ELECTROCHEMISTRY

Electrochemistry
• is the science that unites electricity and chemistry.
• It is the study of the transfer of electrons.
• Its development broadens the view of oxidation with reduction occurring as the reciprocal.

Oxidation Number
Generally, redox reaction is involved in almost all chemical reactions in organic chemistry as well
as inorganic. The processes that are concern in redox reaction includes oxygen atom-transfer,
hydrogen-atom transfer and electron-transfer. The tendency of the elements to attract and hold
bonding electrons bring forth a foundation for the assignment of oxidation number based on the
concept of redox reaction.

The oxidation number (oxidation state) is an integer assigned to each element in a particle that allows
us to keep track of electrons associated with each atom.
• An oxidation number of 0 means the atom has the same number of electrons assigned to it as
there are in the free neutral atom. (Elements are 0.)
• A positive oxidation number means the atom has fewer electrons assigned to it than in the
neutral atom.
• A negative oxidation number means the atoms has more electrons assigned to it than in the
neutral atom.

Rules for Assigning Oxidation Numbers

1. Elements in the free state are 0.
2. H is +1 except in metal hydrides where it is -1.
3. O is –2 except in peroxide where it is –1 and in OF2 where it is +2.
4. In covalent compounds the negative oxidation number is assigned to the most electronegative
atom.
5. The sum of the oxidation numbers in a compound is zero.
6. The sum of the oxidation numbers in a polyatomic ion is the charge of the ion.

Finding the Oxidation Number

1. Write the oxidation number of each known atom below the atom in the formula.
2. Multiply each oxidation number by the number of atoms of that element in the compound.
3. Write an expression indicating the sum of all the oxidation numbers in the formula.
a. Sum = 0 for a compound
b. Sum = charge for a polyatomic ion
Examples:
Cr2O72-
2Cr + 7(-2) = -2
Cr = +6

CO32-
C + 3(-2) = -2
C = +4

HSO4-
S + 1(+1) + 4(-2) = -1
S = +6

Oxidation-Reduction (Redox)
Redox reactions are chemical processes in which the oxidation numbers of an element are
changed.
Oxidation - occurs whenever the oxidation number increases from loss of electrons.
- electrons are products.
Reduction - occurs whenever the oxidation number decreases from gain of electrons.
- electrons are reagents.
OIL RIG: Oxidation Is Loss, Reduction Is Gain
LEO the lion goes GER: Lose Electrons – Oxidation, Gain Electrons – Reduction
Oxidizing Agent – the substance that causes an increase in the oxidation state of another
substance by gaining electrons. It is reduced in the process.
Reducing Agent - the substance that causes an decrease in the oxidation state of another
substance by losing electrons. It is oxidized in the process.
In the reaction between Zn and HCl, we see vigorous bubbles of H2 :
Zn(s) + 2HCl(aq) →ZnCl2(aq) + H2(g)
net ionic equation: Zn(s) + 2H+(aq) →Zn2+(aq) + H2(g)
Oxidation: Zn0 → Zn2+ +2e-
Reduction: 2H+ +2e- →H20
Balancing Redox Equations
A. Balancing Equations by the Method of Half Reactions
Half-reactions are a convenient way of separating oxidation and reduction reactions.
The half-reactions for
Sn2+(aq) + 2Fe3+(aq) → Sn4+(aq) + 2Fe3+(aq)
are
Sn2+(aq) → Sn4+(aq) +2e-
2Fe3+(aq) + 2e- → 2Fe2+(aq)

1. Write down the two half reactions.

2. Balance each half reaction:
a. First with elements other than H and O.
b. Then balance O by adding water.
c. Then balance H by adding H+.
d. Finish by balancing charge by adding electrons.
3. Multiply each half reaction to make the number of electrons equal.
4. Add the reactions and simplify.
5. Check!

Example 1:
The half-reactions for
Sn2+(aq) + 2Fe3+(aq) → Sn4+(aq) + 2Fe3+(aq)
are
Sn2+(aq) → Sn4+(aq) +2e-
2Fe3+(aq) + 2e- → 2Fe2+(aq)
Oxidation: electrons are products.
Reduction: electrons are reagents.
Example 2:
Example 3: For KMnO4 + Na2C2O4
1.The two incomplete half reactions are
MnO4-(aq) → Mn2+(aq)
C2O42-(aq) → 2CO2(g)
2. Adding water and H+ yields
8H+ + MnO4-(aq) → Mn2+(aq) + 4H2O
• There is a charge of 7+ on the left and 2+ on the right. Therefore, 5 electrons
need to be added to the left:
5e- + 8H+ + MnO4-(aq) → Mn2+(aq) + 4H2O
• In the oxalate reaction, there is a 2- charge on the left and a 0 charge on the
right, so we need to add two electrons:
C2O42-(aq) → 2CO2(g) + 2e-
3. To balance the 5 electrons for permanganate and 2 electrons for oxalate, we need 10
electrons for both. Multiplying gives:
10e- + 16H+ + 2MnO4-(aq) → 2Mn2+(aq) + 8H2O
5C2O42-(aq) → 10CO2(g) + 10e-
4. Adding gives:
16H+(aq) + 2MnO4-(aq) + 5C2O42-(aq) → 2Mn2+(aq) + 8H2O(l) + 10CO2(g)
5. Which is balanced!

B. Balancing by Oxidation Number Method

1. Assign oxidation numbers to every element.
2. Write 2 half-reactions using only the 2 elements that changed. One half-reaction must produce
electrons and the other must use electrons.
3. Multiply the half-reactions by the smallest whole number to make sure numbers of electrons
lost are equal to numbers of electrons gained.
4. Transfer the coefficient in front of each substance in the balanced half-reaction to the
substance in the original equation.
5. Balance the remaining elements that are not oxidized or reduced.
6. Check to make sure both sides of the equation have the same number of atoms of each
element.
Example1

Example 2
Pb(s) + PbO2(aq) + H2SO4(aq) → PbSO4(s) + H2O(l)
Step 1: Assign oxidation numbers
Pb(s) + PbO2(aq) + H2SO4(aq) → PbSO4(s) + H2O(l)
0 +4 -2 +1 +6 -2 +2 +6 -2 +1 -2

Step 2: Write the two half reactions

Pb4+ + 2 e- → Pb2+ (reduction)
Pb → Pb2+ + 2 e- (oxidation)
C. Balancing Ionic Redox Equations

Ion-Electron Strategy for Balancing Redox Equations

Acidic Solutions:
1. Write the two half-reactions that contain the elements being oxidized and reduced. Use entire
molecule or ion.
2. Balance elements other than oxygen and hydrogen.
3. Balance Oxygen and Hydrogen.
a. Add H2O to balance oxygen.
b. Add H+ to balance hydrogen.
4. Balance charges by adding electrons.
5. Since the loss and gain of electrons must be equal, multiply each half-reaction by the
appropriate number to make the number of electrons the same in each half-reaction.
6. Add the two half-reactions together, canceling electrons and any other identical substances
that appear on opposite sides of the equation.

Basic Solutions:
1. Balance as if in acid. Then add as many OH- ions to each side of the equation as there are
H+ ions in the equation.
2. Combine OH- with H+ to form H2O.
3. Cancel equal numbers of water molecules that appear on opposite side of the equation.

Example 1. In acidic Solution

Sn2+(aq) + IO4-(aq) → Sn4+(aq) + I-(aq)

1. Write the two half-reactions

oxidation: Sn2+ → Sn4+
reduction: IO4- → I-

2. Balance elements other than oxygen and hydrogen.

oxidation: Sn2+ → Sn4+
reduction: IO4- → I-

3. Balance oxygen and hydrogen.

a. Add H2O to balance oxygen.
Oxidation: Sn2+ → Sn4+ reduction: IO4- → I- + 4H2O
b. Add H+ to balance hydrogen.
oxidation: Sn2+ → Sn4+ reduction: IO4- + 8H+ → I- + 4H2O

4. Balance charges by adding electrons.

oxidation: Sn2+ → Sn4+ + 2e- reduction: 8e- + IO4- + 8H+ → I- + 4H2O

5. Ensure number e- lost = number e- gained

oxidation: 4(Sn2+ → Sn4+ + 2e-) reduction: 8e- + IO4- + 8H+→ I- + 4H2O

4Sn2+ → 4Sn4+ + 8e
 6. Add the two equations together, canceling substances that appear on both sides. Electrons
must always cancel.

oxidation: 4Sn2+ → 4Sn4+ + 8e-

reduction: 8e- + IO4- + 8H+ → I- + 4H2O

Net balanced equation: 4Sn2+ + IO4- + 8H+ → 4Sn4+ + I- + 4H2O

Example 2. In Basic Solution

Zn(s) + NO3-(aq) → NH3(aq) + Zn(OH)42-(aq)

1. Write the two half-reactions

oxidation: Zn → Zn(OH)42-
reduction: NO3- → NH3

2. Balance elements other than oxygen and hydrogen.

oxidation: Zn → Zn(OH)42-
reduction: NO3- → NH3

3. Balance oxygen and hydrogen.

a. Add H2O to balance oxygen.
oxidation: Zn + 4H2O → Zn(OH)42- reduction: NO3- → NH3 + 3H2O
b. Add H+ to balance hydrogen.
oxidation: Zn + 4H2O → Zn(OH)42- + 4H+ reduction: NO3- + 9H+ → NH3 + 3H2O

4. Balance charges by adding electrons.

oxidation: Zn + 4H2O → Zn(OH)42- + 4H+ + 2e- reduction: NO3- + 9H+ + 8e- → NH3 + 3H2O

5. Ensure number e- lost = number e- gained

oxidation: 4(Zn + 4H2O → Zn(OH)42- + 4H+ + 2e-) reduction: NO3- + 9H+ + 8e- → NH3 + 3H2O
4Zn + 16H2O → 4Zn(OH)42- + 16H+ + 8e-)

6. Add the two equations together, canceling substances that appear on both sides. Electrons
must always cancel.
16-3=13 16-9= 7
oxidation: 4Zn + 16H2O → 4Zn(OH)4 + 16H+ + 8e-)
2-

reduction: NO3- + 9H+ + 8e- → NH3 + 3H2O

4Zn + 13H2O + NO3- → 4Zn(OH)4 2- + 7H+ + NH3
Basic Solutions:
1. Add as many OH- ions to each side of the equation as there are
H+ ions in the equation.

7OH - + 4Zn + 13H2O + NO3- → 4Zn(OH)4 2- + 7H+ + 7OH - + NH3

 2. Combine OH- with H+ to form H2O that appear on the same side of the equation.
7OH - + 4Zn + 13H2O + NO3- → 4Zn(OH)4 2- + 7H+ + 7OH - + NH3
7OH - + 4Zn + 13H2O + NO3- → 4Zn(OH)4 2- + 7H2O + NH3

3. Cancel equal numbers of water molecules that appear on opposite side of the equation.
13-7=6
7OH + 4Zn + 13H2O + NO3- → 4Zn(OH)4 2- + 7H2O + NH3
-

Net balanced equation: 7OH - + 4Zn + 6H2O + NO3- → 4Zn(OH)4 2- + NH3

Exercise:

1. Balance the redox equation using the half-reaction method.

a. Cr2O72-(aq) + I-(aq) → Cr3+(aq) + I2(s) (in acidic solution)
b. MnO4-(aq) + C2O42-(aq) → MnO2(s) + CO32-(aq) (in basic solution)
Electrochemistry
• is the science that unites electricity and chemistry.
• It is the study of the transfer of electrons.

Electrochemical reaction
- Is either a chemical reaction that is driven by an external applied voltage, as in
electrolysis or a voltage is created by a chemical reaction, as in a battery

General characteristics of (A) voltaic and (B) electrolytic cells.

 • An electric potential difference is called as voltage. The SI unit of voltage is volts.

• Electric charge is that which causes electrons and ions to attract each other, and repel the
particles of the same kind. Coulomb is the unit used to measure electric charge.

• Current is the flow of charge per unit of time.

• Ampere is the SI unit of electric current, equal to 1C/s.
• One joule of energy is used when 1C moves across a potential of 1V.
• Energy (J)= potential (V) х Charge(C)

Cathode and Reduction

The chemistry that takes place in the cathode is reduction.
If the electronic conductor gives up electrons to the ionic conductor then the electrode is called as a
cathode and the reaction is called as a cathodic reaction.

The flow of electrons and ions at a cathode is shown in the figure below. The copper strip is the
electronic conductor that gives up electrons to the ionic conductor which is the copper (II) sulfate
solution.
 Cu2+ (aq) +2e- → Cu(s)
• During reduction copper is deposited on the metal strip. Solid metal appears as a product.
• This process of depositing a metal on a conductive surface is used in the electroplating of
silver into jewelry and flatware.

Anode and Oxidation

• An anode is an electrode at which electrons are generated.
• A reaction occurring at the anode is anodic reaction.
• Electrons flow in the opposite direction to the positive electric current .
• The figure below shows the reaction of zinc atoms to form zinc ions.

Zn(s)→ Zn2+ (aq)+2e-

• A reaction occurring at an anode is an anodic reaction, and the resulting chemical change is
called oxidation. Zinc atoms are oxidized as they lose electrons at the anode. The metal strip
dissolves as the reaction proceeds.
Reduction reactions always occur with oxidation reactions.
The electrons used in reduction must come from an oxidation reaction.
The overall reaction is called an oxidation reduction reaction, or redox reaction.
 Electrochemical cell
• Electrons produced by an anode must be consumed by a cathodic reaction.
• Therefore an anode must be paired with a cathode. The two electrodes combine in an
electrochemical cell.
• An electrochemical cell can be created by placing metallic electrodes into an electrolyte where
a chemical reaction either uses or generates an electric current.
Types of electrochemical cells:
1. Voltaic or Galvanic Cell
- spontaneous chemical reaction to generate electricity through an exterior circuit (ΔG<0); the
system does work on the surroundings (ΔW<0)
- converts chemical energy into electrical energy

2. Electrolytic Cell
- uses electricity in order to generate a nonspontaneous reaction (ΔG>0); the surrounding
does work on the system (ΔW>0)
- converts electrical energy into chemical energy

A. The Voltaic or Galvanic cell

• Electrochemical cells which generate an electric current ( in which the 2 electrode reactions
occur spontaneously) are called voltaic cells or galvanic cells, and common batteries consist
of one or more such cells.
Components:
1. Electrodes
 - conduct the electricity between cell and surroundings and are dipped into an electrolyte, a
mixture of ions (usually in aqueous solution) that are involved in the reaction or that carry the
charge.

Anode:
- where the oxidation half-reactions occur (AN OX)
- electrons are lost by the substance being oxidized (reducing agent) and leave the cell at
the anode
- electrons are generated at this electrode, therefore, it carries a negative charge

Cathode:
- where the reduction half-reaction occurs (RED CAT)
- electrons are gained by the substance being reduced (oxidizing agent) and enter the cell
at the cathode
- Electrons are consumed at this electrode, therefore, it carries a positive charge
Electrodes may be active or inactive.

Active electrode
- when the metal bars themselves are components of half-reactions
- As the cell operates, the mass of the anode gradually decreases and at the same time
the mass of the cathode increases.

Inactive electrode
- used when there are no reactants or products capable of serving as electrodes
- most common are rods of graphite or platinum: they conduct electrons into or out of the
half-cells but cannot take part in the half-reactions

2. Salt bridge
- consists of an inverted U-shaped glass tubes filled with a relatively inert electrolyte, like
KCl or NaNO3 and agar is often used for gelification
- allows the flow of ions to maintain a balance in electrical charge between the oxidation
and reduction half-cells while keeping the contents of each separate
- necessary to complete the circuit and maintain charge neutrality
Example of a Voltaic cells: Daniel Cell

• In the Daniell cell, copper and zinc electrodes are immersed in a solution of copper (II) sulfate
and zinc sulfate respectively.

• At the anode, zinc is oxidized per the following half reaction:

Zn(s) → Zn2+(aq) + 2e- .

• At the cathode, copper is reduced per the following reaction:

Cu2+(aq) + 2e- → Cu(s) .

• In the Daniell cell a wire and light bulb may connect the two electrodes. Electrons that are
“pulled” from the zinc travel through the wire, which must be a non-reactive conductor,
providing an electrical current that illuminates the bulb.

• In such a cell, the sulfate ions play an important role. Having a negative charge, these anions
build up around the anode to maintain a neutral charge.

• At the cathode the copper (II) cations (positively charged) accumulate to maintain this neutral
charge.

• These two processes cause copper solid to accumulate at the cathode and the zinc electrode
to "dissolve" into the solution.
Anode: Zn(s) → Zn2+(aq) + 2e2
Cathode: Cu2+(aq) + 2e- → Cu(s)

Salt bridge (used to complete the electrical circuit): cations move from anode to cathode,
anions move from cathode to anode

The two solid metals are the electrodes (cathode and anode).
When zinc metal is immersed in a ZnSO4 solution and copper metal metal is immersed in a CuSO4
solution, the following reaction takes place:
Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
Oxidation: Zn(s) → Zn2+(aq) + 2e- (anode)
Reduction: Cu2+(aq) + 2e- → Cu(s) (cathode)
Overall reaction: Zn(s) + Cu (aq) → Zn2+(aq) + Cu(s)
2+

Electrons are transferred from Zn0 to Cu+2 through a wire producing electrical energy.

• The energy released in a spontaneous redox reaction is used to perform electrical work.
• Voltaic or galvanic cells are devices in which electron transfer occurs via an external circuit.
• Voltaic cells are spontaneous.
• If a strip of Zn is placed in a solution of CuSO4, Cu is deposited on the Zn and the Zn dissolves
by forming Zn2+.
• Zn is spontaneously oxidized to Zn2+ by Cu2+.
• The Cu2+ is spontaneously reduced to Cu0 by Zn.
• The entire process is spontaneous.
• The two solid metals are the electrodes (cathode and anode).
A Molecular View of Electrode Processes

• As oxidation occurs, Zn is converted to Zn2+ and 2e-. The electrons flow towards the anode
where they are used in the reduction reaction.
• We expect the Zn electrode to lose mass and the Cu electrode to gain mass.
• “Rules” of voltaic cells:
1. At the anode electrons are products. (Oxidation)
2. At the cathode electrons are reagents. (Reduction)
3. Electrons cannot swim.
• Electrons flow from the anode to the cathode.
• Therefore, the anode is negative and the cathode is positive.
• Electrons cannot flow through the solution, they have to be transported through an external
wire. (Rule 3)
Salt Bridge:
• Anions and cations move through a porous barrier or salt bridge.

• Cations move into the cathodic compartment to neutralize the excess negatively charged ions
(Cathode: Cu2+ + 2e- → Cu, so the counterion of Cu is in excess).
• Anions move into the anodic compartment to neutralize the excess Zn2+ ions formed by
oxidation.
• Consider the spontaneous redox reaction between Zn(s) and Cu2+(aq).
 • During the reaction, Zn(s) is oxidized to Zn2+(aq) and Cu2+(aq) is reduced to Cu(s).
• On the atomic level, a Cu2+(aq) ion comes into contact with a Zn(s) atom on the surface of the
electrode.
• Two electrons are directly transferred from the Zn(s) (forming Zn2+(aq)) to the Cu2+(aq)
(forming Cu(s))
Since neither half reaction will occur independently of the other, the two half cells must be connected
in a way that will allow ions to move freely between them.
A porous barrier or ceramic disk may be used to separate the two solutions while allowing ion flow.
When the half cells are placed in two entirely different and separate containers, a salt bridge is often
used to connect the two cells.
Shorthand Cell Notation

Example 1:
Write the shorthand notations for:
a) 2Ag+(aq) + Ni(s) 2Ag(s) + Ni2+(aq)
b) 2 MnO4- + 16H+ + 10I- 2 Mn2+ + 5I2 + 8H2O

Example 2:
Given the overall equation,
3Ag+(aq) + Cr(s) --> Cr3+(aq) + 3Ag(s)
Draw an electrochemical cell diagram, show the balanced half-cell equations and write the notation
for a voltaic cell that consists of one half-cell with a Cr bar in a 1.0 M Cr(NO3)3 solution, another half-
cell with a Ag bar in a 1.0 M AgNO3 solution, and a KNO3 salt bridge.
SOLUTION:
The half-reactions are:

Ag+(aq) + e- → Ag(s) [reduction; cathode]

Cr(s) → Cr3+(aq) + 3e- [oxidation; anode]

The balanced overall equation is:

3Ag+ + Cr(s) → 3Ag(s) + Cr3+(aq) The cell diagram shows the anode on the left and the
cathode on the right.
 The Electrochemical Cell Potential

⚫ the electrical energy that is proportional to the difference in electrical potential between the two
electrodes
⚫ this is also called the cell potential (Ecell), or the cell voltage or the electromotive force (emf)

- A positive cell potential (Ecell >0) is associated with a spontaneous cell reaction and the
more work the cell can do, the farther the reaction proceeds to the right as written.
- A negative cell potential (Ecell <0) is associated with a nonspontaneous cell reaction.
- If Ecell = 0, the reaction has reached equilibrium and the cell can do no more work.
The SI unit for the cell potential is Volt.
1 V = 1 J/C
For a galvanic cell: Ecell > 0 for a spontaneous process
For an electrolytic cell: Ecell < 0 for a nonspontaneous process

The Standard Electrode Potential, E0cell

- the potential measured at a specified temperature (usually 298K) with no current flowing and
all components in their standard states: 1 atm for gases, 1M for solutions, the pure solid
for electrodes.

The Standard Electrode (Half-cell) Potential, E0half-cell

- the potential associated with a given half-reaction (electrode compartment) when all
components are in their standard states
The Standard Hydrogen Electrode (SHE)
The standard half-cell assumed to be zero (0) is the H2 half-cell. It is a half cell with H2 gas
bubbled in at standard conditions over an inert platinum electrode. The SHE is the universal
reference for reporting relative half-cell potentials. The SHE could be used as either an anode or
cathode depending upon the nature of the half-cell it is used with.

Ereference = 0.00 V (Refer to the Standard Reduction Potential Table).

Standard Reduction (Half-Cell) Potentials
• Standard reduction potentials, Ered are measured relative to the standard hydrogen electrode
(SHE).
• The SHE is the cathode. It consists of a Pt electrode in a tube placed in 1 M H+ solution. H2 is
bubbled through the tube.
• For the SHE, we assign
2H+(aq, 1M) + 2e- → H2(g, 1 atm)
• Ered of zero.
• The emf of a cell can be calculated from standard reduction potentials:
Ecell = Ered (cathode) − Ered (anode)

For any voltaic cell:

The standard cell potential is the difference between the standard electrode potential of the
cathode (reduction) half-cell and the standard electrode potential of the anode (oxidation) half-cell:

E0cell = E0cathode (reduction) + E0anode (oxidation)

Or

E0cell = E0reduction + E0oxidation or E0cell = E0red (reduction) - E0red (oxidation)

 Consider Zn(s) → Zn2+(aq) + 2e-.
We measure Ecell relative to the SHE (cathode):
Ecell = Ered(cathode) - Ered(anode) or Ecell = Ered(cathode) + Eoxi(anode)
0.76 V = 0 V - Ered(anode).
Therefore, Ered(anode) = - 0.76 V.
Standard reduction potentials must be written as reduction reactions:
Zn2+(aq) + 2e- → Zn(s), Ered = -0.76 V.
Since Ered = -0.76 V, we conclude that the reduction of Zn2+ in the presence of the SHE is not
spontaneous.
• The oxidation of Zn with the SHE is spontaneous.
• Changing the stoichiometric coefficient does not affect Ered.
• Therefore,
2Zn2+(aq) + 4e- → 2Zn(s), Ered = -0.76 V.
• Reactions with Ered > 0 are spontaneous reductions relative to the SHE.
• Reactions with Ered < 0 are spontaneous oxidations relative to the SHE.
• The larger the difference between Ered values, the larger Ecell.
• In a voltaic (galvanic) cell (spontaneous) Ered(cathode) is more positive than Ered(anode).
 • Recall
Ecell = Ered (cathode) − Ered (anode)

Oxidizing and Reducing Agents

• The more positive Ered the stronger the oxidizing agent on the left.
• The more negative Ered the stronger the reducing agent on the right.
• A species on the higher to the left of the table of standard reduction potentials will
spontaneously oxidize a species that is lower to the right in the table.
• That is, F2 will oxidize H2 or Li;
Ni2+ will oxidize Al(s).

Determining Standard State Cell Potentials

▪ Write the oxidation and reduction half-reactions for the cell.
▪ Look up the reduction potential, E0reduction, for the reduction half-reaction in the table of
reduction potentials.
▪ Look up the reduction potential for the reverse of the oxidation half-reaction and reverse the
sign to obtain the oxidation potential. For the oxidation half-reaction,
E0oxidation = - E0reduction.
 ▪ Add the potentials of the half-cells to get the overall standard cell potential.
▪ If E0cell is +, the reaction is spontaneous as written. If E0cell is -, the reaction is not
spontaneous.

E0cell = E0reduction + E0oxidation or E0cell = E0red (reduction) - E0red (oxidation)

Example: Find the standard cell potential for an electrochemical cell with the following cell reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
▪ Write the half-reactions for each process.
Oxidation: Zn(s) → Zn2+(aq) + 2e-
Reduction: Cu2+(aq) + 2e- → Cu(s)
▪ Look up the standard potentials for the reduction half-reaction.
E0reduction of Cu2+ = +0.339 V
▪ Look up the standard reduction potential for the reverse of the oxidation reaction and change
the sign.
E0reduction of Zn2+ = - 0.762 V
E0oxidation of Zn = -(-0.762 V) = +0.762 V
▪ Add the cell potentials together to get the overall standard cell potential.
Oxidation: Zn(s) → Zn2+(aq) + 2e- E0ox = - E0red = - (-0.762 V) = +0.762 V
Reduction: Cu2+(aq) + 2e- → Cu(s) E0red = +0.339 V
Overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) E0cell = E0red + E0ox = +1.101 V
(Spontaneous)

When balancing reactions, we sometimes multiply one or both half reactions by a factor so
the electrons cancel. The E0 values DO NOT get multiplied by these factors.

Problem 3:
Calculate E0cell for :
a. Al(s) + 3Ag+(aq) → Al3+(aq) + 3Ag(s)
b. 2 MnO4- + 16 H+ + 10 I- → 2 Mn2+ + 5 I2 + 8 H2O
c. A voltaic cell based on the reaction between aqueous Br2 and Vanadium(III) ions has
E0cell = 1.39V.
Br2(aq) + 2V3+(aq) + 2H2O(l) → 2VO2+(aq) + 4H+(aq) + 2Br-(aq)
What is E0vanadium, the standard electrode potential for the reduction of VO2+ to V3+?

Key points to remember in using the Standard Reduction Potential Table:

▪ E0red is the standard reduction potential and is measured relative to:
 2H+(aq) + 2e- → H2(g) which is assigned the value E0red = 0.00 V

▪ A positive E0red means that a half-reaction will go in the direction indicated (reduction) when
paired with the hydrogen half-reaction:

Cu2+(aq) + 2e- → Cu(s) E0red = +0.340V

H2(g) → 2H+(aq) + 2e- E0red = 0.00V

▪ A negative E0red means that a half-reaction will go in the opposite direction indicated
(oxidation) when paired with the hydrogen half-reaction:
2H+(aq) + 2e- → H2(g) E0red = 0.00V
Zn(s) → Zn2+(aq) + 2e- E0red = -0.763V

▪ In general, for any two half-reactions, the half-reaction with the more positive E0red will proceed
as a reduction, and the other half-reaction will proceed as an oxidation. For a spontaneous
reaction to occur, the half-reaction higher in the table proceeds at the cathode as written, and
the half-reaction lower in the table proceeds at the anode in reverse.

▪ Note that for a reaction to occur the appropriate species must be present. One species must
be reduced and another must be oxidized.

▪ The species that is reduced is called an oxidizing agent and the species that is oxidized is
called a reducing agent. As arranged, the strength of the oxidizing agent (reactant) increases
going up (bottom to top), and the strength of the reducing agent (product) increases going
down (top to bottom).

*Thus, F2(g) is the strongest oxidizing agent (has the largest positive E0), which means
that F-(aq) is the weakest reducing agent. Similarly, Li+(aq) is the weakest oxidizing
agent (has the most negative E0), which means Li(s) is the strongest reducing agent.
Determining Non-standard State Cell Potentials

To determine the cell potential when the conditions are other than standard state (when
concentrations are not 1 molar and/or pressures not at 1 atmosphere):
⚫ Determine the standard state cell potential.
⚫ Determine the new cell potential resulting from the changed conditions.
✓ Determine Q, the reaction quotient.
✓ Determine n, the number of electrons transferred in the reaction.
✓ Determine the Ecell, the cell potential at non-standard state conditions using the Nernst
Equation,
Ecell = E0cell - (RT/nF) ln Q

where,
Ecell = cell potential at non-standard state conditions
E0cell = standard state cell potential
R = constant (8.314 J/mol K)
T = absolute temperature (Kelvin scale)
F = Faraday’s constant (96, 485 C/mole e-)
n = number of moles of electrons transferred in the balanced equation for the reaction
occurring in the cell
[𝐶]𝑐 [𝐷]𝑑
Q = reaction quotient for the reaction: aA + bB --> cC + dD , Q = [𝐴]𝑎[𝐵]𝑏

If the temperature of the cell remains at 250C, the equation can be simplified as

Ecell = E0cell - (0.0257/n) ln Q or Ecell = E0cell - (0.0592/n) log Q

Example 6:

Predict the cell potential for the following reaction when the pressure of the oxygen gas is 2.50 atm,
the hydrogen ion concentration is 0.10 M, and the bromide ion concentration is 0.25 M.
O2(g) + 4H+(aq) + 4Br - (aq) --> 2H2O(l) + 2Br2(l)
1. Calculate the standard cell potential for the reaction, E0cell , using the tabled values:
Oxidation: 4Br - (aq) → 2Br2(l) + 4e- E0ox = E0red = -(+1.077 V) = -1.077 V
Reduction: O2(g) + 4H+(aq) + 4e- --> 2H2O(l) E0red = +1.229 V
Overall: O2(g) + 4H+(aq) + 4Br-(aq) --> 2H2O(l) + 2Br2(l) E0cell = +0.152 V
2. Determine the new cell potential resulting from the changed conditions.
 Calculate the value for the reaction quotient, Q (Note: We calculate Q using molar concentrations
for solutions and pressures for gases. Water and bromine are both liquids, therefore they are not
included in the calculation of Q.)
[𝐶]𝑐 [𝐷]𝑑
Q = [𝐴]𝑎[𝐵]𝑏

1
Q = [𝑃 + ]4 ][𝐵𝑟 − ]4
𝑂2 ][𝐻

1
Q = (2.50 𝑎𝑡𝑚)(0,10 𝑀)4 )(0.25𝑀)4

Q = 1.02 x 𝟏𝟎𝟔
 Calculate the number of moles of electrons transferred in the balanced equation, n.
n = 4 moles of e-
 Substitute values into the Nernst equatuon and solve for the non-standard cell potential, E0cell.
Ecell = E0cell - (0.0257/n) ln Q
Ecell = +0.152 V - (0.0257/4) ln (1.02 x 106) = +0.063 V

Relative Reactivity of Metals

The activity series of metals ranks metals by their ability to “displace” one another from
aqueous solutions. The standard reduction potential table can be used to predict the activity of
metals.

Generalizations:
1. Metals that can displace H2 from acid.
- Those metals that lie below the standard hydrogen (reference) electrode give a positive
E0cell when reducing H+ from an acid to H2.

Ex. Fe(s) + 2H+(aq) → Fe3+(aq) + H2(g)

 The lower the metal is in the table, the more positive the E0cell, the more active the metal.

Ex. K is a more active metal than Ca.

2. Metals that cannot displace H2 from acid.

- Metals that are above the standard hydrogen (reference) half-rection cannot reduce the H+
from acids to displace H2.
- The higher the metal in the list, the more negative is its E0cell for the reduction of H+ to H2,
the lower is its reducing strength, and the less active it is. Thus, gold is less active than
silver, which is less active than copper.
 Ex. 2Ag(s) + 2H+(aq) → 2Ag+(aq) + H2(g) E°cell = -0.80 V (nonspontaneous)

*** this will not happen

3. Metals that can displace H2 from water.

- Metals that can displace H2 from water are metals whose half-reactions lie below that of
H2O:
2H2O(l) + 2e- → H2(g) + 2OH-(aq) E0cell = -0.83V

The alkali metals (Group 1A) and the larger alkaline earth metals (Group 2A) can reduce water, or
“displace H2 from H2O.

Ex. 2Na(s) + 2H2O(l) → 2Na+(aq) + 2H2(g) + 2OH-(aq)

4. Metals that can displace other metals from solution.

We can also predict whether one metal can reduce the aqueous ion of another metal. Any metal
that is lower in the table can reduce the ion of a metal that is higher up, and thus displace that
metal from solution.

Ex. Zinc can displace iron, but Fe cannot displace Zn.

Zn(s) + Fe2+(aq) --> Zn2+(aq) + Fe(s)

Fe(s) + Zn2+(aq) --> no reaction

Relative Reactivity of Metals

If you put a piece of copper wire in 1M AgNO3 a reaction takes place.

Cu(s) + 2AgNO3(aq) → 2Ag(s) + Cu(NO3)2(aq)

If you put a piece of silver wire in 1M Cu(NO3)2 no reaction occurs.

2Ag(s) + Cu(NO3)2(aq) → no reaction

Therefore, copper is a more active metal than silver.

Activity Series of Metals

Activity series: A listing of metallic elements in descending order of reactivity.
Cu is above Ag, which means that Cu can replace Ag in a compound.
 Using the Activity Series
1. The reactivity of the metals listed decreases from top to bottom.
2. A free metal can displace the ion of any metal below it in the activity series.
3. Free metals above H react with acids to liberate H2.
4. Free metals below H don’t react with acids.
5. Reaction conditions like temperature and pressure may affect the relative position of some of
the metals.

B. Electrolytic cell
• In other electrochemical cells an externally supplied electric current is used to drive a chemical
reaction which would not occur spontaneously. Such cells are called electrolytic cells.
An electrolytic cell uses electricity to produce a chemical change for nonspontaneous redox
reaction.
• Electrolytic cells are chemical cells composed of a vessel used to do electrolysis, containing
electrolyte, usually a solution of water or other solvents capable of dissolving various ions into
solution, and a cathode and anode.
• The electrolyte in the cell is inert unless driven by external voltage into a redox reaction with
the anode and cathode.
Electrolysis - is the process in which electrical energy is used to bring about chemical change.
- is used to manufacture Na and NaOH, Cl2 and H2, as well as to purify and electroplate
metals.
 Electrolysis of Molten NaCl

During electrolysis of a pure, molten salt,

the cation will be reduced and
the anion will be oxidized.

Example, decomposition of molten NaCl.

Cathode: 2Na+(l) + 2e- → 2Na(l)
Anode: 2Cl-(l) → Cl2(g) + 2e-.
Net reaction: 2Na+(l) + 2Cl-(l) → Cl2(g) + 2Na(l)

Industrially, electrolysis is used to produce metals like Al.

Electrolysis of water
By using an electrolytic cell composed of water, two electrodes and an external source emf one can
reverse the direction of the process and create hydrogen and oxygen from water and electricity.
The reaction at the anode is the oxidation of water to O2 and acid while the cathode reduces water
into H2 and hydroxide ion. That reaction has a potential of -2.06 V at standard conditions.
Electrolysis of Aqueous Solutions
• Nonspontaneous reactions require an external current in order to force the reaction to proceed.
• Electrolysis reactions are nonspontaneous.
• In voltaic and electrolytic cells:
– reduction occurs at the cathode, and
– oxidation occurs at the anode.
– However, in electrolytic cells, electrons are forced to flow from the anode to cathode.
– In electrolytic cells the anode is positive and the cathode is negative. (In galvanic cells
the anode is negative and the cathode is positive.)

Electrolysis of Aqueous HCl

Cathode – negative electrode
• Hydronium ions migrate to the cathode and are reduced.
• Reaction at the cathode:
H3O+ + 1e- → H0 + H2O
H0 + H0 → H2

Anode – positive electrode

• Chloride ions migrate to the anode and are oxidized.
• Reaction at the anode:
Cl-→ Cl0 + e-
Cl0 + Cl0→ Cl2
Net Reaction:
2HCl (aq) → Cl2 (g) + H2 (g)

Electrolysis of Aqueous Sodium Chloride

Sodium chloride is dissociated and exists as sodium and chloride ions in aqueous solution. Electrolysis of sodium
chloride is easier in aqueous solution. But, water itself can undergo reduction and oxidation reactions at different
potentials. So, the substance that is oxidized or reduced is not sodium and chloride ions alone but it may involve the
water molecule also.
Two competing reactions are possible at both cathode and anode.

At Cathode: reduction reaction: at pH =7

Water can be reduced to hydrogen gas or Sodium ions reduced to sodium metal.
2H2O(l) + 2e– → H2(g) + 2OH– E° = -1.0 V
Na+(l) + e– → Na(l) E° = -2.71V
At anode: Oxidation reaction: at pH =7.
Water can be oxidized to oxygen or chloride ion oxidized to chlorine molecule.
2H2O → O2(g) + 4H+ + 4e– E° =-1.42 V
2Cl– → Cl2 + 2e– E =- 1.36V
Hence, the product of electrolysis of aqueous sodium chloride can be anything between,
i) sodium metal, or hydrogen gas at the cathode and
ii) chlorine or oxygen gas at the anode,
With a side product of sodium hydroxide resulting from the reaction of sodium and water. The product of electrolysis
depends on the concentration of sodium chloride aqueous solution.
a) Very Dilute Aqueous Sodium Chloride Solution
Water has very low conductivity and the small amount of ionic sodium chloride helps the ionic conductivity of the
solution. In small concentration, the electrolysis of water becomes more predominant yielding hydrogen at cathode
and oxygen at the anode.
At cathode: 2H2O + 2e– → H2(g) + 2OH– E° = -1.0 V
At anode: 2H2O → O2(g) + 4H+ + 4e– E° = +1.4 V
Net reaction of electrolysis of very dilute aqueous sodium chloride is given as;
2H2O → H2(g) + 2OH– + O2(g) E° = – 2.4 V
b) High Concentration of Sodium Chloride
At Cathode: reduction reaction: at pH =7
2H2O(l) + 2e– → H2(g) + 2OH– E° = -1.0 V
Na+(l) + e– → Na(l) E° = -2.71V
Reduction (over) potential of water being more positive than the reduction of sodium ions, water is decomposed to
liberate hydrogen at the cathode.
At anode: Oxidation reaction: at pH =7
2H2O → O2(g) + 4H+ + 4e– E° =-1.4 V
2Cl– → Cl2 + 2e– E =- 1.36V
The thermo-dynamical reduction potential of water and chloride is +0.82V and 0.1.36V respectively. Oxidation of
water being more positive is more feasible and so, the evolution of oxygen gas should happen at the anode. But, the
evolution of oxygen from water has an overvoltage of -0.6V making the voltage for the oxidation of water as -1.4V.
Chloride oxidation is more positive than the net voltage of water oxidation. So, chloride is, oxidized to chlorine at the
anode. The net reaction taking place is given as;
At cathode – 2H2O(l) + 2e– → H2(g) + 2OH–
At anode – 2Cl– → Cl2 + 2e–

The overall reaction is as follows;

2H2O(l) + 2Cl– → H2(g) + Cl2 + 2OH–
Or
2H2O(l) + 2NaCl → H2(g) + Cl2 + 2NaOH
At high salt concentration, hydrogen and chlorine is the product of electrolysis with sodium hydroxide as a by
product.
c) Electrolysis of Aqueous Sodium Chloride in Intermediate Concentration
At cathode: reduction of water to hydrogen is more feasible than sodium hydrogen. In all aqueous solutions
reduction of water to hydrogen takes place at cathode compared to the reduction of sodium ion.
At anode: Oxidation potential of water and chloride ions are almost the same (-1.4V and 1.36V respectively).
At higher concentration of sodium chloride, chloride oxidation is favoured kinetically, while at low concentrations
oxidation of water to hydrogen is favoured kinetically. At intermediate concentrations, both water and chloride ions
are oxidized. So, both oxygen and chlorine gases evolve at the anode, simultaneously.
At Cathode: reduction reaction: at pH =7,
2H2O(l) + 2e– → H2(g) + 2OH–
At Anode: Oxidation reaction: at pH =7
2H2O → O2(g) + 4H+ + 4e–
2Cl– → Cl2 + 2e–
Reduction reaction x 3 6H2O(l) + 6e– → 3H2(g) + 6OH–
So, the net reaction is;
4H2O(l) + 2Cl– → 3H2(g) + 2OH– + Cl2 + O2
Or
4H2O(l) + 2NaCl → 3H2(g) + 2NaOH + Cl2 + O2

Sodium chloride electrolysis in aqueous solution yields different products, depending on the relative concentration of
sodium chloride and water. The electrolysis is thermodynamically controlled at very low and high concentrations of
sodium chloride and kinetically controlled at inter-mediatory concentrations.

Factors Affecting Electrolysis

The factors that may affect the electrolysis are;
i) The nature of the electrode
ii) Nature and state of the electrolyte
iii) Nature and electrode potential of ions present in the electrolyte and
iv) Overvoltage at the electrodes.
Electroplating
• Active electrodes: electrodes that take part in electrolysis.
• Example: electrolytic plating.

• Consider an active Ni electrode and another metallic electrode placed in an aqueous solution
of NiSO4:

Anode: Ni(s) → Ni2+(aq) + 2e-

Cathode: Ni2+(aq) + 2e- → Ni(s).

• Ni plates on the inert electrode.

• Electroplating is important in protecting objects from corrosion.

Stoichiometry/Quantitative Aspects of Electrolysis

Faraday’s law of electrolysis states that the amount of substance produced at each electrode is
directly proportional to the quantity of charge flowing through the cell.

The current flowing through the cell is the amount of charge per unit time. Current is measured in
amperes.
Current x time = charge

A summary diagram for the stoichiometry of electrolysis.

Sample Problem. Applying the Relationship Among Current, Time, and Amount of Substance

PROBLEM: A technician plates a faucet with 0.86 g of Cr metal by electrolysis of aqueous

Cr2(SO4)3. If 12.5 min is allowed for the plating, what current is needed?

Solution:

Cr 3+ (aq) + 3e- → Cr(s)

1 mol Cr 3 mol e−
0.86 g Cr x x x = 0.050 mol e−
52.00 g Cr 1 mol Cr

9.65x104 C
Charge (C) = 0.050 mol e− x = 4.8 x 103 C
1 mol e−
charge (C) 4.8 x 103 C 1 min
Current (A) = = x = 6.4 C/s = 6.4 A
time (s) 12.5 min 60 s

How do batteries work

• Electrochemical power sources can be divided into primary cells and secondary cells.

• Primary cells function only as galvanic cells. A primary cell can either be a fuel cell or a battery.
A primary battery is thrown away when its active materials are used up (the battery is “dead”
when the cell reaction has reached equilibrium). Familiar primary cells are in flashlights ,
watches, toys and radio.

• Secondary cells include storage cells, accumulators, or rechargeable batteries . Secondary

cells are an electrochemical cells that can act as a galvanic cell or, on recharge, as an
 electrolytic cell. Secondary cells are in ignition, starting in automobiles (car batteries) and
engine generator sets.

Equilibrium cell voltage

• The voltage of a cell as measured by a voltmeter when no current is flowing. Electrochemical
voltage is given as ∆E.
• Cell potentials are measured using standard hydrogen electrode (SHE).
• SHE is made up of an aqueous solution of a strong acid in which the effective H₃O+
concentration is 1.000M. A platinum electrode is dipped into this solution and a stream of
hydrogen gas at a pressure of 1 atm bubbles in .

Batteries
• A battery is a self-contained electrochemical power source with one or more voltaic cell.
• When the cells are connected in series, greater emfs can be achieved.
Some Common Batteries:

Lead-Acid Battery
A 12 V car battery is a secondary battery and is rechargeable. Consists of 6 cathode/anode
pairs each producing 2 V.
Cathode: PbO2 on a metal grid in sulfuric acid:
PbO2(s) + SO42-(aq) + 4H+(aq) + 2e- → PbSO4(s) + 2H2O(l)
Anode: Pb:
Pb(s) + SO42-(aq) → PbSO4(s) + 2e-

• The overall electrochemical reaction is

PbO2(s) + Pb(s) + 2SO42-(aq) + 4H+(aq) → 2PbSO4(s) + 2H2O(l)
for which
Ecell = Ered(cathode) - Ered(anode)
= (+1.685 V) - (-0.356 V)
= +2.041 V.
• Wood or glass-fiber spacers are used to prevent the electrodes form touching.

Alkaline Battery
Anode: Zn cap:
Zn(s) → Zn2+(aq) + 2e-
 Cathode: MnO2, NH4Cl and C paste:
2NH4+(aq) + 2MnO2(s) + 2e- → Mn2O3(s) + 2NH3(aq) + 2H2O(l)
The graphite rod in the center is an inert cathode.

Alkaline Battery/Coin cell battery

For an alkaline battery, NH4Cl is replaced with KOH.
• Anode: Zn powder mixed in a gel:
Zn(s) → Zn2+(aq) + 2e-
• Cathode: reduction of MnO2.

Fuel Cells
Direct production of electricity from fuels occurs in
a fuel cell.
On Apollo moon flights, the H2-O2 fuel cell was
the primary source of electricity.
Anode: oxidation of hydrogen
2H2(g) → 4H+(aq) + 4e-
Cathode: reduction of oxygen:
O2(g) + 4H+(aq) + 4e- → 2H2O(g)

Corrosion: An Environmental Voltaic Cell

Corrosion is is the process whereby metals are oxidized to their oxides and sulfides.
The rusting of iron is a common form of corrosion.

- Rust is not a direct product of the reaction between Fe and O2, but arises through a
complex electrochemical process.

- Rusting requires moisture, and occurs more quickly at low pH, in ionic solutions, and when the
iron is in contact with a less active metal.
 Since Ered(Fe2+) < Ered(O2) iron can be oxidized by oxygen.
Cathode: O2(g) + 4H+(aq) + 4e- → 2H2O(l).
Anode: 2Fe(s) → 2Fe2+(aq) + 4e-.
Dissolved oxygen in water usually causes the oxidation of iron.
Fe2+ initially formed can be further oxidized to Fe3+ which forms rust, Fe2O3.xH2O(s).
• Oxidation occurs at the site with the greatest concentration of O2.

Preventing Corrosion of Iron

Corrosion can be prevented by coating the iron with paint or another metal.
Galvanized iron is coated with a thin layer of zinc.
Zinc protects the iron since Zn is the anode and Fe the cathode:
Zn2+(aq) +2e- → Zn(s), Ered = -0.76 V
Fe2+(aq) + 2e- → Fe(s), Ered = -0.44 V
With the above standard reduction potentials, Zn is easier to oxidize than Fe.

To protect underground pipelines, a sacrificial anode is added.

The water pipe is turned

into the cathode and an active metal is used as the anode.
Often, Mg is used as the sacrificial anode:
Mg2+(aq) +2e- → Mg(s), Ered = -2.37 V
Fe2+(aq) + 2e- → Fe(s), Ered = -0.44 V