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
 Don’t forget to learn tests for ions for paper 3B.
 Self assessment questions on s-block, group 7 and
tests for ions are included in today’s 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 ions
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
Relative abundance C = 43
B = 29

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

CH4
methane
on
u sti
o mb ) Cl
c
l e te ygen uv 2
ligh
x
mp xs o t
co (

CO2 + H2O mixture of substitution products:

carbon dioxide + water CH3Cl, CH2Cl2, CHCl3, CCl4
(incomplete combustion gives carbon monoxide chloromethane, dichloromethane, etc.
and/or carbon instead of carbon dioxide)
 Alkenes
CH3CH2CH3 CH3CHBrCH2Br
propane 1,2-dibromopropane
Ni H2 Br 2 lvent
cat
aly so
s t in ert

CH3CH CH2
propene
HB

(polymerisation)
e

heat, pressure,
k a lin r (a
q)
al nO 4

catalysts
KM CH3CHBrCH3
2-bromopropane
CH3CHOHCH2OH
propane-1,2-diol
H H H H H H

C C C C C C

CH3 H CH3 H CH3 H

n
poly(propene)
 Alcohols
CH3CH2CH2Cl CH3CH2CH2Br
1-chloropropane O4 1-bromopropane
PC c H 2S lux
l on re f
r, c nder
5
B
K tu
a
he
CH3CH2CH2OH
propan-1-ol

heat (mild oxidation)

O 4 n) h ea r ed
H 2S ratio

acidified K 2Cr2O7
c t un P , I
n d er 2
co eh yd
CH3CH CH2 (d ref
at lux CH3CH2CH2I
h e
propene 1-iodopropane

xs acidified K 2Cr2O7 CH3CH2CO2H

CH3CH2CHO
heat under reflux propanoic acid
propanal

Oxidation of Secondary Alcohols

CH3CHOH CH3 acidified K 2Cr2O7 CH3COCH3

propan-2-ol heat propanone
 Halogenoalkanes

CH3CH CH2 CH3CH2CH2OH

propene h ethano )
(aq eflu x propan-1-ol
eat l
und ic KO H
K O der
r
er H n
refl tu
ux h ea
CH3CH2CH2I
1-iodopropane
H 3 be he eth
N
c d tu at an
l i un olic
a no ale de K
h e r r CN
et in s ef
CH3CH2CH2NH2 e at lu
x CH3CH2CH2CN
h
propylamine butanenitrile
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

CH3CH2CN
CH3CH2I CH2  CH2 CH2BrCH2Br
CH3CH2NH2

CH2  CH2

Answer

CH3CH2I ethanolic KOH

CH2CH2 Br2 CH2BrCH2Br
heat under reflux inert solvent
iodopropane ethene 1,2-dibromethane
 Synthetic Pathways – Examples 1-3

CH2 CH2 HBr(aq) CH3CH2Br ethanolic KCN CH3CH2CN

ethene bromoethane heat, reflux propanenitrile

CH3CH2CH2Br ethanolic KOH CH3CH CH2 Br2 CH3CHBrCH2Br

1-bromopropane heat, reflux propene inert solvent 1,2-dibromopropane

CH3CHICH3 aqueous KOH CH3CHOH CH3 acidified K2Cr2O7 CH3COCH3

2-iodopropane heat, reflux propan-2-ol heat propanone
 Synthetic Pathways – Examples 4-6

CH3CH2OH conc H 2SO4 CH2 CH2 Br2 CH2BrCH2Br

ethanol heat ethene inert solvent 1,2-dibromoethane

CH3CH2OH red P, I 2 CH3CH2I ethanolic NH 3 CH3CH2NH2

ethanol heat, reflux iodoethane heat, sealed tube ethylamine

CH3CH2CH2OH acidified K2Cr2O7 CH3CH2CHO xs acidified K 2Cr2O7 CH3CH2CO2H

propan-1-ol heat propanal heat under reflux 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 = mcpDT
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 DH
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
structures have
relatively low m.p.’s and
b.p.’s
 Substances with big
molecules e.g.
polythene soften on
heating as chains move
SIMPLE MOLECULAR STRUCTURE
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

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
SILICON
DIOXIDE 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
molten or in aqueous solution
 Soluble in polar solvents; insoluble
in non-polar solvents
Cl- Na+  Hard, brittle – may cleave along
GIANT IONIC
STRUCTURE
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
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 (&
GIANT METALLIC
STRUCTURE
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 dipole-
dipole 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

Temperature T1
Number of
molecules
with a Higher Temperature T2
particular
energy Lower activation energy
Fraction
Fraction
if catalyst of
of molecules
present molecules with
at
at temp
temp T
T12
required
with
with required
activation
required activation
energy
activation energy
is now
energy is
is
proportional
much bigger to
proportional at the
to either
the shaded
shaded area
area
under
temperature
under red
bluecurve
curve – much bigger

Kinetic Energy Ea' Ea

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 Aluminium isAluminium is

energy Aluminium oxide
kinetically is
stable
thermodynamically unstable
thermodynamically
relative tooxide
relative stable
to aluminium
relative to
aluminium its
oxide
2Al(s) +1½O2(g)
constituent elements

DH = –1676 kJ mol-1

Al2O3(s)
Moving the position of equilibrium
N2 (g) + 3H2 (g)  2NH3 (g); DH = -92 kJ mol-1

Applied change Position of equilibrium always moves in

direction that counteracts applied change.

Remove some Position of equilibrium moves in direction

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

Position of equilibrium moves in direction

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

Position of equilibrium moves in direction

which decreases total pressure, i.e. in
Increase the total direction which produces fewer moles of gas,
pressure 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 Increases rate of forward Moves in direction to

pressure. reaction if it involves a gas produce fewer gas
and increases rate of reverse molecules.
reaction if it involves a gas.

Increase Increases rate of forward and Moves in

temperature. backward reaction, but not to endothermic
the same extent. direction.

Add a catalyst. Increases rate of forward and No effect.

backward reactions to same
extent.

Increase Increases rate of forward Moves in favour of

concentration of reaction. products.
a reactant.
 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); DH = -92 kJ mol-1
 The manufacture of nitric acid:
4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g); DH = -950 kJ mol-1
 Contact Process for the manufacture of sulphuric acid:
2SO2(g) + O2(g)  2SO3(g) DH = -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 N–O or
C–O 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