mn2+

The manganese is balanced; to balance

the oxygen6 we must add 4 waters to
the right side.

MnO4í ‰‰ Mn2+ + 4 H2O

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 Reduction Half-Reaction

MnO4í ‰‰ Mn2+ + 4 H2O

To balance the hydrogen6 we add 8 H+

to the left side.

8 H+ + MnO4í ‰‰ Mn2+ + 4 H2O

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 Reduction Half-Reaction

8 H+ + MnO4í ‰‰ Mn2+ + 4 H2O

To balance the charge6 we add 5 eí to

the left side.

5 eí + 8 H+ + MnO4í ‰‰ Mn2+ + 4 H2O

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Combining the Half-Reactions

Now we evaluate the two half-reactions
together:

C2O42í ‰‰ 2 CO2 + 2 eí
5 eí + 8 H+ + MnO4í ‰‰ Mn2+ + 4 H2O

To attain the same number of electrons

on each side6 we will multiply the first
reaction by 5 and the second by 2. |

 

 Combining the Half-Reactions

5 C2O42í ‰‰ 10 CO2 + 10 eí
10 eí + 16 H+ + 2 MnO4í ‰‰ 2 Mn2+ + 8 H2O

When we add these together6 we get:

10 eí + 16 H+ + 2 MnO4í + 5 C2O42í ‰‰
2 Mn2+ + 8 H2O + 10 CO2 +10 eí
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 Combining the Half-Reactions

10 eí + 16 H+ + 2 MnO4í + 5 C2O42í ‰‰
2 Mn2+ + 8 H2O + 10 CO2 +10 eí

The only thing that appears on both sides are the

electrons. Subtracting them6 we are left with:

16 H+ + 2 MnO4í + 5 C2O42í ‰‰
2 Mn2+ + 8 H2O + 10 CO2
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 Balancing in Basic Solution

‡ If a reaction occurs in basic solution6 one

can balance it as if it occurred in acid.
‡ Once the equation is balanced6 add OHí
to each side to ³neutralize´ the H+ in the
equation and create water in its place.
‡ If this produces water on both sides6 you
might have to subtract water from each
side.
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åoltaic Cells

In spontaneous
oxidation-reduction
(redox) reactions6
electrons are
transferred and
energy is released.

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 åoltaic Cells

‡ We can use that

energy to do work if
we make the
electrons flow
through an external
device.
‡ We call such a
setup a voltaic cell.

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åoltaic Cells

‡ A typical cell looks

like this.
‡ The oxidation
occurs at the anode.
‡ The reduction
occurs at the
cathode.

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åoltaic Cells

Once even one

electron flows from
the anode to the
cathode6 the
charges in each
beaker would not be
balanced and the
flow of electrons
would stop.
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åoltaic Cells
‡ Therefore6 we use a
salt bridge6 usually a
U-shaped tube that
contains a salt
solution6 to keep the
charges balanced.
6 Cations move toward
the cathode.
6 Anions move toward
the anode.
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 åoltaic Cells
‡ In the cell6 then6
electrons leave the
anode and flow
through the wire to
the cathode.
‡ As the electrons
leave the anode6 the
cations formed
dissolve into the
solution in the
anode compartment.
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 åoltaic Cells
‡ As the electrons
reach the cathode6
cations in the
cathode are
attracted to the now
negative cathode.
‡ The electrons are
taken by the cation6
and the neutral
metal is deposited
on the cathode.
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Electromotive Úorce (emf)

‡ Water only
spontaneously flows
one way in a
waterfall.
‡ Likewise6 electrons
only spontaneously
flow one way in a
redox reaction²from
higher to lower
potential energy.
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 Electromotive Úorce (emf)

‡ The potential difference between the

anode and cathode in a cell is called the
electromotive force (emf).
‡ It is also called the cell potential6 and is
designated |cell

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 Cell Potential

Cell potential is measured in volts (å).

J
1å=1
C

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Standard Reduction Potentials

Reduction
potentials for
many
electrodes
have been
measured and
tabulated.

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Standard Hydrogen Electrode

‡ Their values are referenced to a standard
hydrogen electrode (SHE).
‡ By definition6 the reduction potential for
hydrogen is 0 å:
2 H+ (aq6 1M) + 2 eí ‰‰ H2 (a6 1 atm)

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 Standard Cell Potentials

The cell potential at standard conditions

can be found through this equation:

|cell
m = |red
m (cathode) í |red
m (anode)

Because cell potential is based on

the potential energy per unit of
charge6 it is an intensive property. |

 

Cell Potentials
‡ Úor the oxidation in this cell6
m = í0.76 å
|red

‡ Úor the reduction6

m = +0.34 å
|red

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 Cell Potentials

|cell
m = |red
m (cathode) í |red
m (anode)
= +0.34 å í (í0.76 å)
= +1.10 å

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Oxidizing and Reducing Agents

‡ The strongest
oxidizers have the
most positive
reduction potentials.
‡ The strongest
reducers have the
most negative
reduction potentials.

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Oxidizing and Reducing Agents

The greater the

difference between
the two6 the greater
the voltage of the
cell.

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 Úree Energy
ÿ* for a redox reaction can be found by
using the equation

ÿ* = ínF|

where n is the number of moles of

electrons transferred6 and F is a
constant6 the Úaraday.
1 F = 966485 C/mol = 966485 J/å-mol
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 Úree Energy
Under standard conditions6

ÿ*m = ínF|m

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 Nernst Equation

‡ Remember that
ÿ* = ÿ*m + uT ln Q

‡ This means
ínF| = ínF|m + uT ln Q

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 Nernst Equation

Dividing both sides by ínF6 we get the

Nernst equation:
uT
| = |m í ln Q
nF
or6 using base-10 logarithms6
2.303 uT
| = |m í ln Q
nF
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 Nernst Equation

At room temperature (298 K)6

2.303 uT
= 0.0592 å
F

Thus the equation becomes

0.0592
| = |m í ln Q
n
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 Concentration Cells

‡ Notice that the Nernst equation implies that a cell

could be created that has the same substance at
both electrodes.
‡ Úor such a cell6 |cell
m would be 06 but Q would not.

‡ Therefore6 as long as the concentrations

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are different6 | will not be 0.

 Applications of
Oxidation-Reduction
Reactions

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Batteries

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Alkaline Batteries

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Hydrogen Úuel Cells

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Corrosion and«

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«Corrosion Prevention

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