Welcome to

AS Chemistry Revision Session

Mass Spectrometer
Atomic Structure

and Periodic Table

Organic Chemistry
Thermochemistry
Structure & Bonding
Kinetics
Equilibria
Inorganic Chemistry

Programme for morning

9:10 - 9:20 Introduction
9:20 - 9:45 Mass Spectrometer
9:45 - 10:10 Atomic Structure & Periodic Table
10:10 - 10:35 Organic Chemistry
10:35 - 10:55 Break
10:55 - 11:20 Organic Chemistry (continued)
11:20 - 12:00 Thermochemistry
12:00 - 12:30 Structure & Bonding
12:30 - 12:50 Kinetics & Equilibria
12:50 - 13:10 Key aspects of Inorganic Chem.

Introduction
This session should get you off to a good start

and encourage you to continue.

We will revise important themes that underpin
the whole course and deal with ideas likely to
crop up in questions
We do not have time to cover everything!
The revision pack includes answers to
numerical questions and many other problems
Take the pack away and continue to use it to
support your revision.

Advice about revision

Course Handbook provides general advice about

revision techniques
For each study unit, learn the meaning of relevant key
words in Course Handbook
For topics requiring a lot of factual recall e.g. organic
chemistry, and group chemistry, learn the basic facts
first.
Make use of spider diagrams (for organic) and
revision cards (for group chemistry) to do this.
Copies supplied today
Dont forget to learn tests for ions for paper 3B.
Self assessment questions on s-block, group 7 and
tests for ions are included in todays pack

Mass Spectrometer the instrument

Mass Spectrometer ion formation

Electron bombardment positive

ions formed

Mass Spectrometer - acceleration

Electric field - negatively charged plates

further down tube accelerate positive

Mass Spectrometer - deflection

Magnetic field deflects positive ions

the greater the mass
the less the deflection

Mass Spectrometer - detection

Ions are detected and record made

mass spectrum is a plot of relative
abundance against m/e value

Mass Spectrum Problem

C = 43
B = 29

Relative abundance

A = 15

D = 57
E = 72

m/e

This shows the major peaks in the mass spectrum of

a ketone, X
Identify the peak caused by the molecular ion
Suggest the formulae of the fragmented ions which
give the peaks at m/e values of 15, 29, 43 and 57.
Deduce the structural formula of X

Periodic Table Vertical Trends

Atomic radius increases down groups
Increasing number of shells occupied
Increase in nuclear charge is matched by

equal increase in number of screening

electrons
1st ionisation energy decreases as distance
of outer electron from nucleus increases
Elements become more metallic
increasing ease of positive ion formation

Periodic Table Horizontal Trends

Atomic radius decreases across period
Increase in nuclear charge but no

increase in number of screening electrons

1st ionisation energy increases across
period
Elements become less metallic
decreasing ease of positive ion formation
Tendency to form negative ions increases
as atomic radius decreases

Alkanes
CH
methane

C O 2 + H 2O
carbon dioxide + water
(incomplete combustion gives carbon monoxide
and/or carbon instead of carbon dioxide)

mixture of substitution products:

CH 3 Cl, CH
Cl 2 , CHCl
2
chloromethane, dichloromethane, etc.

, CCl

Alkenes
CH

CH
propane
3

CH

CH 3 CH BrCH
1,2-dibromopropane

CH

3 CH

CH

heat, pressure,
catalysts
(polymerisation)

CH 3 CHBr
2-bromopropane

OH
H

CH

CH

poly(propene)

Br

propene

CH 3 CH OHCH
propane-1,2-diol

CH

CH

Alcohols
CH 3 CH 2 CH
1-chloropropane

Cl

CH 3 CH 2 CH
1-bromopropane

CH

3 CH

2 CH

propan-1-ol

CH
propene

CH

Br

2 OH

acidified K
heat (mild oxidation)

CH

CH 3 CH
1-iodopropane

CH

Cr 2 O
7

CH

CH 2 CH O
propanal
3

xs acidified K
heat under reflux

Oxidation of Secondary Alcohols

CH

CH OH CH
propan-2-ol
3

acidified K
heat

2 Cr 2 O 7

CH 3 C OC H
propanone

Cr 2 O

CH 3 CH 2 C O 2 H
propanoic acid

Halogenoalkanes
CH

CH
propene

CH

CH 3 CH 2 CH
1-iodopropane

CH

CH 2 CH
propylamine
3

NH

CH

CH 2 CH
propan-1-ol

OH

CH

CH 2 CH
butanenitrile

CN

2I

Synthetic Pathways - Example

iodoethane 1,2-dibromoethane
List the compounds you know can be made

directly from starting material

Alongside the first list, make another list of
the compounds that you know can be
converted directly into the product
Find a link between the 2 lists if you are
lucky the same compound will appear in both
(if not you will need to convert a compound
from the 1st list into one from the 2nd and you
will need 3 steps)

Synthetic Pathways - Example

iodoethane 1,2-dibromoethane
CH3CH2OH
CH3CH2I

CH3CH2CN

CH2 CH2

CH2BrCH2Br

CH3CH2NH2
CH2 CH2

Answer

CH 3 CH
iodopropane

2I

ethanolic KOH
heat under reflux

CH

ethene

CH

Br
inert solvent

CH 2 Br CH
1,2-dibromethane

Br

Synthetic Pathways Examples 1-3

CH

ethene

CH

CH 3 CH 2 CH 2 Br ethanolic KOH
heat, reflux
1-bromopropane
CH 3 CHI CH
2-iodopropane

aqueous KOH
heat, reflux

HBr(aq)

CH 3 CH
bromoethane

CH 3 CH CH
propene
CH 3 CHOH CH
propan-2-ol

2B

CH 3 CH
propanenitrile

ethanolic KCN
heat, reflux

Br
inert solvent

CH 3 CH BrCH
1,2-dibromopropane

acidified K
heat

2 Cr 2 O 7

CN

2B

CH 3 C OC H
propanone

Synthetic Pathways Examples 4-6

CH

3 CH

ethanol
CH

CH
ethanol
3

2 OH

OH

CH 3 CH 2 CH 2 OH
propan-1-ol

conc H
heat

SO

CH

CH

ethene

red P, I
heat, reflux

CH 3 CH
iodoethane

acidified K
heat

Cr 2 O

Br
inert solvent

CH 2 BrCH
1,2-dibromoethane

ethanolic NH
heat, sealed tube

CH 3 CH 2 CH O xs acidified K
heat under reflux
propanal

CH 3 CH
ethylamine

Cr 2 O

2B

N H

CH 3 CH 2 C O 2 H
propanoic acid

Thermochemical calculations
Enthalpy of formation from enthalpy

of combustion data
Enthalpy change for any reaction
from enthalpy of formation data
Estimating enthalpy change from bond
enthalpy data

Thermochemical experiments
Calculate energy released / gained for

the quantities actually used = mc pT

Calculate number of moles of reactants

taking part in reaction

Scale up energy change to the number
of moles shown in the thermochemical
equation.
Insert the correct sign for H

Bonding - Covalent
A covalent bond is the electrostatic

force of attraction of two nuclei towards

a shared pair of electrons between
them, one electron in the shared pair
coming from each atom.
A dative covalent bond is the
electrostatic force of attraction of two
nuclei towards a shared pair of
electrons between them, both electrons
in the shared pair coming from the same
atom.

Bonding Molecular Structures

Molecular Structures (simple molecules e.g. water, or big
molecules e.g. polythene)
These are characterised by having strong covalent bonds
within their molecules but weak attractions between their
molecules (i.e. weak intermolecular forces).
Simple molecular

SIMPLE MOLECULAR STRUCTURE

structures have
relatively low m.p.s and
b.p.s
Substances with big
molecules e.g.
polythene soften on
heating as chains move
over each other

Shapes of Molecules
Electron-pair repulsion theory - electron

clouds repel each other and adopt an

arrangement in space so that repulsion
between them is at a minimum.
Count the number of bond pairs and lone
(non-bonded) pairs around the central
atom(s). For the purposes of predicting
molecular shapes, multiple bonds should be
considered as one electron cloud.
The molecular shape is described in terms of
the geometric arrangement of atoms (not the
arrangement of electron clouds)

Predicting bond angles

Common molecular shapes include

linear, trigonal planar, V-shaped,

tetrahedral, trigonal pyramidal, trigonal
bipyramidal and octahedral.
Lone-pair orbitals are more effective in
repulsion than bond pairs (Why is this?)
Multiple bonds are more effective in
repulsion than single bonds.

Giant Molecular Structures 1

SILICON
DIOXIDE

Giant Molecular (Covalent

Network) Structures are
formed by huge numbers of
atoms being linked together
by covalent bonds to form
networks of atoms. The
atoms may be linked in
layers (e.g. in graphite) or in
3-dimensional networks (e.g.
diamond and silicon dioxide)
with strong bonds throughout
the network.

Giant Molecular Structures 2

DIAMOND

Strong covalent bonds

throughout
GRAPHITE

Strong covalent bonds

within layers
Weak Van der Waals
forces between layers

Giant Molecular Structures 3

Graphite is soft & slippery - weak Van der Waals

forces between layers - slip over one another easily.

Diamond is hard - strong covalent bonds
throughout.
Both have high m.p.s and b.p.s because a large
number of strong covalent bonds have to be broken
to break down giant structures into small enough
fragments to produce freely moving particles.
In graphite, each C atom forms only 3 covalent
bonds - leaving one outer electron not involved in
bonding. Spare electrons are delocalised in
between the layers - they are mobile and so
graphite conducts electricity. Diamond is an
electrical insulator because all of the outer
electrons of the C atoms are used in bonding.

Bonding - Ionic
An ionic bond is the electrostatic force of
attraction between oppositely charged ions,
formed as a result of complete electron transfer.
Strong ionic bonds throughout
High m.p. & b.p.
Good electrical conductors when

ClGIANT IONIC
STRUCTURE

molten or in aqueous solution

Soluble in polar solvents; insoluble
in non-polar solvents
Na+ Hard, brittle may cleave along
definite planes

Bonding - Metallic
Metallic bonds are the electrostatic forces of attraction
between the cations in a metallic lattice and the
delocalised valence electrons that surround them.
Malleable bonds non-directional

GIANT METALLIC
STRUCTURE

and layers can slip over each other

without bonds being broken
High b.p.s strong metallic bonds
throughout
Good conductors of electricity (and
heat) electrons are mobile (&
transfer energy between atoms)

Van der Waals Forces

These are the weak electrostatic forces of attraction

between molecules where one end of a temporary

dipole, set up in a molecule as a result of the
fluctuating electron cloud, is attracted towards the
opposite end of a dipole induced in a neighbouring
molecule.
Van der Waals forces are the only intermolecular force
present in non-polar substances.
Van der Waals forces increase in strength with
increasing molecular size (i.e. increasing number of
electrons per molecule).
Van der Waals forces can also be affected by
molecular shape they increase in strength with
increasing surface area of contact between molecules.

Dipole-dipole attractions
These are the electrostatic forces of

attraction between the oppositely charged

ends of permanent dipoles in neighbouring
molecules.
They exist in addition to Van der Waals
forces in polar substances.
A covalent bond is polarised if there is a
difference in electronegativity between the
atoms involved.
The molecule as a whole will not be polar if it
is symmetrical and the effects of the
polarised bonds cancel each other out.

Hydrogen Bonds
This is the electrostatic force of attraction

between a proton that has been denuded of

electrons, by direct attachment to a highly
electronegative atom such as N, O or F, and
the lone pair on another highly
electronegative atom.
Hydrogen bonding leads to stronger
intermolecular forces than ordinary dipoledipole attractions

Polarisation of anions
This leads to some covalent character in compounds

that are primarily ionic

Polarisation of the anion is caused by the
neighbouring cation
It leads to distortion of its electron cloud (no longer
spherical) and some sharing of electron density, i.e.
covalent character
The polarising power of the cation is greatest when it
is small and has a large positive charge (i.e. has a
high charge density)
The polarisability of the anion is greatest when it is
large and has a large negative charge

Kinetics Collision Theory 1

The collision frequency is directly

proportional to the surface area of contact

between the two phases in a heterogeneous
reaction. Therefore increasing the surface
area of contact leads to an increase in
reaction rate
Increasing concentration (or pressure) of
reactant causes the reacting particles to be,
on average, closer together. This increases
the collision frequency between reacting
particles and hence increases reaction rate.

Kinetics Collision Theory 2

Activation energy is the minimum energy needed

upon collision if it is to lead to reaction, i.e. be

successful.
Increasing the temperature increases the average
kinetic energy of the reacting molecules and so a
greater proportion of collisions will have the
necessary activation energy. This leads to an
increase in rate.
Addition of a catalyst allows the reaction to take
place via an alternative pathway which has a lower
overall activation. The reaction rate is increased
because a greater proportion of collisions will now
have the required activation energy.

Maxwell-Boltzmann Distribution

Number of
molecules
with a
particular
energy

Temperature T1
Higher Temperature T2
Lower activation energy
Fraction
of
at
Fraction
of molecules
molecules with
at temp
temp T
T12
if catalyst
present

required
activation
energy
is now
with
activation
energy
is
with required
required
activation
energy
is
much
bigger
at
either
proportional
proportional to
to the
the shaded
shaded area
area
temperature
under
under red
bluecurve
curve much bigger

Kinetic Energy

E a'

Kinetic & Energetic Stability

The enthalpy of formation of aluminium oxide is 1676 kJ mol -1.
However aluminium does not corrode readily, and does not burn
unless the temperature is extremely high. Comment on the
thermodynamic and kinetic stability of aluminium.
high activation
energy

2Al(s) +1O2(g)

Aluminium is
Aluminium
is
Aluminium
oxide
is
kinetically
stable
thermodynamically
unstable
thermodynamically
relative tooxide
relative to
aluminium
stable
relative to
its
aluminium
oxide
constituent elements
H = 1676 kJ mol-1
Al2O3(s)

Moving the position of equilibrium

N2 (g) + 3H2 (g) 2NH3 (g); H = -92 kJ mol1

Applied change

Position of equilibrium always moves in

direction that counteracts applied change.

Remove some
ammonia to decrease
its concentration

Position of equilibrium moves in direction

which increases concentration of ammonia,
i.e. to right.

Decrease the
temperature

Position of equilibrium moves in direction

which increases temperature, i.e. in
exothermic direction which is to the right.

Increase the total

pressure

Position of equilibrium moves in direction which

decreases total pressure, i.e. in direction which
produces fewer moles of gas, which is to the
right.
(In the equation there are 4 moles of gas on the
left, and two moles on the right.)

Kinetics & Equilibria

Factor

Effect on reaction rate

Effect on position of
equilibrium

Increase total
pressure.

Increases rate of forward

reaction if it involves a gas
and increases rate of reverse
reaction if it involves a gas.

Moves in direction to
produce fewer gas
molecules.

Increase
temperature.

Increases rate of forward and

backward reaction, but not to
the same extent.

Moves in
endothermic
direction.

Add a catalyst.

Increases rate of forward and

backward reactions to same
extent.

No effect.

Increase
concentration of
a reactant.

Increases rate of forward

reaction.

Moves in favour of
products.

Industrial Examples
Be able to apply the principles of kinetics and equilibria

three examples of industrial process to predict the

optimum conditions for achieving high yield and rate
be aware that the actual conditions used are often a
compromise and that cost also needs to be taken into
account
Haber Process for manufacture of ammonia:
N2 (g) + 3H2 (g) 2NH3 (g);

H = -92 kJ mol-1

The manufacture of nitric acid:

4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g);

H = -950 kJ mol-1

Contact Process for the manufacture of sulphuric acid:

2SO2(g) + O2(g) 2SO3(g) H = -197 kJ mol-1

Aspects of Inorganic Chemistry

Learn key reactions via summary

cards
Review learning of halogens now
Check learning using self-assessment
questions and answers
Learn Tests for Ions for Paper 3B

Trend in thermal stability of nitrates

& carbonates of s-block metals
On going UP the groups, compounds get
easier to decompose, i.e. need lower
temperature to bring about decomposition.
This is because:
Ionic radius of cation decreases
Therefore charge density increases
Therefore polarising power increases
This leads to greater weakening of NO or

CO bonds in anion

End of Presentation
Further independent
use of pack could
include:
S-Block Metals
Halogens
Chlor-Alkali Industry
Moles (further practice)
Tests for ions
Atomic Structure FAQs