Unit 3 Electrochemistry and Energy

Lesson 3.1 Oxidation-Reduction Reaction

 Republic of the Philippines
WESTERN MINDANAO STATE UNIVERSITY
COLLEGE OF SCIENCE AND MATHEMATICS
CHEMISTRY DEPARTMENT
Normal Road, Baliwasan, Zamboanga City

Lesson 3- Electrochemical Energy

Worksheet 3A

Topic 3 Oxidation-Reduction Reaction

Name: _______________________ Course: __________Date:_________

I. Assigning of Oxidation Numbers or Oxidation States.

Using your Periodic Table (PT) assign the ON or OS of the following:

a. K2CO3 ___________________ d. NaIO3 _______________

b. Ca3(PO4)2 ___________________ e. NO2 _______________

c. KHPO4 ___________________ f. O2 _______________

1. Finding the OSs of the underlined element in each of the following:

Show your solution.
1. Mg3(PO4)2

2. CrCl3

3. Al(IO4)3

4. H2SO3

5. (NH4)2SO4
3. Molecular and Ionic Equation

1. Given the reaction: BaCl2 (aq) +Na2SO4(aq) BaSO4(s) + NaCl (aq)

a. Write the ionic equation for the reaction.
b. Give the net ionic equation

2. Tell what happens when potassium phosphate (K3PO4) solution is combined

with calcium nitrate [(CaNO3)2] solution. Write a) molecular, b) ionic equation
and c) net ionic equation for the reaction

4. Balance the following by redox reaction: Indicate the reducing agent and
the oxidizing agent.

.
1. Fe+2 + MnO4- Fe+3 + Mn-2

2. Mn+2 + H2O2 MnO2 + H2O (basic medium)

 3. Cr2O72- + C2O42- Cr+3 + CO2 (acidic solution)

4. Complete and balance the equation by redox

Zn(s) + CuSO4 (aq)

5. Ni(s) +Pb (NO3)2(aq) Pb(s) +Ni(NO3)2

-End-

Lesson 3.2 Electrochemical Cells: What is this

 and how it Works?

Introduction
In the previous handout on oxidation- reduction (redox) reactions you have
learned that redox reaction are electron-transfer reactions. This kind of reaction is part
and parcel of the world around us. It occurs from the rusting of iron, burning of fossil
fuels to the action of house-hold bleach to name a few. In this lesson, you are going to
apply this knowledge to this new topic about electrochemical cells. The basic
principles and concepts related to electrochemical cells and its components will be
discussed. This knowledge will enable you to understand how it works, what is
involved and the type of energy produced. In addition, you will learn how to develop
an electrochemical cell like a battery.

Objectives:

At the end of this lesson, it is expected that you can:

a. discuss what an electrochemical cells are and its importance.

b. explain how an electrochemical cells work
c. express a cell diagram of an electrochemical cell
d. devise an electrochemical cell

Try This!

There are many a videos in you tube regarding galvanic cells. Please watch and
afterwards answer the following questions.

1. What is a galvanic cell? _____________________________________

_____________________________________________________________________
_________________________________________________________

Explain its importance. __________________________________________

_______________________________________________________________
_______________________________________________________________
_______________________________________________________________
2. Consider the reaction: Zn + CuSO (aq) = ZnSO + Cu
(s) 4 4(aq) (s)

a. What happens to Zn? What about Cu? ______________________

__________________________________________________________________
__________________________________________

b. What substance is reduced? ______________________________

______________________________________________________

c. What substance is oxidized? ______________________________

d. Which is the reducing agent (RA)? _________________________

e. Which is the oxidizing agent (OA)? __________________________

How do you determine that the substance is a reducing agent or the

oxidizing agent? ________________________________________
__________________________________________________________________
__________________________________________

f. How does the electron transfer occur? _______________________

__________________________________________________________________
__________________________________________

g. Show the oxidation-reduction half-reaction:

__________________________________________________________________
__________________________________________________________________
______________________________

h. What do you think will happen if you physically separate the OA from the
RA, how will the transfer of electron take place?
__________________________________________________________________
__________________________________________________________________
______________________________

Think Ahead!
 Would you like to know how you performed? You can compare your answers
with mine below.

1. Galvanic cells are electrochemical cells that produce electrical energy by

spontaneous chemical reaction where oxidation-reduction reaction takes place
separately at the anode and cathode respectively, and the electrons flow through an
external circuit.

Aside from those mentioned in the preceding module, the importance of the
principles of electrochemistry in general is very much applicable in the industry like
the coating of metals with metal oxides through electro deposition and making of
jewelries through electroplating detecting alcohol from drunken drivers through
oxidation-reduction of ethanol, blood sugar of diabetic patients is measured in term
of glucose through its redox potential, and producing electricity through batteries, or
starting a car.

For item #2(a) Zinc (Zn) transfers two (2) electrons (2e) and copper (Cu) accepts
the 2e- as shown: Zn(s) Zn2+ +2e-

Cu+2 + 2e- Cu

For #2 (b) and (c), the substance reduced is copper, for it accepts the two
electrons transferred or donated by Zn and by itself becomes oxidized.

While item #2 (d) and (e), since copper accepts or gains the electron, it acts as
the oxidizing agent, while zinc as the reducing agent. Zinc causes Cu to be reduced
for it transfers 2e- causing an increase in its oxidation state while Cu causes Zinc to
be oxidized causing it oxidation state to be reduced.

For #2(f) occurrence of the transfer of electrons is clearer in redox reactions such as
this: Zn(s) Zn2+ +2e- ; Cu+2 + 2e- Cu

Electrons are transferred directly from the reducing agent (Zn) to the oxidizing agent
(Cu2+) in solution.

For #2(g) here is the half-reaction: Zn(s) Zn 2+ (aq) + 2e- 0xidation

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

For #2 (h) if the OA is physically separated from RA, the transfer of electrons takes
place through an external conducting metal wire (medium). As the reaction
proceeds, it sets up a continuous flow of electrons, producing electricity.

The answers you have given for the above questions are an indication of how
much you know about a part of electrochemistry. There is much for you to tackle. Do
you want to learn more, if so, let’s move on and which at the end of this session you
can even devise an electrochemical cell.
 Read and Ponder!
Electrochemical Cells: What’s this and how it works?

In this section, what electrochemical cells are and its components, how an
electrochemical cells work and how to devise an electrochemical cell will be discussed.
Figure 1 shows a galvanic cell and its components.

Figure1. A galvanic cell, the half-cells are separated; electrons can flow through an
external wire and become available to do electrical work.
www.ausetute.com.au › cell diagram

The device that allows electricity to flow through the use of a natural or
spontaneous reaction is called a galvanic cell. Note that in a galvanic cell referred too
as voltaic cell, zinc pellet is immersed in a ZnSO4 solution and copper pellet is
submersed in a CuSO4 solution.

So, how does it work? It works based on the principle that oxidation of Zn to
Zn+2 and the reduction of Cu+2 to Cu can take place at the same time in a separate
container with the transfer of electrons between them occurring through an external
wire. The zinc and copper pellets served as electrodes. This kind of particular cell
arrangement (Zn and Cu) and solutions ZnSO4 and CuSO4) ii referred to.as Daniel cell.

When the electrochemical cell is constructed in this fashion, a positive cell

potential indicates a spontaneous reaction and that the electrons are flowing from the
left to the right.

In a galvanic cell, the anode is the electrode at which oxidation takes place and
the cathode is the electrode at which reduction occurs. For the Daniel cell, the half –
reactions, which are the oxidation and reduction reactions at the electrodes, are:
Zn electrode (anode): Zn(s) Zn2+(aq) + 2e-

Cu electrode (cathode): Cu+2 +2e- Cu(s)

If unless the two(2) solutions are separated from each other, the Cu+2 ions will react
directly with the zinc pellet:

Cu+2(aq) + Zn(s) Cu(s) + Zn2+(aq)

and no useful work will be obtained.

For the electrical circuit to be completed, these two solutions must be connected
by a wire or conducting medium through which both ions (cations and anions) can
move from one electrode partition to the other. To satisfy this it needs a salt bridge, an
inverted U tube containing an inert material which is an electrolyte solution, whose
ions does not react with other ions in solution or with the electrodes.

During the course of the overall redox reaction, electrons flow externally from
the anode (Zn electrode) through the wire and voltmeter to the cathode( Cu electrode).

In the solutions, the cations (Zn2+, Cu+2 and other cations present) move toward
the cathode, while the anions (SO4-2, and other anions present) move toward the
anode.

What’s the role of the salt bridge? Without the salt bridge connecting the two
solutions, the accumulation of positive charge in the anode partition (as a result of the
formation of Zn ions) and negative charge in the cathode partition (created when some
of the Cu2+ ions are reduced to Cu) would immediately prevent the cell from
operating.

The flow of an electric current from the anode to the cathode, a difference in
electrical potential energy is developed between the electrodes. Experimentally, the
difference in electrical potential between the anode and the cathode is measured by a voltmeter
and the reading (in volts) is referred to as cell voltage. Cell voltage can be referred too
also as electromotive force or emf (E) and cell potential. Note that the voltage of a cell
depends not only in the nature of the electrodes and the ions, but likewise the
concentrations of the ions and the temperature at which the cell is operated.

We can use the notation for representing galvanic cells called cell diagram. For
the above Daniel cell, assuming that the concentrations of Zn 2+ and Cu2+ ions are 1M,
the cell diagram is:

Zn(s)I Zn2+(1M)IICu2+ (1M)I Cu(s)

where, the single vertical line (I) represents a phase boundary. For instance, the zinc
electrode is a solid and the Zn2+ ions from (ZnSO4) are in solution. So, a line is drawn
between Zn and Zn2+ to indicate the phase boundary.

The double vertical lines (II) show the salt bridge. How do we write the cell
diagram? Conventionally, the anode is written first, to the left of the double lines and
the other components appear in the order in which you will encounter them in moving
from the anode to the cathode.
Summary:

In an electrochemical cells like galvanic cell, electrons flow from the anode to
the cathode L to R in the standard galvanic cell. The electrode in the left half-cell is the
anode because oxidation occurs here. The name refers to the flow of anions in the salt
bridge toward it. The electrode in the right half-cell is the cathode because reduction
occurs here.
Oxidation occurs at the anode (the left half-cell in the figure). Reduction occurs at the
cathode. The name refers to the flow of cations in the salt bridge toward it. The cell
potential results from the inherent differences in the nature of the materials used to
make the two half-cells.
The salt bridge must be present to close (complete) the circuit and both an oxidation
and reduction must occur for current to flow.

See if you can do this!

1. Review all the questions in the activity above. Answer those items which you
were not able to answer. Write your answer based on the order indicated above.
______________________________________________________________
______________________________________________________________
____________________________________________
________________________________________________________
________________________________________________________
________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
____________________

2. Discuss how an electrochemical cell is constructed and show a diagram.

Indicating all its components.
 As an output create an electrochemical kit and submit it when we have a
scheduled face to face meeting.

-End-

Lesson 3.3 Standard Reduction Potential: A

Model Reference

Introduction
 The previous module on electrochemical cell focused on galvanic cell, its
components, half-cell reactions using cell diagram of the oxidation-reduction reaction
involved and how it works. The difference in the electrical potential between the
anode and the cathode is measured by a voltmeter and the reading in volts is called
cell voltage or the electromotive force or emf. Notice that the voltage of a cell depends on
the following: nature of the electrodes and the ions, concentration of the ions and the
temperature at which the electrochemical cell operates. A standard or reference is
utilized to regulate or calibrate measurements pertaining to measuring the voltage. In
this module you will continue reading the discussion on electrochemical cells, but this
time the attention is on standard reduction potential. What it is all about, how is it related
to oxidation-reduction reaction and to appreciate its importance and applications.

Objectives:
After completing this module, it is expected that you can:

1. describe what standard reduction potentials is

2. explain the significance, of standard reduction potential of electrodes
3. express the half–reactions and overall reaction of an electrochemical cell
4. calculate the cell voltage or emf of an electrochemical cell using the standard
reduction potential.

Try this!

Work this out! Answer the following questions after watching online video on
you tube pertaining to standard reduction potentials.

Give the meaning of the acronym, symbols or the meaning of the following?
1.
a) “0” _______________________________________________________
b) SHE _____________________________________________________
c) E0 _____________________________________________________
d) E0cell _____________________________________________________

e) Standard-state
__________________________________________________________________
__________________________________________
______________________________________________________
 2. Describe reduction potential
(Eh)_________________________________________________________________
____________________________________________
_____________________________________________________________________
___________________________________________
________________________________________________________

3. What is standard reduction potential?

______________________________________________________________
______________________________________________________________
__________________________________________________
________________________________________________________

4. Conventionally how will you express the equation of standard reduction

potential of a cell? You can express this in two ways.

5. Copper and iron (generally in the form of a (steel) are two of the many metals
used in designing machines. (a) Using standard reduction potentials, identify
the anode and the cathode, and b) determine the cell potential for a galvanic
cell composed of copper and iron.

6. What does the positive (+) and negative (-) sign of standard reduction
potentials E0 tell about the oxidation-reduction of chemicals involved in a half
– reactions?

Think Ahead!

Where you able to answer the questions in the Activity correctly? Try to
examine your answer to each of the items and compare your answer with mine.

For Item #1 here are my answers: a) the superscript “0”stands for standard,
b) SHE refers to standard hydrogen potential
c) E0 is referred to as standard reduction potential or the emf linked with the reduction
when all solutes are 1M and all gases are 1 atm.
d) E0cell, is the standard emf of the cell contributed by both the anode and the cathode.
f) Standard –state is the condition that specifies 1 atmospheric pressure that liquids
and gases are in pure state, and that solutions must be at 1M concentration, subjected
to usually to 250C.

As to item #2 here is my answer- reduction potential (also referred to as

redox potential, oxidation/reduction potential, or Eh) measures the propensity of a
chemical species to gain electrons and thus, be reduced.
For item #3 this symbol (E0) refers to as standard reduction potential because the
voltage obtained is measured under standard conditions: 25 °C.

For Item #4, the equation for the standard reduction potential of cell which is a
contribution from the anode and a contribution from the cathode, can be expressed by
the equation:

E0cell = E0anode - E0cathode or E0cell = E0red – E0ox

For question #5, (see attached standard reduction potentials table to this module)
here is my answer, using the table for reduction potentials, the following are the two
half-reactions:

Fe+2(aq) + 2e- Fe(s) E0 = -0.44 V

Cu+2(aq) + 2e- Cu(s) E0 = 0.337 V

We combine the two half-reactions where iron (Fe) must be oxidized to yield a
positive cell potential

Fe(s) + Cu+2(aq) + 2e- Fe2+(aq) + Cu(s) E0 = ?

a) In this reaction cell, copper is the cathode because copper is reduced; while iron
(Fe) is the anode because it is oxidized.

b) Using this equation: E0cell = E0anode - E0 cathode

E0cell = 0.337 V-(-0.44 V) = 0.78 V

For Item #6, the positive (+) and negative (-) signs of the standard reduction potentials
allows you to predict the extent of the redox reaction. The positive value for E0 can tell
you that the substance is reduced readily and hence is a good oxidizing agent. On the
other hand, if a reduction potential has a negative value, the reaction proceeds readily
in reverse- the substance is reduced. So, a negative standard reduction potential
classify good reducing agents. The product of the half-reaction as illustrated in the
table is the reducing agents because the reverse reaction is oxidation.

The answers you have given for the above questions are an indication of how much
you know or don’t know about a part of electrochemistry. There is much for you to
grasp and understand. Do you want to learn more, if so, let’s move on!

Read and Ponder!

 Standard Reduction Potential: A Model Reference

Recall in your preceding module, the oxidation-reduction reaction of Zn2+ and

Cu2+ in Daniell cell. Assuming that the concentration of both ionic species is 1M, the
measured voltage is 1.10 V at 250C. This obtained voltage is related to the redox
reaction of the two half-cells:

Zn(s) Zn 2+(aq) + 2e- E0 = - 0.763 V

Cu+2 + 2e- Cu (s) E0 = + 0.337 V
Overall reaction: Zn(s) + Cu+2 Zn2+ + Cu(s) E0 = 1.10 V

The measured emf (1.10 V) of the overall reaction indicates that it is the sum of the
electrical potentials at the Zn and Cu electrodes. If you know the potentials of one of
these electrodes you can obtain the potentials of the other by getting the difference
from 1.10V. Just as some acids are stronger than others, the oxidizing and reducing
strengths of various chemicals also have a range of values. To put things in order, the
oxidation-reduction trends of species utilized in electrochemistry, all half-reactions
are tabulated as reductions known as table of standard reduction potentials that
shows the potential of any half-reactions, when connected to a SHE known as standard
hydrogen electrode. The hydrogen electrode is used as a reference point to serve its
purpose. It must be noted that all electrodes must be constructed to meet the
conditions of standard- state, that is, all materials are in thermodynamic standard
states, concentration of solutions must be 1M, and gases have a pressure of 1atm.

The hydrogen gas as reference material is bubbled into aqueous HCl at 25 0C.
Platinum electrode is part of the hydrogen electrode serving two functions. First, it
provides a surface on which dissociation of hydrogen molecules can take place;

H2 2H+ +2e-

Second, it serves as an electrical conductor to external circuit. Under the standard-

state condition, the potential for the reduction of H + at 250C is taken to be zero:

2H+ (1M) +2e- H2 (1atm) E0 = 0 V

Where the superscript “0” represents standard-state conditions, E0 is the standard

reduction potentials or the voltage associated with a reduction reaction at an electrode
when all solutes are 1M and all gases are at 1atm. SHE is referred to as standard
hydrogen electrode. You can download a copy from the internet the list of the
standard reduction potentials for you use in calculating the emf or the voltage of ionic
species in a cell. The table of SRP or standard reduction potentials has several features
worthy of mentioning. First, as expressed in the table, half-reactions are listed as
reductions, the other half-reaction in a cell must be oxidation. Second, some half-
reactions have positive potentials, whereas others have negative potentials measured
with a SHE connected to a positive terminal. If the voltage is positive, the SHE is the
anode- the oxidation site. So, a positive voltage in the SRP means that the half-
reaction proceeds as written(reduction occurs). If the value is negative, the half-
reaction proceeds as an oxidation when connected to SHE, because the SHE is serving
as the cathode.

So, what do these observations imply on the tendency for oxidation and
reduction of chemicals involved in half-reactions? A large, positive value for the SRP,
implies that the substance is reduced easily and therefore a good oxidizing agent.
Conversely, if a reduction potential has a relatively large negative value, the reaction
proceeds in reverse- the substance is oxidized. Hence, negative SRP are good
oxidizing agents. Such sequence of reactivities based on SRPs is sometimes known as
the electrochemical series or electromotive series as commonly referred to.

Moreover, the sign of E0 can be used to predict the extent of a redox reaction. A
positive E0 indicates the redox reaction will favor the formation of products at
equilibrium. Conversely, a negative E 0 means that more reactants than products will
be formed at equilibrium.

Let me give you some important points regarding the table on standard
reduction potentials for calculations.

a. The E0 values apply to the half-cell reactions as read in the L to R direction.

b. The more positive E0 is the greater the tendency for the substance to be
reduced. So, as you see in the table Fluorine (F) has the highest positive E0
as compared to Li, the most negative value. Hence, F 2 is the strongest OA
and Li the weakest OA. Conversely, Li is the strongest RA and F 2, the
weakest RA.
c. The half-cell reaction is reversible. This means that electrodes can act either as
an anode or as a cathode depending on the conditions set.
d. Under standard-state conditions, any species on the left of a given half-reaction
will react spontaneously with a species on the right of any half-reactions located
below it.(diagonal rule)
e. Changing the stoichiometric coefficients of the half-cell reactions does not affect
the value of E0, because electrode potentials are intensive properties. This
means, whether the electrode size is big or small, the E 0 is unaffected.
f. The sign of E0 changes but its magnitude remains the same when we reverse
the reaction,

See if you can do this!

1. The standard reduction potential of copper can be obtained using a cell

with copper electrode and a SHE.
a) Which of the two is the cathode and why?
b) write the cell diagram.
 c) write the half-reactions and the overall reactions.
d) Calculate the E0 of the cell.

2. Assume standard conditions, we can construct a galvanic cell

using copper and sliver. Confirm that the potential of the
following galvanic cell is 0.462 V.

Show your solution.

2. Calculate the standard emf of a cell that uses Ag/Ag+ and Al/Al+3
half-cell reactions. Write the cell reaction that occurs under standard-
state conditions.

Table for Standard Reduction Potentials

Lesson 3.4 Spontaneity of REDOX Reaction:

Introduction

Have you heard of an explosion that occur naturally, and concrete houses near
the sea shore that corrode? Or you have seen that large molecule like gasoline can
react readily with oxygen to produce carbon dioxide (CO 2) and water (H2O). But, your
experience also tells you that the reverse reaction does not occur that is, water vapor
and carbon dioxide are always present in air, but they never react to produce gasoline.
We also know that there are chemical compounds in waste materials, like paper, may
spontaneously react to decay over time. You may notice that there are reactions that
are so slow that it’s hardly for us to observe. These are redox reactions that take place
in nature that such processes taking place spontaneously or that “just occur’ is without
continuous intervention. From the foregoing module pertaining to electrochemical
cells, we are going to relate how E0cell is related to thermodynamics quantities such as
standard free energy ΔG0 and equilibrium constant, K. In this module, you are going
to tell and explain as to why spontaneous process is just occurring and use
mathematics regarding these different quantities as well as predict whether a reaction
is spontaneous or not.

Objectives
At the end of this module, you can:
1. define spontaneous redox reaction
2. explain the relation of E0cell to free energy ΔG0 and K
3. do calculations involving E0 ,ΔG0 and equilibrium K.
4. predict whether a reaction is spontaneous or not

Try this!

Watch a video in you tube or google pertaining to this topic on the

spontaneity of oxidation-reduction reaction. In this activity there are different
terms you need to learn and understand before we can proceed to our main
topic. Then work out on the following items

1. What is free energy (G)? _________________________________________

____________________________________________________________________
______________________________________________________

2. What does this symbol ΔG and ΔG0 mean? Explain the significance of the
latter?________________________________________________________
______________________________________________________________
______________________________________________________________

3. What is equilibrium constant? _____________________________________

_______________________________________________________________
_______________________________________________________________
_______________________________________________________________

4. What does spontaneity of a redox reaction mean? _____________________

________________________________________________________________
________________________________________________________________
________________________________________________________________

5. How would you determine that a redox reaction is spontaneous? __________

________________________________________________________________
________________________________________________________________
 ________________________________________________________________

6. How will you relate reduction potential E 0 to ΔG0?______________________

_______________________________________________________________________
_________________________________________________________

7. What about the relation of E0 with equilibrium constant, K?__________________

________________________________________________________________
________________________________________________________________
________________________________________________________________
________________________________________________________________

Think Ahead!
After you are done answering the questions in the activity part, try to
compare your answer for each item with my answer that follows:

For question # 1, G, is known as the Gibbs free energy refers to energy related to a
chemical reaction that is utilized to do work.

For item #2 the symbol, ΔG means the change in free energy of a system, a state
function that deals with the initial state, such as all reactants, to, final state, such as all
products. In the context of redox reaction in a cell it tells us the maximum
usable energy released (or absorbed) in going from the initial to the final state in the
overall cell reaction. While ΔG0 is referred to as standard free energy as most redox
reactions are carried out in the laboratory under IM and 1 atm. pressure usually at
250C or (298K).

Item #3 Equilibrium constant refers to the ratio of the reactant and product
concentrations for a reversible reaction at equilibrium which is constant. It helps
predict the direction in which a redox reaction will proceed to equilibrium. It can be
utilized to calculate concentrations of reactants and products once equilibrium has
been reached.

For item #4 Spontaneity of redox reaction is a reaction that occurs in a given set of
conditions without intervention or in simple terms reactions that” just occur” in
nature without continuous mediation.

For Item #5 A redox reaction is spontaneous if the standard electrode potential for
the redox reaction, Eo(redox reaction), is positive. If Eo(redox reaction) is positive, the
reaction will proceed in the forward direction (spontaneous).

For item #6, in an electrochemical cell, the Gibbs free energy is related to
the potential by: ΔG°cell = −nFE°cell. If E°cell > 0, then the process is spontaneous.
For item #7 the relation of Eo with the equilibrium constant, K of a redox reaction.
can be derived from the ΔG0 as it relates to equilibrium constant, K by the equation:

ΔG0 = -RT ln K

-nFE0cell = -RT ln K

You can now decipher the relation of E0 to the equilibrium constant in the second
equation. From this second equation, we can calculate the E0cell.

Read and Ponder!

We are done with reduction standard potentials, we shall now focus on how E 0cell is
related to standard free energy ΔG° and equilibrium constant, K. Recall, that in an
electrochemical cell like a galvanic or voltaic cell, chemical energy is transformed to
electrical, which is the product of the emf of the cell and the total electrical charge that
passes through the cell.
Note that the cell potential or emf is important because it is related to maximum
electrical work that can be obtained from the electrochemical cell: W max =qE, where q
is the charge that has moved (through the flow of electrons) and E is the cell potential.
This equation fits the scientific concept of work because something (charge)is moved
by the action of some force(the emf).

Recall that free energy is related to the maximum possible amount of work that can be
done by the system. In the case of a galvanic cell, the work done is electrical work and
we can tell the relationship between free energy and the cell potential as

ΔG = -nFE Eq. 3D.1

The negative sign on the right hand side indicates that the electrical work is done by
the system on the surrounding. Remember, free energy, G, is the energy related to a
chemical reaction that is utilized to do work\ specifically, the change in free energy
(ΔG).representing the maximum work: ΔG = wmax, hence the equation above (3D.1).

The n, represents the number of moles of electrons exchange between the reducing
agent (RA) and the oxidizing agent (OA) in the overall reaction, and F, is the Faraday’s
constant (=96,500J/V,mole e-). Both are positive quantities and ΔG is negative for a
spontaneous process, so Ecell must be positive.

So, for a reaction in which the reactants and products are in a standard state, the
equation above becomes:

ΔG0 = -nFE0 Eq. 3D.2

Recall that ΔG0 is related to equilibrium constant, K of a redox reaction, by this
equation: ΔG0 = -RT ln K. Hence, if we combine the two equations;

-nFE0 = -RT ln K Eq 3D.3

Therefore, from this equation we can solve for the E0cell, which is

E0cell = RT ln K
nF
or
E0cell = 2.303 RT log K Eq 3D.4
nF

The factor of 2.303 is changing the natural log to the common function: ln (10) = 2.303.
Both RT are constants. We are often interested to carry out experiments at standard
temperature of 250 C (298K) we can substitute the values and arrive at this
equation:

E0 = 0.0592 V log K Eq. 3D.5

n

Thus, if one of the three (3) quantities, ΔG 0, E0 or K is known the other two (2) can be
calculated. Below is a table showing the relationship among these three (3).

Table 3D.1 Relationship among ΔG0, E0 or K

ΔG0 K E0cell Reaction under Standard state- condition
Negative ➢ 1 Positive Favors formation of products
0 = 1 0 Reactants and products are = favored
Positive < 1 Negative Favors the reactants

See if you can do this!

1. Using equation 3D.5 if you choose an electrochemical reaction that transfers
only one electron at a potential of 1.0V what would be the K? What does the
value of K tell you?

2. Calculate ΔG0 and K for the following reactions at 250C:

a) Mg(s) + Pb+2 (aq) Mg2+(aq) + Pb(s)

b) Br2(l) +2I-(aq) 2Br-(aq) + I2(s)

3. Given that E0 = 0.52 V for the reduction Cu+2 + e- Cu(s), Calculate the
 E0, ΔG0,, and K for the following reaction at 250C?

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

Lesson 3.5 Effect of Concentration on Cell EMF

 Introduction

In the preceding module, we discussed about spontaneity of redox reaction,

discussed how it occurs and where in reactants and products are in their standard
state. However, we cannot expect standard conditions in real world application. It’s
just like real gases they do not behave like ideal gases. This means that standard
conditions are hard and impossible to achieve. For example, corrosion this is
happening in the real world spontaneously and under nonstandard conditions. How
can we account for any differences that may arise when standard conditions are not
present? This is a very important query with a clear relation with thermodynamics.
Chemists derive a mathematical formula that depicts the relationship between the emf
of a galvanic cell and the concentration of the reactants and products under non-
standard state conditions. In this module, we will learn how concentration influence
the cell’s electromotive force, emf.

Objectives
At the end of this module, you can:

1. describe the principle behind Nernst equation and its importance

2. discuss the effect of concentration on the cell’s emf (Nernst Equation)
3. do calculations of E0 under standard and nonstandard conditions

Try this!
 Read some chemistry books or try to search in Internet regarding this topic,
“effect of concentration on cell electromotive force, emf “or the Nernst equation.
and answer the succeeding questions.

1. What is Nernst equation?__________________________________________

_____________________________________________________________________
_____________________________________________________________________
________________________________________________

2. At what condition is the Nernst equation applied? Explain.________________

______________________________________________________________
______________________________________________________________
______________________________________________________________

3. a.) Express the Nernst equation and discuss all the terms.________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________

b) Cite specific sample of cell reaction and express its Nernst equation.

______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________

Think Ahead!
For Item #1, the Nernst equation is one that relates the reduction potential ofan
electrochemical reaction (half-cell or full cell reaction) to the standard electrode
potential, temperature, and approximated by concentrations of the chemical species
undergoing reduction and oxidation under non-standard conditions.

For Item #2 the Nernst equation can be applied to find the cell potential at any
instant during an ongoing reaction or at conditions other than standard-state and the
reaction quotient (Qc) -mathematical expression of the product of the concentrations
of the products of the reaction divided by the mathematical product of the
concentrations of the reactants.

For Item #3 (a) the Nernst equation can be written as:

 E=E0 – 0.0257 V ln Q or
n
E=E – 0.0257 V log Q
0

where: E is the cell potential; E0 is the reduction potential at standard state; n is

the number of moles of electrons; ln Q is the reaction quotient
(base-10 log Q)

b) For this particular galvanic cell reaction: Zn(s) + Cu2+ Zn2+ + Cu(s), we
can express or write the Nernst equation of this cell at 25 0C as follows:

E = E0 – 0.0257 V log Q
n

E = 1.10 V – 0.0257 V ln [ Zn2+]

2 [Cu2+]
(Note that 2 moles of electrons are transferred per mole of reaction; that is, n=2)

Read and Ponder!

The Effect of Concentration on the cell EMF: The Nernst Equation

As it is pinpointed before that not all redox reactions are happening in a

standard state-condition. There is a mathematical relationship between the emf of a
voltaic cell and the concentration of the reactants and products in a redox reaction
under non-standard condition. Such mathematical relation that defines cell
potentials is known as the Nernst equation as indicated.

E= E0- RT ln Q
n

Here Q is the reaction quotient, a ratio of concentrations of reactants and

products, each raised to the power of its stoichiometric coefficients. So, for the
“generic” reaction:

aA + bB cC + dD

Q = [C]c [D]d
[ A]a[B]b
 Recall that during the course of chemical reaction not all the reactants and
products will be at their standard conditions. Under this states, the relationship
between ΔG and ΔG0 derived from thermodynamics is:

ΔG = ΔG0 + RT ln Q Equation E.1

Since, ΔG = -nFE + ln Q and ΔG0 = -nFE0, the equation can be written as

-nFE = -nFE0 + RT ln Q, and we get

nF

E = E0 - RT ln Q EquationE.2
nF

This equation is known as the Nernst equation. At 250C (298K), the above
equation can be re-expressed as

E= E0- 0.0257 V ln Q Equation E.3

n

Or expressed this equation using base-10 log of Q, we get:

E= E0- 0.0257 V log Q

n

Take for example, as the galvanic or voltaic cell operates, electrons flow from the
anode to the cathode, resulting in product formation and a decrease reactant
concentration. Thus, the Q increases, which means that E decreases. In due course, the
cell reaches equilibrium. At equilibrium, there is no net transfer of electrons, so E=0
and Q=K, where K is the equilibrium constant.

So, of what use is the Nernst equation in a redox reaction? This equation allows us
to calculate E as a function of reactant and product concentration in a redox reaction
under non-standard condition or state.

So take for instance, the Daniell cell previously discussed in of the modules:

Zn(s) + Cu2+ Zn2+ + Cu(s), we can write the Nernst equation of this
as:
E = E0 – 0.0257 V log Q
n
E = 1.10 V – 0.0257 V ln [ Zn2+]
2 [Cu2+]

If the ratio [Zn2+]/[Cu2+] is less than 1, ln [Zn2+]/[Cu2+] is a negative number, so

the second term on the right-side of the preceding equation is positive. Under this
condition, E is greater than the standard emf, E0. If the ratio is greater than 1, E smaller
than E0.
 See if you can do this!
Answer the following and write your answer in a separate clean sheet of paper.

1. Discuss the importance of the Nernst equation and its application.

2. Predict whether the following reaction would proceed spontaneously as

written at 298K.
Co(s) + Fe2+ (aq) = Co+2 + Fe(s), given that [Co2+] =0.15M and [Fe2+] = 0.68 M

3. Suppose that you work for a company that designs the drive mechanisms for
large ships. The materials in this mechanism will obviously come into contact
with environments that enhance corrosion. To estimate that corrosion might
cause, you decide to build a model electrochemical cell using electrolyte
concentration that might be present in your system when it is in service.
Assume that you have cell that has an iron(11) concentration of 0.015 M and a
H+ concentration of 1.0 x 10-3 M. The cell temperature is 380C, and the pressure
of hydrogen gas is maintained at 0.04 atm. What would the cell potential be
under these conditions.

4. What is the emf of a cell consisting of a Pb2+/Pb half-cell and a Pt/H+/H2 half-
cell if [Pb2+] = 0.10 M, [H+] = 0.050 M, PH2 =1.0 atm.

5. Consider a galvanic cell. In a certain experiment, the emf (E) of the cell is
found to be 0.54 V at 250C. Suppose that [Zn2+ = 1.0 M and PH2 =1.0 atm.
Calculate the molar concentration of H+.
Lesson 3.6 Batteries: Single- Used or
Rechargeable?

Introduction

Electrochemical principles and knowledge brought a breakthrough in the field

of that lead to battery technology. You are all familiar with batteries and its
widespread use. It is one source of energy and in our everyday experience we know
that some batteries are rechargeable whereas others are used once and thrown away.
The widespread use of these batteries leads to competition among companies, as
gleaned from commercials in television for particular brands. In this lecture package
or module, we will discuss about batteries, its advantage over a galvanic cell, type of
batteries and its chemistry and advantages application.
 Objectives

After mastering this module, you can:

1. describe what a battery is

2. cite the advantage of a battery over a galvanic cell
3. distinguish between primary and secondary battery
4. discuss several types of batteries
5. describe the chemistry of some common battery types; and
6. explain why each type of battery is suitable for a particular application

Try this!
Read some chemistry books or try to search in Internet regarding this topic
about batteries and after which you can answer the questions that follow: You can
match our answer with my mine.

Let’s have a history review of sort!

He was the first person to realize that the differences in chemical reactivity of
metals could be used to generate electricity of which his work became a precursor to
the development of battery. Who was he? _____________________________

Battery research has long been undertaken by US manufacturing companies. This

person held 147 patents in battery technology. Who is this person? ___________

1. Describe a battery ______________________________________________

_____________________________________________________________________
_______________________________________________________
______________________________________________________________
______________________________________________________________

2. The operation of a battery is similar in principle to that of the galvanic cell, but
there is a distinct advantage of battery with that of the galvanic cell. Discuss its
similarities and advantage over galvanic cells and its limitations.
_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
_________________________________________
 3. There are two general kinds of batteries based on how it is utilized. What are
these two kinds and discuss each. __________________________________
_____________________________________________________________________
_______________________________________________________
______________________________________________________________
______________________________________________________________

4. There are several types of batteries, describe at least 2 and its chemistry.
______________________________________________________________
______________________________________________________________
______________________________________________________________
_____________________________________________________________

Think Ahead
For Item # 1, a battery is a cell, or series of cells that produces electricity that
can be classified as primary and secondary battery based on its application.

For Item #2, we describe a battery as a cell (galvanic or voltaic) or series of cells
that produce electricity as a result of the transfer of electrons, however, a battery
similar to a galvanic cell in principle, but the advantage of a battery over a
galvanic cell is that it is fully self- contained that need no ancillary components
such as salt bridges.

For item #3, the two kinds of batteries based on the context of its application
are the primary and secondary cell. Primary cells are non- rechargeable, or single-use
batteries, while rechargeable batteries are called secondary cells.

The most widespread primary battery is the alkaline battery. Examples of this
kind of battery most used are in flashlights, MP3 players, handheld video games.
These alkaline batteries rely on the same chemistry. The anode in an alkaline
battery is a zinc electrode, and the oxidation half-reaction:

Zn(s) +2 OH-(aq) Zn (OH)2 +2e-

The cathode is derived from MnO2, and the half-reaction is
2MnO2(s) +H2O (l) +2e- Mn2O3(s) +2OH-(aq)

Combining these two half-reactions, we yield a net equation that represents

the chemistry of an alkaline dry cell battery.
 Zn(s) +2 MnO2(s) + H2O Zn(OH)2(s) + Mn2O3 (s)

On the other hand, nickel-cadmium batteries are secondary cells used in cellular
phones, digtal cameras and laptop. The anode in the ni-cad batteries is cadmium,
reacting based on the following equation:

Cd(s) + 2OH- (aq) Cd(OH)(s) + 2e-

The cathode reaction is complex, and is represented by this equation:

NiO(OH)(s) + H2O(l) + e- Ni(OH)2(s) + OH-(aq)

Ni-cad batteries can be expended and recharged many times, but are
sometimes susceptible to performance-decreasing “memory effect”. The
chemistry that gives rise to this effect involves the formation of a thin layer of
material on the electrodes inside the battery, limiting the redox reaction needed
to generate electrical work.

For Item #4, one type of battery is dry cell, a cell without a fluid part known as
the Leclanche battery. This is a primary battery. The voltage produces by a dry cell is
1.5volts.The cell reaction of a Leclanche battery is shown below:

Anode: Zn(s) Zn2+(aq) +2e-

Cathode: 2NH4+(aq) + 2MnO2 +2e- Mn2O3 +2NH3(aq) + H2O(l)
Overall: Zn(s) +2NH4 (aq) +2MnO2(s)
+ Zn+2(aq)+2NH3(aq) +H2O(l)+ MnO2(s)

Read and Ponder

Batteries: Single-Use or Rechargeable?

A battery is a galvanic cell, or a series of combined galvanic cells, that can be
used as a source of electricity at a constant voltage. A battery contains battery
electrochemical cells that can store chemical energy to be converted to electrical
energy. A battery is similar with a galvanic cell that is, it is used to generate electricity
through the use of spontaneous reaction except that for batteries it is fully self-
contained that does not need a salt-bridge as a supplementary components Aside
from classifying batteries into primary and secondary, here in this module we will
discuss the other types of batteries and the chemistry behind and its components and
application.

Leclanche battery is the most common dry cell battery. This is battery or cell
without a fluid used in flashlights, transistor radios, MP3’s, and handheld videos. The
anode of the cell consists of a zinc can that is in contact with MnO 2 and an electrolyte.
The electrolyte, is composed of NH4Cl and ZnCl2 in water, to which starch is added
to thicken the solution to a
paste-like consistency to
prevent leak. (Figure 3F.1)

Figure 3F.1 A dry cell battery interior

(https//www.google.com)

In this battery, the cathode is the carbon rod, immersed in an electrolyte in the
core of the cell . The cell reactions are:

Anode: Zn(s) Zn2+(aq) +2e-

Cathode: 2NH4 (aq) + 2MnO2 +2e
+ - Mn2O3 +2NH3(aq) + H2O(l)
Overall: Zn(s) +2NH4 (aq) +2MnO2(s)
+ Zn+2(aq) +2NH3(aq) +H2O(l) +MnO2(s)

Other primary cells are also used as batteries for certain applications. In some
cases, the battery must be small like mercury batteries. For medical device like heart
pacemaker, a battery should not only be small but long lasting.

Mercury Battery is extensively use in medicine and electronic industries and is

more expensive than the common dry cell. Confined in a stainless steel cylinder,
the mercury battery consists of a zinc anode (amalgamated with mercury) in
contact with a strongly alkaline electrolyte with zinc oxide and mercury (II) oxide.
(Figure 3F.2)
 Figure
3F.2 A mercury
battery interior

(https//www.google.com)

The cell reactions in mercury battery are:

Anode: Zn(Hg) + 2OH-(aq) ZnO(s) + H2O(l) +2e-

Cathode: HgO(s) + H2O(l) +2e- Hg(l) + 2OH- (aq)

Overall: Zn(Hg) + HgO(s) ZnO(s) + Hg(l)

Note that there is no change in electrolyte composition during operation- the

overall cell reaction involves only solid substances. The mercury battery provides a
more constant voltage (1.35 V) than the Leclanche cell. It has a higher capacity and
longer life. These qualities make the Hg battery ideal for use in pacemakers, hearing
aids, electric watches and light meters.

As mentioned above, rechargeable batteries represent the secondary batteries.

Examples of such batteries are nickel-cadmium or ni-cad batteries, nickel-metal-
hydride batteries or lead storage batteries.

The Lead Storage Battery, sometimes known as lead-acid storage battery is

used in automobiles that consists of six identical cells joined together in a series.
Each cell has a lead anode and a cathode made of lead dioxide (PbO2) packed on
a metal plate. (Figure 3F.3)
 Figure 3F.3 A lead storage battery (https//www.google.com)

In the Lead storage battery, both the anode and the cathode are immersed in an
aqueous solution of H2SO4, which acts as the electrolyte. Its cell reactions are:

Anode: Pb(s) + SO42- PbSO4(s) + 2e-

Cathode: PbO2(s) + 4H+(aq) + 2SO42- +2e- PbSO4(s) + 2H2O(l)
Overall: Pb(s) +PbO2(s) +4H+ + SO42-(aq) PbSO4(s) + 2H2O (l)

Each cell produces 2 volts; a total of 12 volts from the six cells that powers the
ignition circuit of automobiles and its other electrical system. This battery delivers
large amounts of current for a short period of time, such as to start an engine. Unlike
the first two batteries above, it is rechargeable. When we say rechargeable, the battery
is reversing the normal electrochemical reaction by applying an external voltage at the
cathode and the anode. The reactions that reload the original materials are:

PbSO4(s) +2e- Pb(s) + SO42-(aq)

PbSO4(s) + 2H2O(l) Pb(s) + PbO2(s) +4H+(aq) + 2SO42-
Overall: 2PbSO4(s) + 2H2O(l) Pb(s) + PbO2(s) +4H+(aq) + 2SO42-(aq)

The overall reaction is the exact opposite of the normal cell reaction.

The Solid-State Lithium Battery is recognized to be the battery of the future,

employs a solid rather than an aqueous or a water-based paste, as the electrolyte
connecting the electrodes. The electrolyte is a polymer material that permits the
passage of ions but not electrons. The cathode is made of either TiS 2 or V6O12.
Its cell voltage can be as high as 3 V, and it can be recharged the same way as
the lead storage battery. Solid-state batteries have found use in pacemakers,
RFID and wearable devices. Figure 3E.4 illustrates how a lithium battery works.
 Figure 3F.4
Lithium
Battery and how it
works

https//www.google.com search

Fuel cells are sourced from fossils which is the major source of energy,
though conversion of such into electrical energy is highly inefficient process. Take
for example the combustion of methane:

CH4(g) + O2 CO2(g) + H2O(l) + energy

Combustion reaction are redox reactions, it is necessary to carry them out

directly by electrochemical way, thus greatly elevating the efficiency of power
production. This can purposely achieved by a device known as fuel cells, a galvanic
cell that requires a continuous supply to keep functioning.

Let us consider hydrogen-oxygen fuel cell. It consists of an electrolyte solution,

like potassium hydroxide (KOH) solution, and two-inert electrodes. Hydrogen and
oxygen are bubbled through the anode and cathode compartments and these are the
reactions that take place:

Anode: 2H2(g) + 4OH-(aq) 4H2O(l) +4e-

Cathode: O2(g) +2H2O(l) + 4e- 4OH-(aq)
Overall: 2H2(g) + O2(g) 2H2O (l)

The standard emf of the cell can be determined as follows (using the reduction
potential table).

E0cell = E0cathode - E0anode

= 0.40 V – (- 0.83 V)
 = 1.23 V

We can say that the cell reaction is spontaneous under standard-state

conditions. Lie platinum in the standard hydrogen electrode, the electrodes have
two-fold functions. They serve as electrical conductors, and they provide the
necessary surfaces for the initial decomposition of the molecules into atomic
species prior to electron transfer. They too serve as electrocatalysts.

Platinum, nickel, and rhodium are good electrocatalysts. This is one of the many
fuels cells and you can read more of fuel cells if you are interested.

See if you can do this

1. Explain the difference between a primary galvanic cell like dry cell and lead
storage cell. __________________________________________________
____________________________________________________________
____________________________________________________________
____________________________________________________________

2. List some advantages and disadvantages of hydrogen as a fuel.

_____________________________________________________________
_____________________________________________________________
_____________________________________________________________
_____________________________________________________________

3. Used the web to determine how fuel cells are used in space exploration. What
are the advantages of fuel cells that make this application so common?
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________

4. Discuss the advantages and disadvantages of fuel cells over conventional

power plants in producing electricity. ________________________________
______________________________________________________________
______________________________________________________________

Lesson 3.7 Corrosion

 Introduction

Experience tells us that a pile of nails left in the open rusts without contact with
another metal. We can infer that the half -cell reaction in the open redox reaction must
involve a non-metal. Corrosion is one instance where electrochemistry is at work with
practical consequences, although not a beneficial one. The electro-chemical reaction in
corrosion may be similar to those of the battery. However, the flow of the electrons is
not seized in a circuit, and the reaction products are generally not as useful as the
original materials. We see many examples of corrosion around us. Rust on iron,
tarnish on silver, and the green patina formed on copper and brass are a few of them.

Objectives
After mastering the topic of this module, you can:

1. define corrosion
2. explain how corrosion occurs and its impact to materials
3. discuss how corrosion can be prevented or minimized

Try this
Read some chemistry books or try to search in Internet regarding this topic
about corrosion and after which you can answer the questions that follow: You can
match your answer with my mine.

1. Shown are pictures of corrosion. Can you identify them?

 a) ________________________ b) _________________

c)

___________________

2. Among these pictures which is the most familiar of corrosion to you?

_______________________________________________________________

3. How does rust on iron occur? _______________________________________

_______________________________________________________________

_______________________________________________________________

Think Ahead
Let us determine how you have fared in the activity. Compare your answers
with mine. Here are my answers to the Activity part. For item #1 a) a tarnish silver
spoon b) copper metal coated with patina c) ship coated with rust.
 Item #2, among the figures presented, the most familiar of corrosion is the ship
coated with rust on the iron-constructed ship.

Fore Item #3, for iron (Fe) to rust oxygen and water must be present. The
reaction involved is that, an area of the metal’s surface serves as the anode, where
oxidation occurs. The electrons given up by Fe reduce atmospheric oxygen to water at
the cathode, which is another area of the same metal’s surface.

Read and Ponder

Corrosion: Cathodic or Anodic?
Corrosion refers to the deterioration of metals by electrochemical process. It is
such with practical consequences, although not a beneficial one. In this process, the
electrochemical reaction may be similar with those of the battery, but the flow of
electrons is not seized in a circuit, and the reaction products are generally not as useful
as the original material. Corrosion generally involves a slow combination of oxygen
with metals. Scientists have identified many different forms of corrosion. The rusting
of the ships’ surface, automobiles are examples of continuous corrosion and the most
common observable forms of corrosion. What conditions are necessary for this process
to occur? Another important form of corrosion is galvanic corrosion that happens
only when two metals contact each other in the presence of suitable electrolyte.
Thus, what’s so special about the contact of two metals? Other forms of corrosion tend
to require specific conditions, yet many of these situations are common in designs for
machinery. Crevice corrosion is a major problem in many large machines. When two
pieces of metal touch each other, they tend to leave a gap. At that gap, or crevice, the
metals are more likely to corrode.

Considerably, the most familiar and common example of corrosion is the

formation of rust on iron. What conditions are necessary for this process to occur? For
this process to occur oxygen gas and water must be present for iron to rust. the
reactions involve are that an area of the metal’s surface serves as the anode, where
oxidation occurs:

Fe(s) Fe2+(aq) + 2e-

The electrons donated by iron reduce atmospheric oxygen to water at the

cathode, which is another area of the same metal’s surface:

O2(g) + 4H+(aq) +4e- 2H2O(l)

The overall reaction is

2Fe(s) + O2(g) +4H+(aq) 2Fe2+(aq) + 2H2O(l)

 Using the standard reduction potentials, we can find the emf for this process.

E0cell = E0cathode –E0anode

= 1.23 V- (-0.44 V)

= 1.67 V

The positive standard emf means that the reaction will favor rust formation.
Note that the reaction happens in an acidic medium; the H + ions are supplied in part
by the reaction of atmospheric carbon dioxide with water to form H 2CO3.

The Fe2+ ions formed at the anode are further oxidized by oxygen:

4Fe2+(aq) + O2(g) +(4+ 2x) H2O(l) Fe2O3.xH2O(l) +8H+

This hydrated form of iron (III) oxide is known as rust. The amount of water
associated with iron oxide varies, so the formula is presented as Fe 2O3.xH2O. Figure
3G.1 shows the mechanism of rust formation.

Figure 3G.1 Mechanism on how rust is formed

The electrical circuit is completed by the migration of electrons and ions; this is
why rusting occurs so rapidly in salt water. In cold climates, salts like NaCl or CaCl 2
are spread on roadways to melt ice and snow are a major cause of rust formation on
automobiles.

Other metallic corrosion (Patina of copper and tarnish for silver)

Metallic corrosion is not limited to iron. Aluminum (Al) metal used to make
useful things to include airplanes, kitchen utensils, and beverage cans corrode readily,
but the corrosion product, Al 2O3 ultimately forms a protective layer that eliminates
further corrosion. In comparison with rust that forms on the surface of iron, however,
is too porous to protect underlying metal. Coinage metal such as copper and silver
corrode, however, much slowly. The redox reactions of these metals are:

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

Ag(s) Ag+(aq) +1e-

Copper forms a layer of copper carbonate (CuCO3) a green substance called

patina, that protects the metal underneath from further corrosion. In like manner,
silver ware that comes into contact with foodstuffs that tarnish silver, develops a layer
of silver sulfide Ag2S.

Corrosion Prevention of Metals

The topic on corrosion gives us an insight on the important factors to consider.

First, the thermodynamic of corrosion, with its large, negative free energy change,
suggests that it will be a pervasive reaction. Second, we observed that the natureof
galvanic corrosion allows us to predict what materials will corrode and in principle
we should be able to use the information to protect the material from corrosion.

These observations have been used to reducing corrosion in a number of ways like:

a. Coating is the most common ways of protecting a metal from corrosion. Some
of these ways is electroplating, painting. Painting is the most common way to
prevent corrosion of materials. But if the paint is scratched, pitted or dented to
expose even the smallest area of bare metal rust will form under the paint
layer.
The surface of iron metal can be made inactive by a process known as
passivation.
b. Cathodic Protection a process in which the metal that is to be protected from
corrosion is made the cathode in what amounts to a galvanic cell. By making
the iron a cathode, it is ensured that it cannot be an anode, and thus, it will not
corrode.
The tendency for iron to oxidize is greatly reduced when it is alloyed with
certain other metals. For example, in stainless steel, an alloy of iron and
chromium, a layer of chromium oxide is formed that protects the iron from
corrosion. A container of iron can be covered with a layer of another metal
like tin (Sn) or zinc (Zn), a tin can is made by applying a thin layer of tin over
iron. Rust formation is prevented as long as the tin layer remains intact. But,
once the surface has been scratched, rusting occurs rapidly. If we look up to
the standard reduction potentials based on the diagonal rule, we find that iron
acts as the anode and tin as the cathode. In the corrosion process:
 Sn2+(aq) +2e- Sn(s) E0 = -0.14 V
Fe2+(aq) +2e- Fe(s) E0 = -0.44 V

The protective process is different for zinc-plated, or galvanized, iron. Zinc is

more easily oxidized than iron based on table of standard potenitals.

Zn2+(aq) +2e- Zn(s) E0 = -0.76 V

So, even if a scratch is exposes the iron, the zinc is still attacked, where the zinc
serves as the anode and the iron as the cathode.

See if you can do this

1. What type of corrosion is associated with each of the following situations?
a. Two metals are touching each other. ____________________________
b. A small crack separate each other ____________________________
c. A metal automobile body rusts in the atmosphere. __________________

2. There are ways of preventing rust to form on a metal, one of which is the
cathode protection method. Discuss how cathode method protection is
carried out.
_______________________________________________________________
_____________________________________________________________________
_________________________________________________________
_______________________________________________________________
Lesson 3.8 Electrolysis

Introduction
Electrochemical reactions can also be driven by outside voltage sources in a
process called electrolysis in contrast to spontaneous reduction-oxidation reaction
that results to transformation of chemical energy to electrical energy. The
underlying principle and the process involving this topic is similar to that take place
in a galvanic cell. Electrolysis is another important aspect of electro chemistry, that
can also serve to produce energy, which we will discuss in this module, examples
and why this process is in contrast with spontaneous redox reaction, its importance
and application.

Objectives
At the end of this module, you can:

1. define electrolysis
2. describe how the process of electrolysis is carried out.
3. discuss the importance of electrolysis and its application
4. do calculations involving electrolytic reactions.

Try this
Try to search in the internet or any chemistry books about electrolysis and
then answer the following questions that follow:
 1. Water (H2O) cannot be broken down into its constituent parts under
normal conditions. Under what electrochemical process can water (H 2O)
be broken down into its respective constituents and describe how?_______
__________________________________________________________
__________________________________________________________
__________________________________________________________
2. What is electrolysis? _________________________________________
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Cite its importance and application______________________________

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3. Give the electrode reaction of the electrolysis of water both in the anode
and the cathode as well as the overall reaction.
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Think Ahead

Were you able to answer all the questions? If you did, good. Try to compare
your answer with mine and see how you fared….

1. Breaking the hydrogen and oxygen in water can be done under an

electrochemical process known as electrolysis in which both the hydrogen
and oxygen molecules separate into individual gases via an electrolytic cell
reactions. Each gas released is induced by an electrode in the presence of a
catalyst.

2. As we all know most reactions simply happen and we termed that as

spontaneous. However, there are reactions that will not occur naturally but
possible to occur if we induced something for it to occur and we refer this
as nonspontaneous. One such process is known as electrolysis a method in
which an electric current (energy) is used to force a reaction to occur.
It is commercially important as a step in the separation of elements from
naturally occurring sources such as ores using an electrolytic cell, and has
significant industrial applications for coating materials with metals. It also
used to prevent corrosion in an electrical apparatus. It can also use in
refining aluminum through passive electrolysis.
 3. For item #3, water is splitted by inducing electric current through the
presence of an electrolyte like acid solution to produce ions to conduct
electricity. The electrode reaction of the electrolysis of water both in the
anode and the cathode are:

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

Cathode: H+(aq) + e- 1/2H2(g)_______
Overall: 2H2O(l) 2H2(g) + O2(g)

Read and Ponder

Electrolysis: Spontaneous or Non-Spontaneous

The spontaneous direction of redox reaction is exploited in a galvanic cell to

produce electrical energy or we can use an external electric current to force a redox
reaction in the nonspontaneous direction. Electrolysis is defined as the process of
passing an electric current through an ionic solution or molten salt to produce a
chemical reaction. It can also be defined as the process in which electrical energy is
used to cause a nonspontaneous chemical reaction to occur. Instead of a galvanic cell,
the apparatus used in carrying the process of electrolysis is known as an electrolytic
cell.

Electrolytic cells are divided into two categories based on the nature of the
electrodes used, where if the electrodes are chemically inert materials that simply
provide a path for electrons, the process is referred to as passive electrolysis. When the
electrodes are part of the electrolytic reaction, we call it active electrolysis. Passive
electrolysis is used in industry to purify metals that corrode easily. Active electrolysis
is used to plate materials to provide resistance to corrosion.

Examples of Electrolysis: Molten Sodium Chloride (NaCl)

Sodium chloride is an ionic compound. In its molten state, it can be electrolyzed

to form sodium metal and chlorine. In molten NaCl the cations and anions, are the
Na+ and Cl- ions respectively. The electrolytic cell contains a pair of electrodes
connected to the battery. The battery serves as an “electron pump”, driving the
electrons to the cathode, where reduction occurs, and withdrawing electrons from the
anode, where oxidation occurs. The reactions involve at the electrodes which serves
as major source of sodium metal and chlorine gas, are:

Anode (oxidation): 2Cl-(l) Cl2 (g) +2e-

Cathode (reduction): 2Na+ +2e- 2Na(l)_____
Overall: 2Na + 2Cl-(l) 2Na (l) + Cl2(g)
 Theoretically, the E0 for the overall process is about -0.4 V, meaning the reaction
is nonspontaneous. This means further that, a minimum of 4 V must be supplied by
the battery to allow reaction to proceed. Aqueous solution of sodium chloride (NaCl)
can likewise be electrolyzed. You can do a research on the electrolysis on this.

Electrolysis of Water- Its importance

Why does a beaker of water placed under normal conditions (25 0C and 1atm)
will not naturally break into Hydrogen and Oxygen? It is because the ΔG 0 for the
reaction is a large positive quantity.

H2O(l) H2(g) + O2(g) ΔG0 = 474.4 kJ/mol

Nonetheless, the breakdown of H2O into its component parts can be done by
inducement. The electrolytic cell consists of a pair of electrodes made of a nonreactive
metal such as platinum, immersed in water. When the electrodes are connected to a
battery, no reaction does take place because there are no enough ions in the pure water
state to bring much of an electric current. Why?
On the other hand, reaction occurs readily in a I M H2SO4 solution because there
are sufficient number of ions to conduct electricity. Gas bubble will immediately
appear at both electrodes. Figure 3H.1 shows the electrode reactions:

The reaction in the anode is:

2H2O(l) O2(g) + 4H+(aq) +4e-

While at the cathode is: H+(aq)

+ e- 1/2H2(g)

Figure 3H.1 Electrolysis of H2O

 The overall reaction of H2O is shown by:

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

Cathode(reduction): 4H+(aq) + e- 1/2H2(g)__________
Overall: 2H2O(l) 2H2(g) + O2(g)

Application of Electrolysis: Electroplating

The process of depositing a thin coat of metal by using electric current is called
electroplating. One placed where we can find electroplated products are the batteries.
The electron collector that provides the external connection for the anode is
electroplated. The metal coating gives this piece of a battery both corrosion protection
and desirable conducting properties. Small parts such as this are plated in bulk by
placing them in a barrel and then placing the barrel in the electrolyte solution. So, how
does this work? Consider the plating of silver to make parts for electrical devices. The
solution from which silver is plated contains CN- (aq) ions which form complexes with
silver. The need for uniform coating makes this step important. The an ode and
cathode in electroplating are as follows:

Anode: Ag(s) + 2CN-(aq) Ag(CN)2(aq) +e-

Cathode : Ag(CN)2 -(aq) +e- Ag(s) +2CN-(aq)

Note that the reactions are reverse of each other is observed is used in most of
the electroplating operations. This is an active kind of electroplating. Galvanic cells
cannot be constructed from such combination- it would have a cell potential of zero-
the fact that an external current drives the electrolysis means that the cell potential is
not critical. Most electroplating processes are designed to run at low voltages but,
hence a zero cell potential is advantageous.
Electrolysis and Stoichiometry

To silver plate an inside of a nut, it is important to know how much material is

being deposited on the surface. If the silver coating is too thick, the nut might not fit
the bolt- threads might become too narrow. So, in electroplating, it is important to
carefully used controlled amounts of materials. But what is the source of information
needed to consider?

The quantitative handling of electrolysis was developed by Faraday. According

to Faraday the mass of product formed at an electrode is proportional to both the
amount of electricity transferred at the electrode and the molar mass of the substance.
The Faraday constant, which is the charge of 1 mole of electrons:F=96,485 C mol -1.
Current vs. Charge

In an electrolytic cell, the current is measured in amperes (A), the observation

is the flow of charge for a period of time. The basic unit of current the amperes (A) is
a derived unit defined as coulomb /sec: 1 C s -1. If a known current passes through an
electrolytic cell for a given time, the charge can easily be computed.

Charge = current x time

Q = I x time

The Q is in coulombs, I in amperes (coulombs/sec), and t in seconds.

So if we can calculate the charge that passes through the electrolytic cell, we
can determine the number of moles of electrons that pass. Assuming we know
how many electrons were needed to reduce each metal cation, we can
calculate the number of moles of material plated. Figure 3H.2 shows the steps
involved in calculating the stoichiometric amounts of substances yielded in
electrolysis.

Current Charge Number Moles of Grams of

Ampere in moles of substance subs.
and time coulomb electrons reduced reduced
or or
oxidized oxidized

Figure 3H.2 Steps involved in computing for quantities of substances

reduced or oxidized in electrolytic process.

See if you can do this

1. In a process called “flash” electroplating, a current of 2.50 x 10 3 A passes
through and electrolytic cell for 5.00 minutes. How many moles of electrons
are driven through the cell?

2. A n aqueous Na2SO4 solution is electrolyzed. If the product formed at the

anode and cathode are oxygen and hydrogen gas respectively, describe the
electrolysis in terms of the reactions at the electrode.
3. An electrolysis cell that deposits gold (from (Au+(aq)) operates for 15.0
minutes at a current of 2.30 A. What mass of gold is deposited?

4. Suppose that you have a part that requires a tin coating. You’ve calculated
that you need to deposit 3.60 g of tin to achieve an adequate coating. If your
electrolysis cell (using Sn+2) runs at 2.00A, how long must you operate the cell
to obtain the desired coating?

-End-