Lone pairs of electrons count toward an area of electron density but as they repel to a much greater

extent they reduce the bond angle by 2.5

Octahedral - 6 bond pairs, 0 lone pairs, 90 (e.g.- SF6)
Trigonal Bipyramidial - 5 bond pairs, 0 lone pairs, 120 and 90 (e.g.- PF5)
Bent - 2 bond pairs, 2 lone pairs, 104.5 (e.g.- H2O)
Trigonal Pyramidial - 3 bond pairs, 1 lone pair, 107 (e.g.- NH3)
Tetrahedral - 4 bond pairs, 0 lone pairs, 109.5 (e.g.- CH4)
Trigonal Planar - 3 bond pairs, 0 lone pairs, 120 (e.g.- BF3)
Linear - 2 bond pairs, 0 lone pairs, 180 (e.g.- BeCl2)
Electrons will repel each other to maximum separation and minimum repulsion. Greatest angles
are between lone pairs of electrons, which cause more repulsion due to a larger electron cloud.

Shapes of molecules
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Carbon Structures
Allotropes are different forms of the same element in the same state. Carbon has three allotropes:
diamond, graphite and fullerenes.
Diamond: Each carbon bonded to four other carbons, tetrahedral crystal lattice structure. High
melting point, extremely hard, good thermal conductor, cannot conduct electricity. Insoluble.
Fullerene: Hollow balls or tubes. Each carbon bonded to three others = conductor. Nanoparticles.
Soluble in organic solvents. Brightly coloured solutions. Delivering drug. Nanotechnology.
Graphite: Sheets of flat hexagons covalently bonded with three bonds each. Fourth electron
delocalised. Weak bonds between layers,slide over each other, used as dry lubricants and pencils.
Delocalised electrons allow electron flow. Less dense than diamond. High melting point. Insoluble
in any solvent.

- HYDROCARBONS: longer hydrocarbon chains have more molecular surface area, more
electrons interact so stronger Londo forces. Branched-chain alkanes have smaller molecular
surface areas and they cannot pack as closely together, so London forces are reduced. Therefore
long-chain alkanes and straight-chain alkanes have higher boiling points.
- Molecules with greater surface areas also have stronger London forcesas they have a bigger
exposed electron cloud.
- Larger molecules have larger electron clouds, meaning stronger London forces.
3) Electrons are constantly moving, the dipoles are being created and destroyed all the time.
2) This dipole can cause another temporary dipole in the opposite direction on a neighbouring
atom. The two dipoles are then attracted to each other.
1) Electrons in charge clouds are always moving very fast. At any particular moment, electrons in
an atom are likely to be more to one side than the other, creating a temporary dipole.
London forces cause all atoms and molecules to be attracted to each other.

Intermolecular Forces
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Electronegativity
Electronegativity is the ability of an atom's nucleus to attract the bonding pair of electrons within a
covalent bond. Covalent bonds can become polarised by differences in electronegativity, making
the covalent bond polar.
A dipole is a difference in charge between two atoms caused by a shift in electron density in the
bond. If the difference becomes large enough the bond is considered as ionic. The greater the
difference in electronegativity, the more polar the bond.
Polar bonds can be cancelled out in a symmetrical molecule, so the whole molecule itself is not
polar. Lone pairs of electrons on the central atom have an effect on the overall polarity and may
cancel out the dipole created by the bonding pairs. If the polar bonds all point in similar directions,
due to the shape of a molecule, the molecule will be polar.
The distance between the two nuclei is the distance where the attractive and repulsive forces
balance each other. (Repulsion due to +vely charged nuclei) This distance is the bond length.
The stronger the attraction between the atoms, the higher the bond enthalpy and the shorter the
bond length. A C=C has greater bond enthalpy and is shorter that a C-C bond, as electron
density between carbon atoms is greater.

Hydrogen bonds increase boiling and melting points. Ice is less dense than liquid water.
Molecules which have hydrogen bonding are usually organic, containing -OH or -NH groups.
Water and ammonia both have hydrogen bonding.
Hydrogen bonding is the strongest intermolecular forces. Hydrogen bond only takes place when
hydrogen is bonded to fluorine, nitrogen or oxygen. This is because these elements are very
electronegative, so they draw the bonding electrons away from the hydrogen atom. The bond
is so polarised and hydrogen has such a high charge density that hydrogen atoms form weak
bonds with lone pairs of electrons on the F, N, O atoms of other molecules.
Electrostatically charged rods placed near a jet of a polar liquid, such as water, will attract the
liquid molecules towards the rod.
These permanent dipole-dipole interactions are stronger than instantaneous dipole-induced dipole
interactions.
Polar molecules have permanent dipole-dipole interactions. The charges on polar molecules
cause weak electrostatic forces of attraction between molecules.

Intermolecular Forces 2
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Solubility
For one substance to dissolve into another, bonds in the substance have to break, bonds in the
solvent have to break and new bonds have to form between the substance and solvent.
Ionic substances dissolve in polar substances such as water. Ions are pulled away from the ionic
lattice by water molecules that they are attracted to. This is hydration. Some ionic substances do
not dissolve as the electrostatic force of attraction between ions is too strong.
Alcohols dissolve in water due to polar -OH bond. Hydrogen bonds form between them. The
carbon chain is not attracted to water so the more carbon atoms there are, the less soluble the
alcohol will be.
Halogenoalkanes contain polar bonds but dipoles are not strong enough to form hydrogen bonds
with water. The hydrogen bonds between water molecules is stronger than the bonds that
would be formed with halogenoalkanes, so halogenoalkanes do not dissolve.
Non-polar substances dissolve best in non-polar solvents. Substances such as ethene have
London forces between their molecules and form similar London forces with non-polar solvents
such as hexane.

Hydroxides: solubility increases down the group. More strongly alkaline solutions formed as you
go down the group due to increase in solubility. Singly charged negative ions tend to increase in
solubility down the group.
Sulphates: solubility decreases down the group. Test for sulphates: add barium chloride and a
white precipitate will form. Compounds containing doubly charged negative ions tend to decrease
in solubility down the group.
Group 2 Hydroxides will do the same with 2H2O as a product
Oxide + Acid > Chloride/Nitrate + H2O
Oxide + Water > Hydroxide
Group 2 + Chlorine > Metal Chloride (solid)
Group 2 + Water > Hydroxide + Hydrogen gas
Group 2 + Oxygen > Metal Oxide (solid)

Group 2 - Alkaline Metals

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Redox
Redox is the transfer of electrons. Oxidation is the gain of oxygen and reduction is the loss of
oxygen.
The oxidation state is a number assigned to an element in a compount according to some rules.
The oxidation state of any elemnt e.g. Fe, H2, O2, Pa, S8 is zero (0).
The oxidation state of oxygen in its compound is -2, except for peroxides like H2O2, in
which the oxidation state for O is -1.
The oxidation state for hydrogen is +1 in its compound, except for metal hydrides, such as
NaH, LiH etc., in which the oxidation state for H is -1.
The oxidation states for other element are then assigned to make the algebraic sum of the
oxidation states equal to the net charge on the molecule or ion.
The following elements usually have the same oxidation states in their compounds:
+1 for alkali metals - Li, Na, K, Rb, Cs;
+2 for alkaline earth metals - Be, Mg, Ca, Sr, Ba;
-1 for halogen except when they form compounds with oxygen or one another.
Disproportionation is when the same species is both oxidised and reduced in the reaction.

Barium - Green
Calcium - Brick Red
Caesium - Blue
Strontium - Scarlet
Potassium - Lilac
Sodium - Orange/Yellow
Lithium/ Rubidium - Red
Flame Tests: Mix a small amount of the compound you're testing with a few drops of hydrochloric
acid. Heat a piece of nichrome or platinum wire in a hot Bunsen flame to clean it. Dip the wire into
the compound mixture and hold over flame to observe colour.
Energy absorbed from the flame causes electrons to move to a higher energy level. This is unstable
so electons move back to originel energy level, whilst emitting energy. The difference in energy
between the higher and lower levels determines the wavelength of the light released.

Flame Tests
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Group 1 and 2 Compounds

Thermal decomposition is the break down of a substance into smaller molecules when heated.
Thermal stability increases down a group: Carbonate and nitrate ions are large and can be
made unstable by the presence of a positively charged ion. The cation polarises the ion, distorting
it. The greater the distortion, the less stable the anion. Large cations cause less distortion than
small cations as they have a smaller charge density.
Group 1 compounds are more thermally stable than Group 2 compounds: Greater charge
causes more distortion so anion is less stable. Group 2 cations have higher charge densities.
Carbonates: Group 1 stable, do not decompose, except lithium carbonate
Group 2 carbonates + heat > Group 2 oxide + CO2
Nitrates: Group 1 decompose to nitrite (e.g. KNO2) and oxygen, except lithium nitrate.
Group 2 decompose to oxygen, nitrogen dioxide (toxic, brown gas) and oxide.

 Chloride Precipitate - Dissolves in dilute ammonia solution

Bromide Precipitate - Dissolves in concentrated ammonia solution
Iodide Precipitate - Insoluble in concentrated ammonia solution
Iodine - Undergoes 2 redox reactions, first one produces Iodine, sulphur dioxide and water.
Iodine reacts with sulphur dioxide to produce H2S, Iodine and water 6HI + SO2 -> H2S + 3I2 +
2H20
Bromine - Bromine is strong enough to reduce sulfuric acid, it happens in a redox reaction. The
products formed are bromine, sulphur dioxide and water 2HBr + H2SO4 -> Br2 +SO2 + 2H20
Sulpuric Acid: Fluorine/Chlorine - Not strong enough reducing agent to reduce the sulphuric
acid, so HX (X being the halide) is formed KCl + H2SO4 >KHSO4 +HCL
Reducing power of halides increases down the group as ionic radius and shielding increases.
They give coloured precipitates with dilute nitric acid and silver nitrate solution: White chloride
precipitate, cream bromide precipitate and yellow iodide precipitate.

Reactions of Halides
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Group 7 - Halogens
Fluorine Pale Yellow, Gas
Chlorine Green, Gas, Colourless in water, Colourless in hexane, Low boiling and melting points
Bromine Orange-Brown, Liquid, Orange-Brown in water, Orange-Red in hexane
Iodine Grey, Solid, Brown in water, Pink/Violet in hexane, high boiling and melting points
Halogens act as oxidising agents. Larger atoms are less reactive due to larger radius and more
shielding. They also become less oxidising and have disproportionation reactions with alkalis:
Cold: 2NaOH + Cl2 > NaCl + NaClO + H2O (salt, chlorate I and water is formed)
Hot: 6NaOH + Cl2 > 5NaCl + NaClO3 + H2O (salt, chlorate III and water is formed)
Halogens also oxidose metals. Fluorine and chlorine react with hot iron to form iron (III) halides
as they are strong oxidising agents. Bromine is weaker and will form a mixture of iron (II) and
iron (III) halides whilst iodine only forms iron (II) iodide.
All halogens, except iodine, will oxidise iron (II) to iron (III) ions in solution. The solution changes
from green to orange.

A homogenous catalyst is in the same state as reactants. It speeds up reactions by forming one
or more intermediate compounds. The activation energy needed to form the intermediates is
lower than making products directly from reactants. Energy profile will have two humps.
Heterogenous catalysts provide a surface where reacting particles may break and make bonds.
With smaller particles of reactant there is a larger surface area on which the reactions can take
place, so the greater the chance of successful collisions
At higher temperatures, a much higher proportion of colliding particles have sufficient activation
energy to react and more particles are able to overcome the activation enthalpy barrier.
At higher concentrations and higher pressures, particles are in closer proximity to each other
encouraging more frequent collisions.
Reactions occur when particles of reactants collide with a minimum activation kinetic energy:

Reaction Rates
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Titrations
Methyl Orange turns tellow to red when adding strong acid to alkali and end point is orange.
Phenolphthalein turns red to colourless when adding weak acid to alkali. End point is pale pink.
You record readings to the nearest 0.05cm^3. This is to the limit of precision of the burette.
The uncertainty of a reading from a burette is the maximum error of + or - 0.05cm^3.
Percentage error can be reduced by measuring and using larger volumes.
To improve the reliability, the experiment should be repeated until you have 2 concordant
titres, within 0.20.
Most systematic errors are from poor technique - always read the burette at eye-level. It
is usually caused by equipment and is repeated throughout the experiment.
Random errors vary with every experiment. This can be due to the subjectivity of endpoint.
Repeating the experiment improves reliability, but accuracy won't be improved. It
eliminates random errors but not systematic errors.
Using contaminated apparatus could make your results inaccurate, so burette needs to be
cleaned with the substance that will go in the burette.

 orange bromine water decolourises in the precence of C=C

Br + H2O --> HOBr + HBr
C=C + HOBr --> CH2BrCH2OH
Bromine Water
HBr - H turns delta positive Br delta negative, H joins one carbon, Br attracted to positive
carbon = CH3CH2Br
Electrophillic Addition with Hydrogen Halides

forms dihalogenoalkane, heterolytic fission, orange to colourless

double bond repels electrons on Br2 polarising it - heterolytic fission occurs
a carbocation is formed - an organic ion containing a positve carbon ion
Br- moves to the positive carbon and bonds to form 1,2-dibromoethane
C=C + Br-Br --> CH2BrCH2+ --> CH2BrCH2Br

Electrophillic Addition with Halogens

Alkenes
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Chemical Equilibria
Chemical equilibria can only be established in closed systems. The reactions have 3 features:
Reactions do not go to completion - there are always products and reactants.
Reactions are reversible
Dynamic - when a reaction appears to have finished, the chemicals continue to react,
but the rate of the forward reaction = rate of the reverse reaction. This is called dynamic
equilibrium.
Le Chatalier's Principle states that: when a change is imposed on a chemical equilibrium, the
reaction responds in such a way to oppose the change.
As a result, the position of equilibrium changes. The conditions that change are temperature,
pressure and concentration. The equlibrium will move to help counteract the effect.
Catalysts have no effect on the position of equilibrium. They cannot increase yield, but equlibrium
is reached faster.

- Needs to be carried out in the absence of air as is anerobic

Problems - Produces only 14% alcohol
C6H12O6 -----> 2CH3CH2OH + 2CO2

Reagents = Yeast and 37C

Fermentaion of Sugars or Carbohydrates

- uses large amounts of energy
Problems - uses non-renewable reactants
H2C=CH2 + H20 ---> CH3CH2OH

Reagents = H3PO4 and 300C 60atm

Hydration of ethene

Making Alcohols
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Alkenes 2
Reduction with Hydrogen / Hydrogenation
gain of hydrogen / loss of oxygen, forms alkane
nickel catalyst at 150 degrees
C=C + H2 --> CH3CH3
Addition Polymerisation
long chain molecules with high Mr made from joining monomers
monomer = unsaturated alkane with C=C, volatile liquids / gases
polymers = saturated, solids due to increased van der waals
Addition of Acidified Manganate (VII)
cold acidified manganate oxidises C=C to form a diol, purple to colourless
ethene --> ethane 1,2 - diol
C=C + [O] + H2O --> CH2OHCH2OH

Remove organic impurities by distilling the mixture. Collect the fraction that boils between 49
and 53 C which is chloroalkane.
Remove any remaining water with anhydrous sodium sulphate.
Add distilled water, shake, and run off lower layer to remove inorganic impurities.
Neutralise the excess acid with sodium hydrogencarbonate solution, until no more gas is
produced. Run the lower layer off.
Allow mixture to settle into layers. Run off aqueous layer, leaving the impure hydrogenoalkane.
Tertiary alcohols are more reactive, so to make a chloroalkane, shake the alcohol with
hydrochloric acid in a separating funnel. Keep releasing the pressure as the product is volatile.

Halogenoalkanes from Tertiary Alcohol

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Halogenoalkanes From Alcohols Using Hydrogen

Halid
Primary and secondary alcohols react too slowly by just shaking.
Bromoalkanes: Rather than using aqueous hydrobromic acid, you treat alcohol with a mixture
of sodium or potassium bromide and concentrated sulphuric acid, producing hydrogen bromide
which reacts with the alcohol. The mixture is warmed to distil off the bromoalkane.
CH3CH2OH + HBr --> CH3CH2Br + H2O
Iodoalkanes: The alcohol is reacted with a mixture of sodium or potassium iodide and
concentrated phosphuric (V) acid, H3PO4, and the iodoalkane is distilled off. The mixture produces
hydrogen iodide which reacts with the alcohol.
CH3CH2OH + HI --> CH3CH2I + H2O
Phosphoric (V) acid is used instead of concentrated sulphuric acid because sulphurc acid oxidises
iodide ions to iodine, producing hardly any hydrogen iodide.

The equation for a reaction is: 2CH3CH2CH3 + 2Na => 2CH3CH2CH2O-Na+ + H2

The reaction is also slower than it is with water.
Reactions are slower with longer chains because there are more van de waal's forces in a longer
chain.
The result is the formation of an alkoxide and hydrogen gas.
The sodium will slowly disappear too.
The result is bubbles, as hydrogen gas is produced.
A small chunk of sodium can be placed in an alcohol.
Sodium metal reacts gently with ethanol, breaking the -OH bonds to produce ionic sodium
ethoxide and hydrogen.

Alcohol and Sodium

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Making Halogenoalkanes from Alcohols using

Phospho
React an alcohol with liquid phosphorus (III) halide, PCl3: 3R-OH + PCl3 --> 3R-Cl + H3PO3
The Phosphorus first reacts with the bromine or iodine to give the phosphorus (III) halide:
2P + 3Br2 --> 2PBr3 ; 2P + 3I2 --> 2PI3
These then react with the alcohol to give the corresponding halogenoalkane which be distilled off
3CH3-CH2-OH + PBr3 --> 3CH3-CH2-Br + H3PO3
3CH3-CH2-OH + PI3 --> 3CH3-CH2-I + H3PO3
Chloroalkanes can be made using Phosphorus (V) Chloride. ROH + PCl5 -> RCl + HCl + POCl3
Test for hydroxyl group: add phosphurus (V) chloride to the unknown liquid. If -OH is present,
steamy fumes of HCl gas can be seen, which dissolve in water to form chloride ions.

 KBr and 50% H2SO4, relfux reaction - the acid oxidises, OH replaced with Br
CH3CH2CH2OH + KBr --> CH3CH2CH2Br + KOH
HCl + NH3 --> NH4Cl - used to test for OH group
nucleophillic subsitution - OH for Cl
CH3CH2CH2OH + PCl5 --> CH3CH2CH2Cl + PCl3 + HCl
Bromide Ions
gives chloroalkane, white flame (HCl) given off, more dense with ammonia fumes
gives sodium alkoxide, effervesence, white film forms, redox reaction, room temp
2CH3CH2CH2OH + 2Na --> 2CH3CH2CH2O-Na+ + H2
Phosphorus (V) Chloride
CH3CH2CH2OH (l) + 4O2 (g) --> 3CO2 (g) + 4H2O
Sodium
Combustion: longer chains give more sooty flame

Alcohol Reactions
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Oxidation of Alcohols
Aldehydes and ketones are carbonyl compounds, with C=O functional group, CnH2nO.
Aldehydes have a hydrogen and one alkyl group. Ketones have two alkyl groups attached to
the carbonyl carbon atom.
Primary alcohols can be both partially and fully oxidised. Partial oxidation takes place when the
products are immediately distilled off so that complete oxidation cannot take place. The product
is an aldehyde. Full oxidation takes place when the reactants are refluxed under heating in a
vertical reflux condenser. Then the products are distilled off. The product is a carboxylic acid.
Refluxing a secondary alcohol with acidified dichromate (VI) will produce a ketone.
Fehling's solution and Benedict's solution are both deep Cu2+ complexes, wgich reduce to
brick-red Cu2O when warmed with an aldehyde, but stay blue with a ketone.
Tollen's reagent is reduced to silver when warmed with an aldehyde, but not with a ketone. The
silver will coat the inside of the apparatus to form a silver mirror.

 gives iodoalkane, reflux reaction, substitution

CH3CH2CH2OH + PI --> CH3CH2CH2I
orange to green, heat under reflux
Fehlings stays blue
CH3CH(OH)CH3 + [O] --> CH3COCH3 + H2O
Phosphorus and Iodine
excess oxidising agent so further oxidation, heat under reflux
Fehlings stays blue, test for by using Na2CO3 - bubbles of CO2 form
CH3CH2CH2OH + 2[O] --> CH3CH2COOH + H2O
Ketone (from secondary alcohol)
add K2Cr2O7 in conc H2SO4, distillation reaction - H2 lost double bond formed
orange --> green (Cr ions 6+ to 3+) Fehlings blue to brick red
CH3CH2CH2OH + [O] --> CH3CH2CHO + H2O
Carboxylic Acid (from primary alcohol)
Aldehyde (from primary alcohol)

Oxidation of Alcohols 2
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Reactions of Halogenoalkanes
Potassium hydroxide: Halogenoalkanes can be reacted with KOH under different conditions in
order to make different products.
In aqueous conditions, a halogenoalkane can be refluxed under heating with KOH to make
an alcohol. This is a nucleophilic substitution reaction. Heterolytic fission takes place.
Hydrolysis occurs through a nucleophilic substitution reaction.
OH- ion has a lone pair of electrons which is attracted to the electron deficient carbon atom
this is also known as nucleophilic attack.
Donating the lone pair leads to a new covalent bond between the O molecule and the
carbon atom as a result this causes a break in the carbon halogen bond by heterolytic
fission forming a halide ion.
Water molecule can also act as a weak nucleophile.

SN1 - substitution nucleophillic 1st order (1 specie in slow step)

C(CH3)3Br + OH- --> C(CH3)3OH + Brlarge CH3 causes steric hindrance - OH cant fit
CH3 stabalise C+ charge by positive induction effect, electrons pushed toward C
so C-Br weak enough to drop

Tertiary

SN2 - substitution nucleophillic 2nd order (2 species in slow step)

CH3Br + OH- --> CH3OH + Brnucleophile attacks from behind due to lack of space
transition state - Br bond weakened

Primary

Nucleophilic Substitution Mechanisms

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Reactions of Halogenoalkanes 2
In ethanoic (alcoholic) conditions, a halogenoalkane can be refluxed under heating with KOH to
make an alkene. This is an elimination reaction.
The mixture of warm alkali dissolved in alcohol must be heated under reflux or the volatile
substances will be lost. CH3-CH2-Br + KOH --> CH2=CH2 + H2O + KBr
Ammonia:
Conditions: Concentrated solution of ammonia at room temperature, or heated in a sealed tube.
Procuct: Amine.
Mechanism: Nucleophilic Susbtitution.
R-Hal + NH3 -> R-NH2 + (H+) + (Hal-)

NO free radicals also destroy ozone. They are formed from nitrogen oxides, which are produced
by car and aircraft engines and thunderstorms.
.

The two reactions above involving chlorine atoms are known as a catalytic cycle because
the chlorine free radicals from CFC's act as a catalyst in the destruction of ozone.
Chlorine free radicals readily react with ozone and change it back to much more stable ordinary
.
.
oxygen. O3 + Cl ==> O2 + ClO and then: ClO + O ==> Cl + O2 - Cl free radical is regenerated
and acts as a catalyst.
CCl2CF2 ==> CClF2 + Cl
.

The chemically stable CFCs diffuse up into the stratosphere and decompose when hit by
ultraviolet light (uv), producing free radicals, including free chlorine atoms, which themselves are
highly reactive free radicals.

Ozone 2
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Ozone
Halogenalkanes are generally unreactive, have low boiling points and are non-flammable, so they
are used as fire-retardants and refrigerants.
Chlorofluorocarbons (CFCs) were found to deplete the ozone layer in the atmosphere,
allowing harmful UV radiation to reach the earth surface, increasing the risk of skin cancer and
eyecateracts.
Ozone is formed in the stratosphere by free radical reactions.
-Ordinary stable oxygen O2 (dioxygen) is split (dissociates) into two by high
energy ultraviolet electromagnetic radiation from the Sun forming free radicals. A 'free' oxygen
atom combines with an oxygen molecule (dioxygen) to form ozone (trioxygen).
. +

O2 + uv ==> O

O + O2 ==> O3
The ozone is a highly reactive and unstable molecule and decomposes into dioxygen when
.
hit by other uv light photons. O3 + uv ==> O2 + O

Redox: any reaction where electrons are transferred between two species.
Reduction: any reaction in which an atom gains electrons.
Oxidation: any reaction in which an atom loses electrons.
Hydrolysis: splitting a molecule into two new molecules by adding H+ and OH- derived from water.
Substitution: one species is replaced by another.
Elimination: small group of atoms break away from a larger molecule.
Polymerisation: joining together the same monomer to form a polymer.
Addition: joining two or more molecules together to form a larger molecule.

Types of Reactions
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Climate Change
The greenhouse effect keeps us alive. The sun emits electromagnetic radiation. Most UV and
infrared is absorbed by atmospheric gases, some of which is reflected back into space from
clouds. Radiation is absorbed by the Earth, causing it to heat up. The earth then radiates energy
back towards space as infrared radiation. Greenhouse gases absorb some of this radiation and
re-emit it in all directions.
Main greenhouse gases are water vapour, carbon dioxide and methane. The molecules absorb
IR radiation to make the bods in the molecule vibrate more. This extra vibrational energy is
passed to other molecules by collisions, giving other molecules kinetic energy, raising the overall
temperature.
Contribution of any particular gas to the greenhouse effect depends on how much radiation one
molecule of the gas absorbs and concentration of that gas in the atmosphere in ppm.
Industrialisation, increase in human pouplation, burning of fossil fuels, deforestation are all
anthropogenic changes, i.e. caused by human activities.
There is a definite correlation between CO2 and temp. rise but some argue that this does not mean
rise in CO2 levels is the cause.

VIADD: Vapourisation, Ionisation, Acceleration, Deflection, Detection

A mass spectrometer determines the mass of a molecule or isotope by measuring the massto-charge ratio of ions. Although mass spectrometers differ considerably in their operation, the
same basic principles occur inside the instrument.

monitoring the breath of patients during surgery whilst under anaesthetic,

analysing molecules in space,
detecting traces of toxic chemicals in contaminated marine life,
detecting banned substances such as steroids in athletics.

Mass spectrometry also has a wide range of industrial and medical applications today, for example:
identify unknown compounds,
determine the abundance of each isotope in an element,
gain further information about the structure and chemical properties of molecules.
Mass spectrometry can be used to:

Mass Spectrometry
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Mechanisms
Free Radical Substitution: formation of free radicals, which attack and substitute.
Nucleophiles: electron pair donors. They are electron rich and are attracted to electron deficient
species such as positive ions, polar bonds and carbocations (e.g. polar carbon-halogen bond).
Electrophiles: electron pair acceptors. THey are attracted to electron rich species such as
negative ions, polar bonds and C=C bonds.
Free radicals: species with unpaired electrons. Cl free radicals are produced when UV light splits
a Cl2 molecule. They are very reactive and react with any species.
Heterolytic Fission: bonds break unevenly. Both electrons from the shared electron pair move
to one atom. This forms two different species: a positively charged cation/electrophile and a
negatively charged anion/nucleophile. Electron transfer is shown by a double-headed arrow.
Homolytic Fission: bond breaks evenly. One electron moves to each atom. forming two
electrically uncharged free radicals. Both atoms have an unpaired electron. Free radicals are very
reactive. Electron transfer is shown by a single-headed arrow.

Each organic compound produces a unique mass spectrum, which can be used as a fingerprint for
identification.
Although the molecular ion peak of two isomers will have the same m/z value, the fragmentation
patterns will be different.
Mass spectrometry can be used to determine the structure of an unknown compound and give
its precise identity.
Fragment ions are often broken up further into smaller fragments. The molecular ion and fragment
ions are detected in the mass spectrometer.
When a molecule is ionised by being impacted on by an electron, excess energy from the ionisation
process can be transferred to the molecular ion, making it vibrate. This causes bonds to weaken
and the molecular ion can split into pieces by fragmentation. Fragmentation results in apositive
fragment ion and a neutral species.
The molecular ion, M+, is the positive ion formed in mass spectrometry when a molecule loses
an electron. It produces the peak with the highest m/z value in the mass spectrum

Mass Spectrometry 2
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Infrared Spectroscopy
Some bonds in some molecules absorb IR radiation. This will make the bond vibrate.
The amount of energy needed to make them vibrate is dependant on the length of the bond, the
strength of the bond and the mass of the atoms involved.
For stronger bonds, higher frequency IR radiation will be required for the molecule to
vibrate.
If there are 2 atoms in the molecule, then only a stretch can occur.
If there are more than this there can be a bend or a stretch. A shift of the partial charges
is required for the bending/stretching to occur.
The stretch can be assymetric or symmetric.
Longer peaks are caused by strong absorption of IR.
Smaller peaks are caused by weaker absorption of IR.
Wider peaks are caused by absorption of IR over a wide range of frequencies.
The unit of measurement for absorbance iswavenumber, a receprical of wavelength.
Only molecules that change polarity as they vibrate (due to dipole movement in polar
bonds) absorb IR.
Only molecules that can absorb IR are greenhouse gases.