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Pairs of electrons will repel each other as far as possible (due to electrostatic repulsion)
Finding the shape:
1. Draw dot and cross
2. Count the number of electron pairs bond pairs and lone pairs
3. Decide the shape adopted by the electron pairs
4. Look at the number of lone pairs and decide the shape adopted by the atom
5. Draw shape, including bond angles
ELECTRON PAIRS
SHAPE
EXAMPLE
2 bond pairs
Linear
BeCl2
180o
3 bond pairs
Trigonal Planar
BCl3
120o
4 bond pairs
Tetrahedral
CH4
109.5o
5 bond pairs
Trigonal Bipyramidal
PCl5
6 bond pairs
Octahedral
SF6
90o
Lone pairs repel more than bond pairs because they are attracted to a single nucleus and not
shared by two atoms
Lone pairs reduce bond angles between bonding pairs. Each lone pair reduces predicted
bond angle between bonding electrons by 2.5 degrees.
ELECTRON PAIRS
SHAPE
EXAMPLE
Trigonal Pyramidal
NH3
107o
Bent/non-linear
H2O
Organic molecules:
Tetrahedral around carbon if saturated e.g. C3H8 or trigonal planar around carbon if there is
a C=C bond.
In C2H4 , the double bond reduces the bond angle further (its electron rich)
Multiple Bonds:
Count as one bond pair of electrons for purpose of determining the shape.
Carbon Structures:
Layers of graphite are weakly bonded to each other London forces. Also has a very high
melting point.
Polar bonds will deflect a stream of water (because water is polar) e.g. CH3Cl deflects, CCl4
doesnt.
Intermolecular Forces:
3 types of forces BETWEEN molecules: London forces/Van der Waals (weakest), Permanent
dipole-dipole and Hydrogen bonding (strongest)
1. London/VdW: Found in ALL molecules. Caused by an unequal distribution of
electrons which makes a temporary dipole. This affects surrounding atoms causing
induced dipoles. The net result is a weak attractive force. Everything has London
forces, and the MORE electrons, the STRONGER/LARGER the force.
2. Permanent dipole-dipoles: delta-plus of one molecule is
attracted to delta-minus of another molecule:
3. Hydrogen bonding: The attraction between a hydrogen
attached to Fluorine, Oxygen or Nitrogen on one molecule and an F, O, N atom on
another molecule. e.g.: hydrogen bonding in water:
Alkane boiling points increase with carbon chain length, because the number of electrons
increases, so more London forces.
Branched chain alkanes have LOWER boiling points than straight chains because they cant
pack as closely together, whereas straight chains can pack together closely (greater surface
area in contact) therefore the IMF forces are greater and they have higher boiling points.
Alcohols have very high boiling points (lower volatility harder to evaporate) due to strong
hydrogen bonding.
Solubiliy:
Affected by bonding, and usually a substance will only dissolve if the strength of the new
bonds formed is the same, or greater than the strength of the bonds that are broken.
Ionic compounds dissolve in polar substances such as water, because the ions are attracted
to the polar molecules and they surround the ions and pull them away from the ionic
lattice. This releases energy known as the hydration enthalpy. This can only happen if the
hydration enthalpy is big enough to overcome the lattice enthalpy. (Hydration vs. Lattice)
Alcohols are soluble in water, because they form hydrogen bonds with it.
Non-polar molecules wont form hydrogen bonds with water, so dont dissolve in it. E.g.
halogenoalkanes like chlorobutane.
Generally like dissolves like
Redox
Oxidation number: the number of electrons that need to be lost or gained to become a
neutral atom.
Uncombined elements are 0
F is always -1, group 1 are +1, group 2 are +2, oxygen is -2 (except in peroxides H2O2 where
its -1), H is +1 (except metal hydrides where its -1)
Oxidation numbers in a neutral compound add up to zero, and in a polyatomic ion add up to
the charge.
Ionic half equations are used for redox processes when oxidation and reduction take place
together in a reaction.
Mn2+ + 4H2O
And
I2 + 2e-
2I
For oxidising agents that contain OXYGEN, e.g. MnO4- , you will need H+ on the LEFT and H2O
on the RIGHT (oxygen cant swim)
The MnO4- half equation has 5e- but the I- equation has 2e- , so to make them both have the
same number of electrons (so they can cancel out when the equations are added together),
the MnO4- equation has to be multiplied by 2, and the I- equation multiplied by 5, so that
they both have 10eThey are then added together to give:
2MnO4- + 16H+ + 10I-
Disproportionation: when one species is both oxidised AND reduced at the same time
e.g.:
Cl2 + H2O
0
HCl + HClO
-1 +1
Have their highest energy electrons in an s sub-shell, hence they are called s-block elements.
Going down the group, there is an extra electron shell compared to the element above, and
the atomic radius is increasing
The outer electrons are increasingly further away from the nucleus; therefore the attractive
force is less.
The extra inner shells shield the outer electrons from the attraction of the nucleus
Therefore, the ionization energies DECREASE down the group (gets easier to remove an e- )
2MgO(s)
Reactivity INCREASES
down group, as the I.E
decreases:
Be doesnt react
Mg with steam
Ca steadily
Sr fairly quick
Ba rapidly
MgO + H2
MgCl2(s)
1. Group 2 oxides react with water to form metal hydroxides, which dissolve. They are also
alkaline
e.g.: CaO(s) + H2O (l)
Ca (OH) 2 (aq)
Generally compounds of group 2 elements that contain singly charged negative ions (e.g.
OH-) INCREASE in solubility down group
Compounds with doubly charged -ve ions (e.g. SO42-) DECREASESolubility
in solubility
of down group.
HYDROXIDES
INCREASES down the
group
Mg (OH) 2 Insoluble
Ca (OH) 2
Sr (OH) 2
Ba (OH) 2 Most soluble
Solubility of
SULFATES DECREASES
down the group
MgSO4 Most soluble
CaSO4
SrSO4
BaSO4
Insoluble
Group 1
Carbonates: From sodium carbonate down group 1, the carbonates will NOT DECOMPOSE
on heating thermally stable.
Nitrates: From sodium nitrate down group 1, the nitrates decompose to form the nitrite
and oxygen
e.g.: KNO3(s)
Potassium
Nitrate
2KNO2(s) + O2 (g)
Potassium
Nitrite
Group 2
Carbonates: Lithium and group 2 carbonates decompose to form an oxide and carbon
dioxide
e.g.: CaCO3(s)
Li2CO3(s)
Nitrates: Lithium and group 2 nitrates decompose to form the oxide, nitrogen dioxide and
oxygen.
e.g.: Ca(NO3)2 (s)
4LiNO3(s)
Flame tests:
1. Mix small amount of compound with few drops of hydrochloric acid
2. Heat a platinum or nichrome wire in hot flame to clean it.
3. Dip the wire into the compound and hold it in hot flame.
Electrons are being excited to higher energy levels by the heat energy. When the electrons
return to the lower energy levels, they emit energy in the form of visible light.
Flame colours of group 1 and 2 compounds:
Group 1: Lithium RED
Sodium YELLOW
Potassium LILAC
Appearance in water
Fluorine
N/A
Appearance in
hydrocarbon solvent
N/A
Chlorine
Green gas
Bromine
Red-brown liquid
Pale yellow/green
solution
Red/brown/orange
Pale yellow/green
solution
Red/brown/orange
Iodine
Grey solid
Brown
Pink/violet
Reactions of halogens:
1. Disproportionation with alkalis NaOH or KOH
COLD alkali to give halide and halate (I) ions:
X2 + 2NaOH
X2(g) + 2OH-(aq)
O.S:
+1
-1
e.g:
I2 + 2NaOH
-1
Sodium
bromate
Metals: e.g. fluorine and chlorine react with iron to form iron (III) halides
Iron is oxidised:
2Fe
2Fe3+ + 6eChlorine is reduced: 3Cl2 + 6e6ClOverall equation: 3Cl2(g) + 2Fe(s)
2FeCl3(s)
Non metals: e.g. chlorine reacts with sulphur to form sulphur (I) chloride. Sulphur is oxidised
to +1 and chlorine is reduced to -1)
S8(s) + 4Cl2(g)
4S2Cl2(l)
Ions: e.g. all halogens except iodine (weak oxidising agent) will oxidise iron (II) ions to iron
(III) ions in solution. The solution will change colour from green to orange.
2Fe2+(aq)
2Fe3+ (aq) + 2e-
Reactions of Halides:
1. Potassium halides with concentrated sulphuric acid:
React to give a hydrogen halide.
The trend in strength of the halide ions as reducing agents is: I- > Br- > ClKCl and H2SO4:
KCl(s) + H2SO4(l)
KHSO4(s) + HCl(g)
But hydrogen chloride is not a strong enough reducing agent to reduce the sulphuric acid, so
reaction stops there. Misty fumes of hydrogen chloride gas will be seen when it comes into contact
with moisture in air. This is NOT a redox reaction O.S of halide and sulphur stay the same (-1 and
+6)
KBr and H2SO4:
KBr(s) + H2SO4(l)
This reaction gives misty fumes of hydrogen bromide gas, and the HBr is strong enough to reduce
the H2SO4 in a redox reaction.
Then this reaction: 2HBr + H2SO4 (l)
O.S of Br:
-1
O.S of S:
+6
OXIDATION
+4
KI with H2SO4:
KI(s) + H2SO4(l)
2HI + H2SO4(l)
KHSO4(S) + HI(g)
I2(s) + SO2(g) + 2H2O(l)
REDUCTION
O.S of I:
Same first two reactions, but because iodine is a very strong reducing agent, it goes
further, and reduces SO2 to H2S :
6HI(g) + SO2(g)
H2S(g) + 3I2(s) + 2H2O(l)
-1
O.S of S:
0
+4
OXIDATION
-2
REDUCTION
With ammonia: react to form white fumes of the corresponding ammonium halide:
NH3 (g) + HCl(g)
NH4Cl(s)
AgX(s)
The colour of precipitate identifies the halide, and they have different solubilitys in ammonia
solution:
Chloride Cl- : White ppt which dissolves in dilute NH3 (aq) and darkens in sunlight
Bromide Br- : Cream ppt, dissolves in concentrated NH3 (aq) and darkens in sunlight
Iodide I- : Yellow ppt, insoluble in concentrated NH3 (aq) and does NOT darken in
sunlight.
The reaction of silver halides with sunlight (decomposition) is:
2AgBr
2Ag + Br2
Number of electrons increases down group, so London forces will increase. Astatine
will be a solid and have the highest boiling temperature.
Electronegativity decreases down group, so astatine will have lowest EN value.
Fluorine will be most oxidising
Kinetics
Reactions only happen when: Particles collide in the correct orientation, and they possess
the activation energy (minimum amount of kinetic energy particles need to react). This is
the collision theory.
Enthalpy profile diagram:
Factors affecting the rate of reaction: concentration, temperature, pressure, surface area
and catalysis.
Factor
Concentration
(solution)
Pressure (gas)
Surface area
(solids)
Temperature
Catalyst
How it affects
rate
Increasing
conc./pressure
increases rate
Increasing
surface area
increases rate
Increasing
temperature
increases rate
Speeds up the
reaction
Explanation
The particles become more crowded, therefore collide
more times which increases the reaction rate.
The smaller the size of reacting particles, the greater the
total surface area. Increasing surface area means larger
area is exposed for reaction and more collisions.
Increasing temperature means the average speed of
reacting particles increases, therefore more collisions per
second.
Lower the activation energy by providing an alternative
route. If activation energy is lower, more particles will
have enough energy to react.
Maxwell-Boltzmann distribution:
Catalysts:
Increase the rate of a reaction by providing an alternative reaction pathway with a lower
activation energy. It is chemically unchanged at the end of the reaction.
Chemical Equilibia
2NO2
ORGANICS Alcohols:
Reactions of alcohols:
1. Combustion of alcohols:
C2H5OH(l) + 3O2(g)
2CO2(g) +3H2O(g)
Observations made:
2CH3CH2O-Na+ + H2 (g)
And the longer the hydrocarbon chain, the less reactive with sodium.
Sodium fizzes,
bubbles form, sodium
disappears, and white
solid product forms
The OH is swapped for the Cl, and this reaction can be used as a test for an OH group. The
steamy fumes that are produced turn blue litmus paper red (because HCl dissolves to form
a strong acid)
To make a chloroalkane, just mix a tertiary alcohol (most reactive) and hydrochloric acid
together. This will give an impure chloroalkane which can be purified.
4. Oxidation of alcohols:
3e-
Cr3+(aq)
Green
The results show that only primary and secondary alcohols can be oxidised, and tertiary
alcohols cannot be oxidised, therefore remains orange.
A primary alcohol can be oxidised to an aldehyde and then to a carboxylic acid. This is
carried out using an oxidising agent: Mixture of sulphuric acid, H2SO4 (souce of H+) and
potassium/sodium dichromate, K2Cr2O7
To stop oxidising at the aldehyde, you must allow the product to distil over
To get the carboxylic acid, you heat under reflux
Primary
alcohol to
aldehyde
Primary alcohol
to carboxylic
acid
HEAT
Refluxing allows you to heat / boil volatile liquids for a long time. The condenser stops the
volatile liquids evaporating off , because any vaporised compounds are cooled, condense
and drip back down to the reaction mixture
Secondary alcohols are oxidised to ketones ONLY. Do not undergo further oxidation.
This can be done by refluxing the secondary alcohol with acidified sodium/potassium
dichromate.
Summary:
Primary alcohol
Aldehyde
Carboxylic acid
Secondary alcohol
Ketone
No reaction
Tertiary alcohol
No reaction
Halogenoalkanes
Reactions of Halogenoalkanes:
Aqueous hydroxide ions need to substitute the halogen. Sodium hydroxide NaOH(aq) or
potassium hydroxide KOH(aq) can be used.
The reaction is called hydrolysis and usually carried out under reflux
Hydrolysis: is a reaction with water or aq hydroxide ions that break a chemical compound
into two compounds
Mechanism:
First step
Second step
If water with dissolved silver nitrate is used, this can tell us about the reactivities of
halogenoalkanes
When water and an alcohol react, and an alcohol is formed, the silver nitrate will react with
the halide ions when they form giving a silver halide precipitate
The precipitate that forms first indicates which halogenoalkanes hydrolyses first:
Tertiary halogenoalkanes precipitate forms immediately
Secondary halogenoalkanes precipitate forms after several seconds
Primary halogenoalkanes precipitate forms after several minutes
This shows that the reactivity is tertiary 3o > secondary 2o > primary 1o
Ammonia NH3 has a lone pair of electrons, and can therefore act as a nucleophile
Alcoholic ammonia ammonia dissolved in ethanol.
Heated under reflux
MECHANISM
Step 1
Step 2
Uses of halogenoalkanes:
Chlorofluorocarbons (CFCs) used to be used in the past because of their unique properties
(non-toxic, non-flammable, unreactive), but it was found that they deplete the ozone layer
in the atmosphere, so are being phased out (see notes later)
Other halogenoalkanes such as hydrofluorocarbons (HFCs) are now used as safer
alternatives.
Mechanisms:
Free radical species with an unpaired electron
Electrophile species that accepts a pair of electrons
Nucleophile species that donates a pair of electrons
Substitution one species is replaced by another
Addition joining two or more molecules together to make a larger molecule
Elimination when a small species is eliminated from a larger molecule
Oxidation loss of electrons. Also is the gain of oxygen/loss of hydrogen
Reduction gain of electrons. Also is the loss of oxygen/gain of hydrogen
Hydrolysis Splitting up using water (usually in form of OH- ions)
Polymerisation joining together monomers into long carbon-chain polymers.
Redox any reaction where electrons are transferred between two species
Homolytic when the bond breaks evenly, and one electron moves to each atom. This
forms two free radicals as both atoms now have an unpaired electron. The unpaired
electron makes free radicals very reactive.
Heterolytic when the bond breaks evenly, and both electrons from the shared electron
pair move to one atom. This forms two different species: a positively charged cation an
electrophile, and a negatively charged anion a nucleophile
When drawing curly arrows double headed arrow shows movement of electron pair; single
headed arrow shows movement of single electron.
Should be able to recall these reaction mechanisms from unit 1: Electrophilic addition and free
radical substitution:
H+ = acidified
OZONE
Ozone molecules O3
The ozone layer is at the edge of the stratosphere
It filters out most of the harmful UV radiation which can damage DNA in cells causing skin
cancer and can also cause eye cataracts.
Ozone is formed when UV radiation from the sun hits oxygen molecules. This forms two free
radicals. The free radicals then combine with other oxygen molecules to form ozone
molecules
O2 + U.V
O* + O*
* = free radical
O2 + O*
O3
The ozone layer is constantly being replaced, and there is a natural balance between
formation of new ozone and breakdown of ozone molecules : O2 + O*
O3
It was discovered that the ozone layer is thinning in places, and a hole in the ozone was
discovered over Antarctica this means that more harmful UV will reach the earth.
The decrease in ozone concentrations is due to CFCs chlorofluorocarbons.
Because of their un-reactivity, CFCs dont decay and reach the upper atmosphere and the
ozone layer, where several reactions happen:
1)
2) The free radicals are catalysts, and react with ozone to form an intermediate ClO*, and O2
Cl*(g) + O3 (g)
O2 (g) + ClO*(g)
ClO*(g) + O3 (g)
2O3 (g)
3O2 (g)
Nitrogen oxides are produced from car and aircraft engines and thunderstorms. Like
chlorine radicals, NO* also act as catalysts :
NO* + O3
O2 + NO2*
NO2* + O3
2O2 + NO*
IR
Some molecules absorb energy from infrared radiation. This makes the bonds vibrate
Vibrations occur in one of 2 ways, a stretching vibration or a bending vibration
1. Bond strength
2. Bond length
3. Mass of atom at either end of the bond
Oxygen O2 , and Nitrogen N2 dont absorb infrared radiation, but CO2 , H2O, nitric acid (NO) ,
and methane (CH4) do absorb infrared radiation. They absorb IR because they change their
polarity as they vibrate (due to the movement of dipoles in polar bonds)
Gases that do absorb IR radiation are called greenhouse gases they stop some of the
radiation emitted by the earth from escaping into space.
We have just seen that the peak on an IR spectra are due to specific bonds (and atoms)
vibrating or stretching.
The frequency at which you find an absorbance peak is therefore unique to bonds and
atoms at each end of the bond.
This means that functional groups will give specific peaks.
Bond
Functional group
Wavenumber/frequency
C=O
1640 - 1750
C- H
Organic compounds
2850 - 3100
2500 - 3300
O- H
Carboxylic acids
(very broad)
O- H
N-H
Amines
3200-3500
C-X
Halogenoalkanes
500-1000
Alcohols:
The IR spectrum for methanol, CH3OH is shown below:
Mass spec
The molecular ion has the same mass as the Mr of the molecule.
As we have a mass and a charge we can use a mass spectrometer to determine the Mr (m/z).
Fragmentation:
Excess energy from the ionisation process causes bonds in the organic molecule to vibrate
and weaken.
This causes the molecule to split or fragment into smaller pieces.
Fragmentation gives a positively charged molecular fragment ion and a neutral molecule:
C2H5OH CH3 + CH2OH+
The fragment ion, CH2OH+ has a mass and charge so we can use a mass spectrometer to
determine the Mr (m/z) of that fragment.
Fragment ions can be broken up further to give a range of m/z values.
The m/z values correspond to the Mr's of the molecule and its fragments.
The Mr of the molecule is always the highest m/z value - i.e. this molecule has not been
fragmented so it must have the highest Mr.
The one below is for ethanol. It has a m/z of 46 which is also its Mr.
Fragmentation patterns:
Mass spectroscopy is used to identify and determine the structures of unknown compounds.
Although 2 isomers will have exactly the same M+ peak, the fragmentation patterns will be
unique to that molecule, like a fingerprint.
In practice mass spectrometers are linked to a database and the spectra is compared until an
exact match is found:
These are the mass spectra for pentane and a structural isomer of pentane, 2 methylbutane.
The M+ peak is the same for each but the fragmentation patterns are different.
When you look at a mass spectrum, other peaks seem to look more important than the M+
peak.
These fragment peaks give clues to the structure of the compound.
Even simple structures give common peaks that can be identified:
m/z
value
15
29
43
57
17
A mass spectrum will not only tell you the Mr (from the M+ peak), but it can also tell you
some of the structural detail.
These peaks have been labelled with a letter:
Green Chemistry
Processes in the chemical industry are being reinvented to make them more sustainable or greener
by:
1.
2.
3.
4.
5.
Changing to renewable resources: e.g. plastics made from crude oil can be made from plant
products
Making more efficient use of energy. E.g. in the pharmaceutical industry microwave
radiation is used to heat the reacting mixture directly rather than using conventional heating
systems which heat the reaction vessel which passes on heat to the reaction mixture less
efficient.
Finding alternatives to very hazardous chemicals e.g. some chemicals can harm humans,
other living organisms or the environment.
Discovering catalysts for reactions with higher atom economies. This is important because a
high atom economy means less waste is produced and this makes the best use of resources.
Reducing waste and preventing pollution of the environment. E.g. creating recyclable or
using products to conserve raw materials and where possible waste should be recycled or
biodegradable.
Infrared radiation IR from the sun has a short wavelength and most of it passes through the
atmosphere and is absorbed by the earths surface.
The earth heats up, and re-emits longer wavelength IR. Any greenhouse gases in the
atmosphere effectively reflect the longer wavelength IR which warms the atmosphere.
The relative greenhouse effect of a gas varies because molecules absorb IR differently.
The global warming potential of a gas combines it ability to absorb IR with its lifetime in
the atmosphere. The concentration of a gas in the atmosphere also affects GWP. E.g. CO2
has a low global warming potential, but the concentrations of it are increasing. CFCs have a
much higher GWP but the overall concentrations are very low.
Anthropogenic: results from human activities, e.g. burning fossil fuels and deforestation.
These increase levels of CO2, methane and other gases over relatively short timescales.
Natural climate change: natural processes such as dissolving of CO2 in sea water or
formation of carbonates in rocks over hundreds of years. Volcanic eruptions can also cause
climate change.
A carbon neutral fuel is one for which the release of CO2 in its manufacture and burning
equals the absorption of CO2 as the raw material is grown or the fuel formed. Only certain
biofuels can be considered carbon neutral
A carbon neutral process occurs when there is no overall carbon emission into the
atmosphere.
A carbon footprint in general is a measure of the amount of carbon dioxide emitted through
the use of fossil fuels. It is often measured in tonnes of carbon dioxide, and can be calculated
for an individual, a household, an organisation or over a product lifecycle for manufactured
goods.
The fuel petrol is definitely not carbon neutral - releases CO2 into atmosphere which was
trapped in the earth millions of years ago.
Bioethanol is more or less carbon neutral- produced by fermentation of sugar from crops.
Its thought of as being carbon neutral as the CO2 released when burnt was removed by the
crop as it grew. However, there are still carbon emissions when considering the whole
process.
Hydrogen gas can be carbon neutral .