AS Chemistry Unit 2 Notes

Shapes of molecules and Ions

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

BOND ANGLES
AND 3D SHAPE

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.

4 election pairs on the central atom based on the tetrahedral shape:

4 bond pairs = tetrahedral (e.g. CH 4 and NH4+) - 109.5o
ELECTRON PAIRS

SHAPE

EXAMPLE

3 bond pairs and 1

lone pair

Trigonal Pyramidal

NH3

BOND ANGLES
AND 3-D SHAPE

107o

2 bond pairs and 2

lone pairs

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.
E.g. CO2 is linear:

Carbon Structures:

Carbon has several allotropes different molecular structures due to

differences in bonding.
Diamond: Each carbon atom forms 4 identical bonds to
neighbouring carbon atoms giving a tetrahedral arrangement.
Because of the strong covalent bonds, diamond has a VERY high
melting temperature, is extremely hard (the hardest known substance)
and cannot conduct electricity no free e-.
Graphite: Carbon atoms in layers. Within a layer, each carbon
atom is bonded to 3 other carbons the 4 th outer e- is delocalised
and free to move: conducts electricity.

Layers of graphite are weakly bonded to each other London forces. Also has
a very high melting point.

Fullerenes: Consist of 32+ carbon atoms. Buckminsterfullerene

has 60 carbon atoms. Ball-shaped molecules. The fourth outer e- is
delocalised, so conduct electricity.
Nanotubes: Fullerenes in the form of tubes. Very small and stiffer than
other known materials. If embedded in polymers they may produce
materials with good electrical conductivity and strength.

Intermediate bonding and bond polarity:

Electronegativity: ability of an atom to attract an electron pair in a

covalent bond. Increases ACROSS the period (Fluorine is the most EN
element) and decreases down groups.
Differences in elecronegativity between two elements will result in
electrons being pulled further to one end, and
there
will be POLARITY in the bond e.g:
If the difference is large enough, electrons will be
transferred IONIC BOND.
Small, highly charged cations (e.g. Al 3+) are highly polarizing, and will
pull electrons toward then very strongly, especially from a large anion
(e.g. I-), resulting in a covalent bond (AlI 3 )

If molecule is SYMMETRICAL, there is no overall polarity. E.g. CCl 4.

The dipoles cancel out.

Unsymmetrical molecules containing polar bonds will be polar

molecules describes as having a permanent dipole.

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:
Trends in physical properties by intermolecular forces:

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.

HF has a high boiling point due to

hydrogen bonding. The graph dips down
to HCl, HBr and HI, which all have
dipole- dipole interactions but the
number of electrons is increasing, so
there are additional London forces
which raise the boiling points.

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

Example question: State and explain the solubility of hexane in water

Hexane molecules are held together by London forces. Water molecules are
held together by hydrogen bonds. Hexane cant make hydrogen bonds with
water, so the two liquids do not mix or dissolve in each other immiscible.

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.
If species are reduced, electrons are on the LEFT
If species are oxidised, electrons are on the RIGHT
Half equations are then added together for the full redox equation
E.g. : The overall equation for the oxidation of I - ions by MnO4- ions is
obtained from the two half equations:
MnO4- + 8H+ + 5e-

Mn2+ + 4H2O
And

2I I2 + 2eFor oxidising agents that contain OXYGEN, e.g. MnO 4- , 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 MnO 4- 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+ + 10I2Mn2+ + 8H2O + 5I2
Disproportionation: when one species is both oxidised AND reduced at
the same time
e.g.:

Cl2 + H2O
0

HCl + HClO
-1
+1

The periodic table Group 2

Have their highest energy electrons in an s sub-shell, hence they are

called s-block elements.

Ionization energy (I.E) trends:

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- )

Reactions of group 2 elements with Oxygen, Water and Chlorine:

1. Burn in Oxygen to form solid oxides, often burning with a bright flame
e.g.: 2Mg (s) + O2 (g)
2MgO(s)
2. React with water to form metal hydroxide and hydrogen:
e.g.:
(aq)

Ca (s) + 2H2O (l)

+ H2 (g)

Reactivity
INCREASES down
Ca (OH)
2
group,
as the
I.E
decreases:
Be doesnt react

Mg reacts rapidly with steam: Mg(s) + H2O (g)

MgO + H2

Mg with steam
Ca steadily

3. React with chlorine to form solid metal chlorides:

e.g.:

Mg(s) + Cl2 (g)

Sr fairly quick

MgCl2(s)

Ba rapidly

Reactions of group 2 OXIDES and HYDROXIDES:

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)

2. Group 2 oxides and hydroxides are BASES

They neutralise dilute acids e.g.: HCl or HNO3

Form the corresponding salt and water
e.g.:

Hydroxides are the same:

MgO(s) + 2HCl (aq)

CaO(s) + 2HNO3 (aq)
Ca (OH)2 (aq) + 2HCl(aq)

MgCl2 (aq) + H2O (l)

Ca (NO3)2 (aq) + H2O (l)
MgCl2 (aq) + H2O (l)

Solubility trends of hydroxides and sulphates:

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-) DECREASE in
solubility
down group.
Solubility
of HYDROXIDES
INCREASES down the group
Solubility of SULFATES DECREASES down the group
Mg (OH) 2 Insoluble
MgSO4
Most soluble
Ca (OH) 2
CaSO4
Sr (OH) 2
SrSO4
Ba (OH) 2 Most soluble
BaSO4
Insoluble

Thermal Stability of group 1 and 2 CARBONATES and NITRATES

Thermal decomposition: when a substance decomposes when heated

The more thermally stable a substance is, the more heat it requires to
break it down.
The carbonate and nitrate ions are LARGE and can be made UNSTABLE by
a cation. The greater the polarising power of the cation, the greater the
distortion and the LESS stable the anion.
The further down the group, the larger the cations and less distortion
caused therefore the MORE stable the carbonate/nitrate anion. Thermal
stability increases down a group.
Group 2 compounds are LESS THERMALLY STABLE than group 1 (more
distortion by +2 cation)

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.: KNO 3(s)
Potassiu
m Nitrate

2KNO 2(s) + O2 (g)

Potassiu
m Nitrite

Group 2

Carbonates: Lithium and group 2 carbonates decompose to form an oxide

and carbon dioxide
e.g.:

CaCO3(s)

CaO(s) + CO2 (g)

Li2CO3(s)

Li2O(s) + CO2 (g)

Nitrates: Lithium and group 2 nitrates decompose to form the oxide,

nitrogen dioxide and oxygen.
e.g.:

Ca(NO 3)2 (s)

4LiNO3(s)

2CaO

(s)

+ 4NO2 (g) + O2(g)

2Li2O(s) + 4NO2 (g) + O2(g)

Testing thermal stability of nitrates and carbonates:

1. Nitrates:
How long it takes until a brown gas - NO 2 is produced. It is toxic, so must
be done in fume cupboard
2. Carbonates:

How long it takes for carbon dioxide to be produced tested using

limewater which turns cloudy.

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

Group 2: Magnesium WHITE

Sodium YELLOW

Calcium BRICK RED

Potassium LILAC

Strontium CRIMSON

RED
Barium GREEN
The periodic table group 7, the HALOGENS

Non-metallic elements, VERY reactive.

Diatomic covalent molecules
OXIDISING agents (they are reduced themselves), and become less
oxidising, or reactive down the group.
Halogen

Physical state and

colour

Appearance in
water

Fluorine

Pale yellow gas

N/A

Appearance in
hydrocarbon
solvent
N/A

Chlorine

Green gas

Bromine

Red-brown liquid

Iodine

Grey solid

Pale yellow/green
solution
Red/brown/orang
e
Brown

Pale yellow/green
solution
Red/brown/orang
e
Pink/violet

Reactions of halogens:
1. Disproportionation with alkalis NaOH or KOH
COLD alkali to give halide and halate (I) ions:
halide and halate (V) ions:
X2 + 2NaOH
NaXO3 + 5NaX +3H2O

NaXO + NaX + H2O

HOT alkali to give

3X2 + 6NaOH

X2(g) + 2OH-(aq)
XO3- (aq) + 5X- + 3H2O
O.S:
+5

XO-(aq) + X-(aq) +H2O

+1

3X2 (g) + 6OH-(aq)

-1

-1

e.g:
I2 + 2NaOH
NaBrO3 + 5NaBr + 3H2O
2. Oxidise metals,

NaIO +

NaI +

H 2O

Sodiu
Sodiu
m
m
non-metals
and ions
iodate iodide

3Br2 + 6NaOH
Sodium
bromate
(V)

Sodiu
m
bromat

Metals: e.g. fluorine and chlorine react with iron to form iron (III) halides
Iron is oxidised:
2Fe
2Fe 3+ + 6eChlorine is reduced: 3Cl2 + 6e
6ClOverall 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)

KHSO4 (s) + HBr(g)

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)

Br2(g) + SO2(g) + 2H2O(l)

O.S of Br:

-1

O.S of S:
REDUCTION

OXIDATION

+6

+4

KI with H2SO4:

O.S of I:
OXIDATION
O.S of S:
REDUCTION

KI(s) + H2SO4(l)
KHSO4(S) + HI(g)
2HI + H2SO4(l)
I2(s) + SO2(g) + 2H2O(l)
Same first two reactions, but because iodine is a very strong
reducing agent, it goes further, and reduces SO 2 to H2S :
6HI(g) + SO2(g)
H2S(g) + 3I2(s) + 2H2O(l)
-1

0
+4

-2

H2S is a toxic gas, and gives a bad egg smell.

2. Hydrogen Halides with ammonia and water

Hydrogen halides are colourless gases. They are very soluble, and
dissolve in water to make STRONG acids:
HCl (g)
H+(aq) + Cl- (aq)
(dissociation)

Hydrogen chloride forms hydrochloric acid; hydrogen bromide forms

hydrobromic acid and so on.

With ammonia: react to form white fumes of the corresponding

ammonium halide:
NH 3 (g) + HCl(g)
NH4Cl(s)

3. Displacement by more reactive halogens

The oxididising strengths of the halogens can be seen in their
displacement reaction with halides.
E.g.
Br 2(aq) + 2KI(aq)
2 KBr(aq) + I2(aq)
The bromine displaces the iodine ions (it oxidises them) giving
iodine I2(aq) and potassium bromide
A halogen will displace a halide from solution if the halide is below
it in the periodic table
4. Silver nitrate solution, and silver halides solubility in ammonia and
reactions with sunlight:

To test for halides in solution:

1. Add dilute nitric acid this removes ions that could interfere with
test and ppt.
2. Add silver nitrate solution (AgNO3(aq) )
A precipitate of the silver halide will form, the reaction is:
Ag + (aq) + X-(aq)

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

Making predictions about fluorine and astatine from trends in group 7:

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.

Maxwell-Boltzmann distribution:

Shows distributions of molecular energies in a gas

When temperature is increased, particles will have more kinetic energy
and move faster. This means that more particles will have energies greater
than the activation energy and will react. This changes the shape of the
Maxwell Boltzmann distribution curve pushing it to the right, with a peak
lower than the original.
Lower
Higher
temperature

Factor
Concentratio
n (solution)
Pressure
(gas)
Surface area
(solids)

Temperature

Catalyst

Total number of
gas molecules
under the curve

How it
affects rate
Increasing
conc./pressu
re increases
rate
Increasing
surface area
increases
rate
Increasing
temperature
increases
rate
Speeds up
the reaction

Only molecules in
this region can
react molecules
have a higher
energy than the
activation energy

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.

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.

Homogenous catalysts: in the same state as the reactants.

Forms intermediates with the reactants, which the products are then
formed from.
The activation energy needed to form the intermediates and the products
from the intermediates is lower than that needed to make the products
directly from the reactants.

Chemical Equilibia

Many
reactions do not go to
completion because the reaction is reversible
Dynamic equilibrium: When the rates of the forward and reverse
reactions are equal. Its dynamic because individual molecules react
continuously. It is at equilibrium because no net change occurs (overall
concentrations remain constant
Equilibrium can only happen in a CLOSED system.

The effect of conditions on the position of equilibrium:

Controlled by Le Chateliers principle: When a system at equilibrium is

subjected to a change, it will behave in such a way to counteract that
change.
Temperature is a very important way to control industrial processes,
because it is the most effective factor (general rule increase in 10K
doubles the rate of reaction.

Pressure is very expensive to use

in equilibrium processes.
The red-brown gas NO2 exists in
equilibrium with pale yellow N2O4 :
N 2O4

2NO2

The forward reaction is endothermic.

If the position of equilibrium shifts to
left the mixture pales
If the position of equilibrium shifts to
right the mixture darkens

ORGANICS Alcohols:

General formula: CnH2n+1OH where

the functional group is C-OH
Examples: CH3OH Methanol used
for fuels and plastics.
CH3CH2OH Ethanol fuels, alcoholic drinks
CH3CH2CH2OH Propan-1-ol
CH3CHOHCH3 - Propan-2- ol
Can be primary secondary or tertiary
alcohols:

Reactions of alcohols:
1. Combustion of alcohols:
C 2H5OH(l) + 3O2(g)

2CO2(g) +3H2O(g)

2. Reaction with Sodium:

2Na(s) + 2CH3CH2OH (l)

2CH3CH2O Na + H2 (g)

Observations
made:

Sodium fizzes,
sodium ethoxide + hydrogen
bubbles form,
And the longer the hydrocarbon chain, the less reactive with sodium.
sodium
disappears, and
3. Substitution reactions to form halogenoalkanes:
Sodium + ethanol

Alcohols react with PCl5 (Phosphorus (v) Chloride), releasing hydrogen

chloride gas which forms misty fumes in air
CH3CH2OH (l) + PCl5
CH3CH2Cl (l) + POCl3 (l) + HCl (g)

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:
Must be familiar with these functional
groups:

To oxidise alcohols we use acidified potassium dichromate solution.

This is orange in colour and is a mixture of sulphuric acid, H2SO4 and
K2Cr2O7.
The orange colour is due to the Cr6+ ions in K2Cr2O7.
If it oxidises (i.e. the Cr6+ ions become reduced) then the solution turns
green.
Cr6+(aq)
Orange

3e-

Cr3+(aq)
Green

Th
e results show that only primary and secondary alcohols can be oxidised,
and tertiary alcohols cannot be oxidised, therefore remains orange.

Oxidation of primary alcohols:

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

This is the distillation apparatus.

The aldehyde has to be distilled off as
it forms as it can be oxidised further
Distillation evaporates and condenses
liquids at different temperatures.
Collect the liquid you want around its
boiling point and discard any others

Primary
alcohol to
carboxylic
acid

When making the carboxylic acid the mixture is

refluxed.
Heated strongly with an excess of the acidified
potassium or sodium dichromate, and the
alcohol will be completely oxidised passing
through the aldehyde stage to form a carboxylic
acid.
Refluxing allows you to heat / boil volatile
liquids for a long time. The condenser stops
the volatile liquids evaporating of , because any vaporised
compounds are cooled, condense and drip back down to the reaction
mixture
HEA
T

Oxidation of secondary alcohols:

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

Halogenoalkanes have the general formula CnH2n+1X. X is a halogen.

Can also be primary, secondary and tertiary like alcohols.
When naming, the halogen part is named first (prefix chloro-, bromo-,
iodo-) followed by name of alkane
E.g. CH3Cl = Cloromethane
CH3CH2Br = Bromoethane
If there is more than one halogen di- and tri- are used to indicate the
number of halogens present, e.g. CH 2BrCH2Br = 1,2-dibromoethane

Reactions of Halogenoalkanes:

Halogenoalkanes contain polar bonds because

the halogen is more electronegative than the
carbon. This leaves a carbon with a delta + charge,
making it open to attack by nucleophiles.
Nucleophiles: attracted to electron deficient atom,
d+ and donate a pair of electrons to form a new covalent
bond
The halogen will be replaced by the nucleophile, which gives a
substitution reaction, giving a new functional group.

1. Halogenoalkanes react with aqueous alkalis to form ALCOHOLS

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:

Water can act as a nucleophile too, but it is a much slower reaction:

First step

Second

The overall equation with

step

water:

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

2. Halogenoalkanes react with alcoholic ammonia to form amines

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

In the second step, and ammonia

molecule removes hydrogen from
the NH3 group to form an
ammonium ion (NH4+)

Step 1

This can then react with the Br- ion

from step 1, to form ammonium
bromide: NH4Br
Overall reaction: with ethanol and
under reflux
Alcoholi

Step 2
3.
c

alkali to
form

alkenes
When a halogenoalkane reacts with alcoholic alkali, e.g. potassium
hydroxide, KOH in hot ethanol, an
alkene is made

This is an elimination
reaction
Heated under reflux

Uses of halogenoalkanes:

Halogenoalkanes are used as fire retardants and refrigerants

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

Bond breaking homolytic and heterolytic:

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 diferent
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:

Hydrogen bromide to alkenes:

Free radical substitution of chlorine in

alkanes:
Initiation, propagation, termination

Predicting the type of mechanism:

Polar bonds always break heterolytically

A nucleophile can attack the d+ atom in a polar bond
An electrophile can attack an electron- rich part of a molecule e.g. the
C=C bond in alkenes

All reagents used in AS chemistry (helpful to learn them):

Nucleophiles: OH-(aq), NH3 (alcoholic), PCl5, NaBr/H2SO4 or PBr5, P/I2

Electrophiles: H2, X2, HX
Oxidation [O]: KMnO4 /H+, K 2Cr2O7/H+
H+ =
Other: KOH in hot ethanol, Cl2 / u.v light, RO OR/ u.v light (polymerisation)
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
O 2 + U.V
O* + O*
O 2 + O*
O3

* = free
The ozone layer is constantly being replaced, and there is a naturalradical

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)

CFCs are broken down by UV light, forming chlorine free radicals

CCl3F2 (g)
CCl2F*(g) + Cl*(g)

2) The free radicals are catalysts, and react with ozone to form an intermediate
ClO*, and O2
The Cl free radical is
Cl*(g) + O3 (g)

O2 (g) + ClO*(g)

regenerated and goes on to

attack other ozone
molecules. This shows that
one CFC molecule can
destroy thousands of ozone

ClO*(g) + O3 (g)

3) The overall reaction is:

2O2 (g) + Cl*(g)

2O 3 (g)

3O2 (g)

(Cl is the catalyst)

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
Every bond vibrates at its own unique frequency depending on:

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 CO 2 , 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.

What the spectrum look like:

The spectrum gives us 'peaks' which are actually absorbance troughs.
These troughs are caused by a frequency of IR light being absorbed from a
bond vibrating bond.
Each 'peak' is characteristic to a specific bond / atoms

Identification of functional groups:

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.

Bon
d

Functional group

Wavenumber/frequ
ency

C= Aldehydes, ketones, carboxylic

O
acids

1640 - 1750

CH

Organic compounds

2850 - 3100

OH

Carboxylic acids

OH

Alcohols (hydrogen bonded)

3200 - 3550 (broad)

N-H

Amines

3200-3500

C-X

Halogenoalkanes

500-1000

2500 - 3300
(very broad)

Alcohols:
The IR spectrum for methanol, CH3OH is shown below:

The peak at 3230 3500 represents an O group in alcohols.

Aldehydes and ketones:

The IR spectrum for

propanal, CH3CHO is
shown:

The peak at 1680 - 1750

represents a C=O group
in aldehydes and
ketones.

Aldehydes and ketones:

The IR spectrum for propanoic
acid, CH3CH2COOH is shown:

The peak at 2500 3300 represents an O H group in a carboxylic

acid.

The peak at 1680 1750 represents a C=O

group in a carboxylic acid.

Mass spec

Ionisation in a mass spectroscope is usually done by electron

bombardment.
Electron bombardment knocks another electron out of the molecule
producing a positive molecular ion -M+.
C2H5OH + e-

C2H5OH+ + 2e-

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.

Identifying fragment ions:

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 Possible identity of
value the fragment ion
15

CH3+

29

C2H5+

43

C3H7+

57

C4H9+

17

OH+

Functional groups are a good place to start, OH = m/z of 17

Some fragments are more difficult to identify as these will have undergone
molecular rearrangement.

Identification of organic structures:

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:

The mass spectrum above has been produced from hexane.

The following reactions show how the molecule could fragment to form the
fragment ions 57 and 43:

Green Chemistry
Processes in the chemical industry are being reinvented to make them more
sustainable or greener by:
1. Changing to renewable resources: e.g. plastics made from crude oil can be

made from plant products

2. 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.
3. Finding alternatives to very hazardous chemicals e.g. some chemicals can
harm humans, other living organisms or the environment.
4. 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.
5. 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.

Effects of greenhouse gases:

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 efectively 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. CO 2 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 and natural climate change:

Anthropogenic: results from human activities, e.g. burning fossil fuels and
deforestation. These increase levels of CO 2, methane and other gases over
relatively short timescales.
Natural climate change: natural processes such as dissolving of CO 2 in sea
water or formation of carbonates in rocks over hundreds of years. Volcanic
eruptions can also cause climate change.

Carbon neutrality and carbon footprint:

A carbon neutral fuel is one for which the release of CO 2 in its manufacture
and burning equals the absorption of CO 2 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 CO 2 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 CO 2
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 .