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Electrochemistry

A.

Introduction

1.

Electrochemistry is _______________________________________________________
________________________________________________________________________
________________________________________________________________________
Electrochemical reactions involve the _________________________________________
________________________________________________________________________
(analogous to proton transfer in acids and bases).

2.

Consider the reaction


2Al(s) + 3CuCl2(aq) AlCl3(aq) + 3Cu(s)
the net ionic equation is

This reaction only involves the ______________________________________________


We can re-write this equation as two separate _________________________

OXIDATION HALF-REACTION

REDUCTION HALF-REACTION

__________ of electrons is ____________________


__________ of electrons is ____________________

VERSION: April 20, 1999

Chemistry 12

When a substance becomes oxidized _________________________________________


________________________________________________________________________
________________________________________________________________________
Zn Zn2+ + 2eU3+ U4+ + e2Cl- Cl2 + 2eWhen a substance becomes reduced __________________________________________
________________________________________________________________________
________________________________________________________________________
Cu2+ + 2e- Cu
V3+ + e- V2+
F2 + 2e- 2F3.

For every reduction reaction there ____________________________________________


________________________________________________________________________
________________________________________________________________________
Reactions involving the loss and gain of electrons are called REDUCTIONOXIDATION reactions or _______________ reactions.
2+

In the reaction, 2Al + 3Cu

2Al

3+

+ 3Cu, Al is referred to as the _______________

________________________________________________________________________
________________________________________________________________________
while Cu

2+

is referred to as the ______________________________________________

________________________________________________________________________
________________________________________________________________________

Unit 5 Electrochemistry (S).doc

The ____________________ _______________ is _______________ during a reaction.


The ____________________ _______________ is _______________ during a reaction.

B.

Oxidation Numbers

1.

An oxidation number is ____________________________________________________


________________________________________________________________________
________________________________________________________________________

2.

Rules for determining oxidation number:


a)

__________________________________________________________________

b)

__________________________________________________________________
__________________________________________________________________
i)

Li , Na , K , and all other group 1 ions have _______________________


____________________________________________________________

ii)

2+

2+

2+

Ca , Ba , Mg , and all other group 2 ions have ___________________


____________________________________________________________

iii)

F-, Cl-, Br-, I- (halogens) are usually ______________________________


___________________________________________________________ .

c)

The oxidation number of _____________________________________________


In peroxides, H2O2, it is 1-.

d)

The oxidation number for ____________________________________________


except in metallic hydrides such as NaH or BaH2 where it is 1-.

e)

All other oxidation numbers are _______________________________________


__________________________________________________________________
__________________________________________________________________

Chemistry 12

EXAMPLE 5.1
Problem:

DETERMINING OXIDATION NUMBERS


Determine the oxidation numbers of each atom for the following:
Na, CCl4, N2O4, PO43-, PbSO4

Solution:

Na = _____
CCl4 = 0 = C + 4(_____)
Cl = _____, C = _____
N2O4 = 0 = 2N + 4(_____)
O = _____, N = _____
PO43- = 3- = P + 4(_____)
O = _____, P = _____
PbSO4 = 0 = Pb2+ + SO42 Pb = _____
SO42- = 2- = S + 4(_____)
O = _____, S = _____

3.

An atoms change in oxidation number indicates whether it is oxidized or reduced. When


________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
ClO3- ClO4- (_____ _____ ; _______________)
H2O2 H2O (_____ _____ ; _______________)
Cr3+ CrO42- (_____ _____ ; _______________)
NO2 N2O3 (_____ _____ ; _______________)

Unit 5 Electrochemistry (S).doc

OXIDATION = __________________________________________________________
REDUCTION = _________________________________________________________

C.

Predicting Spontaneous Reactions

1.

An excerpt from the Table of Reduction Potentials is shown below.

INCREASING
TENDENCY
TO REDUCE

F2 + 2e-
2F

Ag+ + e-
Ag

INCREASING
TENDENCY
TO OXIDIZE

Cu2+ +2e-
Cu
INCREASING
STRENGTH
AS AN
OXIDIZING AGENT

Zn2+ + 2e-
Zn
Li + + e-
Li

INCREASING
STRENGTH
AS A
REDUCING AGENT

The following observation can be made from the Table of Reduction Potentials:
i)

In general, __________________________________________________
____________________________________________________________
____________________________________________________________

ii)

In general, __________________________________________________
____________________________________________________________
____________________________________________________________

iii)

Some metals such as Fe, Sn, Cr, Hg, and Cu ________________________


____________________________________________________________
As a result, __________________________________________________
____________________________________________________________
____________________________________________________________
Remember this point because it means that _________________________

Chemistry 12

____________________________________________________________
e.g.
Cu+ + e-
Cu
(s)

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

The Cu+ ion is found on both left and right sides. Similarly, Sn2+ and
Fe2+ are also found on both sides of the table.
iv)

____________________________________________________________
____________________________________________________________
____________________________________________________________

OXIDIZING AGENTS ___________________________________________________


________________________________________________________________________
REDUCING AGENTS ___________________________________________________
________________________________________________________________________
2.

The table of Standard Reduction Potentials is used in a similar way to the table of
Relative Strengths of Acids. The species at the _______________ __________ have a
tendency to go _______________ while the species at the _______________
__________ have a tendency to go _______________. Each reaction in the table can go
________________________________________________________________________
The half-reaction for Zn and Zn2+ is

If there is a piece of Zn(s) in a solution of Zn2+, you can write either:


Zn2+ + 2e- Zn
or

Zn Zn2+ + 2e-

(written as a _______________)
(written as an _______________)

Unit 5 Electrochemistry (S).doc

Note: When referring to an isolated half-reaction, use equilibrium arrows to show that
the reaction can go forward or backward.
Ag+ + e-
Ag
If the half-reaction is made to undergo either reduction or oxidation as a result of
being part of a redox reaction, the use a one-way arrow.
Ag+ + e- Ag
3.

In a redox reaction, _______________________________________________________


________________________________________________________________________
________________________________________________________________________
Assume that you have Zn in a solution of Zn2+ and Cu in a solution of Cu2+, the two
possible half reactions are
Cu2+ + 2e-
Cu
and

Zn2+ + 2e-
Zn

Of the two oxidizing agents, _____ and _____, the _____ is _______________ on the
left side of the table and has a greater tendency to become _______________. The
reduction reaction will be
Cu2+ + 2e- Cu

Chemistry 12

Of the two reducing agents, _____ and _____, the _____ is _______________ on the
right side of the table and has a greater tendency to become _______________. The
oxidation reaction will be
Zn2+ + 2e- Zn
or re-written as
Zn Zn2+ + 2eThe overall redox reaction which will spontaneously occur is found by adding the two
half-reactions.
Cu2+ + 2eZn

Cu
Zn 2+ + 2e-

When two half-reactions are joined, ________________________________________


________________________________________________________________________
________________________________________________________________________
4.

If you are _____________________________________________, rather than the four


necessary for two complete half-reactions as above, you __________________________
________________________________________________________________________
a)

If ________________________________________________________________
__________________________________________________________________
(i.e., both are oxidizing agents (left) or both reducing agents (right)) then
__________________________________________________________________

Unit 5 Electrochemistry (S).doc

Assume the only reactants are Zn and Cu

Both Cu and Zn can only undergo


2+

Cu

+ 2e Cu
-

Zn 2+ + 2e- Zn

_______________, there is nothing present to


undergo _______________. A complete redox
reaction is not possible. ___________________

Assume the only reactants are Zn2+ and Cu2+


Both Cu2+ and Zn2+ can only undergo
Cu2+ + 2e- Cu
Zn 2+ + 2e- Zn

_______________, there is nothing present to


undergo _______________. A complete redox
reaction is not possible. ___________________

b)

If __________________________________________________ (oxidizing
agent) and __________________________________________________
(reducing agent) there are two possible cases.
i)

The ____________________ _______________ is _______________ on


the table than the reducing agent.
Assume the reactants are Cu2+ and Zn.
Cu2+ + 2e- Cu
Zn 2+ + 2e- Zn

The overall redox reaction is obtained by reversing the oxidation reaction


and adding the two half-reactions.
Cu2+ + 2e Cu
Zn

Zn 2+ + 2e-

This is a ____________________ _______________

10

Chemistry 12

ii)

The ____________________ _______________ is _______________ on


the table than the reducing agent.
Assume the reactants are Zn2+ and Cu.
Cu2+ + 2e- Cu
Zn 2+ + 2e- Zn

In this case, _____ ____________________ occurs.


Notice that this is the reverse reaction to (i). Since the reaction
Cu2+ + Zn Cu + Zn2+
is ____________________ , the reverse reaction is
_________________________

A reaction will be _________________________________________________________


________________________________________________________________________
(reactant to be reduced left) which is _________________________________________
______________________________________________ (reactant to be oxidized right).

Unit 5 Electrochemistry (S).doc

EXAMPLE 5.2
Problem:

11

PREDICTING SPONTANEOUS REACTIONS


Predict whether or not a reaction will occur when the following are mixed.
a) Cl2 and Brb) Sn and Mn
c) Ni2+ and Pb

Solution:

a) Cl2 and Br-

Reaction is _________________________and the overall reaction is

b) Sn and Mn

Both reactants are ____________________________________________


___________________________________________________________
c) Ni2+ and Pb

___________________________________________________________
___________________________________________________________

12

Chemistry 12

5.

In _____________________________________________________________________
________________________________________________________________________
When H+ is present, _______________________________________________________
For example, if you asked whether the reaction of SO42- in a solution of Na2SO4 will
reduce:
SO42- + 4H+ + 2e- H2SO3 + 2H2O

+0.17

your answer should be _____________________________________________________


________________________________________________________________________
________________________________________________________________________

Note: H+ is necessary in many reduction half-reactions; however, there is only ONE

reaction is which H+ is the only substance involved in the reduction half-reaction:


2H+ + 2e- H2(g)

0.00

Unit 5 Electrochemistry (S).doc

13

D.

Balancing Half Reactions

1.

A half-reaction ___________________________________________________________
When balancing half-reactions ______________________________________________
________________________________________________________________________
The steps to balancing a half-reaction are as follows:
Typically you will be starting with a skeleton equation containing the major atoms
involved.
a)

Balance ___________________________________________________________
__________________________________________________________________

b)

Balance ___________________________________________________________
__________________________________________________________________

c)

Assume that solutions are acidic and ____________________________________


__________________________________________________________________

d)

Balance ___________________________________________________________
__________________________________________________________________

14

Chemistry 12

EXAMPLE 5.3
Problem:

BALANCING HALF-REACTIONS IN ACIDIC SOLUTION


Balance the following half-reaction:
Cr2O72- Cr3+

Solution:

Step 1:

Balance ATOMS.
Cr2O72- ____Cr3+

Step 2:

Balance OXYGEN.
Cr2O72- 2Cr3+ + ________

Step 3:

Balance HYDROGEN.
________ + Cr2O72- 2Cr3+ + 7H2O

Step 4:

Balance CHARGE.
________ + 14H+ + Cr2O72- 2Cr3+ + 7H2O

Note:

Electrons are negatively charged, ___________________________


______________________________________________________

2.

Sometimes it will be necessary to balance half-reactions in BASIC solutions. For these


problems, _______________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

Unit 5 Electrochemistry (S).doc

EXAMPLE 5.3
Problem:

15

BALANCING HALF-REACTIONS IN BASIC SOLUTION


Balance the following half-reaction:
MnO4- MnO2

Solution:

Step 1:

Balance ATOMS.
MnO4- MnO2
Atoms already balanced.

Step 2:

Balance OXYGEN.
MnO4- MnO2 + ________

Step 3:

Balance HYDROGEN.
________ + MnO4- MnO2 + 2H2O

Step 4:

Balance CHARGE.
________+ 4H+ + MnO4- MnO2 + 2H2O

Step 5:

Add OH- and cancel out H2O.


________+ 3e- + 4H+ + MnO4- MnO2 + 2H2O + ________
3e- + ________ + MnO4- MnO2 + 2H2O + ________
3e- + ________ + MnO4- MnO2 + ________

16

Chemistry 12

E.

Balancing Redox Equations Using Half-Reactions

1.

An overall redox equation can be obtained by __________________________________


________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

EXAMPLE 5.4
Problem:

BALANCING A REDOX REACTION BY THE HALF-REACTION METHOD


Balance the following half-reaction:
ClO4 + I2 Cl + IO3

Solution:

Step 1:

Break equation into two half-reactions.


________________________
________________________

Step 2:

Balance each half-reaction.


________________________________________
________________________________________

Step 3:

Lowest common multiple between electrons.


In this case LCM is ________, multiply reduction by ____ and
oxidation by ____.
5 x (8e- + 8H+ + ClO4 Cl + 4H2O)
-

4 x (6H2O + I2 2IO3 + 12H+ + 10e-)


____e- + ____H+ + ____ClO4 ____Cl + ____H2O
-

____H2O + ____I2 ____IO3 + ____H+ + ____e-

Unit 5 Electrochemistry (S).doc

17

Step 4:

Add two half-reactions, cancelling out electrons and common


particles.
40e- + 40H+ + 5ClO4 5Cl + 20H2O
-

24H2O + 4I2 8IO3 + 48H+ + 40e______________________________________

Balanced redox equations ___________________________________________________


________________________________________________________________________
________________________________________________________________________
2.

Once again, in basic solutions the final equation can be converted by ________________
________________________________________________________________________
________________________________________________________________________
-

5ClO4 + 4I2 + 4H2O 5Cl + 8IO3 + 8H

For basic solution, add 8OH- to both sides of equation


-

____ + 5ClO4 + 4I2 + 4H2O 5Cl + 8IO3 + 8H + ____


-

____ + 5ClO4 + 4I2 + 4H2O 5Cl + 8IO3 + ____

Cancel out water


8OH- + 5ClO4 + 4I2 + 4H2O 5Cl + 8IO3 + 8H2O
-

8OH- + 5ClO4 + 4I2 5Cl + 8IO3 + ________

18

Chemistry 12

3.

In some redox reactions, ___________________________________________________


________________________________________________________________________
________________________________________________________________________
Such a reaction is called a ________________________
ClO2- ClO3- + ClThe two half-reactions are
ClO2- ClO3ClO2- ClBalanced redox equation is
3ClO2- 2ClO3- + Cl-

F.

Balancing Redox Equations Using Oxidation Numbers

1.

This method involves ______________________________________________________


________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
Remember that an increase in oxidation number is oxidation and a decrease in oxidation
number is reduction. In this method __________________________________________
________________________________________________________________________
________________________________________________________________________

Unit 5 Electrochemistry (S).doc

EXAMPLE 5.5
Problem:

19

BALANCING A REDOX REACTION BY OXIDATION NUMBERS


Balance the following half-reaction:
ClO4 + I2 Cl + IO3

Solution:

Step 1:

Balance atoms.
ClO4 + I2 Cl + 2IO3

Step 2:

Assign oxidation numbers to all atoms involved in a change in


oxidation number (ON = change in oxidation number).

ClO4

Step 3:

I2

Cl

2IO 3

Balance change in oxidation number


In this case LCM is ____, multiply decrease by ____ and increase by
____.
-

____ClO4
Step 4:

____I2

____Cl

____IO3

Balance OXYGENS by adding H2O and HYDROGENS by adding H+.


DO NOT ADD ELECTRONS.

________ + 5ClO4 + 4I2 5Cl + 8IO3 + ________

Remember, ______________________________________________________________
________________________________________________________________________
________________________________________________________________________

20

Chemistry 12

SAMPLE
PROBLEM 5.1
Problem:

BALANCING A REDOX REACTION BY OXIDATION NUMBERS


Balance the following redox reactions by the oxidation number method:
a) MnO4- + Fe2+ Mn2+ + Fe3+ (acidic)
b) S2- + ClO3- Cl- + S (basic)
c) CN- + IO3- I- + CNO- (basic)
d) H2O2 + Cr3+ CrO42- + H2O (acidic)

Solution:
MnO4- + Fe2+ Mn2+ + Fe3+

S2- + ClO3- Cl - + S

CN - + IO3- I - + CNO -

H2O2 + Cr3+ CrO42- + H2O

Unit 5 Electrochemistry (S).doc

21

G.

Redox Titrations

1.

Acid-base titrations are useful for determining the concentration of an unknown sample
of acid or base. In a similar manner, __________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

2.

OXIDIZING AGENTS

One of the most common oxidizing agents used in redox titrations is ________________
The half-reaction:
MnO4- + 8H+ + 5e- Mn2+ + 4H2O

E = 1.49 V

has such a strong tendency to reduce that it will be able to oxidize a large number of
other substances. (The K+ in KMnO4 is left out because it is a spectator ion.)
In acid-base titrations, an ____________________ which changes colour is added to help
identify the ____________________ _______________ of the titration. An indicator is
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
If MnO4- (oxidizing agent) in a burette is added to a solution containing Fe2+ (reducing
agent), the MnO4- is converted to Mn2+ (colourless). ____________________________
________________________________________________________________________
________________________________________________________________________

________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

22

Chemistry 12

EXAMPLE 5.6
Problem:

REDOX TITRATION INVOLVING THE PERMANGANATE ION


A 100.0 mL sample containing FeCl2 is titrated with 0.100 M KMnO4 solution. If
27.45 mL of KMnO4 solution were required to reach the end-point, what was
the [FeCl2]?

Solution:

First we need the balanced redox equation.


Fe
___ Fe

2+

2+

+ MnO4 Fe

3+

+ Mn

+ MnO4 + _______ ___Fe

3+

2+

+ Mn

2+

+ _______

The remainder of the calculation is similar to acid-base titration calculations.


-

Calculate MOLES of MnO4

- 27.45 mL
0.100 M MnO4 x 1000 mL = _______________ mol MnO4

Use MOLE RATIO from balance equation.


0.002745 mol MnO4- x

5 mol Fe

2+

1 mol MnO4

= _______________ mol Fe

Determine CONCENTRATION.
0.0137 mol Fe2+
= _______________M Fe2+
0.100 L
and since Fe2+ and FeCl2 are in a 1:1 ratio, [FeCl2] = _______________.

2+

Unit 5 Electrochemistry (S).doc

3.

23

REDUCING AGENTS

A commonly used reducing agent is __________ or __________. A large number of


substances can oxidize I- to I2 according to the half-reaction
2I- I2 + 2eTitrations involving I- generally involve two consecutive steps:
a)

first, _____________________________________________________________
__________________________________________________________________

b)

second, ___________________________________________________________
__________________________________________________________________
__________________________________________________________________

An example of a reaction involving I- is the reduction of laundry bleach, NaOCl. The


reaction between I- and OCl- proceeds according to:
2I- I2 + 2e2e- + 2H+ + OCl- Cl- + H2O
___________________________________

No attempt is made to add exactly enough I- to react with the OCl-. Rather, __________
________________________________________________________________________
The excess I- does not affect the results; however, _______________________________
________________________________________________________________________
The above reaction between OCl- and I- is the initial reaction because the actual redox
titration involves a second reaction between the I2 produced and the reducing agent
sodium thiosulphate, Na2S2O3.
I2 + 2e- 2I2S2O32- S4O62- + 2e___________________________

24

Chemistry 12

When the addition of S2O32- has reacted most of the I2 present, the brown colour of I2
almost disappears (pale yellow). Some starch solution is then added to the titration,
producing a dark blue colour (from the reaction of starch with the remaining I2 in
solution). After adding the starch, ___________________________________________
________________________________________________________________________
________________________________________________________________________

Unit 5 Electrochemistry (S).doc

EXAMPLE 5.7
Problem:

25

REDOX TITRATION INVOLVING THE IODIDE ION


A 25.00 mL sample of bleach is reacted with excess KI according to the
equation:
2H+ + OCl- + 2I- Cl- + H2O + I2
The I2 produced requires exactly 46.84 mL of 0.7500 M Na2S2O3 to bring the
titration to the endpoint according to the equation:
2S2O32- + I2 S4O62- + 2Iusing starch solution as an indicator. What is the [OCl-] in the bleach?
Note:

The TWO reactions are linked together. The I2 produced in the first
reaction is used up in the second
2H+ + OCl- + 2I- Cl- + H2O + I2
2S2O32- + I2 S4O62- + 2I-

Solution:

First, calculate the moles of S2O3246.84 mL


moles S2O32- = __________ M x 1000 mL/L = _______________ mol S2O32Next, calculate the moles of I2
moles I2 = __________ mol S2O32- x

I2
2S2O32-

= _______________ mol I2

Now moles of OCl - can be calculated


moles OCl - = __________ mol I2 x

OCl I2 = __________ mol OCl

Finally, the [OCl -] can be calculated


0.01757 mol
[OCl -] = 0.02500 L = _______________

26

Chemistry 12

H.

Electrochemical Cells

1.

An _________________________ __________ (galvanic or voltaic cell) is a chemical


system in which __________________________________________________________
________________________________________________________________________
Consider the reaction
2+

Cu

2+

+ Zn Cu + Zn

A spontaneous reaction will occur when zinc metal is placed into a solution of CuSO4;
however, ________________________________________________________________
________________________________________________________________________
This same reaction can used to produce electricity if _____________________________
________________________________________________________________________
2.

An electrochemical cell:

a)

In the electrochemical cell above, we have Zn(s), Zn(NO3)2(aq), Cu(s), and


CuSO4(aq). The half-reactions are:
Cu2+ + 2e-
Cu
Zn2+ + 2e-
Zn

+ 0.34
- 0.76

Unit 5 Electrochemistry (S).doc

27

Since Cu2+ is a ______________________________________ than Zn2+, Cu2+


will become ____________________ and since Zn is a _____________________
than Cu, Zn will become ____________________. The reduction and oxidation
half-reactions that occur will be

__________________________
2+

Cu

2+

+ Zn Cu + Zn

28

Chemistry 12

b)

In the copper cell, ___________________________________________________


__________________________________________________________________
__________________________________________________________________

__________________________________________________________________
__________________________________________________________________

At the copper electrode, copper ions, Cu2+, ______________________________


__________________________________________________________________
The copper electrode is ______________________________________________
__________________________________________________________________
__________________________________________________________________
2+

Cu

+ 2e Cu

In the zinc cell, _____________________________________________________


___________________________________. At the zinc electrode, zinc metal ___
The zinc electrode is ________________________________________________
__________________________________________________________________
2+

Zn Zn

+ 2e

Unit 5 Electrochemistry (S).doc

29

_______________ is the electrode where ____________________ occurs.


_______________ is the electrode where ____________________ occurs.
c)

The two electrodes are connected by a __________________________________


_________________________. Electrons produced at the zinc electrode flow
through the wire to the copper electrode where they reduce copper ions. The
electrons will ______________________________________________________
__________________________________________________________________

__________________________________________________________________
__________________________________________________________________
A __________ _______________ composed of a concentrated solution of a
strong electrolyte, usually KNO3 or KCl, connects the two cells to complete the
circuit. As the two half-reactions occur, _________________________________
__________________________________________________________________
__________________________________________________________________
Water and certain ions, Zn2+ and SO42-, will pass through the salt bridge from
one cell to the other. The positive Zn2+ ions are attracted to the CATHODE so
they are called _______________ while the negative SO42- ions are attracted to
the ANODE so they are called _______________.

__________________________________________________________________
__________________________________________________________________

30

Chemistry 12

Note: There are NO electrons flowing in the solution, only ions. ____________

____________________________________________________________
The salt bridge allow __________________________________________
____________________________________________________________
Since oxidation occurs at the anode, ______________________________
and since reduction occurs at the cathode, the _______________________
__________ as the electrochemical cell operates.

Unit 5 Electrochemistry (S).doc

EXAMPLE 5.8

31

DRAWING AN ELECTROCHEMICAL CELL

Problem:

Assume two half-cells consisting of Pb(s) in a Pb(NO3)2 solution and Zn(s) in a


ZnCl2 solution are connected to make an electrochemical cell. Draw and label
the parts of the cell, write the equations for the individual half-reactions and
overall reaction, and indicate the directions in which the ions and electrons
move.

Solution:

The two half-reactions are:


Pb2+ + 2e-
Pb

- 0.13

Zn2+ + 2e-
Zn

- 0.76

Since Pb2+ is the stronger oxidizing reagent, it will become reduced and Zn(s)
will become oxidized.
The two half-reactions are
Pb2+ + 2e-

Pb

Zn2+ + 2e__________________________
Zn

Pb

2+

+ Zn

Pb + Zn

2+

32

Chemistry 12

I.

Standard Reduction Potentials

1.

The tendency of electrons to flow in an electrochemical cell is called the


____________________, or ____________________ ____________________to do
work.

________________________________________________________________________
________________________________________________________________________
Since electrons cannot flow in an isolated half-cell, ______________________________
________________________________________________________________________
However, the ____________________________________________________________
________________________________________________________________________
A ______________________________________________________________________
________________________________________________________________________
The voltage for the HYDROGEN HALF-CELL is defined to be
2H+ + 2e- H2

E = __________

Where E is the _____________________________________________, in volts and the


in E means _________________________ ____________________
An electrochemical cell is said to be at STANDARD STATE if

it is at __________, and

all gases are at _________________________, and

all elements are in their standard states (normal phases at 25 C), and

all solutions involved in the cell have a ______________________________

Unit 5 Electrochemistry (S).doc

2.

33

All voltages listed in the table of STANDARD REDUCTION POTENTIALS are


determined at standard state and are _________________________________________
________________________________________________________________________
Cu2+ + 2e-
Cu

E = + 0.34

This half-cell has a voltage which is 0.34 V ____________________ than that of the
hydrogen half-cell.
Zn2+ + 2e-
Zn

E = - 0.76

This half-cell has a voltage which is 0.76 V __________ than that of the hydrogen halfcell.
Since the voltage is a measure of the work done, reversing a reduction reaction such as
Zn2+ + 2e- Zn

E = - 0.76

produces ________________________________________________________________
Zn Zn2+ + 2e-

E = + 0.76

________________________________________________________________________
________________________________________________________________________
3.

When two half-reactions are combined, _______________________________________


________________________________________________________________________
________________________________________________________________________

Hg2+ + 2e-
Hg

E = + 0.85 V

Cu2+ + 2e-
Cu

E = + 0.34 V

34

Chemistry 12

The voltage for the overall reaction is

E = __________ V

E = __________ V
_______________________________________________

ECELL = __________ V

The potential of an electrochemical cell is ____________________________________

________________________________________________________________________
________________________________________________________________________

EXAMPLE 5.9

CALCULATING CELL POTENTIALS

Problem:

Calculate the potential of the cell: Ni2+ + Fe Ni + Fe2+.

Solution:

The half-reactions involved are:

Ni 2+ + 2e-
Ni
Fe2+ + 2e-
Fe

E = - 0.26 V
E = - 0.45 V

The voltage for the overall reaction is

E = __________V

E = __________ V

_________________________________________

Note:

ECELL = __________

This reaction is SPONTANEOUS since Ni2+ is higher than Fe and the


reaction has a POSITIVE VOLTAGE.

Unit 5 Electrochemistry (S).doc

EXAMPLE 5.10

35

CALCULATING CELL POTENTIALS

Problem:

Calculate the potential of the cell: Ni + Fe2+ Ni 2++ Fe.

Solution:

The half-reactions involved are:

Ni 2+ + 2e-
Ni
Fe2+ + 2e-
Fe

E = - 0.26 V
E = - 0.45 V

The voltage for the overall reaction is

E = __________ V

Fe2+ + 2e- Fe
E = __________ V
_______________________________________________

Note:

EXAMPLE 5.11

ECELL = __________

This reaction is NOT SPONTANEOUS since Fe2+ is lower than Ni


and the reaction has a NEGATIVE VOLTAGE.

CALCULATING CELL POTENTIALS

Problem:

Calculate the potential of the cell: 3Ag+ + Al 3Ag + Al3+.

Solution:

The half-reactions involved are:

Ag+ + e-
Ag

E = + 0.80 V

Al 3+ + 3e-
Al

E = - 1.66 V

The voltage for the overall reaction is

E = __________ V

E = __________ V
_______________________________________________

Note:

ECELL = __________

Although the Ag+/Ag half-reaction is multiplied by 3 to balance the


electrons, the voltage is NOT multiplied by 3.

36

Chemistry 12

If E is _______________ for a redox reaction, the reaction is expected to be

____________________
If E is ____________________ for a redox reaction, the reaction is

_________________________

Note: Although E can be used to predict if a reaction is spontaneous, it ___________

__________________________________________________________________
__________________________________________________________________
Remember the ____________________ _______________ of a reaction
determines the rate.
In some texts, the reduction of neutral water is given as
2H+ (10-7 M) + 2e-
E = - 0.41 V
H
2(g)

Other texts show this same reaction as


2H O + 2e-
+ 2OH- (10-7 M)
H
2

2(g)

E = - 0.41 V

If a redox reaction occurs in acidic water, the reduction of H+ (at 0.00 V) may
occur and if a redox reaction occurs in a neutral solution, the reduction of neutral
water (at - 0.41 V) may be possible.
4.

The SURFACE AREA of an electrode _______________________________________


________________________________________________________________________
This is because ___________________________________________________________
________________________________________________________________________
Therefore, increasing the surface area of a solid electrode has no effect on the
concentration of the solid. As a result there is no equilibrium shift and no change in halfcell potential.

Unit 5 Electrochemistry (S).doc

37

Increasing the surface are of an electrode does however, __________________________


____________________. The number of electrons transferred per second increases.
This increases the ____________________ of the cell but not the voltage. Increasing the
surface area of the electrode, also _____________________________________________
________________________________________________________________________
5.

When a half-reaction is NOT at standard state, it is ______________________________


________________________________________________________________________
Consider the following half-reaction
Cu2+ + 2e-
Cu

E = + 0.34 V

If the [Cu2+] is _______________ than 1.0 M the equilibrium shifts __________ and the
reduction potential ____________________.
Cu2+ + 2e-
Cu

E > + 0.34 V

If the [Cu2+] is __________ than 1.0 M the equilibrium shifts __________ and the
reduction potential ____________________.
Cu2+ + 2e-
Cu

E < + 0.34 V

Notice that the is omitted from the E symbol since it is not at standard state.
6.

Operating electrochemical cells ______________________________________________


Consider the cell
2Ag+ + Cu 2Ag+ Cu2+
THE REDUCTION REACTION:

2Ag+ + 2e- 2Ag

As the [Ag+] decreases, ____________________________________________________


________________________________________________________________________
As a result, the ___________________________________________________________
________________________________________________________________________

38

Chemistry 12

THE OXIDATION REACTION:

Cu2+ + 2e- Cu

As the [Cu2+] increases, ____________________________________________________


________________________________________________________________________
(the reduction potential of Cu2+ + 2e- Cu increases) Therefore, the ______________
________________________________________________________________________
________________________________________________________________________
Overall, the following occurs as the cell goes to equilibrium.

INITIALLY

AS TIME
PASSES

FINALLY

2Ag+ + 2e- 2Ag

Voltage

ECELL = + 0.46
V

Cu2+ + 2e- Cu

2Ag+ + 2e- 2Ag


Cu2+ + 2e- Cu
ECELL = 0.00 V

________________________________________________________________________
________________________________________________________________________

Unit 5 Electrochemistry (S).doc

39

J.

Selecting Preferred Reactions

1.

When a cell contains a mixture of substances, __________________________________


________________________________________________________________________
Consider the following cell:

Ag

Zn

Zn 2+
-

NO 3

Cu

Ag +
Cu 2+
NO 3

The possible half-reactions are:


_____________________________________________
_____________________________________________
_____________________________________________

When several different reduction half-reactions can occur, _____________________

________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
Therefore, the __________ will reduce and form __________

40

Chemistry 12

When several different oxidation half-reactions can occur, _____________________

________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
Therefore, the __________ will oxidize to form __________
2.

Determining the preferred half-reactions:

First, _____________________________________________________________
__________________________________________________________________

Next, starting at the _________________________________________________


__________________________________________________________________
__________________________________________________________________

Then, starting at the _________________________________________________


__________________________________________________________________
__________________________________________________________________

Unit 5 Electrochemistry (S).doc

EXAMPLE 5.12

41

SELECTING PREFERRED REACTIONS

Problem:

An iron strip is placed in a mixture of Br2(aq) and I2(aq). What is the preferred
reaction which occurs?

Solution:

The species present and the possible reactions are


Br2 + 2e-
2Br

E = + 1.09 V

I 2 + 2e-
2I

E = + 0.54 V

Fe2+ + 2e-
Fe

E = - 0.45 V

The preferred reduction involves __________ and the only oxidation possible
involves __________. The overall reaction is

___________________________

Note: Any ion capable of being reduced ______________________________________

__________________________________________________________________
__________________________________________________________________
__________________________________________________________________
Similarily, any ion capable of being ____________________________________
__________________________________________________________________
__________________________________________________________________
__________________________________________________________________
The following ions are generally considered to be spectator ions:
Na+, K+, Ca2+, Mg2+, SO42- (in neutral solution), and Cl-

42

Chemistry 12

K.

Corrosion of Metals

1.

The term CORROSION simply _____________________________________________


The most common form of corrosion _________________________________________
When a drop of water rests on an iron surface, a spontaneous reaction occurs.
cathode region
(oxygen-rich)
H 2O

Precipitate of
Fe(OH) 2

Fe

anode region
(oxygen-poor)

At the __________________________________________________________________
________________________________________________________________________
Fe(s) Fe2+ + 2eAfter being formed, the Fe2+ ions ____________________________________________
________________________________________________________________________
________________________________________________________________________
As the Fe2+ ions move away, they expose fresh Fe(s) for further oxidation. In the
meantime, the reaction
1
2

O2 + H2O + 2e- 2OH-

is proceeding at the oxygen-rich outer surface of the drop. When the Fe2+ meets the OH, it _____________________________________________________________________
The Fe(OH)2 is eventually __________________________________________________
________________________________________________________________________

Unit 5 Electrochemistry (S).doc

43

Rust is just Fe2O3XH2O, where X is variable. The variability of X explains the


different colours rust can have (red, brown, yellow, black) since differing numbers of
water molecules attached to the Fe2O3 will change the colour of the component.
A metal _________________________________________________________________
________________________________________________________________________
________________________________________________________________________
For example, if iron touches some copper wire and the place where they touch gets wet,
then:
Fe(s) Fe2+ + 2e- (Fe has a greater tendency to oxidize than Cu)
The copper ______________________________________________________________
________________________________________________________________________
________________________________________________________________________
1
2

2.

O2 + H2O + 2e- 2OH-

PREVENTING CORROSION
A.

Isolating The Metal From The Environment

i)

Apply ______________________________________________________
____________________________________________________________
If oxygen and water cannot reach the metal, it will not corrode.

ii)

Apply ______________________________________________________
____________________________________________________________
Tin can be applied to the surface of steel cans. The tin is quickly oxidized
to produce a thin layer of tin oxide which protects the underlying metal
from further corrosion.

44

Chemistry 12

B.

Electrochemical Methods

i)

Cathodic Protection

Recall that __________________________________________________


____________________________________________________________
____________________________________________________________
____________________________________________________________
This implies that we can prevent the corrosion of iron ________________
____________________________________________________________
____________________________________________________________

The term CATHODIC PROTECTION is applied to the process of ____


____________________________________________________________
____________________________________________________________
____________________________________________________________
For example, both ____________________ and __________ are stronger
reducing agents than iron, if pieces of magnesium or zinc are attached to
the surface of iron, the magnesium and zinc will ____________________
____________________________________________________________
Since the substance with the greater tendency to oxidize, Mg, acts as the
_______________, the Fe acts as a _______________ and remains in its
reduced form.
e.g.

Zinc blocks are bolted to iron-hulled ships to prevent them from rusting.
Some modern ships pass a low voltage electric current into the hull from
an electrical generator. This forces electrons into the metal and prevents it
from becoming oxidized.
Galvanized iron involves coating zinc onto the surface of iron sheets.

Unit 5 Electrochemistry (S).doc

45

Some buried gas and oil tanks made from steel have thick braided wire
connected to them. The wire is attached to posts made of magnesium or
zinc.
ii)

Change the Condition of the Surroundings

When iron is placed in contact with water containing oxygen, the halfreaction
1
2

O2 + H2O + 2e- 2OH-

oxidizes the iron. If _______________ is removed from the solution, the


reduction tendency drops drastically.
In addition to removing the oxygen, ______________________________
____________________________________________________________
____________________________________________________________

L.

Electrolysis

1.

ELECTROLYSIS is ______________________________________________________

________________________________________________________________________
________________________________________________________________________
An ____________________ __________ or ELECTROLYSIS CELL is an apparatus
in which electrolysis can occur.

____________________ __________ involve ____________________ redox reactions


that require energy to occur ____________________
____________________ __________ involve ____________________ redox reactions
that release energy ____________________

46

2.

Chemistry 12

ELECTROLYSIS OF A MOLTEN BINARY SALT

A _______________ __________ is made up of only two different elements, e.g. NaCl,


KBr, MgI2, AlF3, etc. When a salt such as NaCl is melted, the ions are free to move
(Note: molten NaCl is NaCl(l), there are only Na+ and Cl- ions present. Do not confuse
with NaCl(aq) which is a solution and contains Na+, Cl-, and H2O).

direct current (DC) power supply


or battery.
(the symbol

+
Na

is sometimes used)

Cl

There is ________________________________________________________________
________________________________________________________________________
The only reactants present are Na+ and ClCl2 + 2e- 2ClNa+ + e- Na

The _______________ reaction is

2Cl- Cl2 + 2e-

E = - 1.36 V

The _______________ reaction is

Na+ + e- Na

E = - 2.71 V

The overall reaction is 2Na+ + 2Cl- 2Na + Cl2

Ecell = - 4.07 V

Note: This is a _________________________ reaction since the oxidizing agent is

below the reducing agent and since the voltage is negative.


To make this cell operate, ___________________________________________________

Unit 5 Electrochemistry (S).doc

47

Since the half-cells are not at standard state, the reduction potentials will be different
from those listed on the table.
3.

ELECTROLYSIS OF AN AQUEOUS SOLUTION

Consider the electrolysis of aqueous sodium iodide, NaI(aq). This __________________


________________________________________________________________________
Once again, _______________ electrodes are used and the cell is set up as follows,

D.C.

Note: During the electrolysis of aqueous solutions, _____________________________

__________________________________________________________________
There are two possible oxidations:
1
2

O2(g) + 2H+ (10-7 M) + 2e-

= + 0.82 V

I2 + 2e-

= + 0.54 V

The oxidation of __________________________________________________________


________________________________________________________________________

48

Chemistry 12

There are two possible reductions:


+ 2e- H2(g) + 2OH- (10-7 M)
+ e- Na

= - 0.41 V

= - 2.71 V

The reduction of __________________________________________________________


________________________________________________________________________

________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
The half-reactions and the overall reaction involving the electrolysis of NaI(aq) are
2H2O + 2e- H2(g) + 2OH- (10-7 M)
2I- I2 + 2e-

so at least + 0.95 V must be applied to the cell.

= - 0.41 V

= - 0.54 V

= - 0.95 V

Unit 5 Electrochemistry (S).doc

49

Note: The concentrations of the materials in cells will not be of concern; as long as

there is sufficient material in the cell you can assume the reactions proceed as
predicted.
In NEUTRAL aqueous solutions, there are two water equations which must be
considered.
OXIDATION:

1
2

O2(g) + 2H + (10-7 M) + 2e - H2O

= + 0.82 V

REDUCTION:

2H2O + 2e- H2(g) + 2OH - (10-7 M)

= - 0.41 V

In ACIDIC solutions there are also two water equations which must be
considered.

4.

O2(g) + 2H + + 2e- H2O

OXIDATION:

1
2

REDUCTION:

2H+ + 2e- H2(g)

= + 1.23 V

= 0.00 V

In practice, it is found that a higher potential than calculated must be applied to cause
electrolysis. The causes are _________________________________________________
________________________________________________________________________
The difference between actual potentials required for electrolysis and the calculated
potential is termed ___________________________________. Overpotentials vary for
each half-cell but the difference in potentials is _________________________________
________________________________________________________________________
As a result of the overpotential effect, when dilute neutral solutions (< 1.0 M) containing
_____ or _____ are electrolyzed

50

Chemistry 12

OXIDATION:

1
2

Cl 2 + 2e- 2Cl -

Br2 + 2e- 2Br -

= + 1.09 V

O2(g) + 2H + (10-7 M) + 2e - H2O

= + 0.82 V

= + 1.36 V
Strength of
Reducing
Agent

we would expect that _____ will be produced. In practice however, we find that _____
or _____ are actually produced.
In addition when dilute solutions of ____________________ are electrolyzed
REDUCTION:
2H2O + 2e- H2(g) + 2OH - (10-7 M)
Strongest
Oxidizing
Agent

= - 0.41 V

Fe2+ + 2e- Fe

= - 0.45 V

Cr3+ + 3e- Cr

= - 0.74 V

Zn 2+ + 2e- Zn

= - 0.76 V

we would expect that _____ is produced but in practice, ____________________ will be


produced.

Electrolysis of aqueous solutions containing Cl- or Br- will produce Cl2 or Br2 at the
anode.
Electrolysis of aqueous solutions containing Fe2+, Cr3+, or Zn2+ will produce Fe, Cr,
or Zn at the cathode.

Unit 5 Electrochemistry (S).doc

EXAMPLE 5.13

51

ELECTROLYSIS REACTIONS

Problem:

What products are formed at the anode and cathode wand what is the overall
reaction when a solution containing NiSO4(aq) is electrolyzed using inert
electrodes? Determine the minimum voltage required.

Solution:

First, the species present ______________________________ and the possible


reactions are
REDUCTION

+ 4H + + 4e- H2SO3 + H 2O

= +0.17 V

+ 2e- Ni

= - 0.26 V

+ 2e- H2 + 2OH - (10-7 M)

= -0.41 V

OXIDATION
1
2

O2(g) + 2H + (10-7 M) + 2e -

= +0.82 V

______________________________________________________________
______________________________________________________________
so the half -reactions that occur are:

Anode:

H2O

Cathode:
H2O + Ni 2+

1
2

1
2

O2(g) + 2H + (10-7 M) + 2e - E

Ni2+ + 2e- Ni

O2(g) + 2H + (10-7 M) + Ni

=
= - 0.26 V
CELL

_____ is produced at the anode, _____ is produced at the cathode and a


voltage of at least __________ must be applied for the reaction to occur.

52

Chemistry 12

EXAMPLE 5.14

ELECTROLYSIS REACTIONS

Problem:

What is the overall reaction which occurs when a 1 M solution of HCl(aq) is


electrolyzed using carbon electrodes?

Solution:

First, the species present H+, Cl -, H2O (acidic) and the possible reactions are
REDUCTION

+ 2e- H2

= +0.00 V

+ 2e- H2 + 2OH - (10-7 M)

= -0.41 V

OXIDATION

1
2

Cl2(g) + 2e-

= +1.36 V

O2(g) + 2H + (10-7 M) + 2e -

= +0.82 V

Due to the high overpotential of H2O, the Cl- is oxidized so the two half
reactions are

H+ + 2e- H2

2Cl- Cl2(g) + 2e- E


H+ + 2Cl- H2 + Cl2

= + 0.00 V

Cathode

Anode

CELL

_____ is produced at the anode, _____ is produced at the cathode and a


voltage of at least __________ must be applied for the reaction to occur.

Unit 5 Electrochemistry (S).doc

5.

53

ELECTROPLATING
ELECTROPLATING is __________________________________________________

________________________________________________________________________
________________________________________________________________________

The ____________________is made out of the material which will receive the metal
plating.

The _________________________ ____________________ contains ions of the


metal which is to be plated onto the cathode.

The _______________ may be made of the same metal which is to be plated out
onto the cathode. (This is normal but an inert electrode can also be used.)

54

Chemistry 12

EXAMPLE 5.15

ELECTROPLATING CELLS

Problem:

Design a cell to electroplate a copper medallion with nickel metal. Include in


the design: the ions present in the solution, the direction of ion flow, the
substance used for the anode and cathode, and the direction of electron flow
when the cell is connected to a DC power source.

Solution:

Since nickel metal must be produce, the reduction reaction is:

The cell is setup as follows:


DC Power
Source

The medallion must have the Ni(s) plated onto it, so it must be the
_______________.

Make the _______________ out of Ni(s) so that the oxidation reaction

Ni(s) Ni2+ + 2ewill ensure a _________________________________________________


___________________________________________________________

Since electrons always flow from ______________________________,


connect DC power in such a way as to supply electrons to the cathode.

The ions needed in solution will Ni2+ and some anion that does NOT form a
precipitate with Ni2+. The NO3- is always a good choice since all nitrates
are soluble.

As with spontaneous reactions, __________________________________


___________________________________________________________
___________________________________________________________

Unit 5 Electrochemistry (S).doc

6.

55

ELECTROREFINING
ELECTROREFINING is _________________________________________________

________________________________________________________________________
________________________________________________________________________

DC Power
Source

At the anode, the small amounts of Zn or Pb present is preferentially oxidized as it is


exposed at the surface. When any exposed Pb/Zn atoms have oxidized and gone into
solution as ions, only the Cu atoms are available to be oxidized. Any Au, Ag, or Pt
atoms present cannot be oxidized because the anode is mostly copper which is oxidized
in preference to Au, Ag, or Pt which simply drop off and accumulate on the bottom of the
cell. This anode sludge can be purified to obtain the valuable metals.