As Chemistry Unit 2

INTERMEDIATE BONDING AND BOND POLARITY
1
Electronegativity and Polar Bonds

Intermediate Bonding and Bond Polarity

Explain the meaning of the term electronegativity as applied to atoms in a covalent bond

Electronegativity is a measure of the ability of an atom to attract a bonding pair of electrons in
a covalent bond.

Electronegativity increases across a period as nuclear charge increases, and decreases down the
group as atomic radius and number of screening electrons increases.

Covalent bonds between atoms of a single element are purely covalent- all the atoms attract
the bonding pair of electrons equally (they have the same electronegativity). For example, a Cl-
Cl bond is purely covalent because both chlorine atoms have the same electronegativity, so the
electrons are shared equally.

Other covalent bonds are partially ionic because there is a difference in electronegativity
between atoms, and therefore the electrons are not shared equally.

Recall that ionic and covalent bonding are the extremes of a continuum of bonding type
and explain this in terms of electronegativity differences leading to bond polarity in bonds
and molecules, and to ionic bonding if the electronegativity is large enough

Ionic and covalent bonding are the extremes of a continuous scale of bonding type. Ionic
bonding involves complete electron transfer and covalent bonding involves equal sharing of
electrons in pairs. In practice, most bonds are neither purely ionic nor purely covalent- they are
intermediate between these two forms, with one type being predominant.

o For pure covalent bonding to occur, the electronegativity of each atom has to be the same
(e.g. when the atoms are from the same element). This means that the electrons are equally
attracted to both nuclei.

o If there is a difference in electronegativity, a dipole is formed. The electrons are not shared
equally between the atoms, and the bond is therefore referred to as polar. The greater the
difference in electronegativity, the more polar the bond.

A dipole is a difference in charge between two atoms caused by a
shift in electron density in the bond.

In this example, the fluorine atom is more electronegative than
the hydrogen atom, and so attracts the electron density more

2
Polar Molecules

strongly. Therefore the fluorine atom is slightly negative (-) and the hydrogen atom slightly
positive (+).

o For ionic bonding to occur, the electronegativity difference needs to be very large.

N.B. Fluorine is the most electronegative element, caesium the least electronegative.

Distinguish between polar bonds and polar molecules and be able to predict whether or
not a given molecule is likely to be polar

Polar bonds are bonds in which electrons are shared unequally between the two atoms.

Non-polar bonds are bonds in which electrons are shared equally between the two atoms.

Polar molecules are molecules which have an overall dipole moment- there is an overall dipole
across the molecule (the positive and negative centres are at separate points).

Non-polar molecules are non-polar because they either have no polar bonds (e.g. Cl2) or they
are symmetrical (CH4).

Some molecules have polar bonds but are not polar. For a molecule to be polar, there has to be a
permanent dipole (charge difference) across the whole molecule.

o Symmetrical molecules are non-polar, because the polar bonds point in opposite directions,
and therefore the dipoles cancel each other out- there is no overall dipole.

o Lone pairs of electrons on the central atom affect the symmetry of the molecule so therefore
they can also cancel out dipoles created by bonding pairs.

Example: Water

Water is polar because it is not symmetrical and contains a polar O-H bond. The oxygen atom is
more electronegative than the hydrogen atom, and hence the bond is polar.

3
Polar Molecules

Carry out experiments to determine the effect of an electrostatic force on jets of liquids
and use the results to determine whether the molecules are polar or non-polar

o A comb or rod is given an electric charge
by rubbing it on a piece of wool

o The resulting electric field around the
comb will attract polar liquids

o Liquids can be tested, and those that are
polar, such as water, are deflected,
whilst those that are non-polar are not
deflected by the electric field.
INTERMOLECULAR FORCES
4
Permanent Dipole Interactions, London Forces
Intermolecular Forces

Demonstrate an understanding of the nature of intermolecular forces resulting from
interactions between permanent dipoles, instantaneous dipoles and induced dipoles
(London forces) and from the formation of hydrogen bonds

Intermolecular forces are attractions between molecules. They are much weaker than
intramolecular forces within molecules (e.g. ionic, covalent bonds).

There are three types of intermolecular force:

Permanent dipole- dipole interactions

Polar molecules have a permanent dipole (a permanent separation of charge). Polar molecules
are attracted to one another by forces called permanent dipole-dipole interactions, in which the
negative end of one molecule is attracted to the positive end of another.

Repulsive forces between similarly charged parts of different molecules also exist, but the
attractive forces between oppositely charged parts are stronger, and therefore the molecules
experience a net attractive force.

London Forces

In a neutral atom, the electrons move around the electron cloud. At any one time, the electron
distribution might lead to the centres of the positive and negative charge failing to coincide,
producing an instantaneous (temporary) dipole.

The instantaneous dipole produces an electric field, which leads to the formation of induced
dipoles in a neighbouring atom. The two atoms are then attracted to each other. The second
dipole can cause yet another dipole in a third atom, and so on.

Because the electrons are constantly moving, the dipoles are being created and destroyed all
the time. Even though the dipoles keep changing, the overall effect is for the atoms to be
attracted to each other.

The instantaneous dipoles spread like this between neighbouring molecules, forming attractions
between molecules. These instantaneous dipole- induced dipole interactions are also known
as London Forces or van der Waal forces. These forces exist between all atoms.
5
London Forces, Hydrogen Bonding

The strength of London Forces depends on:

a) Molecular Size- as the size of the molecules increase, the molecular surface area increases
and the number of electrons increases. The bigger the molecular surface area, the more
space over which electrons can move, and the larger the potential charge separation, and
hence the larger the instantaneous dipole. The more electrons there are, the larger the
charge difference within the molecule, and hence the larger the instantaneous dipole.

b) Molecular Shape- the shape of the molecule also effects the strength of London Forces:

Long-chain alkanes have stronger London Forces than short-chain alkanes

Straight- chain alkanes have stronger London Forces than branched alkanes

This is because:

o Longer molecules have a larger molecular surface area
o Unbranched molecules have larger molecular surface areas and can pack together more
closely, increasing the strength of the attractions between them.

Butane is straight-chained, and therefore forms larger dipoles than 2-methylpropane, which is
branched. Therefore, the London Forces are stronger in butane and hence it has a higher boiling
point.

Hydrogen Bonds

Hydrogen bonding is the interaction between a molecule that contains a hydrogen atom
attached to an electronegative element, and another molecule containing a lone pair of
electrons on an electronegative element.

o Hydrogen bonding only occurs when hydrogen is covalently bonded to fluorine, nitrogen or
oxygen

o Fluorine, nitrogen and oxygen are very electronegative, so they draw the bonding pair of
electrons away from the hydrogen atom.

6
Hydrogen Bonding

o Hydrogen atoms have no inner shells of electrons, and therefore the shift in the electron
cloud leaves the nucleus of the hydrogen atom exposed

o The + hydrogen atoms are attracted to the negative lone pairs of electrons on the fluorine,
nitrogen or oxygen atoms of other molecules.

Overview: Strength of Intermolecular Forces

There are three types of intermolecular forces that can exist between molecules:

o London Forces (weakest type)
o Permanent dipole-dipole interactions
o Hydrogen Bonding (strongest type)

* London Forces are also called instantaneous dipole- induced dipole interactions.

Non-polar molecules only have London forces between them.

7
Physical Properties

Relate the physical properties of materials to the types of intermolecular force present:

i) Trends in the boiling and melting temperatures of alkanes with increasing chain length

The intermolecular forces in non-polar alkanes are London Forces.

The boiling and melting temperatures of straight- chain alkanes increases as the chain length.

This is because the longer the chain length, the higher the molecular surface area, so the greater
the area over which London Forces can form, and therefore the strength of the London Forces
increases.

e.g. Methane vs. Ethane

o No permanent dipole-dipole interactions
o No hydrogen bonding
o Ethane has stronger London Forces

8
Physical Properties

ii) Effect of branching in the carbon chain on the boiling and melting temperatures of alkanes

The boiling and melting temperatures of unbranched alkanes are higher than those of branched
alkanes.

This is because unbranched alkanes can pack together more closely and also have larger
molecular surface areas, so the London Forces are stronger.

e.g. Butane vs. 2-methylpropane

o No hydrogen bonding
o Butane has no branches, so has stronger London Forces

iii) Relatively low volatility (higher boiling temperatures) of alcohols compared to alkanes
with a similar number of electrons

Volatility is a measure of how easily molecules can escape from a liquid. The higher the
volatility, the easier it is for molecules to be lost from the surface, and hence the lower the
boiling point.

Alcohols vs. Alkanes (with same number of electrons)

o Both have London Forces of similar strength
o Alcohols have hydrogen bonding

Alcohols have hydrogen bonding due to the presence of the very polar O-H bond. The hydrogen
bonding is in addition to the London Forces found in both alcohols and alkenes.

Therefore, alcohols have stronger intermolecular bonding due to the presence of hydrogen
bonds, and hence boiling points of alcohols tend to be higher.

9
Physical Properties

iv) The trends in boiling temperatures of the hydrogen halides HF to HI

o Hydrogen Fluoride is particularly high due to the presence of hydrogen bonds and also
because fluorine is very electronegative, and so H-F bonds are very polar, so dipole-
dipole interactions are especially strong.

o Boiling temperature increases from HCl to HI because the size of molecules increases, so
London Forces become stronger.

o However, the size of this increase is limited because the electronegativity of the
halogens decreases from fluorine to iodine. Therefore, H-Cl is a more polar bond than H-
Br or H-I, and hence the dipole-dipole interactions become weaker from HCl to HI.

10
Solubility

Solubility

Carry out experiments to study the solubility of simple molecules in different solvents

Solubility is a measure of the extent to which a solute will dissolve in a solvent. Numerically, it is
the mass of a solute that dissolves in 100g of solvent at a particular temperature.

Dissolving

When a solute dissolves in a solvent, three things have to happen:
Intermolecular forces between solute molecules have to break
Intermolecular forces between solvent molecules have to break
New intermolecular forces have to form between the solute and solvent

Usually a substance will only dissolve if the strength of the new forces formed is the same as, or
greater than, the strength of the forces that are broken.

When carrying out solubility experiments, it is advisable to use a small quantity of solute and a
small volume of solvent.

Solvents

There are two main types of solvents:

Polar solvents, such as water, which have hydrogen bonding and London forces between
molecules.

Non-polar solvents, such as hexane, which have only London forces between molecules.

Interpret given information about solvents and solubility to explain the choice of solvents
in given contexts, discussing the factors that determine solubility including:

i) The solubility of ionic compounds in water in terms of the hydration of the ions

Ionic compounds dissolve in polar solvents such as water.

o Ionic substances are very polar- they contain positive and negative ions.

o The positive ions are attracted to the - oxygen atoms in water molecules.

11
Solubility

o The negative ions are attracted to the + hydrogen atoms.

o The ions are therefore pulled away from the ionic lattice and then surrounded by water
molecules in a process called hydration.

Hydration occurs when water molecules arrange themselves around ions.

The energy required to pull apart the ions is called the lattice energy.
The energy released during hydration is called the hydration energy.

For an ionic substance to dissolve in water, the
hydration energy has to be greater than (or
equal to) the lattice energy.

In other words, the attraction between the ions
and water molecules has to be stronger than
(or equal to) the strength of the attractions
between the ions in the original lattice.

ii) The water solubility of simple alcohols in terms of hydrogen bonding

Alcohols dissolve in water because the alcohol molecules form hydrogen
bonds with water molecules. On dissolving, the OH group on the alcohol
molecules break some of the water-water hydrogen bonds and replace
them with alcohol-water hydrogen bonds.

Alcohols and water both have polar O-H bonds. Therefore, hydrogen
bonds form between the + hydrogen atoms and the lone pairs on the -
oxygen atoms.

12
Solubility

The carbon section of the alcohol molecule is non-polar and is therefore not attracted to water.

The larger the carbon chain, the less polar the molecule, and hence the less soluble the molecule
is in water. Therefore, solubility of alcohols in water decreases with increasing carbon chain
length.

iii) The insolubility of compounds that cannot form hydrogen bonds with water
molecules, e.g. non-polar substances and polar molecules (such as halogenoalkanes)

o Non-polar substances cannot form hydrogen bonds with water, and are therefore insoluble
in water.

o Halogenoalkanes are slightly polar due to the presence of the partially polar carbon-halogen
bonds. However, the dipole across the molecule is very weak, so the forces that would form
between the halogenoalkanes and water molecules are weaker than the strong hydrogen
bonds already present in water.

So, both non-polar substances and slightly polar substances are insoluble in water. This is
because the bonds that form between the substance and water molecules are relatively weak
compared to the hydrogen bonds that exist between water molecules.

Therefore, the substances have insufficient polar character to disrupt the hydrogen bonds
between water molecules.

iv) The solubility in non-aqueous solvents of compounds who have similar intermolecular
forces to those in the solvent

Non-polar substances dissolve in hexane (non-polar solvent)

Non-polar substances (e.g. ethane) and non-polar solvents (hexane) both contain only weak
London forces.

When they are mixed, the London Forces extend throughout the mixture, and form between the
two substances (e.g. between ethane and hexane molecules).

Polar substances do not dissolve in hexane (non-polar solvent)

Polar substances have both London forces and permanent dipole-dipole interactions between
the molecules. If a polar substance dissolved in a non-polar solvent, the new bonds formed

13
Solubility

would be only London forces. Therefore the bonds formed will not be as strong as the bonds
between the original polar molecules.

Alcohols are polar- they have a polar O-H group and a non-polar hydrocarbon chain. Alcohols do
not dissolve in hexane for the same reason. In addition, alcohols have hydrogen bonds between
them, so the difference between the original bonds and the bonds that would be created is even
greater.

Summary

o Highly polar solids, such as ionic compounds, dissolve in water (a polar solvent), but not in
hexane (a non-polar solvent)

o Alcohols dissolve in water (hydrogen bonding), but not in hexane (a non-polar solvent)

o Non-polar substances do not dissolve in water (cannot hydrogen bond with water)

o Some polar substances, such as halogenoalkanes, do not dissolve in water

o Non-polar substances dissolve in non-polar solvents (London forces form between the
molecules)

REDOX
24
Oxidation Numbers

Demonstrate an understanding of:

i) oxidation number- the rules for assigning oxidation numbers

ii)
Oxidation numbers show the total number of electrons which have been removed from an
element (positive oxidation number) or added to an element (negative oxidation number) to get
to its present state.

Example: Reaction of Sodium with Bromine

The loss of an electron from sodium is shown by its
oxidation state increasing from 0 to +1.

In contrast, the gain of an electron by bromine is shown by its
oxidation state decreasing from 0 to -1.

Note: the sum of the oxidation numbers on each side of the
equation should balance

Oxidation numbers in covalent compounds

Oxidation numbers can even be extended to covalent compounds, even though there is no
electron transfer.

o Oxidation numbers are assigned to elements in covalent compounds based upon the
oxidation numbers they would have if the electrons in each bond belonged to the more
electronegative element.

For example, in methane, the carbon is more electronegative than the
hydrogen, so we assign the oxidation numbers as if carbon received an
electron from each of the four hydrogen atoms.

REDOX
25
Oxidation Numbers, Oxidation + Reduction

Rules: Oxidation Numbers

i) The oxidation number of an uncombined element is 0

ii) The oxidation number of an uncombined ion is the same as its charge

iii) The sum of all the oxidation numbers in a neutral compound is zero

iv) The sum of all the oxidation numbers in a charged molecule is equal to the charge of the
molecule (e.g. SO42- has an oxidation number of -2)

v) Fluorine always has an oxidation number of -1

vi) Hydrogen always has an oxidation number of +1.

Except in metal hydrides where it is -1 (and in H2 where it is 0)

vii) Oxygen always has an oxidation number of -2.

Except in peroxides (where it has an oxidation number of -1), and in fluorides where it is
positive

viii) Group 1 elements always have an oxidation number of +1
Group 2 elements always have an oxidation number of +2
Group 3 elements always have an oxidation number of +3

For Practice with oxidation numbers refer to class examples, the textbook and online link.

ii) Oxidation and reduction as electron transfer
iii)

oiii) Oxidation
refers to the loss of electrons.

o Reduction refers to the gain of electrons.

o Oxidation and reduction happen simultaneously (i.e. redox reactions)

iii) Oxidation and reduction in terms of oxidation number changes

o Changes in oxidation number indicates a shift in electron density and therefore indicates
iv)that a redox reaction has taken place
v)

iv)
1
2
REDOX
26
Redox Reactions, Disproportionation Reactions, Ionic half-equations

o The oxidation number of an atom will increase by 1 for each electron lost, and decrease by 1
for each electron gained.

Therefore, reduction leads to a decrease in oxidation number, whilst oxidation leads to an
increase in oxidation number.

In a redox reaction, the oxidising agent gains electrons, whilst the reducing agent loses
electron.

iv) How oxidation number is a useful concept in terms of the classification of reactions as
redox and as disproportionation

Example: Disproportionation Reaction A disproportionation reaction occurs
when the same species is both oxidised

and reduced in the same reaction. There is
2H2O2 2H2O + O2 both an increase and decrease in oxidation
v) number of the species.
The oxidation number of oxygen in H2O2 is -1.
The oxidation number of oxygen in H2O is -2 Oxidation numbers can also help us
The oxidation number of oxygen in O2 is 0. classify reactions as redox- an increase in
oxidation number of one reactant and a
So, oxygen is being oxidised (-1 to 0) and being decrease in oxidation number of the other
reduced (-1 to -2) in the same reaction. reactant indicate that the reaction is
redox.

Write ionic half-equations and use them to construct full ionic equations

See handwritten attachments
vi)

PERIODIC TABLE- GROUPS II & VII
27 Group 2: Ionisation Energies, Reactions

Periodic Table- Group I

Explain the trend in first ionisation energy down group 2
vii)

First Ionisation energy decreases down group two for two reasons:

1) Shielding- as you go down a group, the number of shells between the outermost electron
and the nucleus increases, meaning increased shielding. Therefore, the outermost electron is
held less stably.

2) Atomic Radius- with the addition of more shells, the atomic radius increases and so does the
distance between the outermost electron and the nucleus. Hence, the valence electron is
less strongly attracted to the nucleus, meaning less energy is required to remove it.

Nuclear charge increases down a period, but the two factors above override this.

Recall the reaction of elements in group 2 with oxygen, chlorine and water
viii)

Reactions

When Group 2 elements react, they are oxidised- they lose 2 electrons and their oxidation
number increases from 0 to 2+.

This is because Group 2 elements have two electrons in their outer shell, which they lose in
reactions to form stable noble gas structures.

With Oxygen

The elements burn in oxygen to form solid metal oxides.

o Magnesium burns with a white flame
o Calcium burns with a brick-red flame
o Strontium burns with a crimson-red flame
o Barium burns with a green flame

N.B. Barium burns to form barium peroxide (Ba2O2) as well as barium oxide (BaO)

General Equation: 2M(s) + O2 (g) 2MO(s)
Examples: 2Mg(s) + O2 (g) 2MgO(s)
28 Group 2: Reactions

2Ca(s) + O2 (g) 2CaO(s)

The reactivity of the group 2 metals with oxygen increases down the group. Barium is often
stored under oil to prevent it reacting with oxygen in the air.

With Chlorine

The elements burn in chlorine gas to form white solid metal chlorides.

General Equation: M(s) + Cl2 (g) MCl2(s)

Examples: Mg(s) + Cl2 (g) MgCl2(s)

Ca(s) + Cl2 (g) CaCl2(s)

Again, the reactivity with chlorine increases down the group.

With Water

The elements react with water to form metal hydroxides and hydrogen.

General Equation: M(s) + 2H2O (l) M(OH)2(aq) + H2

Calcium, Strontium, Barium

Calcium, Strontium and Barium react with cold water, for example:

Calcium Ca(s) + 2H2O (l) Ca(OH)2(aq) + H2

The hydroxide forms an alkaline solution.

Magnesium

Magnesium reacts very, very slowly with cold water to form magnesium hydroxide and
hydrogen. However, the reaction stops very quickly because the magnesium hydroxide formed is
insoluble and it coats the magnesium, preventing further any reaction.

29 Group 2: Reactions

Magnesium reacts rapidly with steam to produce magnesium oxide and hydrogen:

Mg(s) + H2O (g) MO2(aq) + H2

Berylium

Beryllium does not react with water due to the thick oxide layer on the surface of the metal.

Reactivities

Once again we can see that the reactivities increase down the group.

Recall the reactions of the oxides of group 2 elements with water and dilute acid, and
their hydroxides with dilute acid.
ix)
Oxides

With Water

The Group 2 metal oxides react with water to form metal hydroxides.

MO(s) + H2O(l) M(OH)2(aq)

However, beryllium oxide does not react with water, whilst magnesium oxide only reacts very
slightly to form insoluble magnesium hydroxide.

With Dilute Acid

The metal oxides are basic, so they neutralise hydrochloric acid or nitric acid to form the
corresponding chloride or nitrate salts.

Hydrochloric Acid MO(s) + 2HCl(aq) MCl2(aq) + H2O(l)

Nitric Acid MO(s) + 2HNO3(aq) M(NO3)2(aq) + H2O(l)

Hydroxides

With Dilute Acid
30 Group 2: Solubility, Thermal Stability

The Group 2 metal hydroxides react with dilute acid in a similar way to the oxides.

Hydrochloric Acid M(OH)2(s) + 2HCl(aq) MCl2(aq) + 2H2O(l)

Nitric Acid M(OH)2(s) + 2HNO3(aq M(NO3)2(aq) + 2H2O(l)

Recall the trends in solubility of the hydroxides and sulphates of group 2 elements

o Group 2 metal hydroxides increase in solubility down the group.
x)

o Group 2 metal sulphates (and carbonates) decrease in solubility down the group.

N.B. Barium Sulphate is insoluble in water
Group 2 nitrates and chlorides are all soluble

Recall the trends in thermal stability of the nitrates and the carbonates of the
elements in groups 1 and 2 and explain these in terms of size and share of the
cations involved

xi)
Thermal decomposition occurs when a substance breaks down when heated.

Thermal stability is a measure of how likely a substance is to decompose- the more stable it is,
the more heat required for it to decompose.

Trend down group 2

Carbonates

The thermal stability of Group 2 carbonates increases down the group
due to the differing polarising ability of the metal ions.

The electron density is evenly distributed in a carbonate ion, as shown on
the right. The red regions have the highest electron density.

31 Group 2: Thermal Stability

When the positive cation is brought near, the electrons of the carbonate ion (which are free to
move within the ion) are attracted to the positive cation. Therefore, there is a shift in electron
density- the electron cloud of the carbonate anion is distorted and therefore the carbonate is
polarised. The diagram shows how the electron cloud has shifted to the oxygen atom nearest to
the positive cation. If heat is applied, the carbon dioxide breaks away and the molecule
decomposes.

Explanation of Trend

o As you go down the group, the polarising ability of the positive metal cation decreases.

The charge of the cation remains constant (2+), but the cation gets larger so its charge
density decreases and hence its polarising power decreases.

o This means that the carbonate ions electron cloud becomes less distorted, so its polarisation
is reduced

o The carbonate ion is less polarised, and hence more energy is required for decomposition to
occur (i.e. for carbon dioxide to split away).

o Thermal stability therefore increases down the group

Nitrates

The explanation for is the same as for the carbonates- thermal stability increases down the
group.

32 Group 2: Thermal Stability

Group 1 vs. Group 2

Group 1 compounds are more thermally stable than Group 2 compounds because:

o Group 1 cations have a 1+ charge, whereas Group 2 cations have a 2+ charge.

o Group 2 cations therefore have a greater polarising power

o The anion in Group 2 compounds is therefore more polarised (because the electron cloud of
anions is more distorted in group 2 compounds)

o Hence, group 2 compounds split up more easily- they are less thermally stable.

Group 1 carbonates and nitrates do not tend to decompose unless temperatures are very high,
apart from Li2CO3 and Li2NO3 (Li+ is very small so hence is quite polarising).

Summary

Group 1 Group 2

Carbonates Decomposes to form a metal Decomposes to form a metal oxide and
oxide and carbon dioxide carbon dioxide

MCO3(s) MO + CO2 MCO3(s) MO + CO2

Nitrates Decomposes to form a metal Decomposes to form a metal oxide,
nitrite and oxygen nitrogen dioxide and oxygen

2MNO3(s) 2NaNO2(s) + O2(g) 2M(NO3)2 (s) 2MO2(s) + 4NO2(s) + O2(g)

Lithium nitrate reacts differently to the other Group 1 nitrates:

4LiNO3(s) 2Li2O(s) + 4NO2(g) + O2(g)

33 Group 2: Flame Tests

Recall the characteristic flame colours formed by Group 1 and Group 2 compounds
and explain their origin in terms of electron transitions

xii)

Flame Test Colours

Group 1 Group 2

Cation
Flame Colour
Cation Flame Colour
Calcium
Brick-Red
Lithium Red
Strontium
Crimson- Red
Sodium Yellow- Orange
Barium
Green
Potassium Lilac
Rubidium Red
Caesium Blue

Origin of Colours

The energy from the flame is absorbed by electrons, who are excited to a higher energy level
(i.e. a higher energy orbital)

When the electrons drop back to their ground state level, they emit energy in the form of
photons of light.

The light emitted has a particular wavelength within the visible spectrum, which determines
what colour is seen

The difference between the higher and lower energy levels determines the wavelength of
the light and therefore determines the colour. Each element has its own characteristic
energy levels, and hence its own characteristic flame colour.

If the wavelength of the emitted light is outside the visible spectrum, no colour is seen. This
is what happens with magnesium.

For some elements the difference between energy levels is too large for the ion to become
excited in a Bunsen burner flame.

34 Group 2: Experiments

Describe and carry out the following:
xiii)
ii) Experiments to study the thermal decomposition of group 1 and 2 nitrates and

carbonates

xiv)
Carbonates

o Set up the experiment as shown

o Measure how long it takes for the limewater (calcium hydroxide) to go milky / cloudy

o Alternatively, you could collect the carbon dioxide in a gas syringe and measure how long it
takes for a certain volume to be produced

Nitrates

o Place the metal nitrate in a test tube, apply heat and either:

1. Measure how long it takes until oxygen relights a glowing splint

2. Measure how long it takes until brown nitrogen dioxide is produced (do this in a fume
cupboard)

3. Collect the gas produced (which will be a combination of O2 and NO2) in a gas syringe,
and measure how long it takes for a certain volume to be produced

35 Group 2: Flame Tests, Titrations

ii) Flame tests on compounds of group 1 and 2

xv)
o Add a few drops of hydrochloric acid to the sample on a watch glass

o Heat a piece of platinum or nichrome wire in a hot Bunsen Flame to clean it

N.B. Platinum and nichrome are chosen because they are relatively unreactive

o Dip the wire into the mixture (containing the acid and sample)

o Hold the wire in a hot Bunsen burner flame and note the colour of the flame

iii) Simple acid-base titrations using a range of indicators, acids and alkalis, to
calculate solution concentrations in g dm-3 and mold m-3 e.g. measuring the residual
alkali present after skinning fruit with potassium hydroxide

Titrations allow you to find out exactly how much acid is required to fully neutralise a certain
quantity
of alkali.

There are several steps to an acid-based titration:
xvi)

1) To make an alkali, dissolve a solid hydroxide compound in water using a beaker.

2) Transfer this solution to a volumetric flask (which has been rinsed with the solution
beforehand), and fill up the flask up to the mark using distilled water

3) Use a pipette filler to remove a fixed volume of alkali, and transfer this to a conical flask
containing an appropriate indicator

4) Rinse the burette with acid, and then fill it up with acid using a small funnel

5) Use the tap on the burette to regulate how much acid is added.

6) Once the end-point has been reached, record the volume of acid used.

The first titration can be done very quickly to find out a rough value for the end-point. Then for
the following titrations, you can add acid quickly until you get close to the end-point, after which
you should add it drop by drop.

36 Group 2: Titrations

Indicators

Universal indicator should not be used because it has a gradual colour change, so will not show a
distinct, sudden end-point.

The following indicators can be used:

o Methyl Orange Alkali- Yellow Neutral- Orange Acid- Red
o Phenolphthalein Alkali- Red Neutral- Pink Acid- Colourless

A strong-acid, weak-base titration requires methyl orange.
A weak-acid, strong-base titration requires phenolphthalein.

Calculating Concentrations

If the concentration of either the acid or alkali is known, it is possible to work out the
concentration of the unknown one using titrations.

Demonstrate an understanding of how to minimize the sources of measurement
uncertainty in volumetric analysis and estimate the overall uncertainty in the
calculated result

xvii)
How to minimise sources of measurement uncertainty

Uncertainty is the amount of error your measurement might have.

It can be reduced by identifying potential errors, and then taking action to prevent them:

o Ensure that the small funnel is removed from the burette before titrating- otherwise, a small
drop of acid could fall into the burette during the titration, which would affect the results.

o When taking measurements (e.g. with volumetric flask or burette), read the mark at eye
level and ensure that measurements are taken from the bottom of the meniscus

o Use more precise equipment (e.g. a more precise burette or weigher)

o Using a larger volume of acid will reduce the % error of the burette

37 Group 2: Titrations
o Using a greater mass of solid will reduce the % error of the weighing scale

o Repeat the experiment until you get two concordant titres- this will improve both accuracy
and reliability

Estimating the overall uncertainty in the calculated result

To work out the total percentage uncertainty:

1) Find the percentage uncertainty of each piece of apparatus

Percentage uncertainty = (uncertainy / reading) x 100

The uncertainty on the burette is 0.1cm3

The scale on a standard burette has marks every 0.1cm3. You can tell which mark the level is
closest to, so any reading wont be more than 0.05cm3 out. In titrations, you take two readings
using the burette (initial and final titres), and each reading has an uncertainty of 0.05cm3, so the
total uncertainty of 0.1cm3.

The uncertainty on the weigher is 0.005g

The mass is given to the nearest 0.01g, the real mass could be up to 0.005g smaller or larger.

2) Add the individual percentage uncertainties together, which gives the percentage

uncertainty in the final result

3) Work out the total uncertainty in the final result

38 Group 7: Physical Properties

Periodic Table- Group VII

Recall the characteristic physical properties of the elements limited to the appearance
of solutions of the elements in water and hydrocarbon solvents

xviii)
Halogens: Introduction

o The term halogens refers to the elements of group 7.

o All halogens exist as non-polar diatomic molecules.

o Halogens have 7 electrons on their outer shell, so they tend to have an oxidation state of -1 in
compounds

o The halogens become less reactive down the group because the atomic radius increases, so
it is harder to for the nucleus to attract an electron.

o The halogens become darker in colour, less soluble in water and less volatile down the
group.

o The non-polar halogens are very soluble in hydrocarbon solvents which are also non-polar.

Halogen Formula Colour Physical Colour in Colour in Hexane
State Water

Chlorine Cl2 Yellow- Green Gas Pale Green Pale Green Solution
Solution

Bromine Br2 Red-Brown Liquid Orange- Orange- Brown Solution

Brown
Solution

Iodine I2 Grey Solid Brown Pink/ Violet Solution

Solution

Halogens: Physical Properties

Bromine gas is red.
Iodine gas is purple.
Fluorine is a pale yellow gas

39 Group 7: Oxidation Reactions

Describe and carry out the following chemical reactions of halogens:

xix)
i) Oxidation reactions with metal and non-metallic elements and ions such as iron (II) and
iron (III) ions in solution

xx)
Halogens have 7 electrons on their outer shell, so need to gain one electron to achieve a noble
gas structure.

To achieve this, the halogens can either bond covalently or form an ionic compound.

Halogens are strong oxidising agents- they achieve a full outer shell by oxidising another
species. Halogens need to attract electrons when they react, and the smaller the halogen, the
more strongly it will attract electrons. Therefore, the oxidising power decreases down the group
as the halogens get larger.

Reaction with Metals

Halogens oxidise metals and become reduced themselves to negative halide ions.

Halogen + Metal Metal Halide

Example: Reaction with Sodium

Chlorine is reduced from an oxidation state of 0 to -1.
Sodium is oxidised from an oxidation state of 0 to +1.

Example: Reaction with Iron

Iron can form Fe2+ or Fe3+ ions.

With the exception of iodine, iron burns in halogen vapour to give iron(III) halides.

40 Group 7: Oxidation Reactions

Oxidising power reduces down the group, so the reaction with chlorine is faster than the
reaction with bromine.

Iodine is less reactive and is a weaker oxidising agent, and only produces iron(II) iodide. This is
because the iodide ions in iron (III) iodide are strong enough reducing agents to reduce the Fe3+
ions to Fe2+ ions. Therefore iron (III) iodide is unstable, so is reduced to iron (II) iodide.

Bromide and chloride ions are weaker reducing agents, and arent powerful enough reducing
agents to reduce Fe2+ ions to Fe3+ ions, and therefore iron (III) bromide and iron (III) chloride are
stable.

Reaction with Non-Metals

Halogens also achieve a full outer shell through covalent bonding. Even though no transfer of
electrons takes place, oxidation and reduction because one element is gaining a greater share of
electrons than the other.

Example: Reaction with Hydrogen

H2 + Cl2 2HCl

Hydrogen is oxidised from an oxidation state of 0 to +1.
Chlorine is reduced from an oxidation state of 0 to -1.

Reaction with Ions

Chlorine and bromine are strong enough oxidising agents to oxidise green iron (II) ions to brown
iron (III) ions. In the process, the chlorine is reduced to chloride ions; the bromine to bromide
ions.

The solution changes colour from green
to orange-brown.
41 Group 7: Disproportionation Reactions

Iodine isn't a strong enough oxidising agent to oxidise iron (II) ions, so there is no reaction. In
fact the reverse reaction happens. Iron (III) ions are strong enough oxidising agents to oxidise
iodide ions to iodine:
ii) Disproportionation Reactions with cold and hot alkali, e.g. hot potassium
hydroxide with iodine to produce potassium iodate
xxi)
Example: Chlorine + Cold Sodium Hydroxide

Chlorine reacts with cold sodium hydroxide to form sodium chloride, sodium chlorate (I) and
water.

This reaction is a disproportionation reaction because chlorine is being both reduced and
oxidised at the same time- some atoms of chlorine are reduced and some are oxidised.

Example: Chlorine + Hot Sodium Hydroxide

Chlorine reacts with hot sodium hydroxide to form sodium chloride, sodium chlorate (V) and
water. This reaction is also a disproportionation reaction.

This reaction begins the same as the reaction with cold NaOH. However, the temperature is high
enough for sodium chlorate (I), NaClO, to decompose rapidly to form NaCl and sodium chlorate
(V), NaClO3.

42 Group 7: Disproportionation Reactions

In the first reaction, sodium chlorate (I) still decomposes, but at a very slow rate. The higher
temperature speeds up the decomposition, leading to the formation of new products.

Example: Iodine + Potassium Hydroxide

Other alkalis, such as potassium hydroxide, can be used.

Cold potassium hydroxide reacts with iodine to form potassium iodide, potassium iodate (I) and
water.

Warm potassium hydroxide reacts with iodine to form potassium iodide, potassium iodate (V)
and water.

The reactions involving bromine and iodine
These are essentially similar to the chlorine, the difference being the temperatures at which
things happen. The tendency to form the ion with the halogen in the +5 oxidation state
increases rapidly as you go down the Group.
Bromine and sodium hydroxide solution

With bromine, the formation of the sodium bromate (V) happens at a much lower temperature-
it occurs at room temperature. If you want to make a solution of sodium bromate (I), you have to
do the reaction at about 0C.

Iodine and sodium hydroxide solution

With iodine, you get sodium iodate (V) at all temperatures.

43 Group 7: Potassium Halides with Acid

Describe and carry out the following reactions:

xxii)
i) Potassium halides with concentrated sulphuric acid, halogens, and silver nitrate
solution

xxiii)
Potassium Halides + Concentrated Sulphuric Acid

The reactions of metal halides with concentrated sulphuric acid shows that there is a trend in the
strength of the halide ions as reducing agents: I- > Br- > Cl-

Potassium Chloride

Potassium chloride reacts with the acid to form hydrogen chloride gas and potassium
hydrogensulphate.

KCl(s) + H2SO4(l) KHSO4(s) + HCl(g)

However, the chloride ions (in HCl) are not strong enough to reduce the sulphuric acid, so the
reaction stops there.

o Steamy white fumes of hydrogen chloride are seen.

Potassium Bromide

Potassium bromide begins by reacting in the same way as potassium chloride, forming
hydrogen bromide gas and potassium hydrogensulphate.

KBr(s) + H2SO4(l) KHSO4(s) + HBr(g)

However, the bromide ions (in HBr) are stronger reducing agents than the chloride ions. The
bromide ions are able to reduce the sulphuric acid in a redox reaction.

HBr(g) + H2SO4(l) Br2(g) + SO2(g) + 2H2O(l)

o Brown fumes can be seen (the steamy white fumes of HCl are contaminated with the brown
colour of bromine vapour)

o Choking fumes of colourless sulphur dioxide can be observed.

44 Group 7: Potassium Halides with Acid
Explanation

The bromide ions in HBr are oxidised to bromine

The sulphuric acid is reduced to sulphur dioxide gas

You can combine these two to give you the full equation:

Potassium Iodide

Potassium iodide begins by reacting in the same way as potassium chloride and bromide,
forming hydrogen iodide gas and potassium hydrogensulphate.
KI(s) + H2SO4(l) KHSO4(s) + HI(g)

Like the bromide ions, iodide ions are able to reduce the sulphuric acid in a redox reaction.

HI(g) + H2SO4(l) I2(g) + SO2(g) + 2H2O(l)

However, iodide ions (in HI) are even stronger reducing agents than bromide ions. Iodide ions
are able to reduce the SO2 to H2S.

6HI(g) + SO2(g) H2S(g) + 3I2(g)

Therefore, the sulphuric acid is reduced to sulphur dioxide and then to hydrogen sulphide. The
overall equation for its reduction is:

o Purple fumes can be seen (the steamy white fumes of HCl are contaminated with purple
iodine vapour- the reaction is exothermic, so iodine vaporises)

o Dark grey solid iodine can be seen condensing around the top of the tube

o Hydrogen sulphide gives a smell of rotten eggs
45 Group 7: Potassium Halides with Halogens

Potassium Halides with Halogens

Potassium halides react with other halogens in displacement (redox) reactions.

The halogens are oxidising agents- with their strength decreasing down the group.

A halogen can oxidise (displace) other halide ions if the halide is below it in the group. In other
words, a halogen higher in the group can oxidise the ions of one lower down.

o You can use an organic solvent like hexane to make changes easier to see. For example, if
you add hexane to the brown iodine solution, a purple iodine-hexane layer will form above
the aqueous solution
N.B. All of the potassium halide solutions are colourless

\

Example: Chlorine Oxidising Iodide Ions
Example: Chlorine Oxidising Bromide Ions
Example: Bromine Oxidising Iodide Ions

Potassium Chloride Potassium Bromide Potassium Iodide
Solution Solution Solution

Chlorine Solution Brown (I2) solution
No reaction Orange (Br2) solution
Colourless formed
formed

Bromine Solution Brown (I2) solution
Orange No reaction No reaction
formed

Iodine Solution
No reaction No reaction No reaction
Brown

46 Group 7: Potassium Halides with Silver Nitrate

Potassium Halides with Silver Nitrate Solution

Silver nitrate solution can be used as a test to find out which halide ions are in an unknown
substance.

1. Dilute nitric acid is added to the unknown halide solution to prevent the precipitation of
any other silver salts

2. Silver nitrate solution is then added, and a precipitate of the insoluble silver halide is
formed:

Silver chloride White precipitate
Silver bromide Cream precipitate
Silver iodide Yellow precipitate

ii) Silver halides with sunlight and their solubilities in aqueous ammonia solution
xxiv)
Solubility in Aqueous Ammonia Solution

Each silver halide has a different solubility in ammonia solution.

Silver chloride dissolves in dilute ammonia solution to give a colourless solution.
Silver bromide dissolves in concentrated ammonia solution to give a colourless solution.
Silver iodide is insoluble in concentrated ammonia solution.

This test is often used as an extension from the coloured precipitates test described above.

Reaction in Sunlight

Silver halides decompose in sunlight, to form silver and the halogen.

Example: 2AgBr 2Ag + Br2
47 Group 7: Hydrogen Halides

The formation of silver means that the precipitates darken in colour.

This is used in film photography- the film contains silver bromide particles that turn to opaque
silver when they are exposed to light.

iii) Hydrogen halides with ammonia and with water (to produce acids)

xxv)
Hydrogen halides are formed from the reaction of a halogen with hydrogen.

Water

All three hydrogen halides are very soluble in water, and form acidic solutions. This is because
the H+(aq) and X- ions dissociate in water.

When we refer to the H+(aq) ion we are referring to the hydroxonium ion, H3O+.

Example: Hydrogen Chloride + Water

Hydrochloric acid is formed.

HBr and HI

Hydrogen bromide and iodide react in the same way with water, forming the acids hydrobromic
acid and hydroiodic acid respectively.

Ammonia

All three hydrogen halides react with ammonia (NH3) to form white fumes of the corresponding
ammonium halide salt.

Example: Hydrogen Chloride + Ammonia

NH3(g) + HCl(g) NH4Cl(s)

White fumes of ammonium chloride are seen.

48 Group 7: Predictions about Fluorine and Astatine

Make predictions about fluorine and astatine and their compounds based on the
trends in the physical and chemical properties of halogens.

xxvi)
Halide ions are reducing agents, and the strength of the reducing agent increases down the
group.

Why do halide ions become stronger reducing agents down the group?

When a halide ion reduces a species, it loses electrons. As you go down the group, the atomic
radius and the number of inner shielding shells increases, so the valence electrons are held less
strongly by the halide ions nucleus. Therefore, the halide ion is more easily oxidised, so is a
stronger reducing agent.

Therefore, fluoride ions will be weak reducing agents, whilst astatide ions will be strong . You
can use this prediction to make further predictions about their reactions:

For example, we can confidently predict that astatine will react with iron to form iron (II)
astatide. This is because astatide ions are strong enough reducing agents to reduce the Fe3+ ions
to Fe2+ ions.

In the same way, we can predict that fluorine will react with iron to form iron (III) fluoride. This is
because fluoride ions are not strong enough reducing agents to reduce the Fe3+ ions to Fe2+ ions.

Fluorine

o It is very volatile- it is a gas at room temperature

o It is a powerful oxidising agent
o Fluoride ions are weak reducing agents
o Fluorine is very electronegative
o It is very reactive
o It is very soluble in water
o It is relatively light in colour

Astatine

o It has a low volatility- It is a solid at room temperature

o It is a weak oxidising agent
o Astatide ions are strong reducing agents
o Astatine is the least electronegative halogen
o It is not very reactive (compared to other halogens)
o It is not very soluble in water
o It is relatively dark in colour
CHEMICAL EQUILIBRIA
49 Dynamic Equilibrium

Chemical Equilibria

Demonstrate an understanding that chemical equilibria are dynamic
xxvii)

A reversible reaction is a reaction which can be made to go in either direction depending on the
conditions.

A dynamic equilibrium occurs when the rate of the forward reaction is equal to the rate of the
backward reaction, so there is no net change in the amount of product or reactant- there is an
equilibrium.

The equilibrium is dynamic because both the forward reaction and backward reaction are
occurring.

A dynamic equilibrium only occurs when the reaction takes place in a closed system, so nothing
can be added or removed from the reaction mixture.

Deduce the qualitative effects of changes of temperature, pressure and concentration

on the position of the equilibrium, e.g. extraction of methane from methane hydrate

Changing the temperature, pressure or concentration of a reversible reaction will shift the
equilibrium. This means that you end up with different amounts of reactants and products at the
equilibrium.

o If the position of the equilibrium moves to the left, you get a higher yield of the
reactants.

o If the position of the equilibrium moves to the right, you get a higher yield of the
products.

If there is a change in the concentration, pressure or temperature, the equilibrium will
move to counteract the change.

For example, if you raise the temperature, the position of the equilibrium will shift to try to cool
down the reaction mixture.
CHEMICAL EQUILIBRIA
50 Shifting the Equilibrium

Similarly, if you raise the pressure or concentration, the position of the equilibrium will shift to
try to reduce it again.

N.B. Catalysts have no effect on the position of the equilibrium- they cannot change the yield,
but they mean the equilibrium is reached faster (because they speed up both the forward and
backward reaction).

Concentration

o If you increase the concentration of one of the reactants, the equilibrium shifts to get rid of
the extra reactant. It does this by making more of the product, so the equilibrium shifts to
the right.

o If you increase the concentration of one of the products, the equilibrium shifts to get rid of
the extra product. It does this by making the reverse reaction go faster, so the equilibrium
shifts to the left.

o Decreasing concentrations has the opposite effect

Pressure
Pressure is caused by gas molecules hitting the sides of their container. The more molecules you
have in the container, the higher the pressure will be. The system can reduce the pressure by
reacting in such a way as to produce fewer molecules, and vice versa.
o If you increase the pressure, the equilibrium shifts to the side with fewer gas molecules, so
the equilibrium shifts to right.

CHEMICAL EQUILIBRIA

o If you decrease the pressure, the equilibrium shifts to the side with more gas molecules, so
the equilibrium shifts to the left.
Temperature

o If you increase the temperature, the equilibrium shifts in the endothermic direction to
absorb the heat.

o If you decrease the temperature, the equilibrium shifts in the exothermic direction to replace
the heat.
CHEMICAL EQUILIBRIA
Industrial Manufacturing
o Manufacturing firms set conditions to shift the equilibrium in a way to maximise the yield of
a product

o Sometimes, even though low pressures or low temperatures might give a higher yield,
compromises are made to ensure that the rate of reaction is relatively high.

o So compromises sometimes have to be made between yield and rate of reaction.

SHAPES OF MOLECULES AND IONS
14 Shapes of Molecules and Ions
Demonstrate an understanding of the use of electron-pair repulsion theory to interpret

and predict the shapes of simple molecules and ions.
o
Electron-pair repulsion theory states that:

o The shape of a molecule or ion depends on the number of electron pairs around the central
atom

o Electron pairs repel each other, so the molecule will arrange itself so that the electron pairs
are as far apart as possible.

o Lone pairs repel more than bond pairs

Greatest repulsion lone pair - lone pair
lone pair - bond pair
Least repulsion bond pair - bond pair

Recall and explain the shapes of BeCl2, BCl3, CH4, NH3, NH4+, H2O, CO2, gaseous PCl5
and SF6 and the simple organic molecules listed in Units 1 and 2.

o

Two electron pairs around the central atom

Example: Beryllium Chloride (BeCl2)

Beryllium is in group 2, but the electronegativity difference between Be and Cl is not great
enough for ions to be formed, so a covalent compound is formed.

o Be has 2 outer electrons, and is forming two covalent bonds. So it has no lone pairs and two
bonding pairs.

Linear

Example: Carbon Dioxide (CO2)

The double bonds act in the same way as single bonds.

15
Shapes of Molecules and Ions

o Carbon has 4 outer electrons, and is forming two double bonds. So it has no lone pairs and
four bonding pairs

Linear

Three electron pairs around the central atom

Example: Boron Fluoride (BF3)

BF3 has the same shape as BCl3.

o Boron has 3 outer electrons, and is forming 3 covalent bonds. So it has no lone pairs and
three bonding pairs.

Trigonal Planar

Example: Sulphur Dioxide (SO2)

o Sulphur has 6 outer electrons, and is forming two double bonds. So it has one lone pair and
two bonding pairs.

There are 2 double bonds and 1 lone pair, which will try to get as
far apart as possible taking up a trigonal planar arrangement.
Because the lone pair isnt counted when you describe the
shape, SO2 is described as non-linear.
The double bonds are slightly stronger than single bonds, so

this cancels out the stronger nature of lone pairs.

16

Four electron pairs around the central atom

Example: Methane (CH4) Tetrahedral

o Carbon has 4 outer electrons, and is forming
four covalent bonds. So it has no lone pair and
four bonding pairs.

Example: Ammonia (NH3)

o Nitrogen has five outer electrons, and is forming three covalent
bonds. So it has one lone pair and three bonding pairs.

The electron pairs arrange themselves in a tetrahedral fashion as in
methane. But the lone pair isnt counted when you describe the shape,
so the shape is pyramidal.
However, remember that there is more repulsion between a lone pair

and a bonding pair than there is between two bonding pairs.
This forces the bonding pairs closer together- reducing the bond angle Pyramidal
from 109.5 to 107.

Example: Water (H2O)

o Oxygen has six outer electrons, and is forming two covalent bonds. So it
has two lone pairs and two bonding pairs.

Yet again, there are four electron pairs around the central atom, so the
arrangement is in a tetrahedral shape.

However, there are two lone pairs so the angle between the bonding pairs is
reduced from 109.5 to 104.5

Also, remember that the lone pairs are not considered when you name the
shape.

Non- linear
17

Example: Ammonium Ion (NH4+)

o N+ has four outer electrons, and is forming four covalent bonds. So it has no lone pairs and
four bonding pairs.

It therefore has the same shape as methane.

Tetrahedral

Example: Hydroxonium Ion (H3O-)

o O+ has four outer electrons, and is forming three covalent bonds. So it has one lone pair and
three bonding pairs.

It therefore has the same shape as ammonia.

Pyramidal


Five electron pairs around the central atom

Example: Phosphorus (V) fluoride

PF5 has the same shape as PCl5.

o Phosphorus has 5 outer electrons, and is forming five covalent bonds. So it has no lone pairs
and five bonding pairs.

Trigonal Bipyramidal

Example: Chlorine trifluoride (ClF3)

o Chlorine has seven outer electrons, and is forming three covalent bonds. So it has two lone
pairs and three bonding pairs.

The lone pairs repel strongly, forcing the bond pairs C-F and C-F closer together.

T-Shaped

19

Six electron pairs around the central atom

Example: Sulphur hexafluoride (SF6)

o Sulphur has six outer electrons, and forms six covalent bonds. So it has no lone pairs and six
bonding pairs.

Octahedral

Example: Xenon tetrafluoride (XeF4)

o Xenon has eight outer electrons, and is forming four covalent bonds. So it has two lone pairs
and four bonding pairs.

Square Planar

-
Example: ClF4

o Cl- has eight outer electrons, and is forming four covalent bonds. So it has two lone pairs and
four bonding pairs

Therefore it has the same shape as XeF4.


Alkanes and Alkenes

In an alkane, all the carbon atoms have a tetrahedral arrangement around them. The angle
between any two bonds/ pairs is 109.5, just as in methane.

In an alkene, all the carbon atoms have a trigonal planar arrangement around them.

However, because double bonds are slightly stronger than single bonds, the angle between a
double bond pair and a single bond pair is greater than the attraction between two single bond
pairs.


Apply the electron- pair repulsion theory to predict the shapes of molecules and ions
analogous to those discussed above.
o
To work out the shape of an ion, just deduct or add the electrons and then use the same
procedure as shown above.

Demonstrate an understanding of the terms bond length and bond angle and preduct
approximate bond angles in simple molecules and ions
o
Bond length is the average distance between the nuclei of two atoms in a covalent bond.

In a covalent bond, the two atoms are held together because both nuclei are attracted to the
same pair of electrons. In a longer bond, the shared electron pair is further from at least one of
the two nuclei, and so the attractions are weaker.
For example, in the hydrogen halides, as the bond gets longer, the distance of the electron pair
from the nucleus of the halogen atom is going to get much greater, and that weakens the bond.

Bond angle is the angle between bonds sharing a common atom

MECHANISMS
66 Types of Reaction

Classify reactions (including those in Unit 1) as addition, elimination, substitution,
oxidation, reduction, hydrolysis or polymerization

xxviii)

Addition Reactions

Addition reactions involve two or more substances reacting together to form a single product.

Example ethene + hydrogen bromide bromoethane

Example ethene + bromine dibromoethane

Both of these reactions are electrophilic addition reactions.

Elimination Reactions

Elimination reactions are organic reactions in which a small group of atoms (at least two) is
removed from a larger molecule, leaving a double bond in the larger molecule.

Example ethanol ethane + water

Substitution Reactions

Substitution reactions involve one species being replaced by another species.

Example bromoethane + water ethanol + hydrogen bromide

This reaction is a nucleophilic substitution reaction

MECHANISMS
67 Types of Reaction

Example methane + chlorine chloromethane + hydrogen chloride

CH4 + Cl2 CH3Cl + HCl

This reaction is a free radical substitution reaction

Oxidation and Reduction Reactions

An oxidation reaction is any reaction in which a species loses electrons (or gains oxygen or loses
hydrogen).

A reduction reaction is any reaction in which a species gains electrons (or loses oxygen or reacts
with hydrogen).

A redox reaction is any reaction where electrons are transferred between species- both
oxidation and reduction take place simultaneously.

Hydrolysis Reactions

A hydrolysis reaction is the splitting up of a molecule by reaction with water.

For example, bromoalkanes can be reacted with water or aqueous alkalis in hydrolysis reactions.
These hydrolysis reactions are also nucleophilic substitution reactions.

Polymerisation Reactions

A polymerisation reaction involves the joining together of small molecules (monomers) to form
a long chain (polymer).

There are two types of polymerisation: addition polymerisation and condensation
polymerisation.

MECHANISMS
68 Bond Fission

Demonstrate an understanding of the concept of a reaction mechanism and that bond
breaking can be homolytic or heterolytic and that the resulting species are either free
radicals, electrophiles or nucleophiles.
xxix)
A reaction mechanism represents what happens to the electrons as bonds break in reactants
and reform in products during a reaction.
Covalent bonds can break in two ways:

Homolytic fission occurs when the electrons in the covalent bond are split evenly between both
atoms (each atom gains one of the bonding electrons).

This leads to the formation of two (uncharged) free radicals- both atoms now have an unpaired
electron. Free radicals are very reactive due to the unpaired electon.

Example

Heterolytic fission occurs when the electrons in the covalent bonds both go to one atom.

This leads to a formation of a positively charged electrophile and a negatively charged
nucleophile.

Give definitions of the terms free radical, electrophile and nucleophile
xxx)
A free radical is an uncharged atom or molecule which has an unpaired valence electron.

The unpaired electron means that free radicals are very reactive and short-lived. They react with
anything- positive, negative or neutral. Therefore, in a free radical reaction you tend to end up
with a mixture of products.

An electrophile is a positively charged species that is attracted to an electron-rich region, where
it acts as an electron pair acceptor.

MECHANISMS
69 Reaction Mechanisms

Electrophiles are short of electrons and therefore are attracted to negative regions, where they
accept a pair of electrons to form a new covalent bond. The negative region that they are
attracted to could be a positive ion or the electron-rich area around a C=C double bond.

A nucleophile is a negatively charged species that is attracted to an electron-deficient region,
where it acts as an electron pair donor.

Nucleophiles donate a pair of electrons to a positive area to form a new covalent bond. The
positive region that they are attracted to could be a positive ion or the + atom in a polar bond
(e.g. the halogen in a polar C-X bond)

Demonstrate an understanding of why it is helpful to classify reagents
xxxi)

Classifying reagants enables you to predict which chemicals will react together and what
products you are likely to get. Therefore it is key to classify reagants to enable you to devise a
reaction mechanism.

Demonstrate an understanding of the link between bond polarity and the type of reaction
mechanism a compound will undergo
xxxii)
If a bond is non-polar, it will break homolytically.
If a bond is polar, it will break heterolytically.

Alkanes have non-polar bonds and have no bonds with high electron density, so they are
not attacked by electrophiles or nucleophiles. They are therefore only attacked by free
radicals- free radical substitution.

Alkenes have non-polar bonds, so they are not attacked by nucleophiles. However, alkenes
contain an accessible cloud of electron density in the bond, so it is attacked by
electrophiles such as Br2 and HBr- electrophilic addition.

The carbon-halogen bond in halogenoalkanes is polar. The + carbon atom can be attacked
by a nucleophiles- nucleophile substitution

The C=O bond is polar, because oxygen is more electronegative than carbon. Although the
C=O bond contains a bond, the + carbon atom is attacked by nucleophiles.

MECHANISMS
70 Ozone Layer
Demonstrate an understanding of how oxygen, O2, and ozone, O3, absorb UV radiation and
explain the part played by emission of oxides of nitrogen, from aircrafts, in the depletion of
the ozone layer, including the free radical mechanism for the reaction and the fact that
oxides act as catalysts.
xxxiii)
o The ozone ozone layer contains most of the atmospheres ozone molecules, O3.

o The ozone layer absorbs UV light, which can damage DNA in cells and cause skin cancer.

Ozone, O3, is constantly being formed and broken up again in the high atmosphere by the action
of ultraviolet light.
Forming ozone
Oxygen molecules absorb ultraviolet light and break up into free radicals.

N.B. oxygen molecules have a double bond, so the free radicals formed have two unpaired
electrons.

These free radicals are very reactive, and they can combine with other oxygen molecules to
form ozone.

Breaking up ozone

UV radiation can also reverse the formation of ozone.

Ozone can be split up again into ordinary oxygen and an oxygen radical by absorbing ultraviolet
light.

So, the ozone layer is continuously being destroyed and replaced as UV light hits the molecules.
An equilibrium is set up, so the concentrations stay fairly constant.

MECHANISMS
71 Ozone Layer and CFCs

Chlorofluorocarbons (CFCs)

Chlorofluorocarbons (CFCs) used to be used extensively in aerosols and as refrigerants.
However, their slow breakdown in the atmosphere produces chlorine free radicals, which
catalyse the destruction of the ozone:
1) Chlorine free radicals, Cl, are formed when CFC s are broken down by UV light. The C-Cl
bond is broken.

e.g. CCl3 CCl2F + Cl
2) The Cl radicals react with ozone, to form an intermediate ClO, and an oxygen
molecule.

3) The chlorine radical is then regenerated by a second reaction, in which the ClO radical
hits an ozone molecule
The chlorine radical is not used up in the reaction, so it acts as a catalyst.

So the overall reaction is: 2O3 3O2 Catalyst- Cl

Alternative Second Reaction

The ClO radical can hit an oxygen radical instead of an ozone molecule, to give a
different second reaction:

Chlorine is still regenerated, so it still acts as a catalyst.

MECHANISMS
72 Ozone Layer

Nitrogen Oxides

Nitrogen oxides, produced by car and aircraft engines, form nitric oxide free radicals, NO,
which also destroy the ozone layer.

NO + O3 O2 + NO2
NO2 + O3 2O2 + NO

NO radicals are regenerated in the same way as chlorine radicals, so they are catalysts.

Discuss and explain, including the mechanisms for the reactions, the science communitys
reasons for recommending that CFCs are no longer used due to their damaging effect on
the ozone layer.
xxxiv)
Chlorofluorocarbons are organic compounds (alkanes) in which all of the hydrogen atoms have
been replaced by atoms of chlorine and fluorine- they are halogenoalkanes.

o CFCs are unreactive, non-flammable and non-toxic.

o They were used in fire extinguishers, as propellants in aerosols, and as refrigerants.

o However, since an international treaty in 1989, the use of CFCs has been phased out. There
were a few permitted uses, such as in medical inhalers

o Since this treaty, CFCs have gradually been replaced by less damaging alternatives

o High levels of CFCs are still in the atmosphere, but there has been a decrease in the rate of
ozone depletion.

Safe Alternatives to CFCs

Hydrochlorofluorocarbons (HCFCs) are a group of organic compounds containing hydrogen,
chlorine, fluorine and carbon.

They are not found naturally, but HCFC production has increased to replace CFCs. HCFCs are
broken down in the lowest part of the atmosphere, so pose a much smaller risk to the ozone
layer. However, HCFCs are very strong greenhouse gases, so they arent perfect alternatives.

Butane is also an alternative to CFCs, but it is flammable. HCFCs and butane are now used as
propellants in aerosol containers instead of CFCs.
ORGANIC CHEMISTRY: ALCOHOLS AND HALOGENOALKANES
53 Alcohols: Primary, Secondary, Tertiary

Alcohols
Give examples of, and recognise, molecules that contain the alcohol functional group

Alcohols are organic molecules which contain an alkyl group and an OH functional group.

Alcohols have the general formula CnH2n+1OH

For example:

Demonstrate an understanding of the nomenclature and structural, displayed and

skeletal formulae of alcohols, and classify them as primary, secondary or tertiary

Alcohols can be primary, secondary or tertiary depending on the position of the OH group.

A primary alcohol is attached to a carbon atom that is attached to two hydrogen atoms and one
alkyl group.

Primary Alcohol Methanol Pentan-1-ol

A secondary alcohol is attached to a carbon atom that is attached to one hydrogen atom and
two alkyl groups.

Secondary Alcohol Butan-2-ol Propan-2-ol

54 Substitution Reactions

A tertiary alcohol is attached to a carbon atom that is attached to no hydrogen atoms and three
alkyl groups.

Tertiary Alcohol 2-methylpropan-2-ol 2-methylpentan-2-ol

Describe the following chemistry of alcohols:

Substitution reactions to form halogenoalkanes, including reaction with PCl5 and its use
as a qualitative test for the presence of the OH group. In addition, understand why a
metal halide and concentrated sulphuric acid should not be used when making a
bromoalkane or an iodoalkane.

The OH can be swapped for a halogen to make a halogenoalkane:

Reacting Alcohols with Hydrogen Halides

Making Chloroalkanes

Tertiary Alcohol + HCl

A tertiary alcohol reacts if it is shaken with concentrated hydrochloric acid at room temperature.
A tertiary halogenoalkane is formed

Tertiary alcohols are more reactive than primary or secondary alcohols. Primary and secondary
alcohols react too slowly to be made in this way.


Making Bromoalkanes or Iodoalkanes

Tertiary Alcohol + HBr or HI

Bromoalkanes and iodoalkanes are more difficult to make than chloroalkanes. HBr and HI are
not easily available. They can be made in situ using concentrated H2SO4 and a metal halide
(e.g. KBr and KI). However, HBr and HI are both oxidised by the H2SO4 (to Br2 and I2), so you
end up with by-products (Br2 and I2) and a reduced yield of halogenoalkane.

Therefore, sulphuric acid should not be used to make bromoalkanes and iodoalkanes.

Instead, phosphoric (V) acid H3PO4 should be used to make HBr or HI in situ (see group 7 topic).

Reacting Alcohols with Phosphorus (III) Halides

Making Chloroalkanes

Alcohol + PCl3
Alcohols react with liquid phosphorus(III) chloride (also called phosphorus trichloride) to make
chloroalkanes.

Making Bromoalkanes and Iodoalkanes

Alcohol + PBr3 or PI3

The reaction is the same as above, except that phosphorus (III) bromide or phosphorus (III)
iodide are made in situ by refluxing the alcohol with red phosphorus and either bromine or
iodine.

The phosphorus first reacts with the bromine or iodine to give the phosphorus(III) halide.


These then react with the alcohol to give the corresponding halogenoalkane which can be
distilled off.

Reacting Alcohols with Phosphorus (V) Chloride

Alcohol + PCl5

Qualitative Test for OH Group

The reaction with PCl5 can be used as a qualitative test for the hydroxyl group (-OH)

o Add solid phosphorus (V) chloride to the unknown liquid

o If OH is present, steamy white fumes of HCl gas will form

o The HCl dissolves in water to form chloride ions, so you can use silver nitrate to test for the
presence of chloride ions

o The steamy white fumes of HCl also turn moist blue litmus paper red

N.B. This is a test for the OH group, not just alcohols, so the OH group in carboxylic acids and
water would give the same reaction.

Oxidation using potassium dichromate (VI) in dilute sulphuric acid on primary alcohols to
produce aldehydes and carboxylic acids and on secondary alcohols to produce ketones

Oxidising Agent
The oxidising agent used in these reactions is a solution of potassium dichromate(VI) acidified
with dilute sulphuric acid. If oxidation occurs, the orange solution containing the dichromate(VI)
ions is reduced to a green solution containing chromium(III) ions.

57 Oxidation Reactions

The electron-half-equation for this reaction is:

Primary Alcohols

o Primary alcohols are oxidised to aldehydes and then to carboxylic acids

Ionic Full Equation

Standard Equations This means oxygen from an oxidising agent

Stage 1

Stage 2

Overall

Displayed Equations

Step 1

Ethanol Ethanal + Water

N.B. This is not a mechanism for the reaction- the blue circle just helps to show which bonds are being broken

Step 2

Ethanal Ethanoic Acid

Secondary Alcohols

o Secondary alcohols are oxidised to produce ketones

Displayed Equation

Tertiary Alcohols

o Tertiary alcohols are not readily oxidised by potassium (VI) dichromate

If you look at what is happening with primary and secondary alcohols, you will see that the
oxidising agent is removing the hydrogen from the -OH group, and a hydrogen from the carbon
atom attached to the -OH. Tertiary alcohols don't have a hydrogen atom attached to that
carbon.
You need to be able to remove those two particular hydrogen atoms in order to set up the
carbon-oxygen double bond


Testing for Different Types of Alcohol

You can use the above reactions to test for the different types of alcohol:

o Add a few drops of the alcohol to a test tube containing potassium dichromate(VI) solution
acidified with dilute sulphuric acid.
o Warm the tube in a hot water bath

Picking out the tertiary alcohol
In the case of a primary or secondary alcohol, the orange solution turns green. With a tertiary
alcohol there is no colour change.
After heating:

Distinguishing between the primary and secondary alcohols
You need to produce enough of the aldehyde (from oxidation of a primary alcohol) or ketone
(from a secondary alcohol) to be able to test them:

Test 1: Warm the sample with blue Benedicts solution

Result: Aldehyde = Brick-Red Precipitate of Cu2O
Ketone = No effect

Test 2: Warm the sample with colourless Tollens reagent

Result: Aldehyde = Grey precipitate of silver produced
Ketone = No effect

60 Preparation of an Organic Liquid

Demonstrate an understanding of, and practice, the preparation of an organic liquid
(reflux and distillation), e.g. oxidation of alcohols

Preparing a Ketone

Example: Preparing butanone from butan-2-ol
Apparatus: Distillation (see below)

Compound Boiling Temperature (degrees Celsius)
Butanone 80
Butan-2-ol 99.5

Gently heat butan-2-ol in acidified potassium dichromate solution, ensuring that the
temperature on the thermometer is kept below 95 degrees.

The butanone will be produced and will distill off and will be collected as the distillate in the
conical flask.

N.B. It is advisable to use only a controlled amount of oxidising agent


Preparing an Aldehyde

Example: Preparing Ethanal from Ethanol
Apparatus: Distillation (see above)

Compound Boiling Temperature (degrees Celsius)
Ethanol 78
Ethanal 21
Ethanoic Acid 118

Gently heat ethanol with potassium dichromate (VI) solution and sulphuric acid in a test tube.

The ethanol will be oxidized to ethanol, and providing the temperature on the thermomemter is
above 21 degrees and below 70 degrees, the distillate is ethanol.

N.B. The ethanol vapourises and is removed from the mixture before it can be oxidized further
to ethanoic acid.

Preparing a Carboxylic Acid

Example: Preparing Ethanoic Acid from Ethanol
Apparatus: Reflux Apparatus (see below)

If you used the apparatus for distillation, as described above, the
aldehyde produced would evaporate off before it had the chance to
react.

You can get around this by using a reflux condenser- a condenser that
fits vertically to the reaction flask. Heating under reflux means you can
increase the temperature of an organic reaction without losing volatile
substances. Any vaporised compounds are cooled, condense and drip
back into the reaction mixture.

Heat the ethanol in excess acidified potassium (VI) dichromate under
reflux conditions.

The vertical reflux (Liebig) condenser prevents ethanol, ethanol and
ethanoic acid vapours from escaping. After the flask has been heated
for some time, all of the ethanol will be converted into ethanoic acid.
Distillation apparatus can then be used to distill off the ethanoic acid.

Exam Tip: When describing these experiments, mention that anti-bumping
granules will be used. These granules simply make the boiling smoother.
62 Halogenoalkanes

Halogenoalkanes

Demonstrate an understanding of the nomenclature and corresponding structural,
displayed and skeletal formulae for halogenoalkanes, including the distinction between
primary, secondary and tertiary structures

A halogenoalkane is just an alkane with at least one hydrogen atom replaced by a halogen
atom. Halogenoalkanes are often also called haloalkanes or alkyl halides.

General Formula = CnH2n+1OH

For example:

Types of Halogenoalkanes

A primary haloakane is a haloalkane in which the halogen is attached to a carbon atom that is
attached to two hydrogen atoms and one alkyl group.

A secondary haloalkane is a haloalkane in which the halogen is attached to a carbon atom that
is attached to one hydrogen atom and two alkyl groups.

A tertiary haloalkane is a haloalkane in which the halogen is attached to a carbon atom that is
attached to no hydrogen atoms and three alkyl groups.

63 Halogenoalkanes

Interpret given data and observations comparing the reactions and reactivity of primary,
secondary and tertiary compounds

If you react a halogenoalkane with water, it reacts to form an alcohol, an H+ ion and a Hal- ion
(halide ion).

If you add silver nitrate solution in the mixture too, the silver ions will react with the halide ions
as soon as they form, giving a silver halide precipitate

Setting up the Experiment

o Set up three different test tubes, each containing a different halogenoalkane (one
primary, one secondary, one tertiary), ethanol (as a solvent) and silver nitrate solution
(this contains the water).

o Measure how long it takes for the silver halide precipitate to form

Silver Chloride = White precipitate
Silver Bromide = Cream precipitate
Silver Iodide = Yellow precipitate

o Tertiary alcohols are the most reactive, so the precipitate should form very quickly
o Secondary alcohols are less reactive, so the precipitate should form relatively quickly
o Primary alcohols are the least reactive, so the precipitate should form slowly.

Comparing Reactivities of Different Haloalkanes

The pattern in strengths of the four carbon-
halogen bonds are:

64 Halogenoalkanes

In order for anything to react with the halogenoalkanes, the carbon-halogen bond has got to be
broken.

The C-Cl bond is more polarised than the C-Br and C-I bonds, because chlorine has the greatest
electronegativity of the three halogens.

Therefore one would expect that the chloroalkanes would be hydrolysed faster than the bromo-
or iodoalkanes. In fact, the opposite is true. This is because the C-Cl bond is the strongest, and
therefore chloroalkanes are the least reactive out of the three.

The trend therefore shows that the bond strength is more important than the bond polarity in
determining the rate of reaction. This also shows that fluoroalkanes are very unreactive due to
the strength of the C-F bonds.

Carry out the preparation of a halogenoalkane from an alcohol

Chloroalkanes

To make chloroalkanes you can simply add an alchohol to either concentrated hydrochloric acid
or PCl3.

Bromoalkanes

Reflux Conditions

To make bromoalkanes, HBr has to be made in situ under reflux conditions.

Phosphoric acid should be added to a micture of the alcohol, a metal bromide (e.g. NaBr), and
water, using a dropping funnel.

The flask containing the alcohol, metal bromide and water should be put into a beaker of cold
water, because the reaction is very exothermic. The phosphoric acid should also be added very
slowly.

The dropping funnel is then removed, and the apparatus is refluxed on a water bath for 30
minutes.

65 Halogenoalkanes

Distillation

Once the halogenoalkane has been produced, it can be distilled from the reaction mixture. The
distillate collected will have two layers- a lower organic layer and an upper aqueous layer.

Bromoalkanes have a low boiling point but are denser than water and almost insoluble in it. To
prevent the bromoalkane from evaporating, it is often collected under water in a flask
surrounded by ice. Sometimes it is simply collected in a tube surrounded by ice without any
water.
The reaction flask is heated gently until no more droplets of bromoalkane collect.

There is likely to be impurities in both the organic layer (e.g. un reacted alcohol, bromine) and in
the aqueous layer (e.g. unreacted alcohol, hydrogen bromide, water).


The aqueous layer is then
discarded. The organic layer
can be purified and finally
redistilled to produce a pure
sample of the bromoalkane.

Discuss the uses of halogenoalkanes, e.g. as fire retardants and modern refrigerants

Uses of Halogenoalkanes

Making polymers
Halogenoalkanes are used to produce many useful polymers, such as poly(chloroethane)

Refrigerants
Some halogenoalkanes are used as refrigerants (e.g. to cool the air in a fridge or air conditioning
system). They are suitable for this because they are easily compressed and they do not corrode
pipework.

Fire retardants
Some non-flammabe halogenoalkanes can be used as fire retardants in fire extinguishers or in
computers. Halogenoalkane extinguishrs contain liquid haloalkanes, which vaporise when
sprayed onto flames, forming a heavy gas which does not burn and which forms a layer over the
flames, excluding oxygen.

Chlorofluoroalkanes (CFCs) are halogenoalkanes in which all the hydrogen atoms have been
replaced by chlorine and fluorine atoms. They are generally unreactive and non-toxic, so tend to
be used as refrigerants and solvents.

However, CFCs were found to be damaging to the ozone layer, and therefore were banned. The
advantages of CFCs could not outweigh the environmental problems they were causing.
KINETICS
73 Collision Theory
and

Kinetics

Recall the factors that influence the rate of chemical reaction, including concentration,
temperature, pressure, surface area and catalysts

Rate of reaction describes the speed with which reactants are used up and products are formed.
Rate of reaction is affected by several factors:

o Concentration
o Temperature
o Pressure
o Surface Area
o Use of Catalysts
Explain the changes in rate based on a qualitative understanding of collision theory

Collision Theory

Collision Theory states that for a reaction to take place between particles, they have to:

o Collide with at least a certain amount of kinetic energy (activation energy)
o Collide in the right direction- the particles need to be facing each other the right way
The activation energy is the minimum amount of kinetic energy required for a collision between
two particles to be successful and lead to a reaction.
The rate of reaction is dependent on the number of successful collision per unit time.

Concentration + Pressure

concentrations and
At high More collisions More successful
pressures, there are more particles per second collisions per second
per unit volume

Surface Area of Solids

Higher surface areas mean there are
more particles of the solid reactant More collisions More successful
per second collisions per second
exposed to particles of the other
reactant
KINETICS
74
Factors Affecting Rate of Reaction

Temperature

At higher temperatures, Particles move More collisions More successful
particles have more around faster per second collisions per second
kinetic energy on average

A greater proportion of
More successful
collisions have energy greater
collisions per second
than the activation energy

Use of Catalyst

The catalyst provides an A greater proportion of
More successful
alternative pathway with a collisions have energy greater
collisions per second
lower activation than the activation energy

Use, in a qualitative way, the Maxwell-Boltzmann model of the distribution of molecular energies
to relate changes of concentration and temperature to the alteration in the rate of reaction

Particles in a reaction mixture do not all have the same kinetic energy- some particles move very
slowly with little energy, whilst other particles move very rapidly with lots of energy. The
Maxwell-Boltzmann distribution illustrates this:

N.B. The x-axis acts as an asymptote for the curve

Different temperatures

At higher temperatures, the peak of the graph is lower and moves to the right. But the area
under each curve is the same at both temperatures because the number of particles remains
constant.

The graph shows that at higher temperatures, there are more particles with energy greater than
the activation energy, shown by the larger shaded region under the curve (but after the
activation energy).
KINETICS
75 Factors Affecting Rate of Reaction

In exams, there might be questions
asking you to label on the activation
energy. Ensure that you draw the
vertical line to the right of both peaks.

Different Concentrations

For higher concentrations, the curve is stretched:

KINETICS

Demonstrate an understanding of the concept of activation energy and its qualitative
relationship to the effect of temperature changes on the rate of reaction

As temperature rises, the average kinetic energy of particles increases, so particles collide with
more energy, and hence a greater proportion of collisions are successful.

Demonstrate an understanding of the role of catalysts in providing alternative reaction

routes of lower activation energy and draw the reaction profile of a catalysed reaction
including the energy level of the intermediate formed with the catalyst

Reaction Profile

Catalysts: Intermediates

o A homogenous catalyst is in the same state of the reactants

o When homogenous a catalyst is used, it works by forming an intermediate

o One of the reactants combines with the catalyst in an initial step to form an intermediate
reactant-catalyst complex
KINETICS

o The complex then reacts with another reactant to give products (and reform the catalyst so
that it can catalyse another collision)

o The reaction profile of a catalysed reaction therefore has two humps- one for each step.

o The activation energy required to form the intermediates (and to form the products from the
intermediates), is lower than the energy needed to make the products directly from
reactants.

The instability of the intermediate is shown by the fact that there are small activation barriers to
its conversion either into the products or back into the reactants again.
Notice that the barrier on the product side of the intermediate is lower than that on the reactant
side. That means that there is a greater chance of it finding the extra bit of energy to convert
into products. It would need a greater amount of energy to convert back to the reactants again.

KINETICS
78 Carrying out Experiments

Carry out simple experiments to demonstrate the factors that influence the rate of chemical
reactions, e.g. the decomposition of hydrogen peroxide

The rate of reaction can be determined in several ways:

o The rate of loss of reactants (e.g. starch spotting tile experiment)
o The rate of formation of products (e.g. measure bubbles formed, collect gas in gas syringe,
measure the decrease in mass of reaction mixture as product is lost)

Decomposition of hydrogen peroxide

o Temperature can be varied using a thermostatic water bath

o pH can be varied using a buffer solution.

o Concentrations can be varied during preparation.

MASS SPECTRA AND IR SPECTROSCOPY
79 Mass Spectrometry

Mass Spectra and IR Spectroscopy
Interpret fragment ion peaks in the mass spectra of simple organic compounds, eg the
difference between propanal and propanone

The formation of molecular ions
When the vaporised organic sample passes into the mass spectrometer, it is bombarded by a
stream of electrons. These electrons repel an electron out of the organic molecule, causing it to
form a positive ion. This ion is called a molecular ion.
The molecular ion is often given the symbol M+ or - the dot in this second version represents
the fact that somewhere in the ion there will be a single unpaired electron. That's one half of
what was originally a pair of electrons - the other half is the electron which was removed in the
ionisation process.

Fragmentation
The molecular ions are energetically unstable, and some of them will break up into smaller
pieces. The simplest case is that a molecular ion breaks into two parts - one of which is another
positive ion, and the other is an uncharged free radical.

The uncharged free radical won't produce a line on the mass spectrum. Only charged particles
will be accelerated, deflected and detected by the mass spectrometer. These uncharged free
radicals will get removed by the vacuum pump.
The ion, X+, will travel through the mass spectrometer just like any other positive ion - and will
produce a line on the spectrum.
Many different fragmentations of the original molecular ion can occur, so you can get a wide
variety of different line on the mass spectrum.
It is important to realise that the pattern of lines in the mass spectrum of an organic compound
tells you something quite different from the pattern of lines in the mass spectrum of an element.
With an element, each line represents a different isotope of that element. With a compound,
each line represents a different fragment produced when the molecular ion breaks up.

80
Mass Spectroscopy

Example: the mass spectrum of pentane
What causes the line at m/z = 57?
C4H9+
C4H9+ would be [CH3CH2CH2CH2]+, and this would be produced by the following fragmentation:
C3H7+
C2H5+
Molecular Masses of Common Fragments
CH3 = 15 C3H7 = 43
C2H5 = 29 OH = 17
81 Mass Spectroscopy
Propanal and Propanone
Even if two compounds contain the same atoms, you can still tell them apart with mass
spectrometry because they do not produce exactly the same set of fragments.
For example, propanal will have a C2H5 fragment but propanone will not.

82 Infra Red Spectroscopy
Use infrared spectra, or data from infrared spectra, to deduce functional groups present in
organic compounds and predict infrared absorptions, given wavenumber data, due to
familiar functional groups. This will be limited to:
i C-H stretching absorptions in alkanes, alkenes and aldehydes
ii O-H stretching absorption in alcohols and carboxylic acids
iii N-H stretching absorption in amines
iv C=O stretching absorption in aldehydes and ketones
v C-X stretching absorption in halogenoalkanes
vi as an analytical tool to show the change in functional groups during the oxidation of an alcohol
to a carbonyl
Bond Functional Group Frequency Type of Absorption

C-H Alkanes 2850 3000 Strong, sharp
C-H Alkenes 3000 3100 Medium, sharp
C-H Aldehydes 2800 2900 Weak, sharp
O-H Alcohols 3200 3600 Medium, broad
O-H Carboxylic Acids 2500 3300 Weak, very broad
NH Amines 3300 3500 Medium, sharp
C=O Aldehydes, Ketones, Carboxylic Acids 1690 1750 Strong, sharp
C- X Haloalkanes 500 1400 Strong, sharp
Fingerprint Region
The region to the right-hand side of the diagram (from about 1500 to 500 cm-1) usually contains
a very complicated series of absorptions. This region is called the fingerprint region, and care
must be taken when analyzing peaks in this region.

Examples of IR Spectrums
This is NOT a carboxylic acid. Although there is both a C=O stretch and an OH stretch, the OH is
indicative of an alcohol, not a carboxylic acid. The acid OH stretch is typically centered around
3000 cm-1, and overlaps with the C-H stretch.

Ethanoic Acid
The possible absorption due to the C-O single bond is queried because it lies in the fingerprint
region. You couldn't be sure that this trough wasn't caused by something else.
Ethanol
The O-H bond in an alcohol absorbs at a higher wavenumber than it does in an acid - somewhere
between 3230 - 3550 cm-1. In fact this absorption would be at a higher number still if the alcohol
isn't hydrogen bonded - for example, in the gas state. All the infra-red spectra on this page are
from liquids - so that possibility will never apply.
Notice the absorption due to the C-H bonds just under 3000 cm-1
Ethyl ethanoate
This time the O-H

absorption is
missing completely.
Don't confuse it
with the C-H trough
fractionally less
than 3000 cm-1. The
presence of the
C=O double bond is
seen at about 1740
cm-1.

Propanone
There is no trough due to

the O-H bond, and there is
a marked absorption at
about 1700 cm-1 due to the
C=O.
2-hydroxypropanoic acid
This is interesting because it

contains two different sorts
of O-H bond - the one in the
acid and the simple
"alcohol" type in the chain
attached to the -COOH
group.
The O-H bond in the acid

group absorbs between
2500 and 3300, the one in
the chain between 3230 and
3550 cm-1. Taken together,
that gives this immense
trough covering the whole
range from 2500 to 3550
cm-1. Lost in that trough as
well will be absorptions due
to the C-H bonds.
Notice also the presence of the strong C=O absorption at about 1730 cm-1.

1-aminobutane
Primary amines contain the -NH2 group, and so have N-H bonds. These absorb somewhere
between 3100 and 3500 cm-1. That double trough (typical of primary amines) can be seen clearly
on the spectrum to the left of the C-H absorptions.

Match each compound to the correct IR spectrum, and give a brief reason for your selection.

Match the following compounds with their IR spectrum. Give your reasoning and evidence.

Based on the IR spectrum and formula given, what functional groups may be present in this
molecule? Provide the name of the functional group and the peak(s) that correspond to that
functional group.

An alcohol is present, as evidenced by the large, broad peak centered around 3400 cm-1. (Also,
the large peak around 1150 cm-1 confirms a C-O single bond).
An alkene is also present. Two peaks lead to this conclusion: the sharp peak around 3100 cm-1,
which is caused by the C-H bond in an alkene, and the small, sharp peak around 1670 cm-1,
which is the C=C bond stretching frequency.


Oxidation of Alcohols

IR spectrums can be used to show the change in functional group during oxuidation of an
alcohol. The spectrum will change from having an OH alcohol peak to:

o An OH carboxylic acid peak and a C=O peak if a carboxylic acid is formed
o A CH aldehyde peak and a C=O peak if an aldehyde is formed
o A C=O peak if a ketone is formed.

Demonstrate an understanding that only molecules which change their polarity as they
vibrate can absorb infrared radiation

How does IR radiation interact with molecules?

IR radiation is absorbed by certain molecules. The extra energy makes the bonds in the molecule
vibrate more, by either stretching or bending.

What property must a molecule possess if it is to absorb infra-red radiation?

Not all molecules absorb IR radiation- only molecules that change their polarity as they vibrate
will absorb IR radiation. Therefore, there has to be partial charges within the molecule for it to
vibrate. Hence, only molecules made of atoms of different elements can absorb IR radiation.

Molecules such as O2 or Cl2 do not absorb IR radiation because they are made of the same type
of atom, and hence there are no partial charges- the bond is perfectly covalent, and there is no
polarity at all.

Why do different molecules have different IR spectrums?
Different molecules absorb different frequencies.
o The bonds in molecules have certain fixed energy levels, called quantized levels. The energy of
a bond can only move from one discrete level to the next.

o This means that only frequencies of radiation corresponding to this amount of energy
(between the two levels) is absorbed.

o For stronger bonds, a higher frequency of IR energy is required to make the bonds vibrate.

How is an IR spectrum produced?
An IR spectrum is produced by passing a range of IR frequencies through a sample in an IR

spectrometer. The resulting spectrum is recorded on a chart recorder.
The spectrum consists of a series od troughs at frequencies where the sample absorbs radiation.
The frequency of IR absorption is measured in wavenumbers, and is shown on the x-axis of an IR

spectrum.
The percentage transmission, which is the percentage of radiation that passes through the
sample, is shown on the y-axis.

Demonstrate an understanding that H2O, CO2, CH4 and NO molecules absorb IR radiation
and are greenhouse gases, whilst O2 and N2 are not.

Gases such as water vapour, carbon dioxide, nitrogen oxide and methane all have molecules
composed of different atoms so they all have polarity and can therefore absorb infrared
radiation- they are therefore all greenhouse gases.

Gases such as oxygen and nitrogen are diatomic molecules with no polarity (because they are
made up of the same atoms). Hence, they do not absorb IR radiation and are not greenhouse
gases.

GREEN CHEMISTRY
92
Changes to the Industry

Green Chemistry

Demonstrate an understanding that the processes in the chemical industry are being
reinvented to make them more sustainable (greener)

Modern factories are designed to be greener- to use fewer finite resources, less energy and
produce less pollution.

The factories aim to be sustainable, which means that they carry out their operations without
inhibiting life for future generations. This means not using up all of the Earths resources, and
not releasing lots of damaging chemicals into the environment.

i. Changing to renewable resources

Many chemicals are traditionally made from non-renewable raw materials (e.g. metal
ores, fossil fuels)

However, chemists have developed alternative ways to make chemicals involving

renewable raw materials. For example, wheat can be used to produce bio oil.
Renewable energy sources can also be used to prevent rapid exhaustion of fossil fuels. For
example, solar power and wind power can be used.

ii. Finding alternatives to very hazardous chemicals
Many chemicals are harmful to either humans, animals, the environment or all three. Alternative
chemicals or alternative methods have been developed to reduce use of such chemicals. For
example:

Lead is commonly used in petrol and in paint. However, alternatives are now available,
such as unleaded petrol and lead-free paints.

The use of CFCs as refrigerants is gradually being phased out in favour of

hydrofluorocarbons, which do not destroy the ozone layer

Many chemical reactions have been redesigned to prevent use of hzourdous chemicals.
For example, instead of using harmful organic solvents, some reactions can be carried
out with one of the reactants acting as a solvent.

GREEN CHEMISTRY
93 Changes to the Industry
iii. Discovering catalysts for reactions with higher atom economies, for example the
development of methods used to produce ethanoic acid based on catalysts of cobalt,
rhodium and iridium
A high atom economy reduces waste- it makes the best use of resources.

Catalysts speed up chemical reactions, which means lower temperatures and pressures can
be used, so less energy is used (the reaction is more energy efficient).

For example, the production of ethanoic acid has developed considerably:

Originally, ethanoic acid was produced by the oxidation of butane using a cobalt catalyst.
This reaction needed a high temperature of 300 degrees and a high pressure of 700 atm.
Also, the atom economy of this reaction was very low- 35%.

A new method soon developed, which involved using methanol and carbon monoxide and a
cobalt iodide catalyst. The reaction had an atom economy of 100%.

The method developed even further. Rhodium iodide was used as a catalyst, and with this
new catalyst, less extreme conditions were required.

A newer catalyst has also developed. Iridium iodide is now used, and the reaction produces
fewer by-products and therefore uses resources more efficiently.

iv. Making more efficient use of energy, e.g. the use of microwave energy to heat
reactions in the pharmaceutical industry
Energy efficiency can be improved in several ways. For example, the pharmaceutical uses
microwave radiation to heat the reacting mixture. This method is more efficient and
controllable than the conventional heating system, which involved heating a reaction vessel
which then passed on the heat to the reaction mixture.

v. Reducing waste and preventing pollution of the environment
Some solid waste can be recycled, which is very beneficial. For example, recycling glass reduces
the use of natural resources (to make glass), whilst the process of recycling glass uses less
energy than the process of making new glass. Some solid waste is also biodegradable.

Other waste goes into landfill sites or is incinerated. However, both of these produce harmful
gases which cause pollution. To prevent this, households are encouraged to reduce waste, whilst
carbon capture schemes have developed to collect the gases and prevent them polluting the
environment.
GREEN CHEMISTRY
94 Greenhouse Effect
Discuss the relative effects of different greenhouse gases as absorbers of IR and hence
on global warming

Greenhouse Effect

The sun emits UV radiation (visible light) and IR Radiation

The radiation reaches the Earths surface and most of this radiation is absorbed by the Earth,
which causes it to heat up

The Earth then re-emit longer wavelength IR radiation towards the sun

Greenhouse gases in the atmosphere absorb some of this longer wavelength IR radiation
and re-emit it in all directions- including back towards the Earth, keeping us warm
This is called the greenhouse effect. The greenhouse effect is vital in keeping the Earth warm-
without it, humans would not be able to survive. However, the greenhouse effect is becoming
greater, which is what causes global warming.

Over the last 100 years, the population of the earth has rapidly risen and countries have become
more industrialised. More and more energy is therefore required, so fossil fuels are being burnt
at an ever-increasing rate, releasing lots of CO2 into the atmosphere. Methane levels have also
risen.

Therefore, there has been a rise in greenhouse gas concentrations, which enhances the
greenhouse effect. This means more heat is being trapped and the Earth is getting warmer-
global warming.

Different Types of Greenhouse Gases

The main greenhouse gases are water vapour, carbon dioxide and methane.

They are greenhouse gases because their molecules absorb IR radiation, making the bonds
in the molecule vibrate more and more.

This extra vibrational energy is passed on to other molecules in the air by collisions, giving
other molecules more kinetic energy and so raising the overall temperature

Water vapour is responsible for a large part of the greenhouse effect, but the concentration
of water vapour has remained relatively constant so we are less concerned about it.

The relative effects of different greenhouse gases depend on their ability to absorb radiation
and the length of their half-life (i.e. how long they last in the atmosphere before reacting and
being broken down)
GREEN CHEMISTRY
95 Climate Change

Discuss the difference between anthropogenic and natural climate change over hundreds
of thousands of years

Natural Climate Change

Natural climate change is due to natural processes occurring on earth (e.g. dissolving of carbon
dioxide in sea).

Natural climate change has been occurring for thousands of years, due to natural processes
including volcanic eruptions and changes in solar activity

For example, the ice ages of the past were due to changes in the Earths orbit around the sun

Anthropogenic Climate Change

Anthropogenic climate change is climate change that is due to human activity (e.g. burning of
fossil fuels, deforestation etc.).

Anthropogenic climate change has grown in size recently

Scientists have established a range of evidence to show that climate change is taking place
more quickly than in the past:

- Tests show that carbon dioxide levels and temperatures are going up

- The concentration of CO2 in sea water is increasing

- Air trapped in ice in polar regions has been compared with air in our atmosphere, and
this comparison has shown rapid changes in CO2 concentration in recent years.
Most scientists agree that recent global warming is anthropogenic- human activities are to
blame for the rise in CO2 levels which has led to global warming.

Demonstrate an understanding of the terms carbon neutrality and carbon footprint.

o A fuel is carbon neutral if the amount of carbon dioxide absorbed when the raw material is
grown (or the fuel is formed) equals the amount of carbon dioxide produced when it is
manufactured and then burned.
A carbon neutral process occurs when there is no net carbon dioxide emission to the
atmosphere. For example, when a tree grows it absorbs carbon dioxide from the atmosphere.
GREEN CHEMISTRY
96 Carbon Neutrality and Carbon Footprint
When the tree is burned, it releases the same amount of carbon dioxide as it absorbed, so the
process is carbon neutral.
o The carbon footprint of an activity is the amount of greenhouse gas produced due to the
activity.
The carbon footprint is measured in terms of the total mass of carbon dioxide produced.
It is possible to measure the carbon footprint of an individual, a household, an organisation or of
a products lifecycle.

All products have a carbon footprint. It takes energy to extract raw materials, make the product
and then transport it. The energy is likely to come from burning fossil fuels.

Similarly, everyone has a carbon footprint. For example, watching TV and driving both have a
carbon footprint.

Trees use up CO2, so you can make an activity carbon neutral by planting enough trees to
remove all of the CO2 thats emitted in doing the activity. This is the principle behind carbon
offsetting.

Apply the concept of carbon neutrality to different fuels, such as petrol, bio-ethanol and
hydrogen

Petrol

Petrol and other fossil fuels contain large amounts of carbon dioxide that used to be in the
atmosphere. Burning these fossil fuels returns this carbon dioxide to the atmosphere. Such fuels
are not carbon-neutral, as they increase the amount of carbon dioxide in the atmosphere.

Bio-Ethanol

Most biofuels, such as bioethanol (produced from maize), are not carbon neutral. Although the
maize absorbs carbon dioxide when it grows, the stages in the production of bioethanol require
energy. For example, transportation and manufacturing releases CO2. Unless the energy is
generated without releasing carbon dioxide, producing biofuels gives out more carbon dioxide
than the crop absorbs.

GREEN CHEMISTRY
97 Carbon Neutrality and Carbon Footprint

Hydrogen

Hydrogen produces only water when it burns, so it is regarded as a clean fuel. However, the
hydrogen has to be manufactured because it does not occur naturally. It can be made chemically
from natural gas (requires heat) or by the electrolysis of water (requires electricity).

Therefore the production of hydrogen releases carbon dioxide, so hydrogen is not carbon-
neutral.

Wind Farms

Even wind farms are not always carbon neutral, because carbon dioxide is emitted in generating
the energy to build it.

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INTERMEDIATE BONDING AND BOND POLARITY

The strength of London Forces depends on:

Long-chain alkanes have stronger London Forces than short-chain alkanes

o The negative ions are attracted to the + hydrogen atoms.

Except in metal hydrides where it is -1 (and in H2 where it is 0)

How to minimise sources of measurement uncertainty

Bromine Br2 Red-Brown Liquid Orange- Orange- Brown Solution

Iodine I2 Grey Solid Brown Pink/ Violet Solution

Bromine and sodium hydroxide solution

N.B. All of the potassium halide solutions are colourless

Example: Chlorine Oxidising Iodide Ions

Example: Chlorine Oxidising Bromide Ions

Example: Bromine Oxidising Iodide Ions

o It is very volatile- it is a gas at room temperature

o It has a low volatility- It is a solid at room temperature

Deduce the qualitative effects of changes of temperature, pressure and concentration

Demonstrate an understanding of the use of electron-pair repulsion theory to interpret

The double bonds are slightly stronger than single bonds, so

However, remember that there is more repulsion between a lone pair

CH4 + Cl2 CH3Cl + HCl

The chlorine radical is not used up in the reaction, so it acts as a catalyst.

So the overall reaction is: 2O3 3O2 Catalyst- Cl

Chlorine is still regenerated, so it still acts as a catalyst.

Demonstrate an understanding of the nomenclature and structural, displayed and

Secondary Alcohol Butan-2-ol Propan-2-ol

Preparing a Carboxylic Acid

Setting up the Experiment

Explain the changes in rate based on a qualitative understanding of collision theory

Demonstrate an understanding of the role of catalysts in providing alternative reaction

The formation of molecular ions

Example: the mass spectrum of pentane

What causes the line at m/z = 57?

What causes the line at m/z = 43?

What causes the line at m/z = 29?

Molecular Masses of Common Fragments

Propanal and Propanone

i C-H stretching absorptions in alkanes, alkenes and aldehydes

ii O-H stretching absorption in alcohols and carboxylic acids

iii N-H stretching absorption in amines

iv C=O stretching absorption in aldehydes and ketones

v C-X stretching absorption in halogenoalkanes

C-H Alkenes 3000 3100 Medium, sharp

C-H Aldehydes 2800 2900 Weak, sharp

O-H Alcohols 3200 3600 Medium, broad

O-H Carboxylic Acids 2500 3300 Weak, very broad

NH Amines 3300 3500 Medium, sharp

C=O Aldehydes, Ketones, Carboxylic Acids 1690 1750 Strong, sharp

C- X Haloalkanes 500 1400 Strong, sharp

This time the O-H

There is no trough due to

This is interesting because it

The O-H bond in the acid

Why do different molecules have different IR spectrums?

Different molecules absorb different frequencies.

How is an IR spectrum produced?

An IR spectrum is produced by passing a range of IR frequencies through a sample in an IR

The frequency of IR absorption is measured in wavenumbers, and is shown on the x-axis of an IR

However, chemists have developed alternative ways to make chemicals involving

The use of CFCs as refrigerants is gradually being phased out in favour of

Different Types of Greenhouse Gases

- The concentration of CO2 in sea water is increasing

Demonstrate an understanding of the terms carbon neutrality and carbon footprint.

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