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 copper, FE.
 Oxidizing agent: iron(II) oxide, FeO (oxidized C into CO2)
 Reducing agent: carbon, C (reduced FeO to Fe)

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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.

Sample Problem

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

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, Cl
 Reducing agent: sodium, Na

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Sample Problem

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, Cl
 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

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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

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

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)

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Voltaic (Galvanic) Cells

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.

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.
+2
Zn(s) Zn (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-)

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.

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.

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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.
 Electrons generated at the anode move 2NH4+1(aq) + 2e- 2NH3(g) + H2(g)
through the external circuit to the copper  The formation of bubbles of hydrogen gas
cathode. around the carbon electrode is called
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.

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.

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.

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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.

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.

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.

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.

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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): H2(g) – 2e 2H+(aq)

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.

Electrolytic Cells

Electrolytic cells – a type of electrochemical cell that works on a chemical system by applying electric current
through the system. The process where electricity is used to bring about a nonspontaneous redox reaction
is called electrolysis.

Electrolysis cells can be divided into two categories based on the electrodes used:

a) Passive Electrolysis – the electrodes are chemically inert materials that simply provide a path for
electrons. This is used in industry to purify metals that corride easily.

b) Active Electrolysis – the electrodes are part of the electrolytic reaction. This is used to plate materials
(electroplating) to provide resistance to corrosion.

A. Passive Electrolysis

a) Electrolysis of Molten or Liquid NaCl

The simplest example of an electrolytic cell is the molten or liquid sodium chloride (NaCl). Sodium
chloride, NaCl(l), when heated to above its melting point (801°C) melts, making Na+ and Cl- ions free flowing.
A source of direct current is connected to a pair of inert electrodes immersed in molten sodium chloride. The
Na+ ions flow toward the negative electrode (cathode) and the Cl- ions flows toward the positive electrode
(anode). The Na+ is reduced to Na and Cl- is oxidized to Cl2.

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Chlorine gas bubbles through the molten sodium chloride into a funnel at the top of the cell. Sodium
metal forms at the cathode then floats through the molten sodium chloride into a sodium collecting ring,
which is very so often drained. An iron gauze (diaphragm) separates the two electrodes to prevent the
explosive reaction that could occur if the product of electrolysis reaction would come in contact. Sodium
chloride can be electrolyzed using the Down’s cell.

Oxidation (anode): 2 Cl- Cl2(g) + 2e

Reduction (cathode): Na+ + 2e- 2 Na(l)

b) Electrolysis of Aqueous NaCl

A solution wherein the solvent is water is an aqueous solution. An aqueous solution of NaCl contains
Na and Cl- ions with H2O molecules. When an aqueous solution of NaCl is electrolyzed using inert electrodes,
+

chlorine gas forms at the anode and hydrogen gas forms at the cathode.

But now, there are two substances that can be reduce at the cathode: Na+ ions and water molecules.
Only the hydrogen ions are discharged at the cathode. The more reactive a metal, the less readily its ion is
reduced on the electrode surface. Nothing happens to the sodium ion, but it is still important. In fact, if
sodium was released (which it isn't), it would immediately react with water to give hydrogen, the same
product you get from the reduction of the hydrogen ion.

Reduction (cathode): (a) Na+ + e- Na(l)

(b) 2 H2O(l) + 2e- H2(g) + 2 OH- (hydroxide ion)

There are also two substances that can be oxidized at the anode: Cl- ions and water molecules. Note
that, if most of the chloride ions have been discharged as chlorine molecules, you can then get some oxygen
gas formed at the anode i.e. like in the electrolysis of water, and chloride ions are being replaced by hydroxide
ions which can be oxidised to oxygen at the anode.

Reduction (cathode): (a) 2 Cl- Cl2(g) + 2e

(b) 2 H2O(l) – 4e- 4H+(aq) + O2 (oxygen gas)

Usually nothing happens to the hydroxide ion but it is important, because, the hydroxide ion, with
the unchanged sodium ion, the residual solution contains sodium hydroxide. In fact this is how sodium
hydroxide is manufactured in the chemical industry. Na+ + OH- NaOH

Summary: electrolysis of aqueous NaCl does not give the same products as electrolysis of molten sodium
chloride. Electrolysis of molten NaCl decomposes into its elements, while electrolysis of aqueous NaCl
solutions gives a mixture of hydrogen and chlorine gas and aqueous sodium hydroxide solution.

c) Electrolysis of Water

A pair of inert electrodes is sealed in the opposite ends of a container with water. The electrodes are
then connected to a battery or another source of electric current. Because water by itself is a very poor
conductor of electricity, a soluble electrolyte such as sulfuric acid, H2SO4 is added to water to supply ions that

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can flow through a solution, thereby completing the electric circuit. Water is slowly electrolyzed collecting
H2 at the anode and O2 at the cathode.

The hydrogen ions (H+) are attracted to the negative cathode and are discharged as hydrogen gas.
The hydrogen ion or water molecules are reduced to hydrogen gas molecules by electron gain at the negative
electrode.

Reduction (cathode): 4H2O + 4e- 2 H2(g) + 4 OH(aq)

The negative sulfate ions (SO42-) or the traces of hydroxide ions (OH–) are attracted to the positive
electrode. But the sulfate ion is too stable and nothing happens (it’s not discharged). Instead either hydroxide
ions or water molecules are discharged and oxidised to form oxygen. The hydroxide ions or water molecules
are oxidised to oxygen gas molecules by electron loss at the positive electrode.

Oxidation (anode): 2H2O(l) 4 H2(aq) + O2(g) + 4e-

Overall equation for the electrolysis of water: 2H2O(l) 2 H2(g) + O2(g)

B. Passive Electrolysis

Electroplating – is the deposition of a thin metallic coating onto an object by the use of electrolysis.

To electroplate an object, the object must have a negative charge. Then the object is immersed into
a solution that contains salt of the metal to be deposited. The metallic ions of the salt carry a positive charge
and are attracted to the negative part. When they reach it, the negatively charged part provides the
electrons to reduce the positively charged ions to metallic form.

The Electrolysis of Copper(II) Sulfate

The electrolyte copper(II) sulfate, provides a high concentration of copper(II) ions Cu 2+ and sulfate
ions SO42– to carry the current during the electrolysis process. There are small concentrations of hydrogen
ions H+ and hydroxide ions (OH–) from the self-ionisation of water itself. The electrolysis will only take place
when electricity is passed through the copper solution.

Details of the electrolysis of copper(II) sulfate solution with two different electrodes (a) graphite
(carbon) electrodes and (b) copper electrodes are as follows:

a) Using Inert Graphite (Carbon) Electrodes

The negative cathode electrode attracts Cu2+ ions (from copper sulfate) and H+ ions (from water).
Only the copper ion is discharged, being reduced to copper metal. The less reactive a metal, the more readily
its ion is reduced on the electrode surface. A copper deposit forms as the positive copper ions are attracted
to the negative electrode (cathode).

Reduction (cathode): Cu2+(aq) + 2e- Cu(s) (positive ion reduction by electron gain)

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The traces of hydrogen ions are not discharged, so you not see any gas collected above the negative
electrode. The blue colour of the copper ion will fade as the copper ions are converted to the copper deposit
on the cathode.

Oxygen gas is formed at the positive electrode, an oxidation reaction (electron loss). The negative
sulfate ions (SO42-) or the traces of hydroxide ions (OH–) are attracted to the positive electrode. But the sulfate
ion is too stable and nothing happens. Instead either hydroxide ions or water molecules are discharged and
oxidised to form oxygen.

Oxidation (anode): 4 OH–(aq) – 4e- 2 H2O(l) + O2(g) (negative ion oxidation by electron loss)

b) Using Copper Electrodes (in Anode)

When Copper(II) sulfate is electrolysed with a copper anode electrode (the cathode can be carbon or
copper), the copper deposit on the cathode (–) equals the copper dissolves at the anode (+). Therefore the
blue colour of the Cu2+ ions stays constant because Cu deposited = Cu dissolved. Both involve a two electron
transfer so it means mass of Cu deposited = mass of Cu dissolving for the same quantity of current flowing
(flow of electrons). You can check this out by weighing the dry electrodes before and after the electrolysis
has taken place. The electrolysis also works with a carbon anode and you see the blackness of the graphite
change to the orange-brown colour of the copper deposit.

Reduction (cathode): Cu2+(aq) + 2e- Cu(s) (copper deposit, reduction by 2e- gained)

It’s the copper anode that is the crucial difference than electrolysing copper sulfate solution with an
inert carbon/graphite/platinum electrode. The negative sulfate ions SO42- (from copper(II) sulfate) or the
traces of hydroxide ions OH– (from water) are attracted to the positive electrode. But both the sulfate ion
and hydroxide ion are too stable and nothing happens to them because the copper anode is preferentially
oxidised to discharge Cu2+ copper ions.

Oxidation (anode): Cu(s) – 2e- Cu2+(aq) (copper dissolves, oxidation by 2e- lost)

Balancing Act

Copper atoms oxidised to copper(II) ions: dissolving of copper in its electrolytic purification or electroplating
(must have positive copper anode). The change involves two electrons per copper atom.

Copper(II) ion reduced to copper atoms: deposition of copper in its electrolytic purification or electroplating
using copper(II) sulfate solution, so the electrode can be copper or other metal to be plated or any other
conducting material. The change involves two electrons per copper ion.

This means for every copper atom that gets oxidised, one copper ion is reduced. Thus, when copper
electrodes are used in the electrolysis of copper sulfate solution, the mass loss of copper from the positive
anode electrode should equal the mass of copper gained and deposited on the negative cathode electrode.

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Summary
As already described already the use of a copper positive anode electrode is the basis of the method
of electroplating any conducting solid with a layer of copper which can be reproduced by electroplating other
conducting materials with zinc (a way of galvanising steel), nickel, silver or chromium ('chromium plating').

The CATHODE object to be electroplated must be a conducting material, usually a metal, and must
be made the negative cathode electrode and completely immersed in the electrolyte solution.

The ANODE is usually a bar of the metal that is being electroplated onto the cathode object, giving a
continuous supply of the coating metal and ensuring the concentration of electrolyte metal ion does not
diminish as the electrolytic plating continues. The metal anode bar must be oxidised to provide a metal ion
that can migrate across to the cathode and be discharged as the electrolysis takes place.

The electrolyte solution must contain ions of the metal that will form the electroplated deposit; and
the ions come from an appropriate salt solution e.g. copper sulfate for copper, silver nitrate for silver, zinc
sulfate for zinc or chromium chloride for chromium coatings.

The anode must be made of the metal that will form the electroplated coating on the positive anode
object e.g. copper or silver.

As the metal is coated on the -ve cathode object, simultaneously the metal of the +ve anode is oxidised to
refresh the solution of metal ions. So there is no depletion of the crucial ion concentration. These positive
ions will migrate towards the negative electrode object to be coated.

The purification of copper by electrolysis amounts to copper plating so all you have to do is swap the
pure negative copper cathode with the metal you want to coat. Swap the impure positive copper anode with
any pure block of the metal you want to form the coating layer on the negative electrode object.

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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) KMnO4 11) Fe2(SO4)3

2) AlBr3 12) Cr2O3
3) Na2Cr2O7 13) Co3(PO4)2
4) H3PO4 14) KNO3
5) HgCl2 15) MgCl2
6) AlPO4 16) BeF2
7) CO2 17) K2MnO4
8) Na2CO3 18) HClO3
9) KBr 19) BrF3
10) KH 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) ammonia
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

CHEMISTRY FOR ENGINEERS (CHEM 114E) BPSU SCIENCE CLUSTER

 ELECTROCHEMICAL METHODS 14

NAME: ________________________________________________ SCORE: ______________

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

ACTIVITY NO. ____

REDUCTION – OXIDATION REACTIONS
I. Classify each of the following half-reactions as oxidation or reduction. Write O for oxidation and R for
reduction.

1) Ca(s)  Ca2+(aq) 11) CO(g)  CO2(g)

2) S(s)  S2+(aq) 12) Zn2+(aq)  Zn(s)
3) MnO4(aq)  MnO2(aq) 13) Al(s)  Al3+(aq)
4) Li(s)  Li+(aq) 14) Ba2+(aq)  Ba(s)
5) Cr2O7(aq)  Cr2+ 15) Ag+(aq)  Ag(s)
6) F2(g)  F-(aq) 16) K(s)  K+(aq)
7) Cu2+(aq)  Cu(s) 17) N2(g)  N4+(aq)
8) H2(g)  H-(aq) 18) SO42-(aq)  SO2(g)
9) O2-(aq)  O2(g) 19) Br-(aq)  Br2(g)
10) N2(g)  NO2(g) 20) Mg2+(aq)  Mg(s)

II. Determine the reducing agent and oxidizing agent in each of the following reactions.

Reducing Oxidizing
Agent agent

1) 2Cr(s) + 3NiSO4(aq)  Cr2(SO4)3(aq) + 3Ni(s)

2) 2HCl (aq) + Ni(s)  NiCl2(aq) + H2 (g)

3) 2AgNO3(aq) + Pb(s)  2Ag(s) + Pb(NO3)2(aq)

4) 2HBr (aq) + Zn(s)  ZnBr2(aq) + H2 (g)

5) 2Al(s) + 3NiCl2(aq)  2AlCl3(aq) + 3Ni(s)

6) H2SO4(aq) + Fe(s)  FeSO4(aq) + H2 (g)

7) Mg + 2HCl  MgCl2 + H2

8) 8KClO3 + C12H22O11  8KCl + 11H2O + 12CO2

9) 2Fe + 3V2O3  Fe2O3 + 6VO

10) 2K2Cr2O7 + 2H2O + 3S  3SO2 + 4KOH + 2Cr2O3

11) 8KClO3 + C12H22O11  8KCl + 11H2O + 12CO2

12) PbS(s) + O2(g)PbO(s) + SO2(g)

13) Al(s) + H2SO4(aq)  Al2(SO4)3(aq) + H2(g)

14) 4H2C2O4 + 2KMnO4  8CO2 + K2O + Mn2O3 + 4H2O

15) Cu (s) + 4HNO3(aq)  Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)

CHEMISTRY FOR ENGINEERS (CHEM 114E) BPSU SCIENCE CLUSTER

 ELECTROCHEMICAL METHODS 15

NAME: ________________________________________________ SCORE: ______________

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

ACTIVITY NO. ____

ELECTROCHEMICAL CELLS
Draw and label the following.

A. Galvanic Cell

B. Electrolytic Cell

CHEMISTRY FOR ENGINEERS (CHEM 114E) BPSU SCIENCE CLUSTER

 ELECTROCHEMICAL METHODS 16

NAME: ________________________________________________ SCORE: ______________

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

LABORATORY 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.
__________________________________________________________________________________
__________________________________________________________________________________
__________________________________________________________________________________

CHEMISTRY FOR ENGINEERS (CHEM 114E) BPSU SCIENCE CLUSTER

 ELECTROCHEMICAL METHODS 17

NAME: ________________________________________________ SCORE: ______________

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

LABORATORY ACTIVITY NO. ____

ELECTROPLATING
Objectives
a) Identify the changes that occur during electroplating.
b) Determine the principle behind electroplating.
c) Discuss the importance of electroplating.

Background
Electroplating is an economically important process, often used to reduce corrosion or improve the
appearance of objects. During electroplating a thin layer of a desirable metal is deposited onto another
object. The object to be plated is attached to the negative post of a power source, causing the object to gain
a negative charge. This will attract positive metallic cations from the electrolytic solution the object is placed
in. In our experiment, positive Cu2+ ions from the bath will become attracted to a nail carrying the negative
charge.

Materials
an iron nail 9V battery two cables with alligator clips
a copper strip 250 mL beaker popsicle stick
1.0 M CuSO4 uninsulated copper wire digital scale

Procedure
1. The nail must be clean for good results. Prepare by polishing with some steel wool. Measure the initial
weight of the nail.
2. Use the uninsulated copper wire to suspend the item to be plated (the nail) into the empty beaker.
3. Attach one end of the black alligator clip to the copper wire supporting the nail and the other end to
the NEGATIVE post of the battery or power source.
4. Place the copper strip, the anode, into the empty beaker. Attach one end of the red alligator clip to the
copper strip and attach the other end to the POSITIVE post of the battery or power source.
5. Carefully pour the CuSO4 solution into the beaker until it is about two-thirds full. Make sure the entire
nail is submerged.
6. Allow the reaction to continue for a 10 minutes or so. Record your observations while electroplating is
continuing.
7. Place the nail into a pre-weighed 50mL beaker. Record the mass of the electroplated nail. The difference
between this value and the initial value of the nail is the amount of copper that came out of solution.
8. Show your copper-plated coin to your teacher for final evaluation.

Results
Mass of nail before electroplating: ________ Mass of nail after electroplating: __________
Mass of copper plated: _________ Time of reaction (minutes): __________

Discussions
1. Write the half-reaction that occurs at the anode of the electrolytic cell. Is it oxidation or reduction?
______________________________________________________________________________________
______________________________________________________________________________________
2. Write the half-reaction that occurs at the cathode of the electrolytic cell. Is it oxidation or reduction?
______________________________________________________________________________________
______________________________________________________________________________________
3. Explain both the flow of copper ions and electrons through the system.
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______________________________________________________________________________________
______________________________________________________________________________________
______________________________________________________________________________________
______________________________________________________________________________________
4. Discuss the importance of electroplating.
______________________________________________________________________________________
______________________________________________________________________________________
______________________________________________________________________________________
______________________________________________________________________________________
______________________________________________________________________________________

CHEMISTRY FOR ENGINEERS (CHEM 114E) BPSU SCIENCE CLUSTER