Topic 1

Formulae, equations and amounts of substance

The mole is the key concept for chemical calculations

DEFINITION: The mole is the amount of substance in grams that has the
same number of particles as there are atoms in 12 grams of carbon-12.

DEFINITION: Relative atomic mass is the weighted mean mass of one

atom compared to one twelfth of the mass of one atom of carbon-12

Molar mass for a compound can be calculated by adding

DEFINITION: Molar mass is the mass in grams of 1 up the mass numbers(from the periodic table) of each
mole of a substance and is given the unit of g mol-1 element in the compound
eg CaCO3 = 40.1 + 12.0 +16.0 x3 = 100.1

For most calculations we will do at A- level we will use the following 3 equations
Learn these equations carefully and what units to use in them.

1. For pure solids, liquids and gases 2. For Gases 3. For solutions

Amount = mass Gas volume (dm3)= amount x 24 Concentration = amount

molar mass volume
This equation give the volume of a
Unit of Mass: grams Unit of concentration: mol dm-3 or M
gas at room pressure (1atm) and
Unit of amount : mol Unit of volume: dm3
room temperature 25oC. Converting volumes

cm3  dm3 ÷ 1000

CHEMISTRY
It is usually best to give
your answers to 3sf cm3  m3 ÷ 1000 000
dm3  m3 ÷ 1000
by

For pure solids, liquids and gases

amount = mass
ABIR Example 1: Calculate the amount, in mol, in 35.0g of
CuSO4
amount = mass/Mr
Mr
= 35/ (63.5 + 32 +16 x4)
Unit of mass: grams = 0.219 mol
Unit of amount : mol

Many questions will involve changes of units

1000 mg =1g
1000 g =1kg
1000kg = 1 tonne
Significant Figures
Give your answers to the same
number of significant figures as the
Example 2: Calculate the amount, in mol, in 75.0mg of number of significant figures for the
CaSO4.2H2O data you given in a question. If you
amount = mass/Mr are given a mixture of different
significant figures, use the smallest
= 0.075/ (40 + 32.0 +16.0 x4 + 18.0x2)
= 4.36x10-4 mol

Page 1
Hydrated salt

A hydrated salt contains water of crystallisation Example 3

Na2SO4 . xH2O has a molar mass of 322.1
.
Cu(NO3)2 6H2O Calculate the value of x
hydrated copper (II) nitrate(V). Molar mass xH2O = 322.1 – (23x2 + 32.1 + 16x4)
= 180
Cu(NO3)2 x = 180/18
Anhydrous copper (II) nitrate(V). =10

This method could be used for measuring mass loss in various

Heating in a crucible thermal decomposition reactions and also for mass gain when
reacting magnesium in oxygen.

The lid improves the accuracy of the

The water of crystallisation in calcium sulfate crystals can be
experiment as it prevents loss of solid
removed as water vapour by heating as shown in the following
from the crucible but should be loose
equation.
fitting to allow gas to escape.
CaSO4.xH2O(s) → CaSO4(s) + xH2O(g)
Method.
•Weigh an empty clean dry crucible and lid .
•Add 2g of hydrated calcium sulfate to the crucible and weigh
again
•Heat strongly with a Bunsen for a couple of minutes
•Allow to cool
•Weigh the crucible and contents again
•Heat crucible again and reweigh until you reach a constant
mass ( do this to ensure reaction is complete).

CHEMISTRY
Large amounts of hydrated calcium sulfate, such as 50g,
should not be used in this experiment as the
decomposition is like to be incomplete. by

ABIR
Small amounts the solid , such as
0.100 g, should not be used in
The crucible needs to be dry otherwise a wet crucible this experiment as errors in
would give an inaccurate result. It would cause mass loss weighing are too high.
to be too large as water would be lost when heating.

Example 4. 3.51 g of hydrated zinc sulfate were heated and 1.97 g of

anhydrous zinc sulfate were obtained.
Calculate the value of the integer x in ZnSO4.xH2O

Calculate the mass of H2O = 3.51 – 1.97 = 1.54g

Calculate moles Calculate moles = 1.54
= 1.97 of H2O
of ZnSO4 161.5 18

= 0.0122 =0.085

Calculate ratio of mole

of ZnSO4 to H2O = 0.0122 = 0.085
0.0122 0.0122
=7
=1
X=7

Page 2
Avogadro's Constant

The mole is the amount of substance in Avogadro's constant

grams that has the same number of There are 6.02 x 1023 atoms in 12 grams of carbon-12. Therefore
particles as there are atoms in 12 grams explained in simpler terms 'One mole of any specified entity
of carbon-12. contains 6.02 x 1023 of that entity':

Avogadro's constant can be used 1 mole of copper atoms will contain 6.02 x 1023 atoms
for atoms, molecules and ions 1 mole of carbon dioxide molecules will contain 6.02 x 1023 molecules
1 mole of sodium ions will contain 6.02 x 1023 ions

No of particles = amount of substance (in mol) X Avogadro's constant

Example 5: How many atoms of tin are Example 6 : Calculate the number of chloride ions in a
there in a 6.00 g sample of tin metal? 25.0 cm3 of a solution of magnesium chloride of
amount = mass/Ar concentration 0.400 mol dm-3
= 6/ 118.7 amount= concentration x volume
= 0.05055 mol MgCl2 = 0.400 x 0.025

Number atoms = amount x 6.02 x 1023 = 0.0100 mol

There are two moles of
= 0.05055 x 6.02 x 1023 Amount of chloride ions = 0.0100 x2 chloride ions for every
= 3.04 x1022 = 0.0200 one mole of MgCl2
Number ions of Cl- = amount x 6.02 x 1023
= 0.0200 x 6.02 x 1023

CHEMISTRY
= 1.204 x1022

by

ABIR
Density calculations are usually used with pure liquids but to work out the mass
Density
from a measured volume. It can also be used with solids and gases.

Density = mass Density is usually given in g cm-3

Care needs to be taken if different units are
volume
used.

Example 7 : Calculate the number of molecules of ethanol in Example 8: There are 980 mol of pure gold in a bar
0.500 dm3 of ethanol (CH3CH2OH) liquid. measuring 10 cm by 20 cm by 50 cm. Calculate the
The density of ethanol is 0.789 g cm-3 density of gold in kg dm−3
Mass = amount x Mr
Mass = density x volume
ethanol = 980 x 197
= 0.789 x 500
= 193060 g
= 394.5g
= 193.06kg
amount = mass/Mr
volume = 10x20x50
= 394.5/ 46.0
= 10 000cm3
= 8.576 mol = 10dm3
Number of molecules= amount x 6.022 x 1023 density = mass/volume
= 8.576 x 6.022 x 1023 = 193/10
= 19.3 kg dm-3
= 5.16 x1024(to 3 sig fig)

Page 3
 Parts per million (ppm)
Concentrations can be given also in parts per million.
This is often used for gases in the atmosphere or in
exhausts, and pollutants in water.

parts per million (ppm) of mass of substance in mixture

= X 1000 000
substance, by mass total mass of mixture

Example 9 : Blood plasma typically contains 20 parts per million (ppm) of

magnesium, by mass.
Calculate the mass of magnesium, in grams, present in 100 g of plasma.

parts per million (ppm) of = mass of substance in mixture

substance, by mass total mass of mixture X 1000 000

20 = mass of substance in mixture X 1000 000

100

mass of substance in mixture = 20 x100/1000 000

= 2 x 10-3 g

CHEMISTRY
by

ABIR

Page 4
Empirical Formula
Definition: An empirical formula is the simplest ratio of atoms of each element in the compound.

General method
The same method can be
Step 1 : Divide each mass (or % mass) by the atomic mass of the element used for the following types
Step 2 : For each of the answers from step 1 divide by the smallest one of of data:
those numbers. 1. masses of each element
in the compound
Step 3: sometimes the numbers calculated in step 2 will need to be multiplied
up to give whole numbers. 2. percentage mass of each
element in the compound
These whole numbers will be the empirical formula.

Example 10 : Calculate the empirical formula for a compound that contains

1.82g of K, 5.93g of I and 2.24g of O
Step1: Divide each mass by the atomic mass of the element
K = 1.82 / 39.1 I = 5.93/126.9 O = 2.24/16
= 0.0465 mol = 0.0467mol = 0.14 mol
Step 2 For each of the answers from step 1 divide by the smallest one of those numbers.
K = 0.0465/0.0465 I = 0.0467/0.0465 O = 0.14 / 0.0465
=1 =1 =3
Empirical formula =KIO3

Molecular formula from empirical formula

CHEMISTRY
Definition: A molecular formula is the actual number of atoms of each element in the compound.
by

ABIR
From the relative molecular mass (Mr) work out how many times the mass of the empirical
formula fits into the Mr.

Example 11 : Determine the molecular formula for

the compound with an empirical formula of C3H6O The Mr does not need to be exact to turn an
and a Mr of 116 empirical formula into the molecular formula
because the molecular formula will be a
C3H6O has a mass of 58 whole number multiple of the empirical
formula.
The empirical formula fits twice into Mr of 116
So the molecular formula is C6H12O2

Page 5
 Concentration of Solutions

A solution is a mixture formed when a solute dissolves in a solvent. In chemistry we most commonly use
water as the solvent to form aqueous solutions. The solute can be a solid, liquid or a gas.

Molar concentration can be measured for solutions. This is calculated by dividing the amount
in moles of the solute by the volume of the solution. The volume is measure is dm3. The unit
of molar concentration is mol dm-3 ; it can also be called molar using symbol M

Concentration = amount Unit of concentration: mol dm-3 or M

volume Unit of Volume: dm3

Converting volumes

A m3 is equivalent to a cube A dm3 is equivalent to a cube A cm3 is equivalent to a cube

100cmx100cmx100cm= 1000000 cm3 10cmx10cmx10cm= 1000 cm3 1cmx1cmx1cm

1 dm3 = 1 litre 1 cm3 = 1 ml

100cm
10cm
10cm 1cm
1cm
10cm 1cm
100cm

100cm 1cm3
1 dm3 or 1 litre

1m3
CHEMISTRY
1 m3 = 1000 dm3 or 1000L by 1 dm3 = 1000 cm3 or 1000 mL

ABIR
To convert m3 into dm3 multiply by 1000 To convert cm3 into dm3 divide by 1000

cm3  dm3 ÷ 1000

cm3  m3 ÷ 1000 000
dm3  m3 ÷ 1000

Example 12 Calculate the concentration of solution Example 13 Calculate the concentration of solution
made by dissolving 5.00 g of Na2CO3 in 250 cm3 water. made by dissolving 10 kg of Na2CO3 in 0.50 m3 water.
amount = mass/Mr amount = mass/Mr
= 5 / (23.0 x2 + 12 +16 x3) = 10 000 / (23.0 x2 + 12 +16 x3)
= 0.0472 mol = 94.2 mol
conc= amount/volume conc= amount/volume
= 0.0472 / 0.25 = 94.2 / 500
= 0.189 mol dm-3 = 0.19 mol dm-3

Page 6
 Mass Concentration

The concentration of a solution can also be To turn concentration measured in mol dm-3 into
measured in terms of mass of solute per volume concentration measured in g dm-3 multiply by Mr of the
of solution substance
conc in g dm-3 = conc in mol dm-3 x Mr
Mass concentration = mass The concentration in g dm-3 is the same as the mass of
volume solute dissolved in 1dm3

Unit of mass concentration: g dm-3

Unit of mass g
Unit of volume: dm3

Ions dissociating
When soluble ionic solids dissolve in water they will dissociate into separate ions. This can lead to the
concentration of ions differing from the concentration of the solute.

Example 14
If 5.86g (0.1 mol) of sodium chloride (NaCl) is dissolved in 1
dm3 of water then the concentration of sodium chloride
solution would be 0.1moldm-3 . NaCl(s) +aq  Na+(aq) + Cl- (aq)
However the 0.1mol sodium chloride would split up to form
0.1 mol of sodium ions and 0.1 mol of chloride ions. The 0.1mol 0.1mol 0.1mol
concentration of sodium ions is therefore 0.1 mol dm-3 and the
concentration of chloride ions is also 0.1 mol dm-3
Example 15
If 9.53g (0.1 mol) of magnesium chloride (MgCl2) is dissolved
in 1 dm3 of water then the concentration of magnesium chloride
solution (MgCl2 aq) would be 0.1moldm-3 . MgCl2(s) +aq  Mg2+(aq) + 2Cl- (aq)
CHEMISTRY
However the 0.1mol magnesium chloride would split up to form
0.1 mol of magnesium ions and 0.2 mol of chloride ions. The
0.1mol 0.1mol 0.2mol
bydm-3 and

ABIR
concentration of magnesium ions is therefore 0.1 mol
the concentration of chloride ions is now 0.2 mol dm-3

Making a solution

• Weigh the sample bottle containing the required mass of Alternatively the known mass of
solid on a 2 d.p. balance solid in the weighing bottle could be
• Transfer to beaker and reweigh sample bottle transferred to beaker, washed and
• Record the difference in mass washings added to the beaker.

• Add 100 cm3 of distilled water to the beaker. Use a glass

rod to stir to help dissolve the solid.

•Sometimes the substance may not dissolve well in cold

water so the beaker and its contents could be heated gently
until all the solid had dissolved.

• Pour solution into a 250 cm3 graduated flask via a funnel. Remember to fill so the bottom of the
• Rinse beaker and funnel and add washings from the meniscus sits on the line on the neck of
beaker and glass rod to the volumetric flask. the flask. With dark liquids like potassium
• make up to the mark with distilled water using a dropping manganate it can be difficult to see the
pipette for last few drops. meniscus.
• Invert flask several times to ensure uniform solution.

Page 7
 Dilutions
Diluting a solution
Using a volumetric pipette is more
accurate than a measuring cylinder
•Pipette 25cm3 of original solution into a 250cm3 because it has a smaller uncertainty
volumetric flask
•make up to the mark with distilled water using a Use a teat pipette to make up to the mark
dropping pipette for last few drops. in volumetric flask to ensure volume of
• Invert flask several times to ensure uniform solution. solution accurately measured and one
doesn’t go over the line

Calculating Dilutions
Diluting a solution will not change the amount of moles of solute present but increase the volume of
solution and hence the concentration will lower
amount= volume x concentration
If amount of moles does not change then
Original volume x original concentration = new diluted volume x new diluted concentration

so new diluted concentration = original concentration x original volume

new diluted volume

The new diluted volume will be equal to the original volume of solution added + the volume of water added.

Example 16
50 cm3 of water are added to 150 cm3 of a 0.20 mol dm-3 NaOH solution. Calculate the concentration of
the diluted solution.
new diluted concentration = original concentration x original volume

CHEMISTRY
new diluted volume
new diluted concentration = 0.20 x 0.150
0.200 by

ABIR
= 0.15 mol dm-3

Example 17
What volume of water in cm3 must be added to dilute 5.00 cm3 of 1.00 mol dm−3 hydrochloric acid so that
it has a concentration of 0.050 mol dm−3 ?
Amount in mol original solution = conc x vol
= 1.00 x 0.005
= 0.005
New volume = amount /conc
= 0.005/0.05
= 0.1dm3 = 100cm3

Volume of water added = 100-5 = 95cm3

Page 8
Ideal Gas Equation

The ideal gas equation applies to all gases and mixtures of gases. If a PV = nRT
mixture of gases is used the value n will be the total moles of all gases
in the mixture. Unit of Pressure (P):Pa
Unit of Volume (V): m3
The biggest problems students have with this equation is choosing and Unit of Temp (T): K
converting to the correct units, so pay close attention to the units. n= moles
R = 8.31 JK–1mol–1

Example 18: Calculate the mass of Cl2 gas that has a pressure of Converting temperature
100 kPa, temperature 20 oC , volume 500 cm3. (R = 8.31)
oC  K add 273
moles = PV/RT
100 kPa = 100 000 Pa
= 100 000 x 0.0005 / (8.31 x 293) 20oC = 20+273= 293K
= 0.0205 mol 500 cm3 = 0.0005 m3

Mass = amount x Mr
= 0.0205 x (35.5 x2)
= 1.46 g

Example 19: 0.150 g of a volatile liquid was injected into a sealed gas syringe. The gas syringe was placed in an oven at
70 oC at a pressure of 100 kPa and a volume of 80 cm3 was measured. Calculate the Mr of the volatile liquid (R =
8.31)
moles = PV/RT 100 kPa = 100 000 Pa
= 100 000 x 0.00008 / (8.31 x 343) 80 cm3 = 0.00008 m3
= 0.00281 mol

Mr = mass/amount
= 0.15 / 0.00281 CHEMISTRY
= 53.4 g mol-1 by

Using a gas syringe

ABIR
Gas syringes can be used for a variety of experiments where the volume of a gas is measured, possibly to
work out moles of gas or to follow reaction rates.

The volume of a gas depends on pressure Make sure you don’t leave
and temperature so when recording volume gaps in your diagram where
it is important to note down the temperature gas could escape
and pressure of the room.

Moles of gas can be calculated from gas

volume (and temperature and pressure)
using ideal gas equation PV = nRT

If drawing a gas syringe make

Potential errors in using a gas syringe
sure you draw it with some
•gas escapes before bung inserted
measurement markings on the
•syringe sticks
barrel to show measurements
• some gases like carbon dioxide or sulphur
can be made.
dioxide are soluble in water so the true amount of
gas is not measured.

Page 9
Changing the Conditions of a gas

Questions may involve the same amount of gas under different conditions.

Example 20
40 cm3 of oxygen and 60 cm3 of carbon dioxide, each at 298 K and 100 kPa, were placed into an
evacuated flask of volume 0.50 dm3. Calculate the pressure of the gas mixture in the flask at 298 K

There are two approaches to solving this

1. Work out amount in mol of gas using ideal gas equation then put back into ideal gas
equation with new conditions
P1V1 = P2V2
2. Or combine the equation n= PV/RT as on right
T1 T2
Can do this as moles of gas do not change

As temperature is the same can make the above equation P1V1 = P2V2
P2 = P1V1 /V2
= 100000 x 1x 10-4 / 5x10-4
= 20 000Pa

Reacting Volumes of Gas

Equal volumes of any gases measured under the same 1 mole of any gas at room
conditions of temperature and pressure contain equal pressure (1atm) and room
numbers of molecules (or atoms if the gas in monatomic) temperature 25oC will have the
volume of 24dm3
Volumes of gases reacting in a balanced equation

CHEMISTRY
can be calculated by simple ratio

by

ABIR
Example 21 If one burnt 500 cm3 of methane at 1atm and 300K what volume of
Oxygen would be needed and what volume of CO2 would be given off under the
same conditions?
CH4(g) + 2 O2(g)  CO2(g) + 2 H2O(l)
1 mole 2 mole 1 mole

500cm3 1dm3 500cm3

Simply multiply
gas volume x2

Example 22 An important reaction which occurs in the catalytic converter of a car is

2CO(g) + 2NO(g)  2CO2(g) + N2(g)
In this reaction, when 500 cm3 of CO reacts with 500 cm3 of NO at 650 °C and at 1 atm.
Calculate the total volume of gases produced at the same temperature and pressure.

2CO(g) + 2NO(g)  2CO2(g) + N2(g) total volume of gases produced = 750cm3

500cm3 500cm3 500cm3 250cm3

Page 10
Converting quantities between different substances using a balanced equation Typically we are given a quantity
of one substance and are asked
N2 + 3H2  2NH3 to work out a quantity for
another substance in the
The balancing (stoichiometric) numbers are mole ratios reaction. Any of the above three
e.g. 1 mol of N2 reacts with 3 mol of H2 to produce 2mol of NH3 equations can be used.

Step 3
Step 1:
Step 2: Convert amount, in mol, of
Use one of the above 3 equations to
Use balanced equation to second substance into quantity
convert any given quantity into
convert amount in mol of initial question asked for using
amount in mol
substance into amount in mol of relevant equation
Mass amount
second substance e.g. amount ,Mr  mass
Volume of gas  amount
Amount gas  vol gas
Conc and vol of solution  amount
amount, vol solution  conc

Example 23: Calculate the mass of carbon dioxide that Example 24: Calculate the mass of copper that reacts
would be produced from heating 5.50 g of sodium completely with 150 cm3 of 1.60 mol dm-3 nitric acid.
hydrogencarbonate. 3Cu + 8HNO3  3Cu(NO3 )2 + 2NO + 4H2O
2NaHCO3  Na2CO3 + CO2 + H2O
Step 1: work out moles of nitric acid
Step 1: work out amount, in mol, of sodium
amount = conc x vol
hydrogencarbonate
= 1.6 x 0.15
amount = mass / Mr
= 0.24 mol
= 5.5 /84
= 0.0655 mol
Step 2: use balanced equation to give moles of Cu
Step 2: use balanced equation to give amount in mol 8 moles HNO3 : 3 moles Cu
of CO2 So 0.24 HNO3 : 0.09 (0.24 x 3/8) mol Cu
2 moles NaHCO3 : 1 moles CO2
So 0.0655 HNO3 : 0.0328mol CO2 CHEMISTRY
by Step 3: work out mass of Cu

ABIR
Step 3: work out mass of CO2 Mass = amount x Mr
Mass = amount x Mr = 0.09 x 63.5
= 0.0328 x 44.0 =5.71g
=1.44g

Example 25: What is the total volume of gas produced in

Example 26: 23.6cm3 of H2SO4 neutralised 25.0cm3 of
dm3 at 333K and 100kPa when 0.651 g of magnesium
0.150 mol dm-3 NaOH. Calculate the concentration of the
nitrate decomposes when heated?
H2SO4
2Mg (NO3)2 (s) 2 MgO (s) + 4NO2 (g) + O2 (g)
H2SO4 + 2NaOH  Na2SO4 +2H2O
Step 1: work out moles of magnesium nitrate
Moles = mass / Mr Step 1: work out moles of sodium hydroxide
= 0.651 / 148.3 amount = conc x vol
= 0.00439 mol = 0.150 x 0.025
= 0. 00375 mol
Step 2: use balanced equation to give moles of gas
Step 2: use balanced equation to give moles of H2SO4
produced
2 moles NaOH : 1 moles H2SO4
2 moles Mg (NO3)2 : 4NO2 (g) + O2 (g) ie 5moles of gas
So 0.00375 NaOH : 0.001875 mol H2SO4
So 0.00439 Mg (NO3)2 : 0.01098( 0.00439 x 5/2) mol gas
Step 3 work out concentration of H2SO4
Step 3: work out volume of gas conc= amount/volume
Volume = nRT/P
= 0.001875 / 0.0236
= (0.01098 x 8.31 x 333 )/ 100000
= 0.000304 m3 = 0.0794 mol dm-3
= 0.303 dm3

Page 11
 % Yield
% yield in a process can be lowered through
actual yield incomplete reactions, side reactions, losses during
percentage yield = x 100 transfers of substances, losses during purification
theoretical yield stages.

Example 27: 25.0g of Fe2O3 was reacted and it produced 10.0g of Fe. What is the percentage yield?
Fe2O3 + 3CO  2Fe + 3 CO2

First calculate maximum mass of Fe that could be produced

Step 1: work out amount in mol of Iron oxide
amount = mass / Mr
=25 / 159.6
= 0.1566 mol

Step 2: use balanced equation to give moles of Fe

1 moles Fe2O3 : 2 moles Fe
So 0.1566 Fe2O3 : 0.313mol Fe
% yield = (actual yield/theoretical yield) x 100
Step 3: work out mass of Fe
Mass = amount x Mr = (10/ 17.48) x 100
= 0.313 x 55.8
=57.2%
=17.5g

% Atom Economy
CHEMISTRY
Mass of useful products Do take into account
percentage byx 100

ABIR
= balancing numbers
atom economy when working out %
Mass of all reactants
atom economy.

Example 28: Calculate the % atom economy for the following reaction where Fe is
the desired product assuming the reaction goes to completion.
Fe2O3 + 3CO  2Fe + 3 CO2
% atom economy = (2 x 55.8)
x 100
(2 x 55.8 + 3x16) + 3 x (12+16)
=45.8%

Sustainable chemistry requires chemists to design Reactions where there is only one product where all
processes with high atom economy that minimise atoms are used making product are ideal and have
production of waste products. 100% atom economy.
e.g. CH2=CH2 + H2  CH3CH3

If a process does have a side, waste product the economics of the process can be improved by selling the bi-product
for other uses

Page 12
 Displacement Reactions
Metal displacement reactions
More reactive metals will displace less reactive metals from their compounds
Mg + CuSO4  Cu + MgSO4
Ionically Mg + Cu2+  Cu + Mg2+

Halogen displacement reactions

A halogen that is a strong oxidising agent will displace a halogen that has a lower oxidising
power from one of its compounds

Cl2(aq) + 2Br – (aq)  2Cl – (aq) + Br2(aq)

See topic 4b Halogens for
Cl2(aq) + 2I – (aq)  2Cl – (aq) + I2(aq)
more detail
Br2(aq) + 2I – (aq)  2Br – (aq) + I2(aq)

Precipitation Reactions

Insoluble salts can be made by mixing appropriate solutions of ions so that a precipitate is formed
Lead nitrate (aq) + sodium chloride (aq)  lead chloride (s) + sodium nitrate (aq)
These are called precipitation reactions. A precipitate is a solid

When making an insoluble salt, normally the salt would be removed by filtration, washed with
distilled water to remove soluble impurities and then dried on filter paper

Writing ionic equations for precipitation reactions

CHEMISTRY
We usually write ionic equations to show precipitation
Spectator ions are ions that are not
reactions. Ionic equations only show the ions that areby

ABIR
• Not changing state
reacting and leave out spectator ions. • Not changing oxidation number

Take full equation Pb(NO3)2 (aq) + 2NaCl (aq)  PbCl2 (s) + 2 NaNO3 (aq)

Separate (aq) solutions Pb2+(aq) + 2NO3-(aq) + 2Na+ (aq)+ 2Cl-(aq)  PbCl2 (s) + 2 Na+(aq)+ 2NO3- (aq)
into ions

Cancel out spectator ions

Pb2+(aq) + 2Cl-(aq)  PbCl2 (s)
leaving ionic equation

Reactions of Acids
Neutralisation reactions form salts
A Salt is formed when the H+ ion
of an acid is replaced
by a metal ion or an ammonium ion Bases neutralise acids. Common bases are
metal oxides, metal hydroxides and ammonia.

The most common strong acids are : An alkali is a soluble base that releases OH-
Hydrochloric ( HCl), sulfuric (H2SO4) and nitric (HNO3) ions in aqueous solution;
acid; The most common alkalis are sodium hydroxide
(NaOH), potassium hydroxide (KOH) and
aqueous ammonia (NH3)

Page 13
Common Acid Reaction Equations
Acid + Carbonate  Salt + Water + Carbon Dioxide
Acid + Base  Salt + Water
H2SO4 + K2CO3  K2SO4 + CO2 + H2O
HCl + NaOH  NaCl +H2O
2HCl + Na2CO3 2NaCl + CO2 + H2O
2HNO3 + Mg(OH)2  Mg(NO3)2 + 2H2O
H2SO4 + 2NaOH  Na2SO4 +2H2O 2HCl + CaCO3  CaCl2 + CO2 + H2O

2HCl + CaO  CaCl2 +H2O Observations : In carbonate reactions there will

be Effervescence due to the CO2 gas evolved
HCl + NH3  NH4Cl and the solid carbonate will dissolve. The
temperature will also increase.

Acid + Metal  Salt + Hydrogen

2HCl + Mg  MgCl2 + H2

Observations: These reaction will

effervesce because H2 gas is evolved
and the metal will dissolve

Ionic equations for reactions of acids with metals, carbonates, bases and alkalis
Ionic equations
acid + metal  salt + hydrogen
2HCl (aq) + Mg (s) MgCl2 (aq) + H2 (g) 2H+ (aq) + Mg (s)  Mg2+ (aq) + H2 (g)

acid + alkali (NaOH)  salt + water

2HNO2 (aq) + Ba(OH)2 (aq)  Ba(NO2)2 (aq) + 2H2O (l) H+ (aq) + OH– (aq)  H2O (l)

acid + carbonate (Na2CO3)  salt + water + CO2

2H+(aq) + CO3 2–(aq)  H2O (l) + CO2 (g)
CHEMISTRY
2HCl (aq)+ Na2CO3 (aq)  2NaCl (aq) + H2O (l)+ CO2 (g)

by

ABIR
Example 29
The equation representing the reaction between copper(II) oxide and dilute sulfuric acid is:
CuO(s) + H2SO4(aq)  CuSO4(aq) + H2O(l)
Write the ionic equation for the reaction.
Only the sulfate ion is a spectator ion in this case because it’s the only ion not changing state.
CuO(s) + 2H+  Cu2+ (aq) + H2O(l)

Method for preparing a soluble salt

If using an insoluble base, metal or solid carbonate

• Add solid base to acid (gently heat to speed up reaction) Use excess solid base/
• Filter off excess solid base metal/carbonate to ensure all acid
• Heat filtrate solution until volume reduced by half reacts/neutralises and that the
• Leave solution to cool and allow remaining water to evaporate product is neutral
slowly and crystals to form
• Filter or pick out crystals
The percentage yield of crystals will
• Leave to dry and put crystals between filter
be less than 100% because some
salt stays in solution. There will also
If using a soluble base be losses on transferring from one
An indicator can be used to show when the acid and alkali have container to another and a loss on
completely reacted to produce a salt solution using the titration filtering.
method. Then repeat reaction without indicator using the same
volumes. Then follow above method from the reducing volume of
solution stage to evaporate neutralised solution to get crystals of
salt

Page 14
 Topic 2
Atomic Structure and the Periodic Table

Details of the three Sub-atomic (fundamental) Particles

Particle Position Relative Mass Relative Charge

Proton Nucleus 1 +1
Neutron Nucleus 1 0 There are various
Electron Orbitals 1/1840 -1 models for atomic
structure
An atom of Lithium (Li) can be represented as follows:

Mass Number 7 Li Atomic Symbol

Atomic Number 3
The atomic number, Z, is the number of protons in the nucleus.
The mass number ,A, is the total number of protons and neutrons in the atom.
Number of neutrons = A - Z
Isotopes Isotopes are atoms with the same number of protons, but different numbers of neutrons.

DEFINITION: Relative isotopic mass is the mass of one atom of an isotope

compared to one twelfth of the mass of one atom of carbon-12

Isotopes have similar chemical properties because they have the same electronic structure.

CHEMISTRY
They may have slightly varying physical properties because they have different masses.

by mean mass of one atom

ABIR
DEFINITION: Relative atomic mass is the weighted
compared to one twelfth of the mass of one atom of carbon-12

DEFINITION: Relative molecular mass is the average mass of a molecule

compared to one twelfth of the mass of one atom of carbon-12

The Mass Spectrometer

The mass spectrometer can be used to determine all the isotopes present in a sample of an element and
to therefore identify elements.

Calculating relative atomic mass

The relative atomic mass quoted on the periodic table is a weighted average of all the isotopes

Fig: spectra for

100 Magnesium from mass
spectrometer
80 78.70%
For each isotope the mass
% abundance

60
24Mg+
spectrometer can measure a m/z
40 (mass/charge ratio) and an abundance
25Mg+ 26Mg+

20 10.13% If asked to give the species for a peak

11.17% in a mass spectrum then give charge
and mass number e.g. 24Mg+
m/z
24 25 26

Page 15
 Sometimes two electrons may be
R.A.M =  (isotopic mass x % abundance) removed from a particle forming a 2+
ion. 24Mg2+ with a 2+ charge would
100 have a m/z of 12

For above example of Mg

R.A.M = [(78.7 x 24) + (10.13 x 25) + (11.17 x 26)] /100 = 24.3 Use these equations to
work out the R.A.M
R.A.M =  (isotopic mass x relative abundance)
If relative abundance is used instead of
total relative abundance percentage abundance use this equation

Mass spectra for Cl2 and Br2

Cl has two isotopes Cl35 (75%) and Cl37(25%) Br has two isotopes Br79 (50%) and Br81(50%)

These lead to the following spectra caused by the diatomic molecules

Br79Br81 +
Br81Br79 +
Cl35Cl35 + relative
relative abundance
abundance Cl35Cl37 + Br79Br79 + Br81Br81 +
Cl37Cl37 +

70 72 74 m/z m/z
158 160 162

Measuring the Mr of a molecule Spectra for C4H10

If a molecule is put through a mass spectrometer it
will often break up and give a series of peaks caused
CHEMISTRY
Mass spectrum for butane
by the fragments. The peak with the largest m/z,
however, will be due to the complete molecule and
by 43

ABIR
will be equal to the Mr of the molecule. This peak is Molecular ion
called the parent ion or molecular ion C4H10+

29

58

Uses of mass spectrometers

• Mass spectrometers have been included in planetary space probes so that elements on other
planets can be identified. Elements on other planets can have a different composition of
isotopes.
• Drug testing in sport to identify chemicals in the blood and to identify breakdown products from
drugs in body
• quality control in pharmaceutical industry and to identify molecules from sample with potential
biological activity
• radioactive dating to determine age of fossils or human remains

Page 16
Electronic Structure
Models of the atom
An early model of the atom was the Bohr model (GCSE model) (2 electrons in first shell, 8 in second etc.) with
electrons in spherical orbits. Early models of atomic structure predicted that atoms and ions with noble gas
electron arrangements should be stable.

The A-level model

Electrons are arranged on: Sub energy levels labelled s ,
p, d and f
Principle energy levels Split
s holds up to 2 electrons Split
Orbitals which hold up
numbered 1,2,3,4.. into to 2 electrons of
p holds up to 6 electrons into
1 is closest to nucleus opposite spin
d holds up to 10 electrons
f holds up to 14 electrons

Shapes of orbitals
Orbitals represent the
Principle level 1 2 3 4 mathematical probabilities of
finding an electron at any point
within certain spatial
Sub-level distributions around the
1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f nucleus.
Each orbital has its own
approximate, three
An atom fills up the sub shells in order of increasing energy (note 3d is dimensional shape.
higher in energy than 4s and so gets filled after the 4s It is not possible to draw the
1s2s2p3s3p 4s3d4p5s4d5p shape of orbitals precisely.

Writing electronic structure using letters and numbers •s sublevels are

Number of electrons spherical
in sub-level
For oxygen 1s2 2s2 2p4
CHEMISTRY
Number of main Name of by

ABIR
energy level type of • p sublevels are shaped
sub-level like dumbbells
Using spin diagrams
For fluorine An arrow is one electron
2p
Box represents one
2s orbital

The arrows going in the

The periodic table is split into
opposite direction represents
1s the different spins of the
blocks. A s block element is
electrons in the orbital one whose outer electron is
filling a s-sub shell

When filling up sub levels with several

orbitals, fill each orbital singly before starting
to pair up the electrons

2p

Electronic structure for ions

When a positive ion is formed electrons are lost When a negative ion is formed electrons are gained
Mg is 1s2 2s2 2p6 3s2 but Mg2+ is 1s2 2s2 2p6 O is 1s2 2s2 2p4 but O2- is 1s2 2s2 2p6

Page 17
 Ionisation Energies
Definition : First ionisation energy Remember these
definitions very carefully
The first ionisation energy is the energy required when one mole of gaseous
atoms forms one mole of gaseous ions with a single positive charge
The equation for 1st ionisation
This is represented by the equation: H(g)  H+ (g) + e- energy always follows the same
pattern.
It does not matter if the atom does
Always gaseous not normally form a +1 ion or is not
gaseous
Definition : Second ionisation energy
The second ionisation energy is the energy required when one mole of
gaseous ions with a single positive charge forms one mole of gaseous
ions with a double positive charge

This is represented by the equation: Ti+ (g)  Ti2+(g) + e-

Factors that affect ionisation energy
There are three main factors
1.The attraction of the nucleus
(The more protons in the nucleus the greater the attraction) Many questions can be
2. The distance of the electrons from the nucleus answered by application
(The bigger the atom the further the outer electrons are from the nucleus and the of these factors
weaker the attraction to the nucleus)
3. Shielding of the attraction of the nucleus
(An electron in an outer shell is repelled by electrons in complete inner shells,
weakening the attraction of the nucleus)

Successive ionisation energies

CHEMISTRY
The patterns in successive ionisation energies for an element give us important
information about the electronic structure for that element.by

ABIR
Why are successive ionisation energies always larger?
The second ionisation energy of an element is always bigger than the first ionisation energy.
When the first electron is removed a positive ion is formed.
The ion increases the attraction on the remaining electrons and so the energy required to
remove the next electron is larger.
How are ionisation energies linked to electronic structure?
Explanation
Ionisation The fifth electron is in a inner
energy shell closer to the nucleus and
therefore attracted much more
Notice the big strongly by the nucleus than the
jump between 4 fourth electron.
and 5. It also does not have any
shielding by inner complete shells
1 2 3 4 5 6 of electron
No of electrons removed

Example: What group must this element be in? Here there is a big jump between the 2nd and 3rd
ionisations energies which means that this
1 2 3 4 5 element must be in group 2 of the periodic table
Ionisation 590 1150 4940 6480 8120 as the 3rd electron is removed from an electron
energy kJ mol-1 shell closer to the nucleus with less shielding and
so has a larger ionisation energy

Page 18
The first Ionisation energy of the elements
The shape of the graph for periods two and
three is similar. A repeating pattern across a
Ionisation energy kJ mol-1

period is called periodicity.

2000

1500 The pattern in the first ionisation energy

gives us useful information about
1000 electronic structure
500
You need to carefully learn the
0 patterns
5 10 15 20
Atomic number

Q. Why has helium the largest first ionisation energy?

A. Its first electron is in the first shell closest to the nucleus and has no
shielding effects from inner shells. He has a bigger first ionisation Many questions can be
energy than H as it has one more proton answered by application of
the 3 factors that control
Q. Why do first ionisation energies decrease down a group? ionisation energy

A. As one goes down a group, the outer electrons are found in shells
further from the nucleus and are more shielded so the attraction of
the nucleus becomes smaller

Q. Why is there a general increase in first ionisation energy across a period?

A. As one goes across a period , the number of protons increases making

the effective attraction of the nucleus greater. The electrons are being

CHEMISTRY
added to the same shell which has the same shielding effect and the
electrons are pulled in closer to the nucleus.
by

ABIR
Q. Why has Na a much lower first ionisation energy than neon?

This is because Na will have its outer electron in a 3s shell further from
the nucleus and is more shielded. So Na’s outer electron is easier to
remove and has a lower ionisation energy.

Q. Why is there a small drop from Mg to Al?

Al is starting to fill a 3p sub shell, whereas Mg has its outer electrons in the 3s
sub shell. The electrons in the 3p subshell are slightly easier to remove because
the 3p electrons are higher in energy and are also slightly shielded by the 3s
electrons
Learn carefully the
explanations for
Q. Why is there a small drop from P to S?
these two small
With sulfur there are 4 electrons in the 3p sub shell and the 4th is starting to doubly fill drops as they are
the first 3p orbital. different to the
When the second electron is added to a 3p orbital there is a slight repulsion between usual factors
the two negatively charged electrons which makes the second electron easier to
remove.
3p 3p
3s 3s
Two electrons of opposite spin in
the same orbital
phosphorus 1s2 2s2 2p63s23p3
sulfur 1s2 2s2 2p63s23p4

Page 19
Patterns in the second ionisation energy.

If the graph of second ionisation or each successive element is plotted then a similar pattern to the first
ionisation energy is observed but all the elements will have shifted one to the left.
5000
Na
2nd Ionisation energy
4500
4000
(kJ/mol) 3500
3000 Ar
2500 S
P
2000 Al Cl
1500
Mg Si
1000
10 12 14 16 18 20
Atomic Number

The group 1 elements are now at the peaks of the graph

Lithium would now have the second largest ionisation of all elements as its second electron
would be removed from the first 1s shell closest to the nucleus and has no shielding effects
from inner shells. Li has a bigger second ionisation energy than He as it has more protons.

CHEMISTRY
by

ABIR

Page 20
 Periodicity

Classification of elements in s, p, d blocks

Elements are classified as s, p or d block, according

to which orbitals the highest energy electrons are in.

Period 2 = Li, Be, B, C, N, O, F, Ne

Period 3 = Na, Mg, Al, Si, P, S, Cl, Ar

Atomic radius 0.18

0.16

atomic radius (nm)

Atomic radii decrease as you move from left to right
0.14
across a period, because the increased number of 0.12
protons create more positive charge attraction for 0.1
electrons which are in the same shell with similar 0.08
shielding. 0.06
0.04
0.02
Exactly the same trend in period 2 0
Na Mg Al Si P S Cl Ar

1st ionisation energy

The general trend across is to increase. This is due to
1st ionisation energy

1600
increasing number of protons as the electrons are being 1400
added to the same shell 1200
(kJ/mol)

1000

CHEMISTRY
There is a small drop between Mg + Al. Mg has its outer 800
600
electrons in the 3s sub shell, whereas Al is starting to fill the
400
3p subshell. Al’s electron is slightly easier to remove
by

ABIR
200
because the 3p electrons are higher in energy. 0
Na Mg Al Si P S Cl Ar
There is a small drop between phosphorous and sulfur.
Sulfur’s outer electron is paired up with an another electron in Exactly the same trend in period 2 with
the same 3p orbital. drops between Be & B and N to O for
When the second electron is added to an orbital there is a same reasons- make sure change 3s
slight repulsion between the two negatively charged and 3p to 2s and 2p in explanation!
electrons which makes the second electron easier to remove.

Melting and boiling points

For Na, Mg, Al- Metallic bonding : strong bonding – gets 3000
stronger the more electrons there are in the outer shell that are
Melting and boiling

2500
released to the sea of electrons. A smaller sized ion with a 2000
points (K)

greater positive charge also makes the bonding stronger. High 1500
energy is needed to break bonds.
1000
Si is Macromolecular: many strong covalent bonds between 500
atoms high energy needed to break covalent bonds– very high
0
mp +bp Na Mg Al Si P S Cl Ar
Cl2 (g), S8 (s), P4 (S)- simple Molecular : weak London forces
between molecules, so little energy is needed to break them – Similar trend in period 2
low mp+ bp Li,Be metallic bonding (high mp)
S8 has a higher mp than P4 because it has more electrons (S8 B,C macromolecular (very high mp)
=128)(P4=60) so has stronger London forces between N2,O2 molecular (gases! Low mp as
molecules small London Forces)
Ne monoatomic gas (very low mp)
Ar is monoatomic weak London Forces between atoms

Page 21
 Topic 3
Bonding and structure

Ionic Bonding
Metal atoms lose electrons to form +ve ions.
Non-metal atoms gain electrons to form -ve ions.

Mg goes from 1s2 2s2 2p63s2

to Mg2+ 1s2 2s2 2p6

O goes from 1s2 2s2 2p4 to

O2- 1s2 2s2 2p6

Ionic crystals have the structure of giant lattices of ions

Ionic bonding is the strong electrostatic force of attraction

between oppositely charged ions formed by electron transfer.

Ionic bonding is stronger and the melting points higher when the ions
are smaller and/ or have higher charges. E.g. MgO has a higher
melting point than NaCl as the ions involved (Mg2+ & O2- are smaller
and have higher charges than those in NaCl , Na+ & Cl- )

Ionic Radii

CHEMISTRY
Positive ions are smaller compared to their atoms because it has one less shell of electrons and the
ratio of protons to electrons has increased so there by
is greater net force on remaining electrons

ABIR
holding them more closely.

The negative ions formed from groups five to seven are larger than the corresponding atoms.
The negative ion has more electrons than the corresponding atom but the same number of protons. So the pull
of the nucleus is shared over more electrons and the attraction per electron is less, making the ion bigger.

N3- O2- F- and Na+ Mg2+ Al3+ all have the same
Ionic
Radius electronic structure (of the noble gas Ne)

There are increasing numbers of protons from N to F

and then Na to Al but the same number of electrons.
The effective nuclear attraction per electron therefore
increases and ions get smaller

N3- O2- F- (Ne) Na+ Mg2+ Al3+

Within a group the size of the Ionic radii increases going down the group. This is because
as one goes down the group the ions have more shells of electrons.

Page 22
Ionic Bonding
Evidence for the existence of ions

X-ray diffraction: Electron density map of NaCl

These maps show the
likelihood of finding The ions are discrete or
electrons in a region separate, because the
electron density falls to zero
The contours are lines of between the ions
equal electron density
The electron density map
The maps show that for NaCl does not, however, show the
•The ions are arranged in a edge of the ion and so it is
regular pattern. difficult to measure the
radius of the ion from an
•The chloride ions are larger than electron density map
the sodium ions

Physical properties of Ionic Compounds

•high melting points ( there are strong attractive forces between the ions)
•non conductor of electricity when solid (ions are held together tightly and can not move)
•conductor of electricity when in solution or molten. ( ions are free to move)
•brittle / easy to cleave apart

CHEMISTRY
by

ABIR
A little force will push the ions along and ions will be next to similar ions. There will be a force
of repulsion between like ions, pushing the layers apart

Migration of ions

-ve
+ve
-ve
+ve

Blue colour of
Cu2+ ions Yellow colour of A drop of potassium Manganate
migrate to the CrO42- ions solution, which is purple, is
negative migrate to the placed on moist filter paper on a
electrode positive microscope slide and the ends
electrode of the slide are connected to a
24 V DC power supply. After ten
minutes the purple colour of the
MnO4- ion has migrated to the
positive electrode
CuCrO4

Page 23
Covalent Bonding

A covalent bond strong and is caused by the electrostatic attraction

between the bonding shared pair of electrons and the two nuclei.

The strength of covalent bond can be demonstrated by the high melting points of giant atomic
structures like diamond and graphite. They have high melting points because they contain many
strong covalent bonds in a macromolecular structure. It takes a lot of energy to break the many
strong bonds.

The X-ray diffractions for the hydrogen

molecule show high concentration of negative
charge between H nuclei. This negative charge
is strongly attracted by both nuclei so attractive
interactions exceed repulsive ones

In a covalent compound there is significant electron

density between the atoms

Electron Configuration Diagrams

CHEMISTRY
O O
by

ABIR
N Cl Cl

H B
H
H x N x
x xx N Cl

N N

Effect of multiple bonds on bond strength and length.

Nuclei joined by multiple (i.e. double and triple) bonds have a greater electron density between them.
This causes an greater force of attraction between the nuclei and the electrons between them, resulting in a
shorter bond length and greater bond strength.

Page 24
Dative Covalent bonding .. +
A Dative covalent bond forms when the O
shared pair of electrons in the covalent bond
H H
come from only one of the bonding atoms. A
dative covalent bond is also called co-ordinate H

bonding.

Cl H
Common examples you should be able to
draw that contain dative covalent bond (e.g.
NH4+, H3O+, NH3BF3)
Cl B N H

The ammonium ion NH4+

Cl H

The direction of the arrow

goes from the atom that is
providing the lone pair to the
atom that is deficient

+
H Two aluminium chloride
+ Cl (AlCl3) molecules join
x together through two dative
N
H
CHEMISTRY
Cl Al x Cl
bonds to form the dimer
Al2Cl6
H
x by x Cl

ABIR
H Cl
Cl x Al Cl Cl
Al
Al
Cl
The dative covalent bond acts like
an ordinary covalent bond when
x Cl Cl
thinking about shape so in NH4+ Cl
the shape is tetrahedral

Page 25
Carbon Allotropes
Macromolecular: Graphite
Macromolecular: diamond
Planar arrangement of carbon
atoms in layers. 3 covalent
Tetrahedral arrangement of
bonds per atom in each layer.
carbon atoms. 4 covalent
4th outer electron per atom is
bonds per atom
delocalised. Delocalised
electrons between layers.

Diamond cannot conduct electricity because all 4 Graphite can conduct electricity well between
electrons per carbon atoms are involved in layers because one electron per carbon is free and
covalent bonds. They are localised and cannot delocalised, so electrons can move easily along
move layers.
It does not conduct electricity between layers
because the energy gap between layers is too
large for easy electron transfer.

Both these macromolecular structures have very high melting points because of strong covalent
forces in the giant structure. It takes a lot of energy to break the many strong covalent bonds.

Graphene

Graphene is a new substance that is a one layer of graphite .i.e. 3 covalent bonds per atom and
the 4th outer electron per atom is delocalised.
These have very high tensile strength because of the strong structure of many strong covalent
bonds
CHEMISTRY
Graphene can conduct electricity well along the structure because one electron per carbon is free
bythe structure.
and delocalised, so electrons can move easily along

Carbon nanotubes
ABIR
These have very high tensile strength because of the strong
structure of many strong covalent bonds

Nanotubes can conduct electricity well along the tube

because one electron per carbon is free and delocalised,
so electrons can move easily along the tube.

Nanotubes have potentially many uses. One being the

potential to us as vehicles to deliver drugs to cells.

There are delocalized electrons in buckminsterfullerene.

Page 26
 Electronegativity and intermediate bonding

Definition F, O, N and Cl are the

most electronegative
Electronegativity is the relative tendency of an atom in a covalent bond atoms
in a molecule to attract electrons in a covalent bond to itself.
The most electronegative
Electronegativity is measured on the Pauling scale (ranges from 0 to 4) element is fluorine and it
is given a value of 4.0
Factors affecting electronegativity
Electronegativity increases across a period as the number of protons increases and the atomic radius
decreases because the electrons in the same shell are pulled in more.
It decreases down a group because the distance between the nucleus and the outer electrons increases and
the shielding of inner shell electrons increases

Intermediate bonding

Ionic and covalent bonding are the extremes of a continuum of bonding type. Differences in
electronegativity between elements can determine where a compound lies on this scale.

A compound containing elements of similar electronegativity and hence a small

electronegativity difference will be purely covalent.

A compound containing elements of very different electronegativity and hence a

very large electronegativity difference (> 1.7) will be ionic.

Formation of a permanent dipole – (polar covalent) bond The element with the
larger
electronegativity in a
CHEMISTRY
A polar covalent bond forms when the elements in the bond have different
electronegativities . (Of around 0.3 to 1.7) polar compound will
be the δ- end
by

ABIR
When a bond is a polar covalent bond it has an unequal distribution of δ+ δ-
electrons in the bond and produces a charge separation, (dipole) δ+ δ- H – Cl
ends.

Polar and Non Polar molecules

Symmetric molecules

A symmetric molecule (all bonds identical and no lone

pairs) will not be polar even if individual bonds within
the molecular are polar.
CO2 is a symmetrical molecule and
The individual dipoles on the bonds ‘cancel out’
is a non-polar molecule
due to the symmetrical shape of the molecule.
There is no net dipole moment: the molecule is
non polar

e.g. CCl4 will be non-polar whereas CH3Cl will be polar H

δ+
C δ-
H Cl
H

Page 27
Experiment effect of charged rod on polar/non-polar liquids

In this experiment, a charged rod (formed by rubbing a

plastic rod) is brought close to a jet of liquid flowing from a
burette.

If the liquid is polar, the jet of liquid will be attracted to the

electrostatic force of the rod. The dipoles in the polar molecules will
all align and the negative end δ- will be attracted to the positive rod ++++++++ +
(or vice versa). The stronger the dipole the more the deflection of the
jet.

Non-polar liquids will not be deflected and attracted to the charged rod

CHEMISTRY
by

ABIR

Page 28
Shape of molecules

Name No No lone Diagram Bond angle Examples

bonding pairs
pairs
linear 2 0 Cl Be Cl 180 CO2, CS2, HCN,
BeF2
Trigonal 3 0 Cl Cl 120 BF3, AlCl3, SO3,
planar NO3-, CO32-
B

Cl
Tetrahedral 4 0 H 109.5 SiCl4, SO42-, ClO4-,
NH4+

H H

Trigonal 3 1 .. 107 NCl3 ,PF3 ,ClO3

pyramidal ,H3O+
N

H
H

Bent 2 2 .. .. 104.5 OCl2, H2S, OF2 ,

CHEMISTRY O SCl2

by

ABIR
H H

Trigonal 5 0 F 120 and 90 PCl5

Bipyramidal F
P F
F

F
Octahedral 6 0 F
90 and 180 SF6
F F

F F

How to explain shape 1. State number of bonding pairs and lone pairs of electrons.
2. State that electron pairs repel and try to get as far apart as possible (or to a
position of minimum repulsion.)
3. If there are no lone pairs state that the electron pairs repel equally
4. If there are lone pairs of electrons, then state that lone pairs repel more than
bonding pairs.
5. State actual shape and bond angle.

Remember lone pairs repel more than bonding pairs and so reduce bond angles (by about 2.5o
per lone pair in above examples)

Page 29
 Occasionally more complex shapes are seen that are variations of octahedral and trigonal
bipyramidal where some of the bonds are replaced with lone pairs. You do not need to learn the
names of these but ought to be able to work out these shapes using the method below

: : X:
:

X X : X : : X

:
:

Square planar Bond angle ~89O Bond angle ~89O Bond angles ~119 + 89O
Bond angle 180O
Bond angle 90O (Reduced by lone pair) (Reduced by lone pairs) (Reduced by lone pair)

e.g XeF4 e.g. BrF5 e.g I3- e .g.ClF3 e.g. SF4 & IF4+

Xe has 8 electrons in its outer Cl has 7 electrons in its outer I has 7 electrons in its outer
shell. 4 F’s add 4 more shell. 3 F’s add 3 more shell. 4 F’s add 4 more
electrons. This makes a total of electrons. This makes a total of electrons. Remove one electron
12 electrons made up of 4 10 electrons made up of 3 bond as positively charged. This
bond pairs and 2 lone pairs. pairs and 2 lone pairs. The makes a total of 10 electrons
The means it is a variation of means it is a variation of the 5 made up of 4 bond pairs and 1
the 6 bond pair shape bond pair shape (trigonal lone pair. The means it is a
(octahedral) bipyramidal) variation of the 5 bond pair
shape (trigonal bipyramidal)

CHEMISTRY
by

ABIR

Page 30
Metallic bonding

Metals consist of giant lattices of metal ions in a sea of delocalised electrons

Definition: Metallic bonding is the electrostatic force of attraction between the

positive metal ions and the delocalised electrons

sodium

The three main factors that affect the strength of metallic bonding are:
1. Number of protons/ Strength of nuclear attraction.
The more protons the stronger the bond
2. Number of delocalised electrons per atom (the outer shell electrons are delocalised)
The more delocalised electrons the stronger the bond
3. Size of ion.
The smaller the ion, the stronger the bond.

Metals have high melting points because the strong electrostatic forces between positive ions
and sea of delocalised electrons require a lot of energy to break

Example
Mg has stronger metallic bonding than Na and hence a higher
melting point. The Metallic bonding gets stronger because in Mg
there are more electrons in the outer shell that are released to the
sea of electrons. The Mg ion is also smaller and has one more
proton. There is therefore a stronger electrostatic attraction

CHEMISTRY
between the positive metal ions and the delocalised electrons
and higher energy is needed to break bonds.
by

ABIR magnesium

Metals can conduct electricity well because the delocalised electrons can move through the structure

Metals are malleable because the positive ions in the lattice are all identical. So the planes of ions
can slide easily over one another. The attractive forces in the lattice are the same whichever ions are
adjacent

Page 31
 Structure: ionic, metallic, molecular and giant covalent (macromolecular).

You should be able to draw the following diagrams or describe the structure in words to
show the four different types of crystal. You should also be able to explain the properties of
these solids.
Giant lattices are present in:
i ionic solids (giant ionic lattices)
ii covalently bonded solids, such as diamond, graphite and silicon(IV) oxide (giant covalent lattices)
iii solid metals (giant metallic lattices)

Ionic: sodium chloride

Giant Ionic lattice showing alternate

Na+ and Cl- ions

Giant Covalent: diamond Giant Covalent: Graphite

Planar arrangement of carbon

Tetrahedral arrangement of atoms in layers. 3 covalent bonds
per atom in each layer. 4th outer
carbon atoms. 4 covalent
electron per atom is delocalised.
bonds per atom Delocalised electrons between
layers.

Both these macromolecular structures have very high melting points because of strong covalent
forces in the giant structure. It takes a lot of energy to break the many strong covalent bonds

Metallic: magnesium or sodium CHEMISTRY

by

ABIR
Use this
diagram Giant metallic lattice showing close
for any packing magnesium ions
metal

Molecular: Ice This is a difficult diagram

to draw.
Molecular: Iodine H H The main point to show is
O a central water molecule
with two ordinary covalent
bonds and two hydrogen
Regular arrangement of I2 H bonds in a tetrahedral
molecules held together by H arrangement
O O
weak London forces H
H H The molecules are held
HO O further apart than in liquid
H H water and this explains the
lower density of ice

Page 32
Bonding and Structure
Bonding Structure Examples

Ionic : electrostatic force of Sodium chloride

attraction between Magnesium oxide
oppositely charged ions Giant Ionic Lattice

Covalent : shared pair of Simple molecular: Iodine

electrons With intermolecular forces (London Ice
forces, permanent dipoles, hydrogen Carbon dioxide
bonds) between molecules Water
Methane

Covalent : shared pair of Macromolecular: Diamond

electrons giant molecular structures. Graphite
Silicon dioxide
Silicon

Metallic: electrostatic Giant metallic Magnesium, Sodium

force of attraction between lattice (all metals)
the metal positive ions and
the delocalised electrons

Only use the words molecules and intermolecular forces when talking about simple molecular substances

Property Ionic Molecular (simple) Macromolecular Metallic

boiling and high- because low- because of high- because of high- strong electrostatic forces
melting
points
of giant lattice
of ions with CHEMISTRY
weak intermolecular
forces between
many strong covalent
bonds in
between positive ions and sea of
delocalised electrons
by

ABIR
strong molecules (specify macromolecular
electrostatic type e.g London structure. Take a lot
forces forces/hydrogen of energy to break the
between bond) many strong bonds
oppositely
charged ions.

Solubility in Generally generally poor insoluble insoluble

water good

conductivity poor: ions poor: no ions to diamond and sand: good: delocalised electrons can
when solid can’t move/ conduct and poor, because move through structure
fixed in lattice electrons are electrons can’t move
localised (fixed in (localised)
place) graphite: good as free
delocalised electrons
between layers

conductivity good: ions can poor: no ions poor (good)

when molten move

general crystalline mostly gases and solids shiny metal

description solids liquids Malleable as the positive ions in
the lattice are all identical. So the
planes of ions can slide easily
over one another
-attractive forces in the lattice are
the same whichever ions are
adjacent

Page 33
 Topic 4
Introduction to Organic Chemistry and Alkanes

Hazards and Risks

A hazard is a substance or procedure that can has the RISK: This is the probability or chance that
potential to do harm. harm will result from the use of a hazardous
Typical hazards are toxic/flammable /harmful/ substance or a procedure
irritant /corrosive /oxidizing/ carcinogenic

In the laboratory we try to minimise the risk

Risks can be reduced by
Irritant - dilute acid and alkalis- wear googles • working on a smaller scale
Corrosive- stronger acids and alkalis wear goggles • taking precautions specific to the hazard
Flammable – keep away from naked flames • using an alternative method that involves
Toxic – wear gloves- avoid skin contact- wash hands after use less hazardous substances
Oxidising- Keep away from flammable / easily oxidised materials

Hazardous substances in low concentrations or amounts will not pose

the same risks as the pure substance.

CHEMISTRY
by

ABIR

Page 34
 Basic definitions to
Hydrocarbon is a compound consisting of hydrogen and carbon only
know
Saturated: Contain single carbon-carbon bonds only Unsaturated : Contains a C=C double bond

Molecular formula: The formula which shows the actual number of each type of atom

Empirical formula: shows the simplest whole number ratio of atoms of each element in the compound

General formula: algebraic formula for a homologous series e.g. CnH2n

Structural formula shows the minimal detail that shows the arrangement of atoms in a molecule, eg for
butane: CH3CH2CH2CH3 or CH3(CH2)2CH3,

Displayed formula: show all the covalent bonds present in a molecule

Drawing Displayed formulae Remember that the shape around the

carbon atom in saturated hydrocarbons is
H H H H
When drawing organic tetrahedral and the bond angle is 109.5o
H C C C C H compounds add the
hydrogen atoms so that each H H
H H H
H C H carbon has 4 bonds
H C C H
H

H H
CHEMISTRY
Skeletal formula shows the simplified organic formula, shown by removing hydrogen atoms from alkyl chains, leaving
just a carbon skeleton and associated functional Groups. by

But-2-ene
ABIR Butan-1-ol
OH

cyclohexane cyclohexene
2-methylbutane

Homologous series are families of organic compounds with the same functional
group and same general formula.
•They show a gradual change in physical properties (e.g. boiling point).
• Each member differs by CH2 from the last.
• They have similar chemical properties.

Functional group is an atom or group of atoms which when present in different molecules
causes them to have similar chemical properties

Page 35
 prefix / suffix
homologous functional example
(* = usual use)
series group
Alkane
C C CH3CH2CH2CH3
-ane Butane

H H
Alkenes C C suffix -ene C C propene
H
H C
H
H

suffix* -ol H H H Propan-1-ol

Alcohols prefix hydroxy-
C OH H C C C O H
OH
H H H

H H H
Halogenoalkanes prefix chloro-
1-chloropropane
H C C C Cl
C halogen
bromo- Cl
H H H
iodo-

O
suffix -al H O
Aldehydes O ethanal
C H
prefix formyl- H C C H

suffix* -one

CHEMISTRY
H O H
O O Propanone
prefix oxo-
H C C C H
Ketones C
by H

ABIR
H

O suffix -oic acid

carboxylic acids H O O Ethanoic acid
C OH
H C C OH

H
OH
O
-yl –oate
C O H O H O methylethanoate
Esters
H C C O C H

H H O

When compounds contain more than one functional group, the order of precedence determines which groups are
named with prefix or suffix forms. The highest precedence group takes the suffix (and the lowest number on the carbon
chain), with all others taking the prefix form. However, double and triple C-C bonds only take suffix form.
Order of priority highest first:
Carboxylic acids >aldehydes>ketones>alcohols>alkenes>halogenoalkanes

Page 36
 General rules for naming carbon chains no of
code
carbons
Count the longest carbon chain and name appropriately
meth 1
Find any branched chains and count how many carbons they contain
eth 2
 Add the appropriate prefix for each branch chain
prop 3
Eg -CH3 methyl or -C2H5 ethyl –C3H7 propyl
1 CH3 but 4

pent 5
2 CH2 hex 6
5 3,5-dimethylheptane
hept 7
H3 C CH CH2 CH CH3
3 4 oct 8
6 CH2 non 9

dec 10
7 CH3

Basic rules for naming functional groups

The functional group is named by a prefix or suffix. e.g. bromoethane, ethanol, propene

•When using a suffix, add in the following way :

If the suffix starts with a vowel- remove the –e from the stem alkane name
e.g. Propan-1-ol, butan-1-amine, ethanoic acid, ethanoylchloride, butanamide

If the suffix starts with a consonant or there are two or more of a functional group meaning di, or tri needs to be
used then do not remove the the –e from the stem alkane name
e.g. Propanenitrile, ethane-1,2-diol, propanedioic acid, propane-1,2,3-triol, Pentane-2,4-dione.
CHEMISTRY
H H H O H
The position of the functional group on the carbon by

ABIR
chain is given by a number – counting from the end
H C C 3 C2 C1 H Butan-1-ol
of the molecule that gives the functional group the 4
lowest number. For aldehydes, carboxylic acids &
H H H H
nitriles, the functional group is always on carbon 1.
H H H

We only include numbers, H C C C H

methylpropane CHCl3 trichloromethane
however, if they are needed H H
to avoid ambiguity. H C H

•The functional groups take precedence over branched 3-methylbut-1-ene is correct and not 2-methylbut-3-ene
chains in giving the lowest number
H H H H H

Where there are two or more of the same groups, di-, tri- , H C C C C C H 2,3-dibromopentane.
tetra-, penta- or hexa- are used. Note the point made above
H H Br H
about the addition of ‘e’ to the stem Br

Words are separated by numbers with dashes CH2FCCl2CH2CH3 2,2-dichloro-1-fluorobutane.

 numbers are separated by commas
CH2FCH2CHBrCH2CH3 3-bromo-1-fluoropentane
If there is more than one functional group or side chain, the
groups are listed in alphabetical order (ignoring any di, tri).

Page 37
Alkenes
2 4
1 3 Double bond between
The double bond will be between two carbons. Use the lower
C2 and C3 so But-2-ene
number of the two to show the position of the double bond

The name for alkenes may include E or Z at start to show Z-but-2-ene

the type of stereoisomer

If more than one double bond is present then suffix Penta-1,3-diene

ends diene or triene. The stem ends in a
The suffix -en for alkenes can go in front of other suffixes. CH2OHCHBrCH=CH2 2-bromobut-3-en-1-ol
The alcohol and carboxylic acid groups have higher priority OH
than the alkene group so take precedence with numbering
E-but-2-enoic acid
O

Halogenoalkanes H H Br H
Class the halogen as a substituent on the C chain and use 2-bromobutane
H C C C C H
the prefix -fluoro, -chloro, -bromo, or –iodo. (Give the
position number if necessary) H H H H
I
Cl

Br
Cl
F Br
2,3-dichloro-1-fluoro-3-methylpentane 5,5-dibromo-4-iodo-3-methylpent-1-ene

Multiple functional group and side chains are listed The alkene group has higher priority than the
halogenoalkane group so it takes the lowest number
CHEMISTRY
in alphabetical order (ignoring any di, tri).
on the carbon chain
by

ABIR
Alcohols
These have the ending -ol and if necessary the position OH

number for the OH group is added between the name Butan-2-ol

CH3 CH CH2 CH3
stem and the –ol 1 2 3 4

If there are two or more -OH groups then di, tri are HO CH2 CH2 OH Ethane-1,2-diol
used.
Add the ‘e’ on to the stem name though. H2C CH CH2 propane-1,2,3-triol
OH OH OH
Cl
The OH group has a higher priority than the
halogenoalkane group and alkene so takes
precedence in numbering. The OH is on carbon 1 OH
Cl
E-3,6-dichlorohex-4-en-1-ol
O
If the compound has an –OH group in addition to another
H3C CH C 2-hydroxypropanoic acid
functional group with a higher priority. The priority group gets
the suffix ending and the OH can be named with the prefix OH OH
hydroxy-:

Page 38
 H
Aldehydes O

An aldehyde’s name ends in –al

It always has the C=O bond on the first carbon of H C C

the chain so it does not need an extra number. It is

by default number one on the chain. H
H

Ethanal

If two aldehyde groups then di is put before –al and an O O

e is added to the stem.
pentanedial

O
Aldehydes have a higher priority than alcohol so the –OH HO
group uses the hydoxy prefix. 4-hydroxybutanal

Ketones H O H

Ketones end in -one H C C C H

When ketones have 5C’s or more in a chain then H H

it needs a number to show the position of the Propanone
double bond. E.g. pentan-2-one
H O H O H
If two ketone groups then di is put before – H C C C C C H
one and an e is added to the stem.

CHEMISTRY
H H H
Pentane-2,4-dione
by

Carboxylic acids
ABIR
These have the ending -oic acid but no number is
necessary for the acid group as it must always be
at the end of the chain. The numbering always
H
H

C
H

C C
O

Propanoic acid

starts from the carboxylic acid end. H H

O H

O O Ethanedioic acid
If there are carboxylic acid groups on both ends of the
C C
chain then it is called a - dioic acid Note the e in this name
HO OH

O
5-hydroxy-4-methylpentanoic acid

OH OH

Page 39
 Isomers
Structural isomers: same molecular formula different structures (or structural formulae)

Structural isomerism can arise from

EDEXCEL does not split structural
•Chain isomerism isomers into the different categories.
•Position isomerism They are all classed as structural
isomers.
•Functional group isomerism
Chain isomers: Compounds with the same molecular formula but different
structures of the carbon skeleton
H
H H H H H H H H H H C H
H H
H C C C C C H H C C C C H
H C C C H
H H H
H H H H H H C H H H
H C H
pentane H
H
2-methylbutane
2,2-dimethylpropane

Position isomers: Compounds with the same molecular formula but different structures
due to different positions of the same functional group on the same carbon skeleton

H H H H H H

H C C C H 1-bromopropane H C C C H 2-bromopropane

Br H H H Br H

Functional group isomers: Compounds with the same molecular formula but
with atoms arranged to give different functional groups
CHEMISTRY
byH

ABIR
H H H
Methoxymethane: an ether
H C C O H ethanol: an alcohol H C O C H

H H
H H

H H
H H
C
H C C H
Cyclohexane- cycloalkane CH3CH2CH2CH2CH=CH2 hexene- alkene
H C C H
C
H H
H H Note: alkene and cyclo alkanes have the same general formula. Hexene
and cyclohexane have the same molecular formula but have a different
functional group

Page 40
4B Alkanes

Alkanes are saturated hydrocarbons Saturated: Contain single carbon-carbon bonds only

General formula alkane CnH2n+2 Hydrocarbon is a compound consisting of

hydrogen and carbon only

Fuels from crude oil

They are obtained from the crude oil in the order of fractional distillation, Alkanes are used as fuels
cracking and reformation of crude oil

Refining crude oil fuel gas (bottled)

20° C
Fractional Distillation: petrol/gasoline
40° C
Petroleum is a mixture consisting mainly naptha (chemicals)
of alkane hydrocarbons Crude 110° C
oil kerosene (jet fuel)
Petroleum fraction: mixture of hydrocarbons with 180° C
a similar chain length and boiling point range diesel oil
250° C
fuel oil
300° C
Furnace
lubricating oils
• Oil is pre-heated 340° C
• then passed into column.
• The fractions condense at different heights bitumen
• The temperature of column decreases upwards
• The separation depends on boiling point.

CHEMISTRY
• Boiling point depends on size of molecules. This is a physical process
• The larger the molecule the larger the London forces involving the splitting of
by weak London forces

ABIR
• Similar molecules (size, bp, mass) condense together
between molecules
• Small molecules condense at the top at lower temperatures
• and big molecules condense at the bottom at higher temperatures.

Cracking Cracking: conversion of large hydrocarbons to smaller molecules by breakage of C-C bonds

High Mr alkanes  smaller Mr alkanes+ alkenes + (hydrogen) Conditions

1. High temperature
2. silica / alumina catalyst

Economic reasons for catalytic cracking

• The petroleum fractions with shorter C chains (e.g. petrol and This is a chemical process
naphtha) are in more demand than larger fractions. involving the splitting of
• To make use of excess larger hydrocarbons and to supply demand strong covalent bonds so
for shorter ones, longer hydrocarbons are cracked. requires high temperatures.
• The products of cracking are more useful and valuable than the
starting materials (e.g. ethene used to make poly(ethene) and
ethane-1,2-diol, and ethanol) The smaller alkanes are used for motor
fuels which burn more efficiently.

Page 41
 Reforming Turns straight chain alkanes into branched and cyclic
alkanes and Aromatic hydrocarbons

Branched and cyclic hydrocarbons burn more cleanly and are used to
give fuels a higher octane number. Used for making motor fuels

Pt catalyst
500 °C
high pressure

octane 2,5-dimethylhexane

CH3

H C H
Pt catalyst C C
CH3CH2CH2CH2CH2CH2CH3 + 4H2
500 °C C C
high pressure H C H

H
heptane methylbenzene

H H H
H H
C H C H
H C C H Pt catalyst C C

H C C H CHEMISTRY
500 °C
high pressure
C C
+ 3H2

C by H C H

ABIR
H H
H H H

cyclohexane benzene

Alkanes as Fuels
Alkanes readily burn in the
Fuel : releases heat energy when burnt presence of oxygen. This
combustion of alkanes is highly
Complete Combustion exothermic, explaining their use
In excess oxygen alkanes will burn with complete combustion as fuels.

The products of complete combustion are CO2 and H2O.

C8H18(g) + 12.5 O2(g)  8CO2(g) + 9 H2O(l)

Incomplete Combustion Incomplete combustion produces

less energy per mole than
If there is a limited amount of oxygen then incomplete combustion
complete combustion.
occurs, producing CO (which is very toxic) and/or C (producing a sooty
flame)
Carbon (soot)/particulates can
CH4(g) + 3/2 O2(g)  CO(g) + 2 H2O(l)
cause global dimming- reflection of
CH4(g) + O2(g)  C(s) + 2 H2O(l)
the sun’s light

Carbon monoxide is an highly toxic but odourless CO is toxic to humans as CO can from a strong bond
gas. It can cause death if it builds up in a enclosed with haemoglobin in red blood cells. This is a stronger
space due to faulty heating appliances. bond than that made with oxygen and so it prevents the
oxygen attaching to the haemoglobin.

Page 42
Pollution from Combustion
Sulfur containing impurities are found in petroleum fractions which
Coal is high in sulfur content, and
produce SO2 when they are burned.
large amounts of sulfur oxides are
S+ O2  SO2 CH3SH+ 3O2  SO2 + CO2 + 2H2O emitted from power stations.

SO2 is acidic and will dissolve in atmospheric water and can produce acid rain.
Nitrogen Oxides NOx
Nitrogen oxides form from the reaction between N2 and O2 inside the car engine.
The high temperature and spark in the engine provides sufficient energy to break strong N2 bond

N2 + O2  2NO N2 + 2O2  2NO2

Pollutant Environmental consequence

Nitrogen oxides (formed when N2 in the air reacts at NO is toxic and can form smog
the high temperatures and spark in the engine) NO2 is toxic and acidic and forms acid rain
Carbon monoxide toxic
Carbon dioxide Contributes towards global warming
Unburnt hydrocarbons (not all fuel burns in the Contributes towards formation of smog
engine)
Soot/particulates Global dimming and respiratory problems

Catalytic converters
These remove CO, NOx and unburned hydrocarbons (e.g. octane,
CHEMISTRY
C8H18) from the exhaust gases, turning them into ‘harmless’ CO2, N2
and H2O.
Converters have a ceramic
honeycomb coated with a thin
by layer of catalyst metals

ABIR
2 CO + 2 NO  2 CO2 + N2 Platinum, Palladium, Rhodium
– to give a large surface area.
C8H18 + 25 NO  8 CO2 + 12½ N2 + 9 H2O

Biofuels

Most fossil fuels come from crude oil, which is a non- Alcohols such as ethanol can be produced
renewable resource. Fossil fuel reserves will eventually from the fermentation of sugars from
run out plants.
Alternative fuels have been developed from renewable Biodiesel is produced by reacting
resources. Alcohols and biodiesel, which can both be vegetable oils with a mixture of alkali and
made from plants, are two examples of renewable plant- methanol
based fuels

Advantages of using Biofuels Disadvantages of Biofuels

Reduction of use of fossil fuels which are finite resources Less food crops may be grown
biofuels are renewable Land not used to grow food crops
Use of biodiesel is more carbon-neutral Rain forests have to be cut down to
Allows fossil fuels to be used as a feedstock for organic provide land
compounds Shortage of fertile soils
No risk of large scale pollution from exploitation of fossil
fuels

Page 43
 Introduction to Mechanisms
To understand how the reaction proceeds we must first understand how bonds are broken in organic mechanisms
There are two ways to break a covalent bond:
1.Homolytic fission:
each atom gets one electron from the covalent bond
one headed arrow shows
movement of one electron
Y X Y
X

The bond has broken in a process called homolytic fission.

When a bond breaks by homolytic fission it forms two Free Radicals. DEFINITION

Free Radicals do not have a charge and are represented by a A Free Radical is a reactive species
which possess an unpaired electron

2. Heterolytic fission: (one atom gets both electrons)

X Y X: - Y+
two headed arrow shows
movement of pair of
OR - electrons
X Y X+ Y:

+ -
xx xx
x

xx
xx

Cl Cl Cl + Cl
CHEMISTRY
x

xx xx

by

ABIR
Heterolytic fission produces IONS

Most organic reactions occur via heterolytic fission, producing ions

The Mechanism:
To understand a reaction fully we must look in detail at how it proceeds step
by step. This is called its mechanism

HO:-
H H The carbon has a small
H H
positive charge because
of the electronegativity
H C C δ+ X δ- H C C OH + X- difference between the
H H carbon and the halogen
H H

We use curly arrows in mechanisms to

A curly arrow will always start
show the movement of an electron pair
from a lone pair of electrons or
showing either breaking or formation of a
covalent bond; the centre of a bond

Page 44
 Free Radical Substitution Reactions of Alkanes
Reaction of alkanes with bromine / chlorine in UV light
In general, alkanes do not react
In the presence of UV light alkanes react with chlorine to form a with many reagents.
mixture of products with the halogens substituting hydrogen atoms. This is because the C-C bond
and the C-H bond are relatively
Overall Reaction strong.
This is the overall reaction, but
CH4 + Cl2  CH3Cl + HCl a more complex mixture of
products is actually formed
methane chloromethane
It proceeds via a series of steps:
The mechanism for this reaction is called a free radical Step one: Initiation
substitution Step two: Propagation
Step three: Termination

Step one Initiation The UV light supplies the energy to break the Cl-Cl bond. It is
Essential condition: UV light broken in preference to the others as it is the weakest.

Cl2  2Cl
.
UV light does not have enough energy to break the C-H bond

The bond has broken in a process called homolytic fission.

Cl Cl Cl each atom gets one electron from the covalent bond

Cl

DEFINITION
When a bond breaks by homolytic fission it forms Free Radicals.

CHEMISTRYApossess
Free Radicals do not have a charge and are represented by a
Free Radical is a reactive species which
an unpaired electron
by

Step two Propagation

CH4 + Cl.  HCl + .CH3

ABIR The chlorine free radicals are very reactive and remove
an H from the methane leaving a methyl free radical

.CH + Cl2  CH3Cl + Cl. The methyl free radical reacts with a Cl2 molecule to
3 produce the main product and another Cl free radical

All propagation steps have a free radical in the reactants and in the products.

As the Cl free radical is regenerated, it can react with several more

alkane molecules in a CHAIN REACTION

Step three Termination Collision of two free radicals does not generate further free radicals:
the chain is TERMINATED.
.CH + Cl .  CH Cl
3 3
.CH . Minor step leading to impurities of ethane in product.
3 + CH3  CH3CH3 Write this step using structural formulae and
Cl . + Cl .  Cl2 don’t use molecular formulae

Page 45
Applying the mechanism to other alkanes
The same mechanism is used: Learn
Example: Write mechanism of Br2 and Propane the patterns in the mechanism

STEP ONE Initiation

Essential condition: UV light
Br2  2Br
. Br2 splits in the same way as Cl2

STEP TWO Propagation

.
CH3CH2CH3 + Br  HBr + CH3CH2CH2
.
Remove one H from the alkane to produce a radical
.
CH3CH2CH2 + Br2  CH3CH2CH2Br + Br
.
To the radical produced in the previous step add a Br
STEP THREE Termination
.
CH3CH2CH2 + Br  CH3CH2CH2Br
.
. .
CH3CH2CH2 + CH3CH2CH2  CH3CH2CH2CH2CH2CH3

Propagation steps for substituting a halogen on a ‘middle’ carbon

.
CH3CH2CH3 + Br  HBr + CH3CH CH3
.
If the question asks for the halogen to be substituted
.
CH3CH CH3 + Br2  CH3CH2BrCH3 + Br
. onto a middle carbon in the chain, it is important to
put the free radical ‘dot’ on the correct carbon in the
propagation stages.

Further substitution reactions

CHEMISTRY
Excess Cl2 present will promote further substitution and could produce CH2Cl2, CHCl3 and CCl4
by

ABIR
These reactions could occur Example propagation steps that would lead to
further substitution
CH3Cl + Cl.  HCl + .CH2Cl
CH3Cl + Cl2  CH2Cl2 + HCl
CH2Cl2 + Cl2  CHCl3 + HCl
CHCl3 + Cl2  CCl4 + HCl . CH Cl + Cl  CH Cl + Cl .
2 2 2 2

Overall reaction equations

You should be able to write overall reaction equations for various reactions
Example 1. Write the overall reaction equation for the formation of CCl4 from CH4 + Cl2

CH4 + 4 Cl2  CCl4 + 4 HCl

Example 2. Write the overall reaction equation for the formation of CFCl3 from CH3F + Cl2
CH3F + 3 Cl2  CFCl3 + 3 HCl

Note HCl is always the side product – never H2

Page 46
 Topic 5
Alkenes

Alkenes contain a carbon-

Alkenes are unsaturated hydrocarbons General formula is CnH2n carbon double bond
somewhere in their structure
H H H H

C C C H
C C Ethene Propene
H H H
H H

H H H H
Numbers need to be H
added to the name when H C C C C H But-2-ene
C C C C H But-1-ene
positional isomers can
occur H H H H H H H H

π bonds are exposed and have high

C=C double covalent bond electron density.
consists of one sigma (σ)
bond and one pi (π) bond. They are therefore vulnerable to attack
by species which ‘like’ electrons: these
C-C sigma bond C-C pi bond species are called electrophiles.

Formation of σ bond

CHEMISTRY
C C by

ABIR
One sp2 orbital from each carbon overlap to
form a single C-C bond called a sigma σ bond sigma σ bond

Rotation can occur around a sigma bond

Formation of π bond
p orbitals

The π bond is formed by

sideways overlap of two p
orbitals on each carbon atom
forming a π-bond above and
below the plane of molecule.

C-C sigma bond The π bond is weaker than

C-C pi bond the σ bond.

The pi bond leads to resultant high electron density above

There is Restricted rotation about a pi bond and below the line between the two nuclei

Page 47
Stereoisomerism

Stereoisomers have the same structural formulae Alkenes can exhibit a type of isomerism
but have a different spatial arrangement of atoms. called E-Z stereoisomerism

E-Z isomers exist due to restricted E-Z stereoisomers arise when:

rotation about the C=C bond (a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of
Single carbon-carbon covalent the double bond
bonds can easily rotate

H H

H H
two different groups H C C H But-1-ene
H C C H attached either end of
C C
the restricted double H H
C C H
bond- leads to EZ H two identical groups attached to
H H H H isomers one end of the restricted double
Z- but-2-ene bond – no E-Z isomers

But-1-ene is a structural isomer of But-2-

H
H These are two ene but does not show E-Z isomerism
C H isomers as the lack
H of rotation around Skeletal formulae can also represent E-Z isomerism
C C the double bonds
H
means one cannot Z-but-2-ene
H C
H
be switched to the
H other
E-but-2-ene
E -but-2-ene

CHEMISTRY
Priority Group: The atom with the bigger
Naming E-Z stereoisomers by

ABIR
atomic number is classed as the priority atom
First determine the priority groups on both sides of
the double bond

Priority Priority Cl H
group Cl Cl group
side 1 side 2 C C
C C
Z-1,2-dichloroethene
H H H Cl E-1,2-dichloroethene
If the priority atom is on the same side of the If the priority atom is on the opposite side of
double bond it is labelled Z from the german the double bond it is labelled E from the
zusammen (The Zame Zide!) german entgegen (The Epposite side!)

cis-trans isomerism is a special case of EIZ isomerism in

which two of the substituent groups are the same. H
H
H H C H
H C C H H
C C
H
C C
H C
H H H H H
H
Z- but-2-ene E- but-2-ene
Can also be called Can also be called
Cis- but-2-ene trans- but-2-ene

Page 48
 Addition Reactions of Alkenes Addition reaction: a reaction where two molecules react
together to produce one

1. Reaction of Alkenes with Hydrogen

Change in functional group: alkene  alkane H H

H H
Reagent: hydrogen
Conditions: Nickel Catalyst C C + H2  H C C H
Type of reaction: Addition/Reduction
H H H H
ethene ethane

Electrophilic Addition: Reactions of Alkenes

A π bond is weaker than a σ bond so less energy is needed to break π bond Definition Electrophile: an
The π bonds in alkenes are areas with high electron density. This is more electron pair acceptor
accessible to electrophilic attack by electrophiles. Alkenes undergo addition
reactions.

2. Reaction of Alkenes with bromine/chlorine

H H
Change in functional group: H H
alkene  dihalogenoalkane
C C + Br2  H C C H
Reagent: Bromine (dissolved in organic solvent)
Conditions: Room temperature (not in UV light) H H Br Br
Mechanism: Electrophilic Addition 1,2-dibromoethane
Type of reagent: Electrophile, Br+
Type of Bond Fission: Heterolytic

As the Br2 molecule H

CHEMISTRY
H H H
H H
by

ABIR
approaches the alkene,
the pi bond electrons + The INTERMEDIATE
C C H C C H H C C H formed, which has a
repel the electron pair in
the Br-Br bond. This δ+ H positive charge on a
H Br Br carbon atom is called a
INDUCES a DIPOLE. Br2 Br Br
becomes polar and :Br - CARBOCATION
ELECTROPHILIC (Brδ+). Brδ-

3. Reaction of Hydrogen Bromide with alkenes

Change in functional group: H H H H H H

alkenehalogenoalkane
H C C C C H + HBr  H C C C C H
Reagent: HCl or HBr
Conditions: Room temperature H H H H H H Br H

Mechanism: Electrophilic Addition But-2-ene 2-bromobutane

Type of reagent: Electrophile, H+
Type of Bond Fission: Heterolytic

HBr is a polar molecule H H H H

H H
because Br is more +
H3C C C CH3
electronegative than H. H3C C C CH3 H3C C C CH3
The H δ + is attracted to δ+
H H H
the electron-rich pi bond. -
Br
Brδ :Br -

Page 49
 If the alkene is unsymmetrical, addition of hydrogen bromide can lead to two isomeric products.
But-1-ene will form a mixture of 1-bromobutane and 2-bromobutane on reaction with hydrogen
bromide :Br -
H
+ H H H H
C CH2
Major
H C C C C H
H3C CH3 product
δ+ δ- 90%
H Br H H Br H

:Br -
H2C CH CH2 CH3 H H
+
C C CH2 CH3 CH2 CH2 CH2 CH3 Minor
product
H Br 10%
H

WHY? In electrophilic addition to alkenes, the major product is

This carbocation intermediate H H H formed via the more stable carbocation intermediate.
is more stable because the
methyl groups on either side H C C C H In exam answers
of the positive carbon are +
•Draw out both carbocations and identify as primary, secondary
electron releasing and reduce and tertiary
H H
the charge on the ion which •State which is the more stable carbocation e.g. secondary more
stabilises it. stable than primary
•State that the more stable carbocation is stabilised because the
The order of stability for carbocations is methyl groups on either (or one) side of the positive carbon are
electron releasing and reduce the charge on the ion.
tertiary > secondary >primary •(If both carbocations are secondary then both will be equally
stable and a 50/50 split will be achieved)

CHEMISTRY
4. Reaction of Potassium Manganate(VII) with Alkenes

Change in functional group: alkene  diol byH H

ABIR
H H H
Reagent: KMnO4 in an acidified solution KMnO4
C C C H H C C C H
Conditions: Room temperature
Type of reaction: Oxidation
H H H OH OH H
Observation: purple colour of MnO4- ion will propene Propane-1,2-diol
decolourise to colourless
This reaction with its colour change can be used as a test
for the alkene functional group. It would not change colour
with alkanes

5. Reaction of Bromine Water with Alkenes

Reagent: Bromine dissolved in water H H H H

Conditions: Room temperature
Type of reaction: Addition C C + BrOH H C C H
Observation: Orange colour of bromine water H H Br OH
will decolourise to colourless

This reaction with its colour change is used as a test for the
alkene functional group.

Page 50
hydration of alkenes to form alcohols This reaction can be called
Industrially alkenes are converted to alcohols in one step rather than the hydration: a reaction where
two in the above sulphuric acid reaction. They are reacted with water in water is added to a molecule
the presence of an acid catalyst.
Essential Conditions

CH2=CH2 (g) + H2O (g)  CH3CH2OH High temperature 300 to 600°C

(l)
High pressure 70 atm
Catalyst of concentrated H3PO4

The high pressures needed mean this cannot be done in the laboratory. It is preferred industrially, however,
as there are no waste products and so has a high atom economy. It would also mean separation of products
is easier (and cheaper) to carry out. See equilibrium chapter for more on the industrial conditions for this
reaction.

Addition Polymers
Addition polymers are formed from alkenes Poly(alkenes) like alkanes are unreactive due to
the strong C-C and C-H bonds.
This is called addition polymerisation

be able to recognise the repeating unit in a poly(alkene)

n

Monomer H H H H H H
Polymer
Ethene Poly(ethene) C C C C C C

CHEMISTRY
H H
H H
CH H 3 CH3 H CH3 H
C C
by

ABIR
C C
n
H CH3 H CH3
n Add the n’s if writing an equation showing the
propene reaction where ‘n’ monomers become ‘n’ repeating
poly(propene)
units
Poly(propene) is recycled

Poly(ethene): is used to make plastics bags,

Poly(propene) is a stiffer polymer, used in
buckets, bottles. It is a flexible, easily moulded,
utensils and containers and fibres in rope
waterproof, chemical proof, and low density
and carpets.
plastic.

It is best to first draw out H CH3

You should be able e.g. For but-2-ene the monomer with groups H CH3
to draw the polymer of atoms arranged around
H3C CH CH CH3 the double bond C C C C
repeating unit for any
alkene H3C H
CH3 H

Page 51
Methods of disposal of waste Polymers

Incineration
Rubbish is burnt and energy produced is used to generate electricity.
Some toxins can be released on incineration. (e.g. Combustion of halogenated plastics (ie PVC) can
lead to the formation of toxic, acidic waste products such as HCl.) Modern incinerators can burn more
efficiently and most toxins and pollutants can be removed. Greenhouse gases will still be emitted
though.
Volume of rubbish is greatly reduced.

Recycling
Saves raw materials- nearly all polymers are formed from compounds sourced/produced from
crude oil. Saves precious resources.
Polymers need collecting/ sorting- expensive process in terms of energy and manpower.
Polymers can only be recycled into the same type – so careful separation needs to be done.
Thermoplastic polymers can be melted down and reshaped.

feedstock for cracking

Polymers can be cracked into small molecules which can be used to make other chemicals and new
polymers- Saves raw materials-

Chemists have designed ways to remove toxic waste products like HCl before they are emitted into the
atmosphere. The waste gases from the incinerator are scrubbed/reacted with a base or carbonate. The
base reacts with the acidic HCl gas, neutralising it (eg CaO + 2HCl  CaCl2 + H2O)

CHEMISTRY
Chemists have also develop biodegradable and compostable polymers. Biodegradable polymers can
be made from substances such as maize and starch
by

ABIR

Page 52