9.

2Production of Materials

1. ethylene.

Ethene (ethylene)

Molecular formula: C2H4

Molar mass: 28.05g/mol
Appearance: colorless gas
Class: alkene hydrocarbon (olefin)
Bonds: 4 x C-H; 1x C=C
Melting point: -169oC
Boiling point: -104oC
Odour: slightly sweet smell
Flammability: Highly inflammable
Polarity: non-polar molecule
Solubility: soluble in non-polar solvents
& insoluble in polar solvents like water
Reactivity: very reactive, the active site
is the double bond, it easily undergoes
addition reactions.

Industrial production of ethylene

Ethylene is produced in the petrochemical

industry by steam cracking. In this
process, gaseous hydrocarbons (e.g.
ethane, or light liquid) are heated to 750
950 C, inducing numerous free radical
reactions followed by immediate quench
to freeze the reactions.

This process converts large hydrocarbons

into smaller ones and introduces
unsaturation (double bonds).

Ethylene is separated from the resulting

complex mixture by repeated
compression and distillation.

In oil refineries, high molecular weight

hydrocarbons are cracked over zeolite
catalysts first and then cracked to ethene

Chemical Properties of ethene

The chemical properties of ethene reflect the reactivity of the
double bond
CH2=CH2 + Br2 ----->

Addition of Bromine:

CH2BrCH2Br
1,2-dibromoethane

CH2=CH2 + Cl2 (+AlCl3 catalyst)----->

Addition of Chlorine:

CH2ClCH2Cl
1,2-dichloroethane

Addition of Hydrogen bromide:

CH2=CH2 + HBr

(+AlCl3 catalyst)

----->

CH3CH2Br
bromoethane

Addition of Hydrogen chloride:

CH2=CH2 + HCl ----->

CH3CH2Cl
chlorooethane

Addition of Hydrogen:

CH2=CH2 + H2

(+Ni catalyst and @ 500oC)

------>

CH3CH3

ethane

Addition of Water:

CH2=CH2 + H2O

(+H3PO4 catalyst and @ 300oC)

ethanol

Combustion

CH2=CH2 + 3O2 ----->

2CO2 + 2H2O

-----> CH3CH2OH

Uses of Ethene
Production of Polythene (polyethylene)
nCH2=CH2 ----> (CH2=CH2)n
Production of ethanol
CH2=CH2 + H2O----> CH3-CH2OH

(H2SO4 catalyst)

Production of 1,2-ethanediol (ethylene glycol)

CH2=CH2 + O2 + H2O --------> CH2OH-CH2OH
Production of many other chemicals e.g. ethylene oxide and
other polymers e.g. PVC and polystyrene
Ethene is also used as a plant hormone to control the ripening
and colour development of fruit
In medicine, in anesthetic mixtures.

Addition Polymerization

LDPE
Polyethylene is produced at a high
pressure (2000 a) and a high temperature
(200 oC). A peroxide ("free-radical"
initiator) initiator starts the
polymerization.
This manufacturing process leads to a
polyethylene which is highly branched (a
typical molecule has many side branches,
instead of single long strand).
A branched structure results in a polymer
with a relatively low density (about 0.91
gcm-3), known as low density polyethylene
or LDPE.
LDPE melts at about 120 oC and is soft,
stretchy, transparent, and not very strong.
It is used in products such as flexible
squeeze bottles or wash bottles,
disposable gloves and many others.

HDPE

The use of metal-based catalysts,

particularly titanium/aluminum (ZieglerNatta) under very mild conditions (1-10 a and
50 o-100 oC), has led to a newer type of
polyethylene.
It has very long (>10,000 monomer units)
linear polyethylene molecules
Because these chains do not possess side
branches, they line up parallel to one another
in an ordered structure.
The efficient lining-up of molecules
results in a higher density material
(density between 0.97 and 0.99 gcm3) named HDPE
HDPE has greater strength and a higher
melting point (130 oC) than the LDPE and is
opaque, rather than transparent like LDPE.
HDPE is used in applications that require
strength and rigidity and is used extensively
as gas pipes, containers, rope, shopping
bags, toys and even boats.

Derivative polymers of ethene

Apart from polyethylene, many other polymers can be made from
ethene . Two of the most important ones are polyvinyl chloride
(PVC) and polystyrene.
The monomers for each of these are:

chloroethene
(vinyl chloride)

ethenylbenzene
(styrene)

The manufacture of polyvinyl chloride (PVC)

involves three steps:
production of the monomer, vinyl chloride
by reacting chlorine gas with ethene
polymerization
blending of the polymer with additives.
PVC is biologically and chemically resistant,
hence is used for most household sewerage
pipes, electrical conduits and other pipe
applications where corrosion would be a
problem with the use of metals..
With the addition of substances called
plasticizers, PVC can be made flexible enough
to be used as a wire insulator and as a cheap
substitute for leather.
However, plasticizers have been an additive of
particular concern as they tend to leach out of
vinyl products like car interiors, shower
curtains, flooring, toys, and other
Some studies indicate that these additives
may contribute to health complications.
Specific plasticizers have been banned in
Europe and major Japanese car
manufacturers have eliminated PVC in their
car interiors from 2007 on.

PVC

The main manufacturing route to styrene

is the direct catalytic dehydrogenation of
ethylbenzene:
Polystyrene is commonly produced in
three forms: extruded polystyrene,
expanded polystyrene foam, and extruded
polystyrene foam, each with a variety of
applications.
Extruded polystyrene (PS) is economical,
and is used for producing many items that
need a rigid and cheap plastic e.g.
disposable cutlery
Polystyrene Petri dishes and other
laboratory containers such as test tubes
and micro-plates play an important role in
biomedical research and science.
Polystyrene foams are good thermal
insulators, and are therefore often used as
building insulation materials.
Polystyrene foams are better know by their
trademark names : Styrofoam and Coolite.
Polystyrene foams are also used in many
applications to do with packaging and
food dispensing

Polystyrene

Alkenes and bromine water

Bromine water (Br2 dissolved in water) is a test for the double bond
in alkenes (hence, alkanes do not react with bromine water)
When shaking an alkene with bromine water (or bubbling a gaseous
alkene through bromine water), will cause the solution to decolourise.
Alkenes de-colourise bromine water.
The major product is 2-bromoethanol (the water also reacts)

Some 1,2-dibromoethane is also formed:

Revision Questions - 1
1) Identify the industrial source of ethylene.
2) Describe a first-hand investigation you performed to compare
the reactivities of appropriate alkenes with the corresponding
alkanes in bromine water
3) Describe a suitable model for the polymerisation process
4) Identify the physical or chemical property of ethylene that
allows it to be readily transformed into many useful products
5) Describe ways into which ethylene serves as a monomer from
which polymers are made
6) Explain the meaning of addition polymerization using the
synthesis of polyethylene as an example
7) Outline the steps in the production of polyethylene
8) Distinguish between polyethylene, polyvinyl chloride and
polystyrene in terms of their: respective monomers; molecular
structure; properties and uses

2. Biomass

Fossil fuels
Fossil fuels (coal, oil and natural gas) are a non-renewable
source of energy and chemicals.
Fossil fuels are found in underground deposits. They were
formed from the remains of plants and animals that lived
more than 300 millions of years ago.
Fossil fuels are very precious to us, because they are nonrenewable, resources. We use them for fuel and to make
many organic chemicals such as: paints, detergents,
polymers, cosmetics and some medicines.
Because biological materials are renewable, they are being
intensely investigated as raw materials for the manufacture
of many modern plastics, drugs and fuels, which are
currently sourced from fossil fuels.
This search has been fuelled by our over-reliance on
increasingly scarce and increasingly expensive fossil fuels
and because of escalating atmospheric levels of
greenhouse gases

Biomass
Biomass is a general term for living material
(plants, animals, fungi, bacteria). The Earth's
biomass represents an enormous store of energy.
Biomass can be regrown, it is a renewable resource
The original source of the energy in biomass is the
Sun.
Plants absorb solar energy and through the
process of photosynthesis convert it to chemical
energy, mostly in the form of carbohydrates and
oils.
Plants make a polysaccharide (carbohydrate) called
Cellulose. They manufacture it through the
condensation polymerization of a monomer called
glucose: C6H12O6

Condensation polymerization
Condensation polymerization is a
reaction between two monomers,
each with at least two reactive
group.
The two monomers react in a
chain reaction to form a polymer.
Water or another small molecule
is removed at each step.
Example: a polyester is formed
when an alkanol with two -OH
groups (a diol) is reacted with an
alkanoic acid with two -COOH
groups.
There are many examples of
condensation polymers:
natural: cellulose; starch;
glycogen, chitin, proteins and
nucleic acids
artificial: nylon; polyesters and
polyamines

Cellulose
Cellulose is a condensation polymer of D-glucose (C6H12O6) with
the formula (C6H10O5)n
Cellulose consists of long chains (up tor tens of thousands) of Dglucose units, joined by 14 glycosidic bonds.
Cellulose is the main structural component of the cell wall of
plants, and is the most common organic compound on Earth about 33% of all plant matter is cellulose.

Cellulose
Most other polysaccharides have
(14) and (16) linkages and
so have coiled and branched
molecules. Cellulose's (14)
linkages result in long straight
chains
This allows the cellulose
molecules to line up next to one
another. Hydrogen bonds hold
these chains close together
forming microfibrils with high
tensile strength
The long carbon chains in
cellulose make it suitable as a
raw material for many of the
compounds currently produced
from fossil fuels.

Uses of cellulose
Cellulose has been used as a heating fuel (wood burning) for a
million years. In the form of paper and cotton it has been used for
thousands of years.
Cellulose has also been used to manufacture special cellulose
derivatives: methyl-cellulose (food thickener) cellulose nitrate (guncotton), cellulose acetate (photographic film) and rayon (textile)
Cellophane is a form of regenerated cellulose used extensively in
the packaging industry.
Cellulose can be digested and converted to ethanol, which can be
used as a fuel for motor-vehicles
Cellulose is fully bio-degradable.

Biopolymers
Use available evidence to gather and present data from secondary sources
and analyse progress in the recent development and use of a named
biopolymer ...

When researching this topic if you 'Google' the term biopolymer the
search results maybe misleading as any natural polymer can be
termed a biopolymer. However in the context of the syllabus you are
expected to research those polymers produced artificially using an
enzyme or a bacterium. A good place to start is to 'Google' the letters
PHB (polyhydroxybutyrate) and then go on from there.
When presenting the results of your research keep in mind the
following main points:
Do not copy and paste
Use only reliable, up-to-date resources
Reference all your work
Include a bibliography

Revision Questions 2
1) Explain what is meant by a condensation polymer using cellulose
as an example
2) Describe condensation polymerization.
3) Describe the structure of cellulose
4) Identify the major component of biomass and explain its potential
as a raw material to replace petrochemicals
5) Discuss the need for alternative sources of the compounds
presently obtained from the petrochemical industry
6) Analyse progress in the recent development and use of a named
biopolymer. This analysis should name the specific enzyme(s) used
or organism used to synthesise the material and an evaluation of
the use or potential use of the polymer produced related to its
properties

3. ethanol

Ethanol ------> Ethene

Ethanol can be dehydrated to give ethene by heating (170C) it
with an excess of concentrated sulphuric (H2SO4) or phosphoric
(H3PO4) acid .
The dehydration of ethanol into ethylene can also be
accomplished more efficiently using solid acid catalysts e.g.
zeolites. However, a slightly higher temperature (200300 C) is
needed

Ethene ------> Ethanol

The hydration of Ethene is carried out by mixing it with steam
at a temperature of 300C and a pressure 60 atmospheres.
This hot mixture is passed over a catalyst consisting of solid
silicon dioxide coated with phosphoric acid
The phosphoric acid catalyst is essential to the reaction as it
donates a proton H+ to the double bond forming a positive
CH3CH2+ radical. This radical removes an OH- group from water,
forming ethanol. The remaining proton from the water is
returned to the phosphoric acid.

Alkanols
A class (known as a homologous series) of organic compounds called
alkanols consists of a hydrocarbon chain with an -OH group replacing any
one or more of the hydrogen atoms.
The name of the alkanol in the series is derived from the alkyl prefix with
the same number of carbon atoms and by substituting the e at the end
with an ol
Methanol and ethanol do not have any isomers (compounds with the same
formula, but different structure) all the higher alkanols have isomers since
the -OH group can be on any of the carbon atoms. The number of isomers
increases with increasing number of carbon atoms.
As well as straight chained alkanols, many alkanols with branched chains
are also possible, and then there are alkanols with more than one OH
group e.g. (2 x OH) = diols; (3 x OH) = triols

Some isomers of pentanol

Ethanol
Ethanol (ethyl alcohol, absolute alcohol) is a volatile, flammable, colorless
liquid with a boiling point of 78.3 oC. Ethanol cannot be separated
completely from water by distillation (no matter how efficient the
fractionating column) - 95% alcohol cannot be further concentrated by
distillation, a drying agent must be used.
Ethanol has the molecular formula: C2H5OH which is often abbreviated to
just EtOH (-C2H5 = Et).
Ethanol is a very versatile solvent, miscible with water and other polar
solvents like acetone, acetic acid and glycerol. It is also miscible with many
non-polar solvents like benzene, carbon tetrachloride, hexane and
chloroform.

Heat of combustion of Alkanols

Alkanols burn with a pale blue, non luminous flame to form
carbon dioxide and steam. e.g. Ethanol
C2H5OH(g) + 3O2 (g) ==> 2CO2(g) + 3H2O(g) H = -1367 kJ / mol
This reaction is exothermic (like all combustions) and each
mole (46g) releases 1367 kJ of energy as heat.
The energy produced can also be converted to kJ / g

Measuring Heats of combustion

Experiment:
Use at least three different alkanols in three
different spirit burners.
Measure accurately the mass of the spirit burner
with the alkanol in it BEFORE and AFTER heating.
Place about 100g of water into a weighed conical
flask and measure the combined mass accurately.
Measure the temperature of the water BEFORE
and AFTER heating.
Heat until there is a temperature change of about
10 oC but measure the two temperatures
accurately.
The heat of combustion (H) is equal to the
product of the temperature rise (t) of a mass, in
grams, (m) of water multiplied by the specific heat
of water (4.186 J/g), assuming no heat losses:
H = 4.186 x m x t
To find H in J/g divide by the mass of alkanol
used-up during the heating of the water.
To find the H in J/ mol, multiply the molar mass
of the alkanol by the H in J/g you obtained.

Uses of ethanol
Ethanol has many uses. This is because of its:
ability to mix with both polar and non-polar compounds
ease and cheapness of manufacture from completely renewable
sources (plants)
relative low toxicity to humans (ethanol is a psychoactive drug,
found in alcoholic beverages and medications)
Here are just a few of ethanol's many uses:
Personal care products: e.g. in hairspray, mouthwash, after
shave lotion, cologne and perfume
Pharmaceuticals: e.g. in cough treatments, decongestants, iodine
solution and many others
Cleaning products: e.g. disinfectant spray, window cleaners and
methylated spirits.
Industrial: e.g. paints, lacquer, and explosives;
Foods: e.g. extracts, flavorings, glazes and alcoholic beverages.
Transport: e.g. Fuel and/or fuel additive.

Fermentation
Humans have been fermenting sugars for
thousands of years to obtain alcoholic
beverages like wine, beer and mead.
These beverages may have been created as
far back as 7,000 BCE in parts of the Middle
East.
Fermentation is the conversion of a sugar
such as glucose, fructose or sucrose into
ethanol using yeasts (fungi).
Yeasts carry out the fermentation on sugars in
the absence of oxygen, hence it is called
anaerobic fermentation.

Fermentation of glucose
The reaction froths due to the evolution of CO2 gas.
This evolution can be monitored by measuring the mass lost during the
reaction. It can be confirmed by bubbling it through lime water ( a
solution of calcium hydroxide). The lime water turns 'milky' (a white
precipitate of calcium carbonate) when it reacts with carbon dioxide.
The reaction works best at about 30 to 35 degrees as at this
temperature the yeast is most active. Since the fermentation is
anaerobic, it works best in the absence of oxygen.
The fermentation stops when the ethanol concentration reaches about
15% . The ethanol is toxic to the yeast ( the yeast is killed by its own
pollution, let's hope we are smarter).
The ethanol formed, can be separated up to 95% pure by fractional
distillation.

Industrial Production of EtOH

Conventional Production of Ethanol starts
with a sugar crop like sugar cane
(Australia & Brazil) or sugar beet (Europe)
or a grain crop like starch from corn (USA).
These are then treated to extract the sugar
or to breakdown the starch into sugar.
The sugar is then fermented with yeast to
produce the ethanol.
The ethanol is distilled and dried and
shipped to the service centre (usually as a
mixture with petrol)

Cellulosic Ethanol
Cellulose biomass: anything that is mostly cellulose
(agricultural plant wastes, corn husks, cereal
straws, sugarcane waste, plant wastes like sawdust
and paper pulp and energy crops grown specifically
for fuel production, such as grass)
Cellulose biomass is in virtually unlimited supply
and does not require vast areas of land to be
cultivated.
Cellulosic ethanol is produced from cellulose
biomass. This must be treated with action dilute
acid or with the enzyme cellulase to first convert it
to glucose, then the glucose can be fermented in the
usual manner (with yeast)
Ethanol produced from cellulose biomass could be
price competitive with gasoline and would use-up a
lot of waste material.

Ethanol as a
fuel

When pure ethanol burns, only water

and carbon dioxide are formed.
Burning petrol produces a lot of toxic
pollutants
Why Bioethanol ?
Rising oil / fuel prices
Uncertainty of oil supply due to
political instability
Ethanol is renewable (we can
grow more plants)
Oil is non-renewable (it takes
millions of years to replace)
Greenhouse gases caused by
fuel emissions could be reduced
by the use of ethanol
Ethanol/gasoline mixtures are already
in use:
Gasohol (90%gasoline10%ethanol)
E85 (15% gasoline-85%ethanol)

Ethanol as a fuel
Advantages:
It is a renewable fuel made from plants
It is not a fossil-fuel: manufacturing it
and burning it does not release harmful
gases.
Ethanol is biodegradable without
harmful effects on the environment
It significantly reduces harmful exhaust
emissions from cars.
Ethanol-gasoline blends, dramatically
reduce emissions of hydrocarbons, a
major contributor to the depletion of
the ozone layer.
High-level ethanol blends reduce
nitrogen oxide emissions by up to 20%
Sulphur dioxide and particulate matter
(PM) emissions are significantly
decreased with ethanol.
Major oils spills will be very rare.

Disadvantages:
Ethanol as an alternative fuel is, at
present, costly to produce
Ethanol has a smaller energy output
per gram than petrol. It takes about 1.5
times more ethanol than petrol to travel
the same distance
At present ethanol produced from
sugar-high crops requires vast
amounts of land to grow the crops.
Ethanol production, like all processes,
generates waste products that must be
disposed. The waste product from
ethanol production, called swill, can be
used as a soil conditioner on land, but
is extremely toxic to aquatic life.
Another problem is that ethanol
burning may increase the emission of
new pollutants like acetylaldehyde.

Revision Questions - 3
1)
2)
3)
4)
5)
6)
7)

8)
9)

Describe the production of ethanol.

Describe and account for the many uses of ethanol as a solvent.
Outline the use of ethanol as a fuel.
Describe conditions under which fermentation of sugars is
promoted.
Summarise the chemistry of the fermentation process.
Define the molar heat of combustion of a compound.
In an experiment , 50g of water were heated using a weighed spirit
burner filled with ethanol. Over a period of time the temperature of
the water rose from 19 oC to 24 oC. At this time the spirit burner was
reweighed and it was found that the spirit burner now lost 40 g
during the heating process. Use this data to find the heat of
combustion of ethanol per gram and per mole.
Describe the dehydration of ethanol to ethylene.
Assess the potential of ethanol as an alternative fuel and discuss
the advantages and disadvantages of its use

Revision Questions - 4
1) Name and draw the straight chain molecular structures of two of
the isomers of this alkanol: C6H14O
2) Using a chemical equation demonstrate the addition of water to
ethylene.
3) Summarise the processes involved in the industrial production of
ethanol from sugar cane
4) Describe the use of ethanol as an alternative car fuel.
5) Evaluate the current and predict the future success of ethanol as a
fuel.
6) Describe a first-hand investigation you performed to carry out the
fermentation of glucose. Include a chemical equation and identify
reasons for a change in mass during the process.
7) Describe a first-hand investigation your performed to compare the
heats of combustion of at least three liquid alkanols.
8) Evaluate the differences between expressing the heat of
combustion of a fuel per gram or per mole

4. Redox

Metal displacement from solution

A displacement Reaction is a
chemical process in which one
metal changes places with
another in solution: i.e. it
displaces it.
When a piece of zinc metal is
dropped into a beaker of blue
copper(II) sulfate solution:
The zinc slowly dissolves,
forming zinc ions
The copper comes out of
the solution as metallic
copper.
Copper ions gain
electrons from the zinc
atoms as the zinc forms
ions.

Metal displacement from

solution
The copper atoms form a redbrown metal layer on the surface
of the piece of zinc.
The blue of the solution eventually
fades, as the copper is displaced.
The more active metal will displace
a less active metal from solution
A more active metal is a stronger
reductant (A reductant loses
electrons, and is itself oxidised)
An activity series lists metals in
order of decreasing strength as
reductants

Activity series of metals

The activity series of metals based on the Standard Potentials:
K>Na>Ba>Ca>Mg>Al>Mn>Zn>Fe>Ni>Sn>Pb>Cu>Ag
In the list shown above the most active metal is potassium (K) (strongest
reductant ...most easily oxidised) and the least active metal is silver (Ag)
(strongest oxidant ...most easily reduced)
The activity series shows a gradually increasing reluctance in displacing
hydrogen from solution: for example: the most reactive metals will react
with just cold water (K, Na, Li etc) whereas the less reactive metals will
need to react with acid to displace hydrogen (Fe, Ni, Sn etc)

Activity series
of metals
The metals that are below
hydrogen in the activity
series will not displace it
from solution at all, even in
boiling hot acid.
Hence, the reaction of a
metal with acid to produce
hydrogen gas and a salt is an
oxidation-reduction.
Potassium and sodium are
so very reactive that they will
displace hydrogen from
water in a violent, often
exploding, reaction.

Oxidation
State
Oxidation state is a number
assigned to an element in a
compound.
This number enables us to
describe oxidation-reduction
reactions, and balancing
redox chemical reactions.
The higher the oxidation
state of a given atom, the
greater is its degree of
oxidation;
The lower the oxidation state,
the greater is its degree of
reduction
Some metals can have a
number of oxidation states in
their compounds. Their
oxidation state is expressed
as a roman numeral: e.g. Iron
II Chloride - FeCl2

Oxidation Numbers
Oxidation number is worked out
according to the rules below:

Examples:
Species

Element

O.N.

O2

H2O

-2

Na

Na

NaOH

Na

+1

H2SO4

+6

SO2

+4

S8

The oxidation state of a free element

(uncombined or combined to itself) is 0
Hydrogen has an oxidation state of +1
and oxygen has an oxidation state of
-2 in most compounds.(Exceptions
are: hydrogen has an oxidation state of
-1 in hydrides of active metals, e.g.
LiH, and oxygen has an oxidation state
of -1 in peroxides, e.g. H2O2)
In a neutral molecule, the algebraic
sum of oxidation states of all atoms,
must be equal to 0
In mono-atomic ions, the oxidation
state is equal to the net charge on the
ions
In poly-atomic ions, the algebraic sum
of the oxidation states of the
constituent atoms must be equal to the
charge on the ion

Galvanic Cells

A Galvanic cell consists of two half-cells.

Each half-cell has one electrode, e.g. plates
of Zn (zinc) and Cu (copper); and each has an
electrolyte, e.g.. aqueous solutions of zinc
nitrate and copper sulfate (free ions conduct a
current through the solutions)
Each half-cell has its own half-reaction.
The electrons will flow from the more
negative electrode (Zn) to the more positive
electrode (Cu), because the electrons have
negative charge
By definition, the anode is the electrode
where oxidation takes place.
An essential part of a Galvanic Cell is the salt
bridge. The salt bridge serves the vital role of
allowing each half-cell's charge to be
balanced (completing the electric circuit)
while preventing the solutions from mixing
with each other.
Galvanic cells, are conventionally described
using the following notation:
Zn(s) | Zn+2(aq) || Cu+2(aq) | Cu(s)
(anode)------------------------(cathode)

Making Galvanic cells

A Galvanic cell is made up of two
half-cells each containing a metal
electrode and the same metal's
ions in solution.
A salt bridge is needed to
complete the circuit. Potassium
nitrate is used as both potassium
and the nitrate will not react and
precipitate with any of the metal
salts used in the half-cells
In addition, a voltmeter is needed
if the potential (Eo) of the cell is to
be measured.
The potential of the cell will
depend on the difference in
reactivities of the two metals
Try different metal combinations
and measure the potential for
each.

The dry cell

The dry cell is a galvanic cell
with a semi-dry electrolyte (a
moist paste of ammonium
chloride).
The anode is the zinc outer
container
The cathode is the manganese
IV dioxide powder (mixed with
graphite powder to make it
conducting)
The carbon rod is the other
electrode and is protected by a
metal cap.
Its nominal potential is 1.5 volts
2NH4+(aq) + 2MnO2(s) + 2eZn (s)

Mn2O3(s) + 2NH3(g) + H2O(l)

Zn+2(aq) + 2e-

The dry cell

This cell is the first type of fully portable 'battery' and
has helped the development of many portable
appliances.
Its nominal potential is 1.5 volts. A number can be
connected in series, if higher voltages are needed or
in parallel if more power is needed.
With use, the anode dissolves, as the zinc is oxidised.
Eventually, the casing develops holes and leaks.
Alkaline cells (batteries) are powered by the same the
transfer of electrons from zinc to manganese but the
electrolyte in the paste is replaced with potassium
hydroxide.
Alkaline batteries last five to eight times longer than
normal dry cells.

The lead-acid
battery

A lead-acid battery is a Galvanic cell. The anode

is lead metal (spongy) and the cathode is lead IV
oxide, The electrolyte is dilute sulfuric acid.
The nominal potential of this cell is 2 volts.
Commonly a number (or battery) of these cells is
connected in series to produce 6 and 12 volt
batteries.
This type of battery can be recharged by applying
a current to reverse electron flow and hence
reverse each half equation.
In the charged state each cell contains electrodes
of lead and of lead (IV) dioxide (PbO2) in an
electrolyte solution of sulfuric acid (6 Molar) .
In the discharged state both electrodes turn into
lead(II) sulfate (PbSO4) and the electrolyte loses
sulfate ions and becomes more and more dilute
H2SO4.

The lead-acid battery

The lead-acid battery is most commonly known
as the car battery (this has been its major
purpose)
Its charge can be monitored electronically or by
measuring the concentration of the sulfuric acid
(usually, by measuring its density or specific
gravity)
It has one of the lowest energy-to-weight ratio
(lead is very dense and hence lead acid batteries
are very heavy). This means that they are not
very portable (unless carried by a vehicle like a
car or motorcycle)
Lead is a toxic heavy metal, hence car batteries
pose an environmental problem (recycling the
lead is the best solution, at present)

Fuel cell vs. Lead-acid battery

Fuel cell
Chemistry:

Anode side: 2H2(g)

4H+(aq) + 4eCathode side: O2(g) + 4H+(aq) + 4e2H2O(l)
Net reaction: 2H2(g) + O2(g)
2H2O(l)
A fuel cell is an electrochemical energy conversion device. A fuel cell converts the chemicals
hydrogen and oxygen into water, and in the process it produces electricity. With a fuel cell,
chemicals constantly flow into the cell so it never goes dead.
Cost and practicality:
The fuel cell has a potential efficiency of 80%. But there are losses converting the electric energy
to mechanical energy; its overall efficiency is about 60%
At present, fuel cells are very expensive because they require expensive metals like Platinum or
Gold as catalysts. Research focuses on making fuel cells more affordable.
Their primary fuel is Hydrogen gas. Ways of safely manufacturing, dispensing and storing this very
explosive gas, are the main challenge.
Impact on Society
The fuel cell's potential to change society is enormous as it could not only replace the toxic leadacid battery but also the internal combustion engine as a source of power in future electric
powered cars
Impact on the environment
The fuel cell is almost totally pollution free, producing just a little heat and water.

Fuel cell vs. Lead-acid battery

Lead-acid battery (car battery)
Chemistry:
(See a previous slide)
A battery has all of its chemicals stored inside, and it converts those chemicals into electricity.
This means that a battery eventually "goes dead" and you either throw it away or recharge it.
Cost and practicality:
The battery is about 90% efficient, if used to power an electric car the efficiency drops to 70%.
But its weight to energy ratio is very high compared to the fuel cell. When used with a petrol
powered engine the overall efficiency drops to 25%
Because car batteries have been manufactured and used extensively for many decades they are
about as cheap as we can make them and are very practical.
Impact on Society
Over the decades the car battery has been extremely useful in helping with the development of a
society powered by fossil fuels. Now, with the problems with fossil fuels, global warming and
increasing pollution its effect on society has become a problem
Impact on the environment
Lead is a very toxic chemical. Once it enters the human body it remains and builds up over the
years causing neurological problems. Handling it and disposing of waste is expensive and
dangerous
The internal combustion engine, with which the lead-acid battery has been primarily associated,
has become a serious environmental problem.

Calculating potentials
There are always two half equations to consider one of them must be a reduction and the
other must be an oxidation. All the data you will need can be obtained from a standard
potential series sheet.
Example: Calculate the nominal potential of a galvanic cell having a magnesium electrode
and a silver electrode.
Step 1 write the cell in standard notation
Mg(s) | Mg+2(aq) || Ag+1(aq) | Ag(s)
(anode)------------------------(cathode)
Remember the more reactive metal (higher in a reduction potential list) is the anode and is oxidised

Step 2 write the two half equations include their potentials, reverse the oxidation and
change the sign on its potential:
oxidation: Mg(s)
Mg+2(aq) + 2e- ......... +2.37 V
reduction: Ag+1(aq) + e-

Ag(s) ......

+0.22 V

You must balance the number of electrons to be the same for both half equations, but the potentials
remain the same:

reduction: 2Ag+1(aq) + 2e-

2Ag(s) ......

+0.22 V

Step 3 - Complete the process by adding the equations and the potentials
redox: Mg(s) + 2Ag+1(aq )
Mg+2(aq ) + 2Ag(s)......... +2.59V
Note: if the potential for the cell results in a negative number then you have either not chosen the
oxidant/reductant correctly or have forgotten to change signs.

Revision Questions - 5
1) Explain the displacement of a metal from solution in terms of transfer of
electrons
2) Describe the activity series of metals
3) Identify the relationship between displacement of metal ions in solution by
other metals to the activity series of metals
4) Find the oxidation state of the metal in each of the following species:
Cu(s); CuO; Cu2O; Al2O3 and HAuCl4
5) Account for the electrons lost or gained when MnO4- is reduced to Mn2+
6) Describe and explain the galvanic cell using copper and iron electrodes in
terms of the oxidation/reduction reactions that occur.
7) Draw and label a galvanic cell you have studied and label: the direction of
electron flow; the anode, the cathode, electrode; the electrolytes in each
cell; the sat bridge and calculate the nominal voltage produced.
8) Describe a first-hand investigation you performed to identify the conditions
under which a galvanic cell is produced
9) Account for the need of a salt bridge.

Revision Questions - 6
1) Describe a first-hand investigation you performed to measure the
difference in potential of different combinations of metals in an electrolyte
solution
2) Describe the structure and chemistry of a dry cell or a lead-acid cell.
3) Compare and evaluate one of the following: button cell; fuel cell; vanadium
redox cell; lithium cell; liquid junction photovoltaic device (e.g. the Gratzel
cell) and compare it to a dry cell or lead-acid battery in terms of:
(i)chemistry; (ii) cost and practicality; (iii) impact on society and (iv)
environmental impact
4) Calculate the potential developed by the galvanic cells below, for each
write balanced half equations and a redox equation:
Al(s) | Al+3(aq) || Ni+2(aq) | Ni(s)
Fe(s) | Fe+2(aq) || Pb+2(aq) | Pb(s)
Mn(s) | Mn+2(aq) || H+(aq) | 1/2H2(s)
Cu(s) | Cu+2(aq) || Ag+(aq) | Ag(s)

5.

Nuclear chemistry

Isotopes
Atoms of the same element can have
different numbers of neutrons; the
different possible versions of each
element are called isotopes.
Most elements found naturally are
composed of two or more stable
isotopes (e.g. natural Chlorine is
composed of 75.8% 35Cl (or Cl-35)
and 24.2% 37Cl, hence its atomic
mass is 35.5)
Some Isotopes are radioactive
because their nuclei are not stable.
Some elements don't have any
stable isotopes: e.g. technetium (Tc)
promethium (Pm), and all the
elements beyond bismuth (atomic
number 83).

Isotopes
Protons are positively charged and
hence repel each other strongly,
neutrons are neutral.
At the very small distances (10-15m)
within the nucleus a very strong
force between neutrons and protons
called the Strong Force comes into
play, and keeps the nuclei from
exploding apart.
In lighter elements the number of
neutrons is similar to the number of
protons.
In heavier elements more neutrons
than protons are needed for stability.
Atoms with too few neutrons, or too
many protons are unstable and emit
radiation, hence they are called
radioactive isotopes.

Radioactive Isotopes
Radioactive isotopes emit
radiation, in the form of
particles or electromagnetic
waves.
The type of radiation emitted
depends on the type of decay of
the radioactive atom
There are many types of
radioactive decay, but the three
main types are: alpha, beta, and
gamma decay.

Alpha decay ( )
An alpha particle( ) is a helium nucleus 42He2+
Alpha decay occurs because the nucleus has too many
protons which cause excessive repulsion.
In alpha decay, the new nucleus is reduced in both atomic
number and mass number: (Z2) and (A4)
Alpha particles have a very short range and a low
power of penetration. When ingested into the body;
they have great destructive power and may cause
maximum damage no emitters are used for
medical uses. Americium-241 is an alpha emitting
isotope and is used for smoke detection.

Beta decay ( )
There are two types of beta decay: emission of an
electron ( -) and emission of a positron ( +)
In electron decay, the new nucleus is increased in
atomic number but the mass number remains the
same:(Z+1)
In positron decay, the new nucleus is reduced in atomic
number but the mass number remains the same:(Z-1)
Beta particles have greater range of penetration than
alpha particles, but still much less than gamma rays.
The radiation hazard from betas is greatest if they are
ingested. Beta emitters are mostly used for industrial
purposes.

Gamma decay ( )
Gamma rays are very short wave and very high energy
electromagnetic photons and therefore are very
penetrating.
Gamma decay occurs because the nucleus is excited. The
nucleus emits a particle to achieve lower, more stable, energy
state.
In gamma ray emission both the atomic number and mass
number remain unchanged
Gamma rays are the most penetrating and hence are
the most dangerous because of their ability to
penetrate through most materials.

Detection of Radioactivity
The three types of radiation are known as
ionizing radiation because they cause
materials to ionize e.g. air
Ionizing radiation cannot be detected by the
senses. The damage it causes to the body is
cumulative, and is related to the total dose
received.
Their ability to ionize substances is utilised to
detect their presence by:
physical methods: scintillation counters,
Geiger counters and electroscope
discharging
chemical methods: effect on
photographic emulsions and fluorescence
of substances like zinc sulfide

Detection
Hand-held meters (e.g. GeigerMueller meters) measure the
presence and quantity of
radiation in the environment.
The Geiger-Mueller tube
contains gas that ionizes and
produces a small pulse of
electricity each time it is ionized
by radiation.
Body-worn dosimeters measure
the exposure to radiation
accumulated by persons
working in radiation risk areas.
They can be in the form of
badges, rings or pens. They
contain photographic film.

Transuranic
elements

All the elements with an atomic number greater

than 92 (more than Uranium) are known as
Transuranic elements
They are all artificial and are synthesized using
nuclear reactors or particle accelerators.
All transuranic elements are radioactive.
In 1940, Edwin, Mattison and McMillan, were
first to produce a transuranium element number
93, Neptunium.
Elements above 104 are known as Super heavy
elements, SHE.

Making new elements

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Production of the transactinide

hassium (108Hs) by bombarding
208Pb with 58Fe ions using a
linear accelerator at GSI,
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Ma entist
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F-18 A medically useful isotope

Positron emission tomography (PET scan), is used to diagnose or
treat a variety of diseases.
Pairs of gamma rays are emitted by the positron-emitting isotope,
fluorine-18. The gamma rays are produced when a positron and an
electron annihilate each other.
The F-18 is introduced into the body on a biologically active
molecule called FDG, (Fluorodeoxyglucose or 2-fluoro-2-deoxy-Dglucose).
F-18 it is made using either a cyclotron or linear particle accelerator
to bombard a target of pure or enriched 18O-water.
Then it is attached to a glucose molecule in a hot cell
(radioisotope chemistry preparation chamber)

F-18 a medically useful isotope

The FDG molecule is carried by the bloodstream as if it were
normal glucose to areas where blood flow is higher than normal
e.g. tumors.
PET scans can: detect cancer; determine whether a cancer has
spread in the body; determine blood flow to the heart muscle;
determine the effects of a heart attack, or myocardial infarction,
on areas of the heart; evaluate brain abnormalities and to map
normal human brain and heart function
Because of its relatively short half-life and the very small
amounts of radiation involved F-18 causes minimal damage to
the body and is excreted completely.

Co-60 an industrial isotope

Cobalt is a hard, brittle, gray metal with a bluish tint. Naturally
occurring cobalt (Co) is composed of one stable isotope: 59Co.
Many radioisotopes of cobalt have been made. The most stable
being 60Co with a half-life of 5.2714 y
Co-60 is useful as a gamma ray source because it can be produced
by exposing natural cobalt pellets encased in a nickel shell to
neutrons in a reactor for about 5 years
Co-60 is used both medically and industrially

Co-60 an industrial isotope

Uses
sterilization of medical supplies, and medical waste;
radiation treatment of foods for sterilization (The powerful gamma rays kill
bacteria and other pathogens, without damaging the product. After the radiation
ceases, the product is not left radioactive. This process is sometimes called
"cold pasteurization.");
industrial radiography (e.g., weld integrity radio graphs);
density measurements (e.g., concrete density)
Determining/monitoring the thickness of metal sheets/pipes
Irradiation is also used as a quarantine measure for such items as tropical
fruits,
A major way of controlling insects without the use of chemicals is the Sterile
Insect Technique. Male insects are sterilized by controlled doses of gamma ray
exposure. e.g. Male flies mate a number of times whereas female flies only mate
once, hence sterile males will ensure many eggs will not be laid

Isotopes good or bad?

Radioisotopes have been used in medicine to detect and cure a number of
diseases.
Their production depends on a nuclear industry based on nuclear waste
producing nuclear reactors.

Revision Questions - 7
1) Define a transuranic element and describe how transuranic
elements are produced
2) Describe how commercial radioisotopes are produced
3) Identify instruments and processes that can be used to detect
radiation
4) Identify one use of a named radioisotope in industry and describe
the way is used in terms of their chemical properties
5) Identify one use of a named radioisotope in medicine and
describe the way is used in terms of their chemical properties
6) Describe recent discoveries of elements
7) Analyse benefits and problems associated with the use of
radioactive isotopes in identified industries and medicine
8) Distinguish between stable and radioactive isotopes and describe
the conditions under which a nucleus is unstable