Slide 1

Electrochemistry has something to do with electricity and chemistry.

Slide 2

ELECTROCHEMISTRY

• the study of the relationships between chemical reactions and

electricity

1. Certain chemical reactions can create electricity

2. Electricity can make certain chemical reactions happen that
wouldn’t happen otherwise

• Electricity – the movement of electrons through something

There are two main ways that chemical reactions and electricity interact:
1. Certain chemical reactions can create electricity. This is a spontaneous process and happens on its own.
2. Electricity can make certain chemical reactions happen that wouldn’t happen otherwise. Through the
help of electricity, a nonspontaneous chemical reaction can happen.

Electricity is just the movement of electrons through “something” (e.g. wire, light bulb, battery, etc.).

Slide 3

1. Certain chemical reactions can create electricity.

• These chemical reactions are Oxidation-Reduction Reactions (Redox)

2. Electricity can make certain chemical reactions happen that wouldn’t

happen otherwise
• Electricity can force electrons to move between atoms to make redox
reactions to happen

1) In redox reactions, there is movement of electrons or electrons move between atoms. A redox reaction
is a simultaneous process wherein one atom loses its electrons (oxidation) and the other atom gains
(reduction) the electron. Electricity is produced by movement of electrons from substance A to
substance B through a wire between the substances.

2) In cases where a substance does not readily lose its electrons (e.g. “hard to get” substance C), a battery
can be connected between substance C and D to pull the electrons from C and push it to D.
Slide 4

1. CERTAIN CHEMICAL REACTIONS CAN CREATE ELECTRICITY

“The energy released in a spontaneous redox reaction may be used to

perform electrical work.”

• Cell – an electronic device that converts the electrical energy to

chemical energy or chemical energy to electrical energy

Voltaic or Galvanic Cell

• Utilizes spontaneous redox reaction to produce electricity
• Devices in which electron transfer occurs via an external circuit rather
than directly between reactants

The voltaic or galvanic cell uses the first type of interaction where certain chemical reactions create electricity. This utilizes
spontaneous redox reaction to produce electricity. It is spontaneous since one atom pulls the electrons of another atom
to itself and the latter atom naturally releases its electrons.

Slide 5

VOLTAIC OR GALVANIC CELL

This is a diagram and an actual picture of a voltaic cell of a Zn-Cu system. There are two solutions, ZnSO4 (clear) and CuSO4
(blue) in separate beakers. A Zn metal and Cu metal are inserted into the ZnSO4 and CuSO4 solutions, respectively. These
metals are connected to each other with a wire and a voltmeter in between. Electricity is produced in this chemical
reaction as can be seen in the reading at the voltmeter which is 1.10 V. The two solutions are also connected with a salt
bridge. As can be seen in the diagram, the Zn side undergoes oxidation while the Cu side undergoes reduction.

Slide 6
 GALVANIC CELL

Neutral cation

This process happens on its own → spontaneous

How will we know if a reaction will occur spontaneously?

Compared to copper, zinc has a weaker pull for electrons that is why it spontaneously loses its electrons to
Copper or its ion (Cu2+), which has a stronger pull for electrons. Zinc loses its electrons, thus it undergoes
oxidation; Cu2+ gains electrons, so it is reduced.
This process happens on its own or it is spontaneous. Why is this spontaneous? How will you know that the
electrons will move from Zn to Cu? How will we know that Cu has a stronger pull of electrons?
Slide 7

STANDARD
REDUCTION
POTENTIALS

• The stronger the

pull of electrons

This is a table of the Standard Reduction Potentials (E°red) of the reduction half-reactions of a few atoms/molecules. The
more positive the E°red (in Volts) the stronger the pull of electrons. The E°red of Cu is +0.34 V while that of Zn is -0.76 V.
Since Cu has a more positive E°red than Zn, thus, Cu has a stronger pull of electrons and as a result Zn will spontaneously
give its electrons to Cu.

Slide 8
 VOLTAIC/GALVANIC CELL CONSISTS OF:
1. Electrode – the two metals that are connected by the external circuit (Zn and Cu)
anode – where oxidation occurs (AO; An Ox) – Zn
cathode – where reduction occurs (CR; Red Cat) – Cu

2. Oxidation half-reaction (anode): Zn(s) → Zn2+(aq) + 2e-

Reduction half-reaction (cathode): Cu2+(aq) + 2e- → Cu(s)

Overall rxn: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Zn is spontaneously oxidized to Zn2+ while

Cu2+ is spontaneously reduced to Cu

3. Salt bridge – used to complete the circuit

A voltaic cell consists of 3 parts – the electrodes, the redox half-reactions, and the salt bridge.

• The electrodes, which are the two metals connected by the wire, are classified as the anode or the cathode. Oxidation
occurs at the anode (AO or An Ox) and reduction occurs at the cathode (CR or Red Cat). In the Zn-Cu system, the
electrons flow from Zn to Cu. The Zn is the anode since it undergoes oxidation and Cu is the cathode since it undergoes
reduction.
• Oxidation occurs at the anode so the oxidation half-reaction is Zn(s) → Zn2+(aq) + 2e-; Reduction occurs at the cathode
so the reduction half-reaction is Cu2+(aq) + 2e- → Cu(s). Take note of their physical states. These half-reactions can be
summed up to make the overall reaction Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s).
• The salt bridge is used to complete the circuit and its importance will be discussed later.
COMPONENTS OF A VOLTAIC CELL AND HOW IT WORKS
Slide 9 Slide 10

VOLTAIC/GALVANIC CELL: VOLTAIC/GALVANIC CELL:

The two solutions, ZnSO4 and CuSO4, in separate beakers. Zn and Cu metal connected by a wire are inserted into each.

Slide 11 Slide 12

VOLTAIC/GALVANIC CELL: VOLTAIC/GALVANIC CELL:

The electrons spontaneously flow from Zn to Cu. Electricity is produced in this system, it can light up a bulb.
Slide 13 Slide 14

VOLTAIC/GALVANIC CELL: VOLTAIC/GALVANIC CELL:

A salt bridge connects the two solutions. Now, let us magnify the cell. The metals are neutral atoms (Zn and Cu) while the
solutions are made up of ions (Zn2+ and Cu2+). We will not show the SO42- ions in the solution for now.

Slide 15 Slide 16

VOLTAIC/GALVANIC CELL: VOLTAIC/GALVANIC CELL:

Gives off its electrons Gives off its electrons

Since Zn has a weaker pull for electrons, one Zn atom in the metal (encircled black) will give off its electrons. The two
electrons (encircled red) will travel through the wire to the Cu metal.

Slide 17 Slide 18

VOLTAIC/GALVANIC CELL: VOLTAIC/GALVANIC CELL:

Gives off its electrons Gives off its electrons

The Cu2+ in the solution wants the two electrons because it wants to be stable, so it gains them. While the Zn that loses its
two electrons become Zn2+ so it becomes part of the solution. Neutral atoms make up the solid metal, while metal ions
usually dissolve in water.

Slide 19 Slide 20

VOLTAIC/GALVANIC CELL: VOLTAIC/GALVANIC CELL:

Gives off its electrons Gives off its electrons

As the reaction progresses, more and more Zn(s) lose their electrons and become Zn2+(aq), and more and more Cu2+(aq)
gain the electrons so they become Cu(s) and attach to the Cu metal. Eventually, the Zn anode since it loses becomes
“slimmer” and the Cu cathode since it gains become bigger.
SALT BRIDGE
Slide 21 Slide 22

VOLTAIC/GALVANIC CELL: Salt bridge – helps to balance out the charge VOLTAIC/GALVANIC CELL: Salt bridge – helps to balance out the charge

Charges balances out Charges balances out Charges balances out

Charges balances out

The salt bridge helps to balance the charges. Now the SO42- are now shown in the solutions. As more Zn turn to Zn2+ and
more Cu2+ turn to Cu, the positive charge builds up in the anode solution while the negative charge builds up in the cathode.

Slide 23 Slide 24

VOLTAIC/GALVANIC CELL: Salt bridge – helps to balance out the charge VOLTAIC/GALVANIC CELL: Salt bridge – helps to balance out the charge

Charges balances out Charges balances out Charges balances out

Charges balances out

The salt bridge is filled with a salt solution (e.g. NaCl). Either ends, stoppered by cotton plugs, are dipped in either solutions.
The negative ions, Cl-, travels to the anode, while the positive ions, Na+, travels to the cathode to neutralize the charges.
Slide 25

CELL DIAGRAM/NOTATION:
ANODE – oxidation; placed at the LEFT of the diagram
CATHODE – reduction; placed at the RIGHT of the diagram

Boundary between different phases: | (single vertical line)

Boundary between half cell compartments, e.g. salt bridge:
|| (double vertical lines)

Species in aqueous solution are placed on either side of ||

Different species in same solution are separated by a comma

Cu-Zn system: Zn(s)|Zn2+(aq)||Cu2+(aq)|Cu(s)

Anode: Salt Cathode:
Half cell bridge Half cell
(Oxidation) (Reduction)

If we write the voltaic cell in paper, we call it the cell diagram or cell notation (boxed red). The anode is written at the left
side, while the cathode is written at the right side. The electrodes are separated by the salt bridge, symbolized by two
vertical lines (||). The phases of each electrode is separated by a single vertical line (|).
Slide 26

RULES ON VOLTAIC/GALVANIC CELL:

1. ANODE: oxidation occurs; electrons are products; negative

2. CATHODE: reduction occurs; electrons are reactants; positive
3. The flow of electrons is from anode to cathode and it requires an
external wire since electrons cannot flow through the solution.
4. The transfer of ions through a salt bridge maintains electrical
neutrality for the two compartments

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

Cathode: positive (Cu2+(aq) + 2e- → Cu(s))
Electron flow

In a voltaic cell, the anode where oxidation occurs is negative, and the cathode where reduction occurs is positive. The
flow of electrons is from the anode to the cathode and it requires an external wire to produce electricity. The salt bridge
maintains the electrical neutrality of the two compartments.
Slide 27

SUMMARY: The voltaic cell of the Zn-Cu system utilizes the spontaneous redox reaction to produce electricity. This
chemical reaction is spontaneous since Cu, which has a stronger pull for electrons, oxidizes the Zn so that it loses it
electrons naturally because it has a weaker pull for electrons than Cu. Oxidation happens at the Zn anode [Zn(s) →
Zn2+(aq)] while reduction happens at the Cu cathode [Cu2+(aq) → Cu(s)].

Slide 28

The electricity produced by the Zn-Cu system is 1.10 V. As reaction progresses, the Zn anode will significantly lessen in
mass while the Cu cathode will significantly increase in mass.
Slide 29

Zn metal in CuSO4 solution

A strip of Zn metal is in contact with a CuSO4 solution. Even though they are not connected by a wire, the redox reaction
will still be spontaneous. As the reaction progresses, eventually, the blue color of the Cu2+(aq) ion fades and the Cu2+ will
be converted to Cu (black deposits on Zn). At the same time, Zn begins to dissolve. Do you think this reaction can create
electricity if they are not connected with a wire?

Slide 30

EXAMPLES OF VOLTAIC/GALVANIC CELL:

Non-rechargeable battery: A, AA, AAA

Slide 31

2. ELECTRICITY CAN MAKE CERTAIN CHEMICAL REACTIONS

HAPPEN THAT WOULDN’T HAPPEN OTHERWISE
- ELECTROLYSIS

Electrolytic Cell
• nonspontaneous reactions that require
an external circuit or outside electrical
source to drive the non-spontaneous
redox reaction
• Electrons are forced to flow from the
anode to the cathode
• Anode: oxidation; Cathode: reduction
(as in voltaic cell)
• Anode: positive; Cathode: negative
(opposite in voltaic cell)

The second type of interaction where electricity can make certain chemical reactions happen that would not happen
otherwise is possible through electrolysis and its cell is called the electrolytic cell. In this type of cell, a nonspontaneous
reaction can occur through the help of an external circuit or outside electrical source such as a battery. The electrodes are
forced to flow from the anode to the cathode. The electrolytic cell is similar with a galvanic cell such that the anode is
where oxidation occurs, and the cathode is where reduction occurs. But the anode in the electrolytic cell is positive while
the cathode is negative.

Slide 32

ELECTROLYSIS
H2O → H2(g) + O2(g)

Does not happen on its own → nonspontaneous

Take a look at the equation above. H2O does not break down to H2(g) and O2(g) naturally thus, this is a nonspontaneous
process. More evidence of this can be seen by the change in their oxidation numbers (ON). The H gains electrons so it is
reduced (ON is from +1 to 0), while O loses its electrons, so it is oxidized (ON from -2 to 0). For a spontaneous process to
occur, oxygen must give it electrons to hydrogen. But that could never happen spontaneously since oxygen has a stronger
pull for electrons while hydrogen has a weaker pull, as can be seen in their standard reduction potentials (E°red) at the next
table. Thus, in order for this to happen, electrolysis should be performed.
Slide 33

STANDARD
REDUCTION
POTENTIALS

• The stronger the

pull of electrons

The standard reduction potentials (E°red) of Oxygen (O2) and Hydrogen (H2). Oxygen has a more positive E°red compared to
hydrogen thus, it has a stronger pull for electrons.

Slide 34

ELECTROLYTIC CELL:

Anode – oxidation; positive

Cathode – reduction; negative

In an electrolytic cell, the two electrodes are dipped in the same solution. The electrons from the anode are pulled by an
external circuit (e.g. battery) and pushed to the cathode. The anode is still the site for oxidation and the cathode for
reduction. But the anode now is the positive terminal while the cathode is the negative terminal.
Slide 35

ELECTROLYSIS OF WATER: 2H2O → 2H2 + O2

Anode: positive (remove electrons)
2H2O → O2 + 4H+ + 4e-

Cathode: negative (supply electrons)

2H2O + 2e- → H2 + 2OH-

Bubbles begin to go up

Components of a Simple Electrolytic Cell: The beaker is filled with water and a small amount of electrolyte, such as sulfuric
acid (H2SO4). The electrodes (e.g. carbon rod, pencil lead) are connected to a battery with a wire. The anode, where O2
will be produced, is connected to the positive terminal while the cathode, where H2 will be produced, is connected to the
negative terminal. The electrodes are inserted inside separate test tubes that are placed upside down into the solution.
Once the reaction starts, there will be bubbling inside the test tubes. After some time, it can be observed that there is
more empty space in the test tube of the cathode. This is because there is twice as much H 2(g) produced as O2(g) as can
be seen in the balanced equation above. For every 2 moles of H2O, 2 moles of H2 are produced while only 1 mole of O2 is
produced. The electricity produced here 1.15 V, enough to light up a small indicator LED.

Slide 36

Video demonstration of electrolysis and hydrogen fuel cell.

Slide 37

ELECTROLYSIS OF OTHER AQUEOUS SOLUTIONS:

1. Decomposition of molten NaCl

2. Electrolysis of NaF

EXAMPLES OF ELECTROLYTIC CELL:

Rechargeable battery (cellphones, laptop, etc.) or electroplating.

While the battery is being used in the device it is a galvanic cell function (using the
redox energy to produce electricity). While the battery is charging it is an
electrolytic cell function (using outside electricity to reverse the completed redox
reaction).

Rechargeable batteries are galvanic cell when it is being used but an electrolytic cell when it is charging.

Slide 38

ELECTROPLATING:
- The coating of one type of metal with another type of metal
- Ex. Cu coated with Ag

- Electroplating is a type of electrolysis

Electroplating or the coating of one type of metal with another type of metal is electrolysis. Take for example, Cu coated
with silver, Ag, which is a very common practice in creating fancy or fake jewelry. This is electrolysis since Cu has a lower
E°red than Ag. For it to be spontaneous, Cu should coat Ag but we want it to be the other way around, so electrolysis is
employed. The Ag(s) is the anode, the Cu(s) (e.g. ring, piece of jewelry) is the cathode, and the solution has Ag 2+(aq) ions.
The Ag(s) is oxidized and the electrons travel through the battery to Cu(s). The electrons are gained by the Ag2+(aq) in the
solution and the Ag2+(aq) becomes Ag(s) which sticks to the surface of the Cu(s). As the reaction progress, more Ag(s) are
being oxidized to Ag2+(aq) which are in turn reduced to Ag(s) at the surface of the Cu(s). The reaction can be stopped when
the Cu metal is now fully coated with Ag. So now, do not wonder why some silver or gold jewelry are very cheap. It is
because they are only coated. They are not the real ones but only “gold-plated.”
Slide 39

GALVANIZATION:

- The process of applying a protective zinc coating to steel or iron, to

prevent it from rusting

Another common material being used nowadays is what we call “galvanized” metals. It is also coating metal to another
metal but this time it is a spontaneous process, thus, the name, galvanization. For example, Zn coats Fe. Zn has a lower
E°red than Fe the reaction is spontaneous and Zn can coat Fe.

Slide 40

SUMMARY ON GALVANIC AND ELECTROLYTIC CELL

The first type of cell where certain chemical reactions can create electricity is called the voltaic of galvanic cell. The second
type of cell where electricity can make certain chemical reactions happen that wouldn’t happen otherwise is the
electrolytic cell.
Slide 41

CELL POTENTIAL UNDER STANDARD CONDITIONS

Why do electrons transfer

spontaneously from Zn to Cu2+?
Why are there reduction potentials?
How was it determined?

DIFFERENCE IN POTENTIAL ENERGY

Why do electrons transfer spontaneously from Zn to Cu2+? How are reduction potentials determined? In a simple
sense, we can compare the electron flow to the flow of water in a waterfall. Water flows spontaneously over a
waterfall because of a difference in potential energy between the top of the falls and the bottom. In a similar
fashion, electrons flow spontaneously through an external circuit from the anode of a voltaic cell to the cathode
because of the difference in potential energy. The electrons flow spontaneously toward the electrode with the
more positive electrical potential.

Slide 42

Potential Difference – the difference in potential energy per electrical charge

between two electrodes; measured in volts (V)

1 V = potential difference required to impart

1 joule (J) of energy to a charge of coulomb (C).

Cell potential, Ecell – the potential difference between the two electrodes of a
voltaic cell
- Also called the electromotive (“causing electron motion”) force or emf
Standard cell potential or standard emf, E°cell – cell potential at standard
conditions (25 °C, 1 atm, 1 M concentrations for reactants and products in solution)

Ex. Zn(s) + Cu2+(aq, 1 M) → Zn2+ (aq, 1 M) + Cu(s) E°cell = +1.10 V

The potential difference between the two electrodes of a voltaic cell is called the cell potential, E cell. Because
the potential difference provides the driving force that pushes electrons through the external circuit, we also
call it the electromotive force, or emf. Because Ecell is measured in volts, it is also commonly called the voltage
of the cell. The cell potential under standard conditions is called either the standard cell potential or standard
emf and is denoted E°cell.
Slide 43

STANDARD REDUCTION POTENTIALS

Standard cell potential for Zn and Cu2+:
Zn(s) + Cu2+(aq, 1 M) → Zn2+ (aq, 1 M) + Cu(s) E°cell = +1.10 V

Voltaic cell standard cell potential depends on the particular cathode and
anode half-cells

Cell potential – difference between two half-cell potentials

The potential for the REDUCTION reaction is the chosen potential, by

convention.
Thus, standard half-cell potentials are tabulated for reduction reactions:
Standard Reduction Potentials, E°red

The E°cell depends on the particular cathode and anode half-cells. For example, in the Zn-Cu system, the E°cell is
1.10 V. But if we change Zn or change Cu, the E°cell will no longer be 1.10 V. We could, in principle, tabulate the
E°cell for all possible anode/cathode combinations but that is impractical, and it is not necessary to undertake
such an arduous task. The solution? Assign a standard potential to each half-cell and use these half-cell potentials
to determine E°cell. By convention, the potential associated with each electrode is the potential for reduction at
that electrode, regardless if it is experiencing oxidation or reduction in the actual reaction. Thus, standard half-
cell potentials are tabulated for reduction reactions (see table of next slide), which means they are standard
reduction potentials, E°red: E°cell = E°red (cathode) - E°red (anode). Half-reactions, however, are reversible being
able to operate as either reductions or oxidations.
Slide 44

E°cell = E°red (cathode) - E°red (anode)

Reference half-reaction: H2+(aq) to H2(g)

2H+(aq, 1M) + 2 e- → H2(g, 1atm) E°red = 0 V
- Called the Standard Hydrogen Electrode (SHE)

Ex. Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)

Zn (anode), H+ (cathode), E°cell = +0.76 V
E°cell = E°red (cathode) - E°red (anode)
+0.76 V = 0 V - E°red (anode)
E°red (anode) = -0.76 V

Note: We write the reaction as reduction whenever we

assign an electrical potential to a half-reaction.

It is not possible to measure the E°red of a half-reaction directly but we can determine the E°red of other half reactions
relative to a reference value. The reference half-reaction is the reduction of H+(aq) to H2(g) and is called the standard
hydrogen electrode (SHE). It is assigned an E°red of 0 V. Using E°cell = E°red (cathode) - E°red (anode), we can determine
the E°red of Zn. The E°cell of the Zn-SHE system is +0.76 V, and by definition, the E°red of SHE is 0 V, thus, the E°red
(anode) of Zn is -0.76 V.
Slide 45

A SHE consists of a platinum wire connected to a piece of platinum foil covered with finely divided platinum that serves
as an inert surface for the reaction. The SHE allows the Pt to be in contact with both 1 M H +(aq) and a stream of hydrogen
gas at 1 atm. The SHE can operate as either the anode or cathode of a cell, depending on the nature of the other electrode.
The cell potential of the Zn-SHE system is 0.76 V.

Slide 46

Standard reduction potential - Intensive property

→changing the stoichiometric coefficient in a half-reaction does not affect the
value of the standard reduction potential
→ the reduction of 10 mol Zn2+ is the same as that for 1 mol Zn2+

Ex. Calculating E°red from E°cell

For the reaction: Zn(s) + Cu2+(aq, 1 M) → Zn2+ (aq, 1 M) + Cu(s) E°cell = 1.10V
2+
Given that the standard reduction potential of Zn to Zn(s) is -0.76 V, calculate the
E°red for the reduction of Cu2+ to Cu:
Cu2+ (aq, 1M) + 2 e- → Cu(s)

E°cell = E°red (cathode) - E°red (anode)

E°red (cathode) = 1.10 V – 0.76 V = 0.34 V

The E°red of other half-reactions can be determined using E°cell = E°red (cathode) - E°red (anode). There is a more
complete list of standard reduction potentials found in the Appendixes of textbooks.
Slide 47

If E°red > 0 (positive)

- greater tendency for reduction to occur
under standard conditions

If E°red < 0 (negative)

- Lesser tendency for reduction to occur
relative to SHE

For each half-reaction, the E°red provides a measure of the tendency for reduction to occur: The more positive the
value of E°red, the greater the tendency for reduction under standard conditions. Consequently, the more
negative the value of E°red, the greater tendency for oxidation under standard conditions. In the Zn-Cu system,
the E°red of the cathode, Cu (+0.34 V), is more positive than that of the anode, Zn (-0.76 V). Thus, electrons flow
spontaneously through the external circuit from the electrode with the more negative E° red to the electrode with
the more positive E°red. Furthermore, Cu was reduced and Zn was oxidized.

Slide 48

STRENGTHS OF OXIDIZING
AND REDUCING AGENTS
1. The more positive the E°red, the stronger
the oxidizing agent or it is more easily
reduced (written in the table as
reactant)
2. The more positive the E°red, the more
spontaneous is the reduction reaction
(oxidation reaction is less spontaneous)
3. The more negative the E°red, the
stronger the reducing agent or more
easily oxidized
4. The more negative the E°red, the more
spontaneous is the oxidation reaction
(reduction reaction is less spontaneous)

The substance reduced (SR) is the oxidizing agent (OA). The substance oxidized (SO) is the reducing agent (RA).
Slide 49

F2(g), having the most positive E°red, is the easiest to reduce or the strongest oxidizing agent while Li(s), having the most
negative E°red, is the most difficult to reduce or is the weakest oxidizing agent. The reverse reaction, however, is the
opposite. In terms of strongest reducing agent or easiest to oxidize, Li(s) being at the bottom of the list is the strongest RA
and easiest to oxidize and F2(g), being at the top of the list is the most difficult to oxidize or the weakest RA.

Slide 50

Example:

1. Choose from each pair the stronger

oxidizing agent:
a. H+ and Li+
b. Fe3+ and I2
c. Ag+ and Ni2+

2. Arrange the following in increasing order of

reducing power: NO3-, Ag+, Cr2O72-

3. A voltaic cell is based on the ff:

Cd2+(aq) + 2e- → Cd(s) E°red = -0.430 V
Sn2+(aq) + 2e- → Sn(s) E°red = -0.136 V

Determine (a) the half-reactions that occur at

the cathode and the anode, and (b) the
standard cell potential

1) a. H+ b. Fe3+ c. Ag+ are the stronger OA because they have more positive E°red values.
2) Increasing reducing power or reducing agent: Cr2O72- < NO3- < Ag+. Since Cr2O72- has the most positive
E°red, thus, it has the least reducing power.
3) The two half-reactions reactions are written as reduction reactions. The hint for (a) is the identity of the
cell which is voltaic cell. This means that the anode should be the one with the most negative E°red.
Thus, Cd(s) is the anode and Sn(s) is the cathode. We write the half-reaction at the anode as oxidation
reaction: Cd(s) → Cd2+(aq) + 2e-, and the cathode as reduction: Sn2+(aq) + 2e- → Sn(s).
b. E°cell = E°red (cathode) – E°red (anode) = -0.136 V – (-0.430 V) = 0.294 V
Slide 51

FREE ENERGY AND REDOX REACTIONS

E° = E°red (reduction process) - E°red (oxidation process)

1. A positive E indicates a spontaneous process

2. A negative E indicates a nonspontaneous process

E° = standard conditions
E = nonstandard conditions

Voltaic cells use spontaneous redox reactions to produce a positive cell potential. We can use this fact together with half-
cell potentials to decide whether a given redox reaction is spontaneous. It is useful to make the E°cell equation more
general so that we can see how it pertains to general redox reactions, not just reactions in voltaic cells. We have dropped
the “cell” to indicate that the calculated emf does not necessarily refer to a voltaic cell. Also, we have generalized the E°red
by using the terms reduction and oxidation rather than cathode and anode. We can now make a general
statement about the spontaneity of a reaction and its associated emf, E: A positive value of E indicates a
spontaneous process; a negative value of E indicates a nonspontaneous process. We use E to represent the emf
under nonstandard conditions and E° to indicate the standard emf.

Slide 52

Example:

1. Determine whether the ff reactions

are spontaneous under standard
conditions:
a. Cu(s) + 2H+(aq) → Cu2+(aq) + H2(g)
b. Cl2(g) + 2I-(aq) → 2 Cl-(aq) + I2(s)

E° = E°red (reduction) - E°red (oxidation)

1a) Cu undergoes oxidation (Cu → Cu2+) while SHE undergoes reduction (2H + → H2). E° = E°red (reduction) – E°red
(oxidation). E° = 0 V – (+0.34 V) = -0.34V. Thus, it is nonspontaneous in the direction written and spontaneous at the
reverse reaction.
1b) Cl undergoes reduction (Cl2 → 2Cl-) while I undergoes oxidation (2I- → I2+). E° = 1.36 V – (+0.54 V) = 0.82 V. Spontaneous
in the forward reaction. This could be used to build a voltaic cell.
Slide 53

EFFECT OF CONCENTRATION ON CELL EMF

• As a voltaic cell is discharged, the reactants are consumed and the

products are generated, so concentrations change.

• The emf progressively drops until E = 0 V.

• A voltaic cell is functional until E = 0 at which point equilibrium has been
established (we say that the cell is dead)

The fate of a battery. When does a battery die?

Slide 54

CELL POTENTIAL UNDER NONSTANDARD CONDITIONS

- First derived by Walther Nernst
Where:
n = number of moles of electrons transferred
F = Faraday’s constant. 96,485 J/V-mol
∆G = ∆G° + RTlnQ E = emf of a redox rxn

∆G = -nFE (relationship between emf and the free-energy change)

-nFE = -nFE + RT ln Q
E = E° - lnQ Nernst Equation
E = E° - log Q
At 298 K, E = E° - log Q

The change in Gibbs free energy, ΔG, is a measure of the spontaneity of a process that occurs at constant temperature
and pressure. The emf, E, of a redox reaction also indicates whether the reaction is spontaneous. The relationship between
emf and the free-energy change is ΔG = nFE. ΔG° is also related to the equilibrium constant, Q, thus, at 298 K, the E is
equal to the equation above (boxed red). Remember only that equation.
E = emf at nonstandard conditions, E° = emf at standard conditions
n = number of moles of electrons transferred in the redox equation
Q = equilibrium constant; for the reaction aA+ bB → cC + dD
[ ]𝑐 [𝐷]𝑑
Q= where [ ] is the concentration of the substance; only applicable for solutions
[𝐴]𝑎 [𝐵]𝑏
Slide 55

Example:
What is the E for the following reaction if [Zn 2+] = 0.050M and [Cu2+] = 5.0 M?
E° = 1.10 V.

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

E = E° - log Q

[ ]
n = 2, E = 1.10 V - log
[ ]
E = 1.10 V - log
E = 1.16 V

Q is only applicable to solutions and not to solids.

The E is greater than the E°. Thus, increasing [Cu2+] or the reactant and decreasing [Zn2+] or the product increases the
emf of the cell relative to std conditions (E° = 1.10 V).

Slide 56

NOTE:
• Increasing the concentration of reactants or decreasing the concentration of
products increases the driving force of the reaction, resulting in a higher emf.

• Decreasing the concentration of reactants or increasing the concentration of

products causes the emf to decrease from its value under standard conditions.
Slide 57

Example:

1. Calculate E for the voltaic cell:

Al(s)| Al3+ (0.36 M) || Sn4+ (0.086 M), Sn2+ (0.54 M) | Pt

Oxidation: 2[Al (s) → Al3+(aq) + 3 e-] E° = -1.676

Reduction: 3[Sn4+ (aq) + 2e- → Sn2+(aq)] E° = 0.154
Net: 2 Al (s) + 3 Sn4+ → 2 Al3+(aq) + 3 Sn2+ (aq) E°= 0.154 –(-1.676)=1.830

𝐴
Q= = = 32

n = 6 electrons E = 1.830 V - log 32 = 1.815 V

Determine first E°. Al undergoes oxidation and is the anode, being at the left side of the cell diagram. Sn undergoes
reduction and is the cathode. Thus E° = E°red (cathode or reduction) - E°red (anode or oxidation). For the number of electrons
transferred, multiply a factor that would equalize them. Thus, the total number of moles of electrons transferred is 6.
Input the given concentrations and corresponding coefficients of substances to determine Q. Finally, input everything in
the equation to determine E. E is < E°.

Slide 58

BATTERIES
- Portable, self-contained electrochemical power source consisting of one or
more voltaic cells

Types of Battery:
1. Lead-Acid Battery
2. Alkaline Battery
3. Nickel-Cadmium, Nickel-Metal-Hydride, and Lithium-Ion Batteries
4. Fuel Cells
Slide 59

LEAD-ACID BATTERY

Slide 60

ALKALINE BATTERY
Slide 61

Slide 62

- Undesirable redox reaction

CORROSION - Metal is attacked by a substance in the environment and
converted to an unwanted compound

Slide 63

PREVENTING CORROSION