School Science Lessons
Topic 15 Electrochemistry, electrochemical
cells, electrolytic cells
Updated 2009-06-23
Please send comments to: J.Elfick@uq.edu.au
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Table of contents
3.59.0
Conductors of electricity, electrical conductivity
15.00 Electrolytes
15.1.0
Electroplating
15.2.0 Oxidation and reduction,
redox reactions
15.3.0 Rusting, corrosion
15.5.0
Electrolysis
15.4.0 Electrical conductivity of a substance
15.6.0 Electrochemical cells
15.7.0 Electrode potential of
metals
32.5.0
Power and energy
32.6.0
Circuit analysis, house
circuits
32.7.0 Instruments to detect electric
current
33.3.0 Cells and Batteries
33.4.0 Dry cells, Leclanche cell,
flashlight
battery
33.5.0 Lead accumulator cell, car
battery
33.6.0 Thermoelectricity
33.7.0 Piezoelectricity
3.59.0
Conductors of electricity, electrical conductivity
3.59.1 Substances that conduct electricity
3.59.2 Electrical conductivity of solids
3.59.3 Electrical conductivity of melted solids,
fused solids
3.59.4 Electrical conductivity of liquids
6.38 Electricity conductors (primary)
15.00 Electrolytes
8.6
Prepare electrolyte for a lead accumulator
cell
15.01
Conductivity of solutions of
different electrolytes
15.02 Strong electrolytes
15.03 Identify lead ions in an unknown
solution
15.04 Weak electrolytes
15.05 Electrolytes in the blood and urine
15.1.0
Electroplating
15.1.1 Faraday's first law
15.1.1.1 Test Faraday's first law
with copper and copper (II) sulfate solution
15.1.1.2 Test Faraday's first law
with other metals
15.1.2 Electroplating, copper
plating
15.1.3 Electroplating, chromium
plating
15.1.4 Electroplate, nickel plating
15.1.5 Electroplating, silver
plating
15.1.6 Electroplating, zinc plating
of copper
15.1.7 Electroforming with copper
15.1.8 Anodize aluminium
15.1.9 Silvering and desilvering,
plating and
deplating silver
15.1.10 Electroplating copper,
copper flashing
of iron
15.1.11 Lead tree and tin tree
15.1.12 Electroplating with silver
15.1.13 Cucumber pickle frying
15.1.14 Silver coulometer
15.2.0 Oxidation and reduction,
redox reactions, Oxidation is a loss of electrons and reduction is a
gain of electrons
15.2.01 Oxidation occurs when:
15.2.02 Reduction occurs when:
3.76
Reduction of potassium permanganate with sulfur dioxide
12.17.1
Reactions of manganese
(II) salts, Mn
12.17.2
Prepare manganates, MnO42-
12.17.3
Prepare potassium
permanganate, KMnO4
12.17.4
Reactions of permanganate
ion,
MnO4-
15.2.1 Oxygen as an oxidizing agent
15.2.2 Chlorine as an oxidizing agent
15.2.2.1 Bromine as an oxidizing
agent
15.2.3 Potassium dichromate as an
oxidizing agent
12.5.6
Prepare potassium
dichromate, K2Cr2O7
15.2.4.1
Potassium manganate (VII)
oxidizes iron (II) to iron (III)
15.2.4.2 Potassium manganate (VII)
oxidizes glycerol to carbon dioxide and water
15.2.4.3 Potassium manganate (VII)
solution liberates chlorine from hydrochloric acid
15.2.5
Concentrated nitric acid as an
oxidizing agent
15.2.5.1 Nitrous acid as an
oxidizing agent or a reducing agent
15.2.6 Sulfuric acid as an oxidizing
agent
15.2.7 Hydrogen peroxide as an
oxidizing agent
15.2.8 Tests for oxidizing agents by
change in colour of iron (II) to iron (III)
15.2.9 Tests for oxidizing agents by
change of colour of iron with copper (II) sulfate
15.2.10 Tests for oxidizing agents by
change of colour of zinc with copper (II) sulfate
15.2.11 Breath test for alcohol using
potassium dichromate
15.2.12 Breath test for alcohol using
a breath analyser ("breathalyser")
15.2.13 Potassium chlorate and
potassium persulfate as oxidizing agents
15.2.14 Hydrogen sulfide as a
reducing agent
15.2.15 Sulfurous acid as a reducing agent,
ionization reaction
15.3.0
Rusting, corrosion
3.52
Conditions necessary for rusting
3.52.1
The mass of iron and its temperature increases during rusting
3.52.2
Oxygen combines with iron during rusting
3.52.3
Metals can prevent rusting
12.8.1
Reactions of iron (II) salts and
iron
(IlI) salts, Prussian blue
12.8.2
Rusting
12.8.3
Oxidation of iron (II) salt
12.8.4
Burn steel wool
12.8.5
Reduction of iron (IlI)
salts
12.8.6
Heat iron filings with
powdered sulfur
12.8.7
Prepare iron (II) oxide,
FeO
12.8.8
Heat
iron (II) sulfide, (FeS2,
pyrite, fool's gold)
12.8.9
Prepare iron (IlI)
oxide, Fe2O3
12.8.10
Show that black iron oxide is
a
mixed base
12.8.11
Iron displace hydrogen from sulfuric
acid to form iron (II) sulfate
12.8.12
Iron displaces hydrogen
from hydrochloric acid to form pale green iron (II) chloride
12.8.13
Heat hydrated
iron
chlorides
12.8.14
Prepare iron (II) ammonium
sulfate
(NH4)2SO4.FeSO4.6H2O
15.3.1
Rusting of iron wire
15.3.2 Corrosion of magnesium
15.3.3 Rusting of steel wool
15.3.4 Need for oxygen for rusting
15.3.5 Need for oxygen for corrosion
of magnesium
15.3.6 Iron gains weight during rusting
15.3.8 Oxidation can affect air
pressure
15.3.9 Rate of rusting under
separates conditions
15.3.10 Rate of rusting of iron wire
15.3.11 Rate of rusting with steel
wool
15.3.12 Conditions necessary for
rusting
15.3.13 Electrochemical prevention
of rusting,
cathodic protection
15.3.13.01 Cathodic protection
15.3.13.1 Rate of corrosion
affected by formation of electric cells
15.3.14 Restore bronze coins,
corrosion of alloys
15.3.15 Corrosion of aluminium
15.3.16 Clean tarnished silver
15.6.0
Electrochemical cells
3.84
Electrical energy from a simple cell, displacement of copper by zinc
3.84.1
Electrochemical cell, voltaic cell, galvanic cell
3.84.2
Test a simple cell with different metals
3.84.3
Test a simple electric cell with copper and zinc in dilute sulfuric
acid
3.84.4
Simple galvanic cell, zinc in hydrochloric acid
3.84.5
A voltaic cell with a salt bridge
3.85
Daniell cell
3.86
Electrode potentials of metals
3.87
Lead accumulator cell
3.88
Dry cells, Leclanche cell
3.89
Movement of copper and chromate ions
3.90
Movement of ions between
microscope slides, Cu2+
ions, CO2+ ions
15.6.13
Magnesium / copper battery
15.6.14 Nickel / cadmium battery,
NiCad battery
15.7.0 Electrode
potential
of metals
33.3.1 Simple electric cell
33.3.2 Voltaic cell, Daniell cell,
with salt
bridge
33.3.3 Coin cells
33.3.4 Lemon cell
33.3.5 Simple chemical rectifier
33.3.6 Put chocolate wrapper cell in
the mouth
33.3.7 Noisy potato cell
33.3.8 Hydrogen / oxygen fuel cell
33.3.9 Ionic migration
33.3.10
Ionic
friction
33.3.11 EMF dependence on electrode
material
33.3.12 Contact potential difference
33.3.13 Crowsfoot or gravity cell
15.7.0
Electrode potential of metals
15.7.1 Potential difference from combining half
cells, zinc and iron
15.7.2 Potential difference from combining
half cells, Zn and Cu, Zn and Pb
15.7.3 Differences in potential on
an iron nail
3.59.1
Substances that conduct electricity
See diagram 3.59.1
The carbon rods in the
stopper should be 5 min apart. Use crocodile clips to attach a
conducting wire between one battery
terminals and the bulb and the other battery terminal and one of the
carbon rods. The bulb should light when a current passes so lightly
touch both carbon rods with copper wire to make
the bulb light and show that the circuit is works. Prepare separate
beakers of sugar, sodium carbonate, sodium chloride and laundry starch.
Dip in the carbon rods in each beaker and record whether the bulb
lights up to show that the solution is conducting
electricity between the carbon rods. Add water to each beaker. Dip in
the carbon rods in each solution beaker and record whether the bulb
lights. Wash the rods thoroughly under the tap after dipping in each
solution. Note any signs of chemical reaction in the beaker. None
of
the original solid substances conduct electricity. Sodium carbonate
solution and sodium chloride solution conduct electricity. These
solutions are electrolytes. Solutions of sugar, starch and methylated
spirit do not conduct electricity. They are non-electrolytes. Repeat
the experiment by testing dilute hydrochloric acid and dilute sodium
hydroxide. Acids, salts, and alkalis are electrolytes. When dissolved
in water to
form solutions or melted into liquids by heating, they conduct
electricity. Electrolytes are usually decomposed when electric
current passes through them, electrolysis. In electrolysis, the carbon
rod (electrode) connected to the negative
(-) terminal of the battery is the cathode, and the electrode connected
to the positive (+) terminal is the anode. Gases from the decomposition
of electrolytes may be seen as bubbles on the electrodes.
3.59.2 Electrical
conductivity of solids
See diagram 3.59: Electrical
conductivity
apparatus
Use two carbon electrodes from torch batteries, a non-conducting
support for
the
electrodes, crocodile clips or crunched aluminium foil for connections,
light bulbs to show when current flows, and a 6 V dry cell power
source. Test the conductivity of solids by making a good contact
between
the cleaned surface of the solid and the two electrodes. Confirm that
metals and carbon conduct electricity. Test the conductivity of
non-metallic and crystals, e.g. calcite
(crystalline calcium carbonate) candle wax, copper
(II) sulfate-5-water, ethanedioic acid-2-water (oxalic acid) glass
rod, naphthalene, plastics, octadecanoic acid, sucrose (cane sugar)
sodium chloride crystals, sodium nitrate, sugar crystals, sulfur, wax.
None of these
solid compounds is a good conductor.
3.59.3 Electrical conductivity of melted solids,
fused solids
Be careful! Do not let the
carbon
electrodes ignite and burn.
Grip two carbon electrodes from used dry cell batteries with the
crocodile clips. Test the conductivity of the melt by dipping in the
electrodes. Wait for the electrodes to reach the same temperature. This
ensures that the electrodes are in contact with the liquid and not the
solidified melt. Scrape and clean the electrodes between each test.
1. Melt substances that are solids at room temperature, but heat very
gently, otherwise they may ignite and burn, e.g. candle wax, cellulose
acetate (acetate rayon) lead metal, lead bromide, naphthalene, nylon,
octadecanoic acid (stearic acid) polyethylene, polythene, Perspex,
potassium iodide (m.p. 682oC) sodium chloride, sodium
nitrate, solder, sulfur, tin metal. Melted solids vary in their
conductivity. Only molten metals, alkalis and salts are good
conductors. Sugar and sulfur are non-conductors.
2. Glass can be a conductor. Heat a glass rod until it becomes very
hot and begins to soften. Test the hot, soft part with the conductivity
apparatus. When molten, glass is a good conductor of electricity.
3.59.4 Electrical conductivity of liquids
Pure substances that are gases or liquids at room temperature are not
good conductors, but the liquid metal mercury is a good conductor.
1. Clean and dry the carbon electrodes between each test. To test the
conductivity of liquids, immerse the ends of carbon electrodes 3 mm
apart in acetone, copper (II) sulfate
solution, methylated spirit, liquid paraffin, olive oil,
peanut oil, sodium chloride solution, sugar solution, turpentine
(mineral turps) vinegar.
2. Test the conductivity of solutions, e.g. 2 M concentration
of the following:
2.1 Strong electrolytes, e.g. copper (II) sulfate,
hydrochloric acid, potassium hydroxide, sodium chloride, sodium
hydroxide, sodium nitrate, sulfuric acid.
2.2 Weak electrolytes:
ammonia solution, benzoic acid, ethanoic acid (acetic acid). Always
wash the electrodes thoroughly after testing each solution. Solutions
of acids alkalis and metallic salts are generally good
conductors. Solutions of sugar and alcohol are non-conductors.
Solutions of other types of substances in water and in other liquids
are generally non-conductors.
3. Test demineralized water for
conductivity. The bulb does not light. Very gradually stir small
crystals of sodium chloride into the water. Note any light from the
light bulb as the salt dissolves. Similarly test distilled water, tap
water and mineral water.
4. If a commercial conductivity meter is available,
nonelectrolytes show a very small current but a completely dissociated
strong electrolyte e.g. 0.1 M HCl, shows a current > 100 mA.
4.1 Dilute 5 mL of 0.1 M solution of:
4.1.1 HCl,
4.1.2 NaOH to 50 mL.
Test
each reactant solution then mix the two solutions and test half
the volume of the product solution. The conductivity of the
product solution is less than the conductivity of each of the reactant
solutions.
4.2 Test 5 mL of 0.1 M solutions of
4.2.1 acetic acid, HC2H3O2,
4.2.2 aqueous ammonia solution.
Test each
reactant solution then mix the two solutions and test half the volume
of the product solution.
4.3 Test 5 mL of 0.1 M solutions of:
4.3.1 H2SO4,
4.3.2 Ba(OH)2.
Add 3 drops of 0.1% thymol blue indicator
solution to the sulfuric acid solution then add drops of the 0.1
M Ba(OH)2 solution while stirring until the indicator
changes from pink to yellow to blue. Test the conductivity of the
product solution.
15.01
Conductivity of solutions of
different electrolytes
An electrolyte can conduct an electric current in the fused state, or
in solution, and it is decomposed while conducting the current.
Electrolytes dissolve in water to produce solutions that conduct
electric current. As the concentration of the electrolyte in solution
increases, the conductivity of the solution increases. A strong
electrolyte breaks up almost entirely when it dissolves to produce an
aqueous solution. Water is a very weak electrolyte and a poor conductor
of electricity so some electrolyte must be dissolved in it to increase
its conductivity.
15.02 Strong electrolytes
1. Add drops of sodium hydroxide solution to each of three separate
solutions of copper (II) sulfate, copper (II) chloride, copper (II)
nitrate. Observe the blue precipitate in each case. These solutions
contain only the copper (II) ion in common, so assume that this ion
was responsible for the formation of the precipitate.
2. Add drops of barium chloride solution to
separate solutions of
copper (II) sulfate, sulfuric acid and sodium sulfate. In each case you
can attribute the result the presence of the sulfate ion.
3. Add drops of ferric chloride solution to
separate solutions of
sodium hydroxide, potassium hydroxide and calcium hydroxide. These
experiments with solutions of strong electrolytes suggest that the
properties of such solutions are the sum of the properties of the ions
present. The properties of copper (II) sulfate solution are made
up of the properties of the copper (II) ion and the sulfate ion. The
copper (II) ion, Cu2+, causes the blue-green colour of the
solution, and is responsible for the formation of many precipitates
when other substances are added to the solution. The sulfate ion
contributes no colour but forms precipitates with many other ions, such
as Ba2+, when these are added to copper (II) sulfate
solution.
15.03 Identify lead ions in an unknown solution
Prepare separate solutions of lead nitrate, iron (III) chloride and
barium chloride. Test a small portion of each solution in turn with
dilute hydrochloric acid, dilute sulfuric acid and sodium hydroxide
solution. Tabulate your results. Note that lead nitrate solution always
produces a precipitate. Also, iron (III) chloride solution gives a
precipitate only when sodium hydroxide solution is added. Barium
chloride solution gives a precipitate with both sulfuric acid and
sodium hydroxide solutions.
15.04 Weak electrolytes
Smell very carefully a bottle containing some dilute ammonia
solution. The smell of ammonia suggests the presence of ammonia
molecules that must have come from the solution. Add a few drops of
iron (III) chloride to a little ammonia solution. From the results of a
previous experiment with iron (III) chloride, the brown precipitate
obtained confirms the presence of the hydroxide ion in ammonia
solution. Thus ammonia solution has properties due not only to the ions
that are present but also because of ammonia molecules. From similar
experiments, you can find that the properties of solutions of weak
electrolytes are made up from the properties of the unionized molecules
and the properties of the ions produced from them. In such solutions,
the ions and molecules are in equilibrium with each other.
15.05 Electrolytes in the
blood and urine
In medical use electrolyte refers to the ions. So serum electrolyte
refers to sodium, potassium or chloride ions that function in cardiac
rhythm, skeletal muscle contraction and nerve transmission. The level
of bicarbonate ion is important for the acid-base balance in the blood.
The urine electrolytes, sodium and potassium, indicate electrolyte
balance and how hormones affect the function of the kidney.
15.2.01 Oxidation occurs when:
1.1 The substance combines with oxygen, i.e. the addition of oxygen to
an
element or compound, e.g. burning the substance in air.
C (s) + O2 (g) --> CO2 (g)
2Mg + O2 –> 2MgO
2CO + O2 –> 2CO2
1.2 The substance loses hydrogen, e.g. In the following reaction, the
concentrated
acid loses hydrogen and changes to chlorine.
4HCl (aq) + MnO2 (s) --> MnCl2 (aq) + 2H2O
(l)
+ Cl2 (g)
The removal of hydrogen from a compound. In the following equations H2S
is oxidized:
2H2S + O2 –> 2S + 2H2O
H2S + Cl2 –> S + 2HCl
1.3 Oxidation is an increase of valence. In the following equation
divalent iron is oxidized to trivalent iron.
2FeCl2 + Cl2 --> 2FeCl3
2Fe2+ + Cl2 --> 2Fe3+ + 2Cl-
1.4 Oxidation is the loss of electron (s), e.g. when a ferrous ion
changes to a ferric ion.
e2+ - e- --> Fe3+
15.2.02 Reduction
occurs when:
2.1 A substance loses oxygen, e.g. In the following reaction Copper
(II) oxide
loses oxygen and changes to copper.
CuO (s) + H2 (g) --> Cu (s) + H2O (g)
2.2 A substance gains hydrogen, e.g. In this reaction, nitrogen gains
hydrogen to become ammonia.
N2 (g) + 3H2 (g) --> NH3 (g)
nitrogen + hydrogen --> ammonia
2.3 An oxidizing agent helps the oxidation of another chemical. An
oxidizing agent is a substance which causes oxidation. An oxidizing
agent is easily reduced, i.e. it gains electrons easily. The oxidizing
agent gains the electrons and the substance being oxidized loses
electrons. During oxidation, the oxidizing agent is reduced. When
ferric chloride solution is added to stannous chloride solution, ferric
chloride is reduced and stannous chloride is oxidized.
Sn2+ + 2Fe3+ --> Sn4+ + 2Fe2+
Sn2+ - 2e- --> Sn4+ (oxidation)
2Fe3+ + 2e- --> 2Fe3+
(reduction)
2.4 A reducing agent helps the reduction of another chemical. A
reducing
agent is easily oxidized, i.e. it loses electrons easily. Examples of
reducing agents include the following:
Zn metal that is easily oxidized to zinc ion, Zn2+
Hydrogen sulfide that reacts with chlorine to form sulfur
Carbon reduces lead (II) oxide to lead.
Carbon monoxide reduces Fe (III) oxide to iron in a blast furnace.
2.5 Oxidation and reduction reactions (redox reactions) must occur
together. In a redox reaction, the same number of electrons is gained
in the reduction as is lost in the oxidation. In the following
reaction, O2 is an oxidizing agent and the H2 is
a reducing agent:
2H2 (g) + O2 (g) --> 2H2O (l)
15.2.1 Oxygen as an oxidizing agent
See 7.1.1: Chemical changes, burn
magnesium
Oxygen molecules (O2) gain electrons to form oxide ions (O2-).
15.2.2 Chlorine as an oxidizing agent
See 13.4.7: Reactions of chlorine
with
sodium
Chlorine molecules (Cl2) gain electrons to form chloride
ions (Cl-).
2FeCl2 + Cl2 --> 2FeCl3
2Fe2+ (aq) + Cl2 --> 2Fe3+ (aq)
+ 2Cl- (aq)
15.2.2.1 Bromine as an oxidizing agent
Add drops of bromine water to 2 cm of ferrous sulfate in a
test-tube. The green ferrous salt turns yellow, forming a ferric salt.
2Fe2+ + Br2 --> 2Fe3+ + 2Br-
Fe2+ - e- --> Fe3+ (ferrous ion
oxidized)
Br2 + 2e- + 2Br- (bromine reduced)
To prove the presence of a ferric salt, add sodium hydroxide solution
to form a brown precipitate of ferric hydroxide.
15.2.3 Potassium dichromate as an oxidizing agent
Add potassium dichromate solution and drops of dilute sulfuric acid
to iron (II) sulfate solution. The dichromate ion (Cr2O72+)
is reduced to Cr3+ and the solution changes from orange to
green. The iron (II) ions (Fe2+) are oxidized to iron (III)
ions (Fe3+).
Cr2O72+ (aq) + 14H+ (aq) +
6e--
--> 2Cr3+ (aq) + 7H2O (l)
6Fe2+ (aq) --> 6Fe3+ (aq) + e-
Cr2O72+ (aq) + 14H+ (aq) +
6Fe2+ (aq)
--> 2Cr3+ + 7H2O (l) + 6Fe3+ (aq)
15.2.4.1 Potassium permanganate (VII)
oxidizes
iron (II) to iron (III)
Add potassium permanganate solution and drops of dilute sulfuric
acid to iron (II) sulfate solution. The manganate (VII) ions (MnO4-)
are reduced to manganese (II) ions (Mn2+). The iron (II)
ions (Fe2+) are oxidized to iron (III) ions (Fe3+).
MnO4- (aq) + 8H+ (aq) + 5e-->
Mn2+ (aq) + 4H2O (l)
5Fe2+ (aq) --> 5Fe3+ (aq) + e-
MnO4- (aq) + 8H+ (aq) + 5Fe2+
(aq)
--> Mn2+ (aq) + 4H2O (l) + 5Fe3+
(aq)
15.2.4.2 Potassium permanganate (VII)
oxidizes glycerol to carbon dioxide and water
Put 3 g of fine crystal potassium permanganate on a coffee in lid
on sand. Make a hole in the centre of the potassium permanganate and
pour 1 mL glycerol (propane-1,2,3-triol) into the hole. Boil then cool
the glycerol first if it has already absorbed water. Observe a bright
pink flame and steam given off. Dissolve the residue in water and note
a green solution [Mn (VI)] and brown solid [Mn (IV)].
15.2.4.3 Potassium permanganate solution
liberates chlorine from hydrochloric acid
Do this experiment in a fume cupboard. Add potassium permanganate
solution to 2 cm of concentrated hydrochloric acid solution in a
test-tube with damp filter paper over the edge of the opening. Chlorine
gas is given off. Be careful! The damp filter paper becomes bleached.
2MnO4- (aq) + 16H (aq)+ + 10Cl- -->
2Mn2+ (aq) + 8H2O (l) + 5Cl2 (g)
10Cl- (aq) - 10e- --> 5Cl2
(chloride
ion oxidized)
2MnO4- (aq) + 16H+ (aq) + 10e- -->
2Mn2+ (aq)
+ 6H2O (l) (permanganate ion reduced)
15.2.5 Concentrated nitric acid as an oxidizing
agent
See 12.3.12: Reactions of
concentrated nitric acid and copper
Concentrated nitric acid as an oxidizing agent precipitates sulfur from
hydrogen sulfide as a yellow suspension.
H2S <–> 2H+ + S2-
2H+ + S2- + 2H+ + NO3-
--> S + 2H2O + 2NO2
S2- - 2e- --> S (sulfide ion oxidized)
4H+ + 2NO3- + 2e- --> 2H2O
+ 2NO2 (nitric acid reduced)
15.2.5.1 Nitrous acid as an oxidizing agent or a
reducing agent
1. Nitrous acid can act as an oxidizing agent. Slowly add sodium
nitrite solution to potassium iodide solution acidified with dilute
sulfuric acid. Iodine forms showing that the
nitrous acid produced by the action of the dilute acid on the sodium
nitrite has oxidized the potassium iodide. The nitrous acid has itself
been reduced to nitric oxide. The nitric oxide forms brown fumes of
nitrogen dioxide when it contacts the oxygen of the air.
2NO2- + 2I- + 4H+ –> I2
+ 2NO + 2H2O
When acting as an oxidizing agent, nitrous acid gains electrons and is
reduced to nitric oxide.
2NO2- + 4H+ + 2e- --> 2H2O
+ 2NO
2. Nitrous acid can act as a reducing agent. Acidify potassium
permanganate solution with dilute sulfuric acid and add sodium nitrite
solution until the colour of the potassium permanganate just
disappears. Note the absence of brown fumes of nitrogen dioxide. The
solution contains nitric acid and can be tested by the nitrate test.
The potassium permanganate has oxidized the nitrous acid to nitric
acid. The potassium permanganate is reduced to manganous salts.
2MnO4- + 6H+ + 5NO2-
--> 2Mn2+ + 3H2O + 5NO3-
Nitrous acid here acts as a reducing agent; it loses electrons and is
oxidized to nitric acid.
NO2- + H2O - 2e- --> NO3-
+ 2H+
15.2.6 Sulfuric acid as
an oxidizing agent
See 12.3.13: Reactions of
concentrated sulfuric
acid and copper
15.2.7 Hydrogen peroxide
as an oxidizing agent
Hydrogen peroxide turns an iodide solution brown, forming
iodine and perhaps precipitating black crystals of iodine.
1. Add drops of hydrogen peroxide solution to 2 cm of potassium iodide
solution in a test-tube.
2H+ + 2I- + H2O -->. 2H2O
+ I2
2I- - 2e- --> I2 (iodide ion
oxidized)
2H+ + H2O2 + 2e- --> 2H2O
(H2O2 is reduced)
2. Add drops of potassium iodide solution to 20 vols (6%)
hydrogen
peroxide solution. Then add the same number of drops of dilute sulfuric
acid. Heat gently. Note any colour change. Add drops of starch
solution. A blue black colour suggested oxidation of 2I- to I2.
H2O2 (aq) + 2H+ (aq) + 2e--
--> 2H2O (l)
2I- (aq) --> I2 (s) + 2e-
H2O2 (aq) + 2H+ (aq) + 2I-
(aq)
--> I2 (s) + 2H2O (l)
Or
I2 (s) + I- (aq) --> I3-
(aq)
H2O2 (aq) + 2H+ (aq) + 3I-
(aq)
--> I3- (aq) + 2H2O (l)
15.2.8 Tests for oxidizing agents by change in
colour of iron (II) to iron (III)
Prepare a fresh solution of iron (II) sulfate by dissolving iron
filings in dilute sulfuric acid. When the reaction stops, filter the
solution. The filtrate is acidified iron (II) sulfate solution that is
green. Add the test solutions and gently heat. If the solution turns
brown, Fe2+ has changed to Fe3+ because of
the
presence of an oxidizing agent.
15.2.9 Tests for oxidizing agents by change of
colour of iron with copper (II) sulfate
Add Iron to copper (II) sulfate solution. Note the colour change.
The copper ion is an oxidizing agent. The blue colour is removed as
copper forms.
Cu2+ (aq) + Fe (s) --> Fe2+ (aq) + Cu (s)
15.2.10 Tests for oxidizing agents by change of
colour of zinc with copper (II) sulfate
In this reaction, the copper ion Cu2+ attracts electrons
better than the zinc ion, Zn2+. The Zn is oxidized to zinc
ions and the copper is reduced to copper metal. Red copper precipitates
and the solution lose its blue colour.
Add pieces of zinc to copper (II) sulfate solution. The zinc
corrodes and goes into solution. Red copper precipitates and the
solution lose its blue colour. Add excess zinc so that all the copper
precipitates.
Decant the solution and evaporate to leave zinc sulfate crystals. Add
excess zinc so that all the copper precipitates. Decant the solution
and evaporate to leave zinc sulfate crystals.
Zn (s) + CuSO4 (aq) --> Cu (s) + ZnSO4 (aq)
Zn (s) + Cu2+ (aq) --> Cu (s) + Zn2+
15.2.11 Breath test for alcohol using
potassium dichromate
The breath after drinking contains ethanol vapour, which can be
oxidized by potassium dichromate (K2Cr2O7)
and the orange dichromate will be reduced to green chromium ions (Cr3+).
Add 1 mL of 0.05% potassium dichromate solution and one
drop of
concentrated sulfuric acid to a small test-tube. Pour 10 mL pure
ethanol (absolute alcohol) into a small distilling flask. Heat the
flask slowly. Pass the ethanol vapour through the potassium dichromate
solution. The colour of the solution changes from orange to green.
Cr2O72- (aq) + 8H+ (aq) + 3C2H5OH
(l)
--> 2Cr3+ (aq) + 3CH3CHO (l) + H2O
(l)
K2Cr2O7 + 4H2SO4 +
3C2H5OH --> K2SO4 + Cr2(SO4)3
+ 3CH3CHO + H2O
K2Cr2O7 + 4H2SO4 +
7CH3CHO --> K2SO4 + Cr2(SO4)3
+ 7CH3COOH
15.2.12 Breath test for alcohol using a breath
analyser ("breathalyser")
Test a breath analyser used by police or hospital staff. In some
countries the breath testing apparatus used by police to detect
motorists who have consumed too much alcohol is called a
"breathalyser". Borrow a breath testing apparatus from the police.
Ethanol vapour in the breath reduces orange potassium dichromate (K2Cr2O7)
to green chromium ions (Cr3+). The legal limit in some
countries is 80 mg of ethanol per 100 mL of blood.
15.2.13 Potassium chlorate and potassium
persulfate as oxidizing agents
Arrange in test-tube pairs 2 cm of 1. acidified potassium iodide
solution 2. acidified ferrous sulfate solution 3. hydrogen sulfide
solution 4. concentrated hydrochloric acid. Adding 0.55 cc of
potassium chlorate to one set and add 0.55 cc potassium persulfate to
the other set. Note the reaction and warm to completion if necessary.
Note in which case the reaction occurs more readily. Both potassium
chlorate and potassium persulfate are powerful oxidizing agents. The
persulfate ion oxidizes by accepting electrons to become sulfate ions,
e.g., using potassium iodide.
S2O82- + 2I- --> 2SO42-
+ I2
S2O82- + 2e- -->2SO42-
(persulfate ion reduced)
15.2.14 Hydrogen sulfide as a reducing agent
The use of Kipp's apparatus as a source of hydrogen sulfide is
NOT recommended in this document.
1. In a fume cupboard, pass hydrogen sulfide gas into a dilute
acidified potassium permanganate solution. The colour of the potassium
permanganate disappears but a milky precipitate of sulfur remains.
2MnO4- + 6H+ + 5H2S –> 2Mn2+
+ 8H2O + 5S (s)
2. Pass hydrogen sulfide for ten minutes through a dilute solution of
ferric chloride acidified with a few drops of hydrochloric acid. The
colour will change from yellow to green. Boil the solution in a dish
for two minutes to expel hydrogen sulfide, filter through a double
filter paper to remove sulfur, and add caustic soda solution in excess
to the filtrate. A dirty green precipitate of ferrous hydroxide will be
obtained showing that the ferric ion has been reduced to ferrous ions
2Fe3+ + H2S --> 2Fe2+ + 2H+
+ S (s)
15.2.15 Sulfurous acid as a reducing agent,
ionization reaction
Ionization reaction
H2SO3 + H2O <--> H3O+
+ HSO3-
HSO3- + H2O <--> H3O+
+ SO32-
1. In a fume cupboard, pass sulfur dioxide or sulfurous acid
into a dilute acidified potassium permanganate solution. The colour of
the potassium permanganate disappears but no precipitate of sulfur is
formed. The sulfurous acid has been oxidized to sulfuric acid
2MnO4- + 6H+ + 5SO32-
--> 2Mn2+ + 3H2O + 5SO42-
2. Pass sulfur dioxide continuously through a dilute solution
of ferric chloride. The liquid turns red because of the formation of a
complex
sulfite. Transfer the solution to a dish and boil for a few minutes on
a tripod and gauze. The resulting solution will be pale green or
colourless. Add caustic soda solution in excess to a sample where a
dirty green precipitate of ferrous hydroxide shows that reduction is
complete.
2Fe3+ + SO32+ + H2O -->
2Fe2+ + SO42- + 2H+
3. Dissolve potassium iodate in water in a boiling tube and pass of
sulfur dioxide through it. The iodate is reduced to iodine that is
deposited as black crystals.
IO3- + 3SO32- --> I-
+ 3SO43-
5I- + IO3- + 6H+ –> 3I2
(s) + 3H2O
If the stream of sulfur dioxide continues for a few minutes, the
solution goes clear because of the formation of hydrogen iodide.
I2 + SO32- + H2O –> 2I-
+ SO42- + 2H+
15.3.0 Rusting, corrosion
See also 3.52.1:
The mass of iron and its temperature increases during rusting
Rusting is an electrochemical
process that needs water and oxygen.
At the anode:
Fe (s) --> Fe2+ (aq) + 2e-
At the cathode:
O2 (aq) + 2H2O (l) + 4e-->
4OH- (aq) or
1/2O2 + H2O + 2e- --> 2OH-
The Fe(OH)2 solution oxidizes to rust (Fe2O3.xH2O,
hydrated iron oxide) Corrosion refers to the unwanted oxidation of
metals. Both air and water are necessary for the corrosion of iron.
Corrosion is caused by the unwanted oxidation of metals. Both air and
water are necessary for corrosion of iron. When in moist air, iron is
very liable to form rust, most of which is Fe2O3.xH2O.
Rust forms on the surface because of the action of water and oxygen on
it. You can show that oxygen occupies about one fifth of the atmosphere
by volume based on the decrease in the air volume during rusting.
15.3.1 Rusting of iron wire
See diagram 15.3.1
Polish 0.4 g (about 130 cm long) of thin iron wire (or thin wire
gauze) and curl it into a small ball. Push the ball into the bottom of
a 10 mL graduated cylinder. Add water to immerse the iron wire and
cover the mouth of the cylinder with a slice of glass. Holding the
glass slice, invert the cylinder and adjust the water height to a
certain mark (say, "9.0 mL") by carefully moving the glass slice. Stand
the inverted graduated cylinder over a dish containing water and remove
the glass slice. After two days, much reddish brown rust forms on the
surface of the iron wire and the water level rises to show a one fifth
decrease (about 1.8 mL if the original water level is adjusted to
"9.0") in the air volume inside the cylinder.
15.3.2 Corrosion of magnesium
Repeat the experiment with magnesium ribbon replacing iron wire.
The water height inside the graduated cylinder will go down to give an
increase in the air volume. This result comes from the hydrogen gas
formed in the reaction of magnesium with water.
15.3.3 Rusting of steel wool
See diagram 15.3.3
1. Use two measuring cylinders. Push steel wool into the bottom of one
measuring cylinder. Leave the other as a control. Pour 50 mL water into
each measuring cylinder. Hold a piece of cardboard over the mouth of
each measuring cylinder and invert it over a shallow dish containing
water. Remove the cardboard. Adjust the height of the water in each
inverted measuring cylinder by blowing in air with a bent pipette so
that the height of water in the two measuring cylinders is the same.
Leave the experiment for several days.
2. Repeat the experiment with salty water. The rusting occurs more
quickly not because the sodium chloride takes part in the reaction but
because it makes the water more conduction. Similarly the presence of
sulfur dioxide in the air in cities and industrial sites increases the
rate of rusting.
Fe + 1/2O2 + H2 (from water) -->
Fe(OH)2 [iron (II) hydroxide]
4Fe(OH)2 + O2 --> 2Fe2O3.3H2O
+ H2O [iron (III) oxide]
The Fe(OH)2 in solution is oxidized to Fe2O3.
15.3.4 Need for oxygen for rusting
1. Compare the heights of water in the two measuring cylinders in the
previous experiment. The water level is higher in the cylinder
containing the rusted steel wool. The height of water rises until the
original volume of air in the cylinder decrease by one fifth. The
proportion represents how much oxygen is in air. The lost oxygen is
combined with the iron of the steel wool to form rust.
2. Moisten inside a test-tube with water. Put iron filings in the
bottom of the test-tube and insert a piece of cotton wool to keep them
in place. Invert the test-tube in a beaker that is one third full of
water. The water levels inside and outside the test-tube should be the
same. Mark the original water level on the outside surface of the
test-tube. After two days, the iron rusts and the water level rise
inside the tube until it is steady. About one fifth of the original air
in the test-tube is used up. This suggests that when iron filings rust,
oxygen is used.
15.3.5 Need for oxygen for corrosion of magnesium
Repeat the experiment with magnesium ribbon replacing steel wool.
15.3.6 Iron gains weight during rusting
When iron rusts, it changes from Fe to Fe2O3.xH2O.
Weigh some dry iron filings. Leave in moist air for two days. Note
any increase in weight as rust forms.
15.3.8 Oxidation can affect air pressure
Wash a small piece of steel wool in methylated spirit to remove
any grease. When it is dry, put it in a test-tube with a one-hole
stopper
fitted with a 40 cm length of glass tubing. Clamp the test-tube with
the end of the glass tubing under water. Note the level of the water in
the tubing at the start of the experiment and after one hour and two
hours. Water rises up the tubing as oxygen is used to form rust.
15.3.9 Rate of rusting under separate conditions
Use three test-tubes inverted over water. Push steel wool moistened
with ethanoic acid (acetic acid) water, oil. The reaction forms rust
first in 2.1 then 2.2 then 2.3.
15.3.10 Rate of rusting of iron wire
Fill a 30 mL wide necked bottle with a big ball of polished thin
iron wire (about 0.6 g). Add water to soak the iron wire and then pour
the water out. Stopper the mouth of the bottle with a rubber stopper
fitted with a 40 cm straight glass tube. Invert the bottle and clamp it
on an iron stand with the end of the glass tube under the water in a
beaker. Mark the original water level on the outside of the glass tube.
Note the water height every hour. The water level rises slowly in the
first five hours and then goes up at a faster speed of about 0.5-0.6 cm
an hour. After one day, rising of the water level slows again.
15.3.11 Rate of rusting of steel wool
Fit a small wide mouth bottle with a rubber stopper and a glass
tube about 3 m long. Fit the bottle with a rubber stopper and a
glass tube about 3 m long. Use a bundle of steel wool that is
big enough to fill the bottle. Remove any oil from the steel wool by
washing it in petrol then leaving it to dry. Put the steel wool in the
bottle and insert the stopper fitted with a glass tube. Invert the
bottle and support it with the end of the tube under water. Record the
water level in the tube each hour.
15.3.12 Conditions necessary for rusting
See diagram 15.3.6
Rusting needs air and water and increases if the water contains salts.
You can prevent rusting by painting outside surfaces or by oiling
machinery surfaces or by absorbing moisture with silica gel to protect
delicate machinery, e.g. cameras or microscope parts.
Use four test-tubes fitted with corks each containing two identical
clean nails. Use rainwater. Half the nail is in contact with water and
half the nail is in contact with air. This is the control test-tube.
Put anhydrous calcium chloride or silica gel in the test-tube. Plug the
test-tube with cotton wool. The nail is in contact with air, but is not
in contact with moisture. Pour water into the test-tube and boil for
some minutes to expel all the dissolved air. Pour oil on the surface of
the water to form an airtight layer. The nail is contact with water,
but is not in contact with air. Use salt water. Half the nail is in
contact with the salt water and half the nail is in contact with air.
The nail is in contact with air and salt water. You can see more
rusting in test-tube 1.4 than test-tube 1.1. You see no rusting in
test-tubes 1.2. and 1.3.
15.3.13 Electrochemical prevention of rusting,
cathodic protection
A "tin can" is made by covering sheets of iron with tin plate to
exclude oxygen. If the "tin can" is scratched and it is wet, the iron
corrodes very rapidly because an electrochemical cell is set up.
Wrap a piece of aluminium foil around the lower part of a nail. Put
the nail and metal in a test-tube. Add tap water to cover the lower
part of the nail. Use these metals: control (no metal) magnesium
ribbon, zinc foil, copper wire, tin foil. Put the test-tubes in a
test-tube rack put stoppers on the test-tubes and leave them
undisturbed for several days. If a very small amount of sodium chloride
is added to each test-tube, rusting can occur within an hour. Rusting
first starts in the test-tubes containing copper or tin, then it starts
in the control. Iron is more active than copper or tin, so the iron
forms the positive ion Fe2+ to react with negative ions in
solution to form precipitates of rust on the nail. No rusting occurs in
the test-tubes containing magnesium ribbon or zinc, but the more active
magnesium or zinc form ions that react with negative ions to form white
precipitates.
15.3.13.01 Cathodic protection
Cathodic protection can protect iron ships and bridges from corrosion.
A more electronegative metal, e.g. zinc, is attached as a "sacrificial
anode" that goes into solution instead of the iron. Also, you can apply
direct current to make the iron into a cathode.
Wooden sailing ships were protected from fouling organisms by the
release of copper ions from copper sheathing of the ship's bottom.
However, copper sheathing on an iron bottom ship produced an
electrochemical cell in the sea water that corroded the iron.
This could be prevented by attaching blocks of zinc the bottom to give
cathodic protection to the copper.
15.3.13.1 Rate of corrosion affected by
formation of electric cells
Thoroughly clean short narrow strips of the metals magnesium, zinc,
copper and tin and also clean five pieces of pure iron wire. Twist a
piece of iron wire tightly around each of the other metals. Into five
clean beakers place about equal volumes of tap water. Place the
single piece of iron wire in the water in one beaker and place one of
the twisted pairs of metal strips in each of the other beakers. Record
your observations after one hour, one day, one week. Zinc is used as a
protective coating of iron for galvanized iron sheets and galvanized
screws and bolts. If the coating is scratched, in the zinc iron rain
water cell the zinc corrodes to protect the iron. Also, blocks of zinc
are attached to iron ships, bridges and wharfs. In this sacrificial
corrosion the zinc corrodes away to protect the less active iron. Iron
is coated with tin to make tin plate for tin cans and jam tins.
However, if the tin is scratched, the iron corrodes more rapidly than
if it were not covered by tin.
15.3.14 Restore bronze coins, corrosion of alloys
Brown "copper coins" are usually alloys of zinc and tin in copper.
"Silver" coins are alloys of nickel in copper. Some "gold" coins are
alloys of aluminium and nickel in copper. Corrosion is common in alloys
if the metals are not evenly mixed. Old coins and statues made of
copper alloys and other copper materials exposed to moist air are often
covered with blue-green verdigris that is basic copper (II) carbonate
CuCO3.Cu(OH)2.H2O. New "copper" coins
are shiny, but they soon lose their shine and become a dark copper
colour because of a layer of black copper (II) oxide. Old copper coins
may
be very black between the raised areas for the numbers.
Put drops of vinegar on a copper coin. Leave the coin until the
liquid is evaporated. Green blue crystals are left on the coin surface.
Scrape off the crystals and wash the coin. The coin now looks shiny
because black copper (II) oxide is removed. Use dilute hydrochloric
acid to make "new" shiny coins.
15.3.15 Corrosion of aluminium
Put a piece of aluminium foil in water. Put a copper coin on the
foil and leave it for some days. A simple aluminium /copper cell forms
and a small electric current can be detected with an ammeter. The
aluminium foil has holes where the coin lies on it. The water appears
cloudy because of the fine particles of aluminium released during
corrosion.
15.3.16 Clean tarnished silver
The surface of silver can react with chemicals in the air to form black
silver sulfide, e.g. silver spoons used for eating eggs that contain
sulfur proteins. You can polish off the silver sulfide or dissolve it
using a commercial silver dip that contains ammonia or thiourea but in
each case you lose some silver. You can save the silver by using the
following oxidation reduction reaction that reverses the corrosion
process. However, some jewellery designers deliberately create a black
patina on sunken surfaces as a background contrast to bright silver
surfaces, so they soak the jewellery in potassium sulfide, liver of
sulphur, and later buff polish the silver surfaces. Never try to clean
silver with household bleach because a hard coat of oxide forms that is
very difficult to remove using the methods below.
1. To clean the silver, put a sheet of aluminium in the bottom of a
beaker. Put the silver to be cleaned on the aluminium and add baking
soda solution (sodium hydrogen carbonate). Warm the solution. The
sulfur transfers to the aluminium to form aluminium sulfide and the
silver becomes shiny again. Clean tarnished silver with aluminium foil.
2. Add 10 g of sodium bicarbonate (NaHCO3, baking soda) to
hot water in a plastic container. Wrap the tarnished silver in
aluminium foil and immerse it in the solution for hours until the
silver sheen is restored. The sodium bicarbonate dissolves any
aluminium oxide on the aluminium surface.
3Ag2S (s) + 2Al (s) –> 2Al3+ (aq) + 3S2-
(aq)
+ 6Ag (s)
3. Rub the tarnished silver with "Brasso" or toothpaste, not the
gel-type toothpaste, or buff polish the surfaces.
4. Soak the tarnished silver in dilute ammonia solution, cloudy ammonia.
5. Soak the tarnished silver in borax and soap solution in hot water.
15.4.0 Electrical conductivity of a substance
Conductance or conductivity or is the ratio of the current flowing
though a conductor to the potential difference between its ends, i.e.
the electric field causing the current to flow. Conductance or
conductivity is the reciprocal of resistance or resistivity. The SI
unit for conductance is the "siemens", S. The SI unit for its
reciprocal is ohms (omega). Pure substances that are gases or liquids
at room temperature are not good conductors, e.g. water, alcohol, and
olive oil. The liquid metal, mercury, is an exception. Fused solids
vary in their conductivity. Molten metals, alkalis and salts are good
conductors. Other fused solids are not good conductors. The salts
sodium chloride and sodium nitrate, as fused liquids, are good
conductors but fused sugar and sulfur are non-conductors.
Use a 6 volt battery and two crocodile clips to grasp the cleaned
surface of the solids. Use a light bulb to show when current is
flowing. Record the solids, melted solids, liquids, and aqueous
solutions that do or do not conduct electricity.
15.6.0 Electrochemical cells
Electrochemical cells (Voltaic cells)
form electricity from chemical
reactions. The cell is made up of two half cells. Each half cell
consists of an electrode in contact with an electrolyte. It is usually
a metal in contact with one of the metal salt solutions.
15.6.13 Magnesium / copper battery
Connect the external circuit before adding the sodium sulfate
solution. Clean copper in dilute nitric acid and clean magnesium ribbon
in 1 M hydrochloric acid.
Half cells: 1. Magnesium ribbon in contact with 0.5 M sodium sulfate
solution, in a jar.
2. Copper strip in contact with 0.5 M copper (II)
sulfate solution, in a dialysis tubing bag, then in the same jar
1. Mg (s) --> Mg2+ (aq) + 2e- (Eo 2.36
V at 25oC, 1 atmosphere pressure)
2. 1/2 H2 --> H+ + 2e- (Eo =
0)
3. Cu (s) --> Cu2+ (aq) + 2e- (Eo =
-0.337 V)
4. Mg (s) + Cu2+ (aq) --> Mg2+ (aq) + Cu (s)
EMF = Eo (oxidation) - Eo (reduction) so EMF =
2.36 - (-0.337) = 2.7 V
At the anode: Oxygen is liberated: 4OH- --> O2+
2H2O + 4e-
At the cathode: Hydrogen ions are not reduced to H2 because
the Eo of reaction 2., where Eo = 0 V, is
greater than the Eo of reaction 3. (where Eo =
-0.337 V.)
15.6.14 Nickel / cadmium battery, NiCad battery
Rechargeable battery used to power various small devices, e.g. electric
toothbrush. During discharge:
At the cathode: nickel (IV) hydroxide + 2 electrons --> nickel
(II) hydroxide (reduction)
At the anode: cadmium - 2 electrons --> cadmium (II) hydroxide
(oxidation)
Some people think that this kind of battery shows a "memory effect",
i.e. after recharging, the battery later runs down only to the capacity
at which last recharged. The solution is to let the battery discharge
almost completely before recharging. Constant recharging after use for
a short time may produce overcharging and change the form of cadmium
crystals in the battery resulting in slower release of electric current
and apparent lower voltage.
15.7.0 Electrode potential of metals
See also :
Standard
electrode potential, electrode potential, reduction potential, E0
|
See also 3.86:
Electrode potentials of metals
Values of electrode potentials of metals are derived from comparisons
with the hydrogen cell under standardized conditions of 1 M solution at
25oC and 1 atmosphere (101.2 kPa) pressure. The standard
hydrogen cell is hydrogen gas from a platinum electrode in 1 M solution
of H+. If E0 value is +ve, then the preferred
direction of electron flow is left to right. The ion or atom with the
greater value of E0 will attract electrons more easily. A
positive value for E0 means that particles in the half cell
attract electrons more easily than particles in the hydrogen half cell.
If more than one reaction could occur, the reaction that does occur is
the reaction that would form the greatest voltage.
Standard reduction potentials (E0)
| K+ + e- --> K |
E0 = -2.92 V |
| Ba2+ + 2e- --> Ba |
E0 = -2.90 V |
| Ca2+ + 2e- --> Ca |
E0 = -2.87 V |
| Na+ + e- --> Na |
E0 = -2.71 V |
| Mg2+ + 2e- --> Mg |
E0 = -2.34 V |
| Al3+ + 3e- --> Al |
E0 = -1.67 V |
| Mn2+ + 2e- --> Mn |
E0 = -1.05 V |
| Zn2+ + 2e- --> Zn |
E0 = -0.76 V |
| Cr3+ + 3e- --> Cr |
E0 = -0.71 V |
| Fe2+ + 2e- --> Fe |
E0 = -0.44 V |
| Ni2+ + 2e- --> Ni |
E0 = -0.25 V |
| Sn2+ + 2e- --> Sn |
E0 = -0.14 V |
| Pb2+ + 2e- --> Pb |
E0 = -0.13 V |
| 2H+ + 2e- --> 2H |
E0 = 0.00 V |
| Cu2+ + 2e- --> Cu |
E0 = +0.35 V |
| Ag+ + e- --> Ag |
E0 = +0.80 V |
| Hg2+ + 2e- --> Hg |
E0 = +0.85 V |
15.7.1 Potential difference from combining half
cells, zinc and iron
To measure the potential difference of a zinc half cell connected
to an iron half cell. Use a strip of zinc metal in a zinc chloride
solution and an iron nail in iron (II) sulfate solution. Connect the
two half cells with a strip of filter paper soaked in potassium
chloride solution to act as a salt bridge. Complete the circuit by
connecting leads from each metal to a voltmeter. Read the voltmeter.
Electrons flow with potential difference of 0.32 V.
Zn (s) --> Zn2+ (aq) + 2e- (E0= +
0.76 V)
Fe2+ + 2e- --> Fe (aq) (E0 = -0.44
V)
Zn (s) + Fe2+ --> Zn2+ + Fe (s) (E0=
+ 0.32 V)
15.7.2 Potential difference from combining
half cells, Zn and Cu, Zn and Pb
If Zn E0 = -0.76 V set up cells to measure the E0 values
of copper (copper in copper (II) sulfate solution) and lead (lead in
lead (II) nitrate solution).
15.7.3 Differences in potential on an iron nail
Soak 1 gm agar in 100 mL water for two hours then boil until
dissolved. Add phenolphthalein indicator and add acid or alkali until
pH = 8. Add drops of freshly prepared potassium ferricyanide solution
and pour into a Petri dish. Add a very clean nail and place the petri
dish on an overhead projector. After some hours, a pink colour forms
around the shaft of the nail because of hydroxide ions and blue-green
colour forms around the head of the nail because of Fe2+
ions.
The stressed head shows positive potential and the unstressed shaft
shows negative potential.
At the anode: Fe (s) --> 6 Fe2+ (aq) + 2e-
At the cathode: O2 (aq) + 2H2O (l) + 4e-- -->
4OH- (aq)