ELECTROCHEMICAL METHODS 1

Electrochemistry deals with the study of the connection between oxidation-reduction reactions and
the flow of electrons. Since the total number of electrons loss must be equal to the total number of electrons
gain, electrons are very significant in any redox reactions.

REDOX REACTIONS

Redox reaction is a reaction where oxidation of one substance and reduction of other substance take
place simultaneously.

Oxidation

Reducing agent Redox Reaction Oxidizing agent

Reduction

Oxidation Reduction
 Gains oxygen  Loses oxygen
 Loses hydrogen  Gains hydrogen
 Loses electrons  Gains electrons
 Increase in oxidation number  Decrease in oxidation number
Example: Example:
Gain of oxygen Loss of oxygen

2 Mg(s) + O2(g) 2 MgO(s) Zn(s) + CuO(s) ZnO(s) +Cu

Loss of hydrogen Gain of hydrogen

H2S(g) + Cl2(g) 2 HCl(g) + S(g) H2 (g) + Cl2(g) 2 HCl(g)

Oxidizing Agents Reducing Agents

 Substances that cause oxidation in the  Substances that cause reduction in the
substance they react with substance they react with
 The substance being reduced  The substance being oxidized
 Gains electrons  Loses electrons
Example:
Oxidation (gain of oxygen)

2 CuO(s) + C(s) 2 Cu(s) + CO2

Reduction (loss of oxygen)

 Oxidation occurs when carbon, C gains oxygen to form carbon dioxide, CO2.
 Reduction occurs when copper(II) oxide, CuO loses oxygen to form copper, Cu.
 Oxidizing agent: copper(II) oxide, CuO (oxidized C into CO2)
 Reducing agent: carbon, C (reduced CuO to Cu)

Oxidation (gain of oxygen)

2 FeO(s) + C(s) 2 Fe(s) + CO2

Reduction (loss of oxygen)

 Oxidation occurs when carbon, C gains oxygen to form carbon dioxide, CO2.
 Reduction occurs when iron(II) oxide, FeO loses oxygen to form iron, Fe.
 Oxidizing agent: iron(II) oxide, FeO (oxidized C into CO2)
 Reducing agent: carbon, C (reduced FeO to Fe)
 ELECTROCHEMICAL METHODS 2

Oxidation Number

Oxidation number or oxidation state refers to the number of electrons transferred from one atom to other
atom.

Rules in assigning oxidation number

1) The oxidation number of an atom or molecule of an 0 0 0 0 0 0
element in free state is zero. H2 O2 Cl Na Fe Ca
2) The oxidation numbers of hydrogen and oxygen are +1 -1 +1 -1 +1 -2
+1 and –2 respectively, but sometimes oxygen carries H2 O2 Na H2 H2 O2
a -1 in peroxide compound and in hydrides, the
charge of hydrogen is -1. H2O2 NaH H2O
3) The sum of oxidation numbers of a compound is zero. Carbon dioxide, CO2 : (+4) + (2)(-2) = 0
4) The sum of oxidation numbers of polyatomic ion is
Sulfate, SO4-2 : (+6) + 4(-2) = -2
equal to the charge of the polyatomic ion.

Worked Example 1.1

Determine the oxidation number of the underlined element.

a) KMnO4

Given: K = +1 O = -2 Let x be the oxidation number of Mn

Solution:

1(+1) + 1(x) + 4(-2) =0

1 + x + (-8) =0
x–7 =0
x = +7 is the oxidation number of Mn

b) Al2(Cr2O7)3

Given: Al = +3 O = -2 Let x be the oxidation number of Cr

Solution:

2(+3) + 6(x) + 21(-2) =0

6 + 6x + (-42) =0
6x – 36 =0
6x = +36
6x = +36
6 6
x = 6 is the oxidation number of Cr

Oxidation Number and Electron Transfer in Redox Reactions

Oxidation Number Electron Transfer

Increases Decreases Loss Gain

Oxidation Reduction Oxidation Reduction

Oxidation

2 Na0(s) + Cl20(g) 2 Na+1Cl-1

Reduction

 Oxidation occurs when sodium, Na oxidation number increases from 0 to +1 as it loses electron to form
sodium ion. Na(s) Na+1(aq) + e-
 Reduction occurs when chlorine, Cl oxidation number decreases from 0 to -1 as it gains electron to
form chlorine ion. Cl2(g) + 2e- 2Cl-1(aq)
 Oxidizing agent: chlorine, Cl2
 Reducing agent: sodium, Na
 ELECTROCHEMICAL METHODS 3

Worked Example 1.2

Identify the oxidizing agent and reducing agent in each of the following equations.

a) 2Fe + 3Cl2 2FeCl3

Solution:

Step 1. Write the oxidation state of each of the element above the chemical symbol from the reactants to
products.
0 0 +3 -1
2Fe + 3Cl2 2FeCl3

Step 2. Identify the element which undergoes a changed in oxidation state.

Oxidation (0 to +3)

0 0 +3 -1
2Fe + 3Cl2 2FeCl3

Reduction (0 to -1)
 Oxidizing agent: chlorine, Cl2
 Reducing agent: iron, Fe

b) CuO + NH3 N2 + H2O + Cu

Solution:

Step 1. Write the oxidation state of each of the element above the chemical symbol from the reactants to
products.
+2 -2 -3 +1 0 +1 -2 0
CuO + NH3 N2 + H2O + Cu

Step 2. Identify the element which undergoes a changed in oxidation state.

Reduction (+2 to 0)

+2 -2 -3 +1 0 +1 -2 0
CuO + NH3 N2 + H2O + Cu

Oxidation (-3 to 0)
 Oxidizing agent: copper(II) oxide, CuO
 Reducing agent: ammonia, NH3

Displacement of a Metal from its Salt Solution in Redox Reaction

Displacement reaction – a reaction in which one element (metal or non-metal) displaces another element
(metal or non-metal) from its salt solution.

Metal Positive ion

K K+1 + e- Electropositivity
Electropositivity
Na Na+1 + e- decreases
increases
Ca Ca+2 + 2e-
Mg Mg+2 + 2e-
Tendency of Al Al+3 + 3e- Tendency of
metal atoms to Zn Zn+2 + 2e- metal atoms to
donate electrons accept electrons
Fe Fe+2 + 2e-
increases increases
Sn Sn+2 + 2e-
Pb Pb+2 + 2e-
Strength of the H H+1 + e- Strength of the
metal as a Cu Cu+2 + 2e- metal as a
reducing agent Ag Ag+1 + e- oxidizing agent
increases Au Au+3 + 3e- increases
 ELECTROCHEMICAL METHODS 4

Displacement of Halogen from its Halide Solution in Redox Reaction

Electronegativity increases Halogen Halide ion Electronegativity decreases

F2(g) + 2e- 2F-1(aq)
Cl2(g) + 2e- 2Cl-1(aq)
Strength of the halogen as Br2(g) + 2e- 2Br-1(aq) Strength of the halide ion as
an oxidizing agent I2(g) + 2e- 2I-1(aq) a reducing agent increases
increases

Balancing Redox Reactions

Balancing redox reactions is slightly more complex than balancing standard reactions, but still follows
a relatively simple set of rules. One major difference is the necessity to know the half-reactions of the
involved reactants; a half-reaction table is very useful for this. Half-reactions are often useful in that two half
reactions can be added to get a total net equation. Although the half-reactions must be known to complete
a redox reaction, it is often possible to figure them out without having to use a half-reaction table. This is
demonstrated in the acidic and basic solution examples. Besides the general rules for neutral conditions,
additional rules must be applied for aqueous reactions in acidic or basic conditions.

Half Equation Method

In this method, the equation is separated into two half-equations; one for oxidation and one for
reduction.

Each equation is balanced by adjusting coefficients and adding H2O, H+, and e- in this order:

1. Balance elements in the equation other than O and H.

2. Balance the oxygen atoms by adding the appropriate number of water (H 2O) molecules to the
opposite side of the equation.
3. Balance the hydrogen atoms (including those added in step 2 to balance the oxygen atom) by adding
H+ ions to the opposite side of the equation.
4. Add up the charges on each side. Make them equal by adding enough electrons (e-) to the more
positive side. (Rule of thumb: e- and H+ are almost always on the same side.)
5. The e- on each side must be made equal; if they are not equal, they must be multiplied by
appropriate integers (the lowest common multiple) to be made the same.
6. The half-equations are added together, canceling out the electrons to form one balanced equation.
Common terms should also be canceled out.
(If the equation is being balanced in a basic solution, through the addition of one more step, the
appropriate number of OH- must be added to turn the remaining H+ into water molecules.)
7. The equation can now be checked to make sure that it is balanced.

Neutral Conditions

The first step to balance any redox reaction is to separate the reaction into half-reactions. The
substance being reduced will have electrons as reactants, and the oxidized substance will have electrons as
products. Sometimes it is necessary to determine which half-reaction will be oxidized and which will be
reduced. In this case, whichever half-reaction has a higher reduction potential will be reduced and the other
oxidized.

Worked Example 1.3 Balancing in Neutral Solution

Cu+(aq) + Fe(s) Fe3+(aq) + Cu(s)

Step 1: Separate the half-reactions. This yields:

Reduction: Cu+(aq) + e- Cu(s)

Oxidation: Fe(s) Fe3+(aq) + 3e-

Step 2: Balance the electrons in the equations. In this case, the electrons are simply balanced by multiplying
the entire Cu+(aq) + e-  Cu(s) half-reaction by 3 and leaving the other half reaction as it is. This gives:

Reduction: 3Cu+(aq) + 3e- 3Cu(s)

Oxidation: Fe(s) Fe3+(aq) + 3e-

 ELECTROCHEMICAL METHODS 5

Step 3: Adding the equations give:

3Cu+(aq) + 3e- + Fe(s) 3Cu(s) + Fe3+(aq) + 3e-

Step 4. The electrons cancel out and the balanced equation is left.

3Cu+(aq) + 3e- + Fe(s) 3Cu(s) + Fe3+(aq) + 3e-

3Cu+(aq) + Fe(s) 3Cu(s) + Fe3+(aq)

Acidic Conditions

Acidic conditions usually implies a solution with an excess of H+ concentration, hence making the
solution acidic. The balancing starts by separating the reaction into half-reactions. However, instead of
immediately balancing the electrons, balance all the elements in the half-reactions that are not hydrogen
and oxygen. Then, add H2O molecules to balance any oxygen atoms. Next, balance the hydrogen atoms by
adding protons (H+). Now, balance the charge by adding electrons and scale the electrons (multiply by the
lowest common multiple) so that they will cancel out when added together. Finally, add the two half-
reactions and cancel out common terms.

Worked Example 1.4 Balancing in Acidic Solution

Cr2O72− (aq) + HNO2(aq) Cr3+(aq) + NO3−(aq)

Step 1: Separate the half-reactions. The table provided does not have acidic or basic half-reactions, so just
write out what is known.

Cr2O72− (aq) Cr3+(aq)

HNO2(aq) NO3−(aq)

Step 2: Balance elements other than O and H. In this example, only chromium needs to be balanced. This
gives:

Cr2O72− (aq) 2Cr3+(aq)

HNO2(aq) NO3−(aq)

Step 3: Add H2O to balance oxygen. The chromium reaction needs to be balanced by adding 7 H2O molecules.
The other reaction also needs to be balanced by adding one water molecule. This yields:

Cr2O72−(aq) 2Cr3+(aq) + 7 H2O(l)

HNO2(aq) + H2O(l) NO3−(aq)

Step 4: Balance hydrogen by adding protons (H+). 14 protons need to be added to the left side of the
chromium reaction to balance the 14 hydrogen (2 per water molecule * 7 water molecules). 3 protons need
to be added to the right side of the other reaction.

Cr2O72−(aq) + 14H+(aq) 2Cr3+(aq) + 7 H2O(l)

HNO2(aq) + H2O(l) NO3−(aq) + 3 H+(aq)

Step 5: Balance the charge of each equation with electrons.

(-2) (1) + (+1)(14) = +12 (+3) (2) = +6

Cr2O7 2− (aq) + 14 H + (aq) 2 Cr 3+

(aq) + 7 H2O(l)

To balance, add 6 electrons (each with a charge of -1) to the left side:

6e- + Cr2O72−(aq) + 14H+(aq) 2Cr3+(aq) + 7 H2O(l)

For the other reaction, there is no charge on the left and a (3+) + (-1) = 2+ charge on the right. So add 2
electrons to the right side:

HNO2(aq) + H2O(l) NO3−(aq) + 3 H+(aq) + 2e-

 ELECTROCHEMICAL METHODS 6

Step 6: Scale the reactions so that the electrons are equal.

The chromium reaction has 6e-.

6e- + Cr2O72−(aq) + 14H+(aq) 2Cr3+(aq) + 7 H2O(l)

The other reaction has 2e-, so it should be multiplied by 3.

3 • HNO2(aq) + H2O(l) NO3−(aq) + 3 H+(aq) + 2e-
This gives:
3HNO2(aq) + 3H2O(l) 3NO3−(aq) + 9 H+(aq) + 6e-

Step 7: Add the reactions and cancel out common terms.

14 - 9 = 5 H+ 7 - 3 = 4 H2O
H2O
6e- + Cr2O72−(aq) + 14H+(aq) + 3HNO2(aq) + 3H2O(l) 2Cr3+(aq) + 7 H2O(l) + 3NO3−(aq) + 9H+(aq) + 6e-

This gives:
Cr2O72−(aq) + 5H+(aq) + 3HNO2(aq) 2Cr3+(aq) + 4 H2O(l) + 3NO3−(aq)

Basic Conditions

Bases dissolve into OH- ions in solution; hence, balancing redox reactions in basic conditions requires
OH-. Follow the same steps as for acidic conditions. The only difference is adding hydroxide ions (OH -) to
each side of the net reaction to balance any H+. OH- and H+ ions on the same side of a reaction should be
added together to form water. Again, any common terms can be cancelled out.

Worked Example 1.5 Balancing in Basic Solution

Ag(s) + Zn2+(aq) Ag2O(aq) + Zn(s)

Go through all the same steps as if it was in acidic conditions.

Step 1: Separate the half-reactions.

Oxidation: Ag(s) Ag2O(aq)

Reduction: Zn2+(aq) Zn(s)

Step 2: Balance elements other than O and H.

2Ag(s) Ag2O(aq)

Zn2+(aq) Zn(s)

Step 3: Add H2O to balance oxygen.

H2O + 2Ag(s) Ag2O(aq)

Zn2+(aq) Zn(s)

Step 4: Balance hydrogen with protons.

H2O(l) + 2Ag(s) Ag2O(aq) + 2H+(aq)

Zn2+(aq) Zn(s)

Step 5: Balance the charge with e-.

H2O(l) + 2Ag(s) Ag2O(aq) + 2H+(aq) + 2e-

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

Step 6: Scale the reactions so that they have an equal amount of electrons. In this case, it is already done.

Step 7: Add the reactions and cancel the electrons.

H2O(l) + 2Ag(s) + Zn2+(aq) + 2e- Ag2O(aq) + 2H+(aq) + 2e- + Zn(s)

H2O(l) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + 2H+(aq) + Zn(s)

 ELECTROCHEMICAL METHODS 7

Step 8: Add OH- to balance H+. There are 2 net protons in this equation, so add 2 OH- ions to each side.

2 OH-(aq) + H2O(l) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + 2H+(aq) + Zn(s) + 2 OH-(aq)

Step 9: Combine OH- ions and H+ ions that are present on the same side to form water.

2 OH-(aq) + H2O(l) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + 2H+(aq) + Zn(s) + 2 OH-(aq)

2 OH-(aq) + H2O(l) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + Zn(s) + 2 H2O(l)

Step 10: Cancel common terms.

2 OH-(aq) + 2Ag(s) + Zn2+(aq) Ag2O(aq) + Zn(s) + H2O(l)

Electrochemical Cells

Electrochemical cells are made up of two metallic conductors called electrodes in contact with
electrical medium called electrolyte. Electrochemical cells spontaneously produce electrical current called
electromotive force (EMF) as a result of the electrical potential that exists between two reactions. These
reactions involve the gaining of electrons (reduction) and the loss of electrons (oxidation).

Electrochemical cells are of two types:

1. Voltaic cells, also called galvanic cells
2. Electrolytic cells

Figure 1.1 Electrochemical Cells

Galvanic Cell Electrolytic Cell

Consists of two electrodes (two

Consists of two electrodes
different metals) dipped into an
(usually carbon) dipped into an
electrolyte.
electrolyte.
Do not need external energy BASIC STRUCTURE
Need external energy sources.
sources.
Anode is positive and cathode is
Cathode is positive and anode is
negative.
negative.

Changes chemical energy into ENERGY Changes electrical energy into

electrical energy CONVERSION chemical energy

Reducing agent loses electrons Anions lose electrons at the

at the anode. TRANSFER OF anode.
Oxidizing agent gains electrons ELECTRONS Cations gains electrons at the
at the cathode. cathode.

Occurs at the anode OXIDATION Occurs at the anode

(negative terminal) PROCESS (positive terminal)

Occurs at the cathode REDUCTION Occurs at the cathode

(positive terminal) PROCESS (negative terminal)
 ELECTROCHEMICAL METHODS 8

Voltaic (Galvanic) Cells

In redox reactions, electrons are transferred from one species to another. If the reaction is
spontaneous, energy is released, which can then be used to do useful work. To harness this energy, the
reaction must be split into two separate half reactions: the oxidation and reduction reactions. The reactions
are put into two different containers and a wire is used to drive the electrons from one side to the other. In
doing so, a Voltaic/ Galvanic Cell is created.

Half Cells

Half of the redox reaction occurs at each half cell. Therefore, we can say that in each half-cell a half-
reaction is taking place. When the two halves are linked together with a wire and a salt bridge, an
electrochemical cell is created.

Figure 1.2. This is a half cell and the strip of metal is the electrode.

Electrodes

An electrode is strip of metal on which the reaction takes place. In a voltaic cell, the oxidation and
reduction of metals occurs at the electrodes. There are two electrodes in a voltaic cell, one in each half-cell.
The cathode is where reduction takes place and oxidation takes place at the anode.

Standard Hydrogen Electrode

A Standard Hydrogen Electrode (SHE) is an electrode that scientists use for reference on all half-cell
potential reactions. The value of the standard electrode potential is zero, which forms the basis one needs
to calculate cell potentials using different electrodes or different concentrations. It is important to have this
common reference electrode just as it is important for the International Bureau of Weights and Measures to
keep a sealed piece of metal that is used to reference the S.I. Kilogram.

Flow of Electrons

Electrons always flow from the anode to the cathode or from the oxidation half cell to the reduction
half cell. In terms of Eocell of the half reactions, the electrons will flow from the more negative half reaction
to the more positive half reaction. A cell diagram is a representation of an electrochemical cell.

Representing Half Cells: Cell Diagrams

Figure 1.3. The Cell Diagram

When drawing a cell diagram, we follow the following conventions. The anode is always placed on
the left side, and the cathode is placed on the right side. The salt bridge is represented by double vertical
lines (||). The difference in the phase of an element is represented by a single vertical line (|), while changes
in oxidation states are represented by commas (,).

Worked Example 1.6

2Ag+(aq) + Cu(s) ⇌ Cu2+(aq)+ 2Ag(s)

 ELECTROCHEMICAL METHODS 9

Step 1: Write the two half-reactions.

Ag+(aq) + e− ⇌ Ag(s)

Cu(s) ⇌ Cu2+(aq) + 2e−

Step 2: Identify the cathode and anode.

Cu(s) is losing electrons thus being oxidized; oxidation occurs at the anode.
Anode (where oxidation occurs): Cu(s) ⇌ Cu2+(aq) + 2e−

Ag+ is gaining electrons thus is being reduced; reduction happens at the cathode.
Cathode (where reduction occurs): Ag+(aq) + e− ⇌ Ag(s)

Step 3: Construct the Cell Diagram.

Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)

Cell Voltage/Cell Potential

The readings from the voltmeter give the reaction's cell voltage or potential difference between its
two half-cells. Cell voltage is also known as cell potential or electromotive force (emf) and it is shown as the
symbol E°cell .

The Eo values are tabulated with all solutes at 1 M and all gases at 1 atm. These values are called
standard reduction potentials. Each half-reaction has a different reduction potential, the difference of two
reduction potentials gives the voltage of the electrochemical cell. If Eocell is positive the reaction is
spontaneous and it is a voltaic cell. If the Eocell is negative, the reaction is non-spontaneous and it is referred
to as an electrolytic cell.

Table 1.1. Standard Reduction Potential Values

Reduction Half-Reaction Standard Reduction Potential (V)

F2(g)+2e- → 2F-(aq) +2.87
O2(g)+4H+(aq)+4e- → 2H2O(l) +1.23
Br2(l)+2e- → 2Br-(aq) +1.09
Ag+(aq)+e- → Ag(s) +0.80
Fe3+(aq)+e- → Fe2+(aq) +0.77
I2(l)+2e- → 2I+(aq) +0.54
Cu2+(aq)+2e- → Cu(s) +0.34
Sn4+(aq)+2e- → Sn2+(aq) +0.15
S(s)+2H+(aq)+2e- → H2S(g) +0.14
2H+(aq)+2e- → H2(g) 0.00
Sn2+(aq)+2e- → Sn(g) -0.14
V3+(aq)+e- → V2+(aq) -0.26
Fe2+(aq)+2e- → Fe(s) -0.44
Cr3+(aq)+3e- → Cr(s) -0.74
Zn2+(aq)+2e- → Zn(s) -0.76
Mn2+(aq)+2e- → Mn(s) -1.18
Na+(aq)+e- → Na(s) -2.71
Li+(aq)+e- → Li(s) -3.04
 ELECTROCHEMICAL METHODS 10

Worked Example 1.6 Calculating E° cell at Standard State

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Step 1: Write the half-reactions for each process.

Oxidation: Zn(s) → Zn2+(aq) + 2e-

Reduction: Cu2+(aq) + 2e- → Cu(s)

Step 2: Look up the standard potential for the reduction half-reaction.

Cu2+(aq) + 2e- → Cu(s) E⁰red = +0.34 V

Step 3: Look up the standard reduction potential for the reverse of the oxidation reaction and change the
sign.
Zn2+(aq) + 2e- → Zn(s) E⁰red= –0.76 V
2+
Zn(s) → Zn (aq) + 2e- E⁰ox= +0.76 V

4. Add the cell potentials to get the overall standard cell potential.

E⁰cell = E⁰red + E⁰ox

E⁰cell = +0.34 V + +0.76 V
E⁰cell = +1.1 V (the reaction is spontaneous and the cell is voltaic)

The Daniell Cell

Redox Reactions at the Electrodes of Daniell Cell

Daniell cell – is an electrochemical cell named after John Frederic Daniell, the British chemist who invented
it in 1836. It is made up of zinc, Zn plate dipped into zinc sulphate solution and copper, Cu plate dipped into
copper(II) sulphate, CuSO4 solution.

Figure 1.4 The Daniell Cell

The electrodes act as a terminal, or a holding place, for electrons. A wire connects the electrodes,
but nothing happens until you put a salt bridge between the two containers. The salt bridge, normally a U-
shaped hollow tube filled with a concentrated salt solution, provides a way for ions to move from one
container to the other to keep the solutions electrically neutral. With the salt bridge in place, electrons can
start to flow.

At the anode (negative terminal) At the cathode (positive terminal)

 Zinc loses electrons and is oxidized to zinc ion,  Copper ion gains electrons and is reduced to
Zn+2 copper metal, Cu.
 Oxidation occurs and zinc acts as reducing  Reduction occurs and copper ion acts as
agent. oxidizing agent.
Zn(s) Zn+2(aq) + 2e- Cu+2(aq) + 2e- Cu(s)
 Electrons generated at the anode move
through the external circuit to the copper
cathode.
Overall reaction that occurs in the Daniell cell

Oxidation (loss of e-)

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

Reduction (gain of e-)

 ELECTROCHEMICAL METHODS 11

This cell will produce a little over one volt. You can get just a little more voltage if you make the
solutions that the electrodes are in very concentrated. Although historically important, it is no longer used
commercially.

Cells and Batteries

Redox reactions involve the transfer of electrons between two species. The flow of electrons is an
electrical current. Redox reactions can therefore be used to generate electrical current. This is the basis of
batteries and fuel cells.

A cell is a store of chemical energy in a closed system. All reactants and products are contained within
the casing of the cell.

A battery is more than one cell connected together in a series arrangement. When a conductor is
connected across the two terminals, a circuit is formed and electrons flow through it. By connecting more
than one cell together, the electromotive force is increased. The battery voltage is the sum of the voltages
of each of the cells. A battery is a closed system which contains the high energy reactants and the low energy
products in a sealed unit.

Rechargeable and Non-rechargeable Cells

There are two types of cell: non-rechargeable and rechargeable. They are also known as primary and
secondary cells. Primary cells can only be used once. Secondary cells can be recharged and reused. Smaller
cells contain fewer reactants and produce less electrical energy. However, the reaction voltage doesn’t
change with cell size.

Primary cells

A primary cell can only be used once because it transfers stored chemical energy into electrical energy
by a non-reversible chemical reaction. Primary cells are usually cheaper to buy. They are more reliable as
they do not discharge much when they are not in use. This makes them more useful for applications such as
smoke detectors.

Redox Reactions at the Electrodes of Dry Cells

A dry cell is a voltaic cell where electrolyte is a paste.

A. Common dry cell (acidic) – made up of a zinc, Zn container as the anode (negative terminal) and a
carbon, C (graphite) rod as the cathode (positive terminal). The electrolyte used is a paste containing
ammonium chloride NH4Cl, zinc chloride ZnCl2 and water,H2O.

Figure 1.4 Carbon-Zinc Cell

At the anode (negative terminal) At the cathode (positive terminal)

 Zinc loses electrons and is oxidized to zinc ion,  Ammonium ion, NH4+1 gains electrons and is
Zn+2 reduced into ammonia gas,NH3 and hydrogen
 Oxidation occurs and zinc acts as reducing gas,H2.
agent.  Reduction occurs and NH4+1 acts as oxidizing
Zn(s) Zn+2(aq) + 2e- agent.
2NH4+1(aq) + 2e- 2NH3(g) + H2(g)
 ELECTROCHEMICAL METHODS 12

 Electrons generated at the anode move  The formation of bubbles of hydrogen gas
through the external circuit to the copper around the carbon electrode is called
cathode. polarization of the cell. Manganese(IV) oxide,
MnO2 is used to oxidize the hydrogen.
Precipitation reaction:
2MnO2(s) + H2(g) Mn2O3(s) + H2O(l)
 The overall reaction at the cathode is
2NH4+1 + 2MnO2 + 2e- 2NH3 + Mn2O3 + H2O
Overall reaction that occurs in the common dry cell

Oxidation (loss of e-)

Zn(s) + 2NH4+1(aq) + 2MnO2(s) Zn+2(aq) + 2NH3(g) + Mn2O3(s) + H2O(l)

Reduction (loss of hydrogen)

Dry cells costs cheap, however they are not rechargeable. They also have poor shelf life. To increase
your battery shelf life, refrigerate it prior to use. Decreasing the temperature would mean decreasing its
reaction rate.

B. Alkaline Dry Cell – modified example of common dry cell that uses potassium hydroxide, KOH rather
than ammonium chloride NH4Cl in the paste, producing somewhat different reaction at the
electrodes.

Figure 1.5 Button Cell

Oxidation (anode): Zn(l) + 2OH(aq) ZnO(s) + H2O(l) + 2e-

Reduction (cathode): 2MnO2(s) + H2O(l) + 2e- Mn2O3(s) + 2OH(aq)

The alkaline dry cell lasts much longer as the zinc anode corrodes less rapidly under basic
conditions than under acidic conditions. It maintains a steady voltage of about 1.5 V under high
current loads and generates about more than half the common dry cell of the same size.

Other types of alkaline dry cell batteries are the silver battery in which silver metal serves as
an inert cathode to support the reduction of silver oxide (Ag2O) and the oxidation of zinc (anode) in
a basic medium. The type of battery commonly used for calculators is the mercury cell. In this type
of battery, HgO serves as the oxidizing agent (cathode) in a basic medium, while zinc metal serves as
the anode.

Secondary Cells

Secondary Cells are more environment friendly than primary cells as they can be recharged and reused many
times. They are more expensive to buy and require charging equipment.

Redox Reactions at the Electrodes of Rechargeable Batteries

A. Lead Acid Battery - a battery which uses sponge lead, Pb and lead(IV) oxide, PbO2 for the conversion of
the chemical energy into electrical power. The lead acid battery is most commonly used in the
automobiles and power stations because it has higher cell voltage and lower cost.

The electrolyte used in the battery is 35% sulfuric acid (commonly called battery acid) and 65% water
solution. All lead-acid batteries operate on the same fundamental reactions. When the sulfuric acid
dissolves, its molecules break up into positive hydrogen ions (2H+) and sulphate negative ions (SO4—) and
move freely.
As the battery discharges, the active materials in the electrodes lead(IV) oxide, PbO2 in the cathode
and sponge lead, Pb in the anode) react with sulfuric acid in the electrolyte to form lead(II) sulfate and
water.
 ELECTROCHEMICAL METHODS 13

As the battery recharges, the lead(II) sulfate on both electrodes converts back to lead(IV) oxide, PbO2
in the cathode and and sponge lead, Pb in the anode and the sulfate ions are driven back to electrolyte
solution to form sulfuric acid, H2SO4.

Figure 1.6 Discharging Figure 1.7 Recharging Figure 1.8 Lead Acid Battery

discharge
Oxidation (anode): Pb(s) + SO4-2(aq) PbSO4(s) + 2e- = (1.685 V)
charge

discharge
Reduction (cathode) : PbO2(s) + 4H+(aq) + SO4-2(aq) PbSO4(s) + 2H2O(l) = (0.356 V)
charge
Overall Reaction:
discharge
Pb(s) + PbO2(s) + 4H+(aq) + SO4-2(aq) PbSO4(s) + 2H2O(l) = (2.041 V)
charge

The maximum open circuit voltage that can developed by a single acid cell is 2.041 V. the lead storage
battery used as a power source in automobiles is made up of six lead acid cells. When hooked in series the
produced a total of 12 volts which powers the ignition, power brakes, power steering and power locks and
windows.

B. Nickel – Cadmium Battery – widely used in portable, electronic equipment and power tools. The active
components of a rechargeable Ni-Cd battery in the charged state consist of nickel hydroxide (NiOOH) in
the cathode and cadmium (Cd) in the anode. For the electrolyte, usually caustic solution (potassium
hydroxide, KOH) is used. Due to their low internal resistance and the very good current conducting
properties, Ni-Cd cells can supply extremely high currents and can be recharged rapidly.

Figure 1.9 Nickel-Cadmium Battery

Oxidation(anode): Cd(s) + 2OH−(aq) Cd(OH)2(s) + 2e−

Reduction (cathode): 2NiOOH(s) + 2H2O(l) + 2e− 2Ni(OH)2(s) + 2OH−(aq)

Overall Reaction:
Cd(s) + 2NiOOH(s) + 2H2O(l) Cd(OH)2(s) + 2Ni(OH)2(s)

The Ni-Cd battery, also called nicads, is lightweight and produces a constant voltage during
discharge. It provides about 1.4 volts. However, nicads suffer from memory discharge. If they are discharged
only partially and then recharged, they develop the tendency to need recharging after only a short use. These
batteries are more efficient if totally discharged before recharging. Nicads must also be properly disposed
because of the toxicity of cadmium and its compound.
 ELECTROCHEMICAL METHODS 14

Fuel cells

A fuel cell converts chemical energy into electrical energy in a similar fashion to a battery. However,
a fuel cell is an open system – reactants flow in and products flow out, rather than being stored in the cell.

Redox Reactions at the Electrodes of Hydrogen Fuel Cells

Hydrogen fuel cells produce electricity through the reaction of hydrogen with oxygen. The electrolyte
used is aqueous potassium hydroxide.

The reaction which takes place in a hydrogen fuel cell is: 2H2 + O2 2H2O

The hydrogen molecules enter the left side of the cell. As

they contact the anode they release electrons to form positively
charged hydrogen ions. The hydrogen ions cross the permeable
membrane. They will combine with oxygen and free electrons from
the cathode to form water molecules.

Oxidation (anode): 2H2(g) 4H+(aq) + 4e–

Reduction (cathode): 4H+(aq) + O2(g) + 4e 2H2O(g)

The only waste product is water vapour. Hydrogen fuel cell

is very much like a battery that can be recharged while you are
drawing power from it. Instead of recharging using electricity,
however, it uses hydrogen and oxygen. Figure 1.10 Hydrogen Fuel Cell

Calculating the energy

Bond energies can be used to calculate the amount of energy given out by the reaction in a hydrogen
fuel cell. Energy is taken in to break bonds, and released when bonds are created.

Table 1.2 Bond Energies

Bond Bond Energy (kJ)

H–H 432
O=O 498
O–H 463

Energy for bond-breaking Energy from bond-making

= 2 H-H + O=O = 4 H-O
= (2 x 432) + 498 = 4 x 463
= 1362 kJ 1852 kJ

Total energy change = energy in – energy out

= 1362 kJ – 1852 kJ = –490 kJ

In exothermic reactions, the products have less enthalpy than reactants, as a result, an exothermic
reaction is said to have a negative enthalpy reaction. This means that the energy required to break the
bonds in the reactants is less than the energy released when new bonds form in the products. Excess
energy from the reaction is released as heat and light.

Production of hydrogen

Hydrogen is a very reactive element and must be produced by a chemical reaction before it can be
used in a fuel cell. There are currently two main methods of manufacturing hydrogen:
 reaction of hydrocarbons with steam
 electrolysis of acidified water.

Although a hydrogen fuel cell is not directly polluting, processes used to produce hydrogen can be.
Electricity for electrolysis is often produced by fossil fuel power stations. Carbon dioxide is produced from
the reaction of hydrocarbons with steam.
 ELECTROCHEMICAL METHODS 15

Transporting and storing hydrogen

Hydrogen is an explosive gas with a very low boiling point. It is difficult to transport and store. Several
methods have been developed.

A. Liquid under pressure

Hydrogen can be forced in to liquid state under high pressure. It requires very low temperature and
a special container to prevent it from boiling. This is an expensive method of storage.

B. Adsorption

Hydrogen can be adsorbed on to a solid material. This can take place at low pressure and close to room
temperature. However, currently the materials being used for adsorption must be replaced regularly.

C. Absorption

Hydrogen can be absorbed by solid materials. Hydrogen atoms enter spaces in metal alloys lattices,
forming hydrides. However, these alloys deteriorate over time and need to be replaced regularly.

Advantages of hydrogen fuel cells

 Hydrogen has a low density, making vehicles light and efficient.
 Hydrogen gives out more energy per gram than conventional fuels.

Disadvantages of hydrogen fuel cells

 The production, storage and distribution of hydrogen for use in fuel cells relies heavily on energy
from fossil fuels.
 Pure hydrogen is expensive and highly flammable.

One way around these problems is to replace hydrogen with a more convenient substance. Methanol,
natural gas and propane have all shown potential for use in fuel cells.

Hydrogen-rich fuels

With the difficulty in transporting and storing hydrogen, some fuel cell vehicles use hydrogen-rich
fuels which are converted to hydrogen by an onboard ‘reformer’.

The reformer uses temperatures of 250–300°C to favour reactions generating hydrogen gas.
Hydrogen-rich fuels include methanol, natural gas and petrol.

Reactions in a direct methanol fuel cell

Oxidation (anode): CH3OH + H2O 6H+ + 6e- + CO2

Reduction (cathode): 3/2O2 + 6H+ + 6e- 3H2O

Overall equation: CH3OH + 3/2O2 2H2O + CO2

Ethanol fuel cell

Ethanol is a less toxic and more energy-dense alcohol than methanol. Research into developing an
ethanol fuel cell is ongoing. Currently, platinum-based catalysts are used to oxidize ethanol, but don’t achieve
complete oxidation. Cheaper, more efficient catalysts capable of fully oxidizing ethanol are needed.

Ethanol can be made from renewable sources, such as the fermentation of sugar. These energy
resources are considered carbon neutral – the amount of carbon dioxide they release is equal to the amount
absorbed during growth.
 ELECTROCHEMICAL METHODS 16

NAME: ________________________________________________ SCORE: ______________

YR & SEC: _______________ GROUP NO. _______ DATE: _______________

ACTIVITY NO. ____

DETERMINATION OF OXIDATION NUMBER

I. Determine the oxidation number of the following elements.

1) Na 11) F
2) Ba 12) Br
3) K 13) P
4) Al 14) Cs
5) O 15) Mg
6) Ca 16) Pb
7) N 17) Li
8) C 18) I
9) S 19) Zn
10) Fe 20) Ag

II. Determine the oxidation number of the underlined element.

1) Fe(OH)3 11) Ca(NO3)2

2) KHCO3 12) Ag2SO3
3) Na2Cr2O7 13) Co3(PO4)2
4) H3PO4 14) Pb3(PO4)4
5) HgCl2 15) MgCl2
6) AlPO4 16) BeF2
7) BeSO4 17) K2MnO4
8) Na2CO3 18) HClO3
9) Mg3(PO4)2 19) Sn(NO3)2
10) CaCO3 20) H2SO4

III. Write the correct formula each of the following polyatomic ions then determine the oxidation number of
the first element.

Formula Oxidation no.

1) nitrate
2) ammonium
3) peroxide
4) perchlorate
5) sulfite
6) bromate
7) dichromate
8) oxalate
9) carbonate
10) permanganate
11) arsenate
12) chromate
13) borate
14) hypochlorite
15) nitrite
16) sulfate
17) bicarbonate
18) cyanate
19) cyanide
20) iodate
 ELECTROCHEMICAL METHODS 17

NAME: ________________________________________________ SCORE: ______________

YR & SEC: _______________ GROUP NO. _______ DATE: _______________

ACTIVITY NO. ____

REDOX REACTIONS
IV. Determine what is oxidized and what is reduced in each reaction. Identify the oxidizing agent and the
reducing agent, also.

Oxidizing Reducing
Reactions Oxidized Reduced
agent agent
1. 2Sr + O2  2SrO

2. 2Li + S  Li2S
3. 2Cs + Br2  2CsBr

4. 3Mg + N2  Mg3N2

5. 4Fe + 3O2  2Fe2O3

6. Cl2 + 2NaBr  2NaCl + Br2

7. Si + 2F2  SiF4
8. 2Ca + O2  2CaO

9. Mg + 2HCl  MgCl2 + H2

10. 2Na + 2H2O  2NaOH + H2

V. Given the following half – reactions, draw a voltaic cell. Label the anode and the cathode, show the
direction of electron flow, and the direction of ion movement. Assume both are in chloride solutions.
Write the Cell Notation and calculate the electromotive force.

1) Cu2+(aq) + 2e– → Cu (s) and Ag(s) → Ag+ (aq) + e–

2) Pb(s) → Pb2+(aq) + 2e– and Cr3+(aq) + 3e– → Cr(s)

 ELECTROCHEMICAL METHODS 18

NAME: ________________________________________________ SCORE: ______________

YR & SEC: _______________ GROUP NO. _______ DATE: _______________

ACTIVITY NO. ____

BALANCING REDOX REACTIONS 1
Balance each redox reaction in acidic solution.

1. Mn 2+ + BiO3- MnO4- + Bi3+

2. MnO4- + Cl- Mn2+ + Cl2

3. ClO3- + Cl- Cl2 + ClO2

 ELECTROCHEMICAL METHODS 19

NAME: ________________________________________________ SCORE: ______________

YR & SEC: _______________ GROUP NO. _______ DATE: _______________

ACTIVITY NO. ____

BALANCING REDOX REACTIONS 2
Balance each redox reaction in basic solution.

1. Mn2+ + H2O2 MnO2 + H2O

2. Zn + NO3- Zn(OH)2 + NH3

3. CN- + MnO4- CNO- + MnO2

 ELECTROCHEMICAL METHODS 20

NAME: ________________________________________________ SCORE: ______________

YR & SEC: _______________ GROUP NO. _______ DATE: _______________

ACTIVITY NO. ____

DETERMINATION OF EMF OF A CELL

A. Given the following SRP values: Cu2+ / Cu = + 0.34 V and Ag+ / Ag = + 0.80 V

1. EMF:

2. Cathode reaction:

3. Anode reaction:

4. Cell diagram:

5. Cell type:

B. Given the following SRP values: Al3+ / Al = – 1.676 V and Sn2+ / Sn = – 0.137 V

6. EMF:

7. Cathode reaction:

8. Anode reaction:

9. Cell diagram:

10. Cell type:

B. Given the following SRP values: Cu2+ / Cu = + 0.34 V and Sn2+ / Sn = – 0.137 V

11. EMF:

12. Cathode reaction:

13. Anode reaction:

14. Cell diagram:

15. Cell type:

 ELECTROCHEMICAL METHODS 21

NAME: ________________________________________________ SCORE: ______________

YR & SEC: _______________ GROUP NO. _______ DATE: _______________

ACTIVITY NO. ____

THE DANIELL CELL
Objectives
a) Construct a Daniell Cell.
b) Observe how an electrochemical cell works.

Background
The Daniell cell consists primarily of a zinc bar immersed in zinc sulfate, ZnSO4 solution and a copper
bar immersed in a copper(II) sulfate, CuSO4 solution. The cell operates on the principle that the oxidation of
Zn to Zn2+ and reduction of Cu2+ to Cu can be made to take place simultaneously in separate locations with
the transfer of electrons between them occurring through an external wire. The zinc and copper bars are
called electrodes.

Materials
ZnSO4 solution NaCl solution two cables with alligator clips
CuSO4 solution beakers, 2 voltmeter
a strip of zinc plastic tube or U-tube distilled water
a strip of copper cotton digital scale

Procedure
1. Preparation of Solutions:
 ZnSO4 solution – Dissolve 30 g ZnSO4 in 200 mL
distilled water
 CuSO4 solution – Dissolve 30 g CuSO4 in 200 mL
distilled water
 NaCl solution – Dissolve 10 g NaCl in 100 mL
distilled water
2. Place a zinc strip in the solution of zinc sulfate.
3. Place a copper strip in the solution of copper sulfate.
4. Use a wire to connect these strips as shown in figure 1.
When you measure the voltage across these electrodes,
you should find it to be about 1.1 volts.
5. Put a salt bridge between the two containers by using a
U-shaped tube filled with saline solution. You can make one with the plastic tube. Fill the tube with NaCl
solution. Plug the ends with the cotton so that the saline solution will remain in the bridge and not mix
with the electrolytes.

Discussions
1. Which electrodes acts as the anode? Cathode?
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2. Explain what happens in each electrodes (anode and cathode).
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3. What serves as the conducting medium through which ions can move?
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4. Write the equations of half reactions that occur in each electrodes.
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5. Write the equation of the overall redox reaction and identify the reducing and oxidizing agents.
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