Moles and Equations

Relative Atomic Mass the weighted average mass of naturally

occurring atoms of an element relative to a scale where the mass of
an atom of carbon-12 is exactly 12 atomic mass units
o Ar[element Y] = (average mass of one atom of element
Y *12)/(mass of one
atom of carbon 12)
o Determining Ar from mass spectra:
Multiply each isotopic mass by its percentage
abundance
Add the figures together
Divide by 100
Isotopes are atoms of the same element with the same proton
number but different neutron number
o So have different physical properties but same chemical
properties
o Use a mass spectrometer to measure the mass of each
isotope present in an element and the relative isotopic
abundance
Relative Isotopic Mass- the average weighted mass of an isotope
of an element relative to a scale where an atom of the carbon-12
isotope is exactly 12 units.
Relative Formula Mass-the mass of one formula unit of a
compound measured on a scale on which an atom of the carbon-12
isotope has a mass of exactly 12 units
Relative Molecular Mass- the mass of a molecule measured on a
scale on which an atom of the carbon-12 isotope has a mass of
exactly 12 units
One mole of a substance is the amount of substance that has the
same number of specific particles as there are atoms in 12g of
carbon-12.
Molar mass mass of one mole of a substance; units are gmol-1
Avogadro Constant value is 6.02*1023; the number of particles in
one mole of a substance
Number of Moles= (mass of substance in grams)/(molar
mass)
Percentage Composition by mass= (atomic mass*mass of
particular substance in a compound*100)/molar mass of
compound
Empirical formulae the simplest whole number ratio of the
elements present in one molecule or formula of the compound
Molecular formulae- shows the total number of atoms of each
element present in a compound
o The formula of an ionic compound is the same as its empirical
formulae

NOTE: MUST USE STATE SYMBOLS IN IONIC

EQUATIONS
o The empirical and molecular formulae for simple inorganic
compounds are often the same
o Organic molecules have different empirical and molecular
formulae
Concentration of a solution= (number of moles of
solution)/volume; units moldm-3
Avogadros hypothesis: at ideal gas conditions equal volumes of
all gases have the same number of molecules. At rtp(at 25C and 1
atm) one mole of any gas has a volume of 24.0 dm3.
Volume of any gas at rtp: 24*number of moles of any gas
Atomic Structure

Each atom has nearly all of its mass concentrated in a tiny region in
the centre of an atom called the nucleus.
Three types of subatomic particles- protons and neutrons in the
nucleus (nucleons) and electrons orbiting the nucleus in shells
Subatomic
Symbol
Relative Mass
Relative
Particles
charge
Proton
p
1
+1
Neutron
n
1
0
Electron
e
1/1840
-1
Nucleon Number or Mass Number = number of protons +
number of neutrons
Beams of protons and electrons are deflected by electric fields but
not neutrons
All atoms of the same element have the same number of protons
In a neutral atom, number of protons=number of electrons
In a positively charged ion number of protons>number of electrons
In a negatively charged ion number of protons<number of electrons

Electrons in Atoms

Electrons are arranged outside the nucleus in principal energy

levels/shells
These levels are numbered according to how far they are from the
nucleus
Lowest energy level=1 is closest to nucleus
Shell 1 can hold up to 2 electrons
Shell 2 can hold up to 8 electrons
Shell 3 can hold up to 18 electrons
Shell 4 can hold up to 32 electrons
1st Ionisation energy the amount of energy needed to remove
one electron from each atom in one mole of gaseous atoms to form
1 mole of gaseous 1+ ions. Units are kJ mol-1
Successive ionisation energies- the amount of energy required
to remove the first,then the second,then the third electron and so
on from a gaseous atom or ion producing an ion with one more
positive charge each time
for each element the successive ionisation energies increase. The
charge on the ion gets bigger as each electron is removed. So there is
a greater attractive force between the positively charged protons and
the remaining negatively charged electrons. So more energy is required
to overcome the attractive forces
a big difference between some ionisation energies is due to the fact
that for the second ionisation energy the electron is being removed
from a shell closer to the nucleus
Factors influencing ionisation energies:
The size of the nuclear charge: ionisation energy increases as atomic
number increases because the positive nuclear charge increases. The
bigger the positive nuclear charge the greater the attraction between
the nucleus and the electrons. So more energy is required to overcome
the attractive forces.
Distance of outer electrons from the nucleus The force of attraction
between positive nucleus and negative electrons decreases rapidly as
the distance between them increases. The further the electron is from
the nucleus, the lower its ionisation energy
Shielding effect of inner electrons electrons in full inner shells repel
electrons in outer shells so they prevent the full nuclear charge from
being felt by the outer electrons. As the number of full electron shells
between the valence electrons and the nucleus increases, the shielding
effect increases, so the ionisation energy is lower.
Can use successive ionisation energies to predict electronic
configuration of an element and confirm the number of valence
electrons hence the group the element belongs to

Principal Quantum Levels can be divided into subshells

o Each principal quantum shell has a different number of subshells
If n=1 can hold a maximum of two electrons in an s subshell
If n=2 can hold a maximum of eight electrons 2 electrons in an
s subshell and 6 electrons in an p subshell
If n=3 can hold a maximum of eighteen electrons - 2 electrons
in an s subshell and 6 electrons in an p subshell and 10
electrons in a d subshell
An atomic orbital is a region of space around the nucleus of an
atom that can be occupied by one or two electrons
Each orbital can hold a maximum of two electrons as long as
they are in opposite spin so s subshell has one orbital, p subshell
has
three
orbitals
and d
subshell
has five
orbitals

The most stable electronic configuration is the one that has

the lowest amount of energy.
The order in which the subshells are filled depends on their relative
energy

electronic configuration of copper: 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Electronic configuration of chromium: 1s2 2s2 2p6 3s2 3p6 3d5 4s1

Elements in Groups 1 and 2 have outer electrons in a s subshell

Elements in Groups 3 to 18 have outer electrons in a p subshell
Elements that electrons to the d subshells are called d-block
elements

o
o
o
o

o
o
o
o

Electrons in the same region of space repel each other because they
have the same charge. So electrons will occupy separate orbitals in
the same subshell to minimise repulsion. So electrons have spin in
same direction
Spin-pair repulsion when electrons are paired in the same orbital
which can cause ionisation energy to decrease
Across a period, the ionisation energy generally increases
due to:
The nuclear charge increasing
The distance between the nucleus and the outer electrons remaining
constant
The shielding remains constant
If electron in p or d subshell it is further from nucleus so ionisation
energy decreases
Down a group the ionisation energies decrease leading to a
higher reactivity due to:
Even though the nuclear charge increases there is less attraction
between nucleus and valence electrons due to:
Increased distance between nucleus and valence electrons
Shielding increases
Two factors outweigh the increased nuclear charge

o
o

o
o
o
o
o
o

o
o
o
o
o

Chemical bonding
Ionic Bonding is the electrostatic force between positively charged
cations and negatively charged anions; cations lose electrons and
anions gain electrons
Charge on ion depends on the number of electrons gained or
lost
A three dimensional lattice is formed using alternating cations
and anions
An ionic bond/electrovalent bond is formed between cations and
anions.
The electrostatic forces of attraction between cations and
anions is very strong
Atoms between molecules are held together by strong intramolecular
forces but the intermolecular forces between two molecules is weak
Types of intermolecular forces:
Van-der-Waals forces
Permanent dipole-dipole forces
Hydrogen Bonds
When two non-metals combine they share one or more pairs of
electrons
A shared pair of electrons is called a single covalent bond or bond
pair
Pairs of electrons not used in bonding are called lone pairs
Double Covalent Bond some atoms can bond together by sharing
two pairs of electrons
Triple Covalent Bond some atoms can bond together by sharing
three pairs of electrons
A co-ordinate bond or dative covalent bond is formed when one
atom provides both the electrons needed for a covalent bond
Need one atom having a lone pair of electrons and a second
atom having an unfilled orbital to accept the lone pair
Represented by an arrow. Head of arrow points away from
the lone pair that forms the bond
Double bonds are shorter than single bonds due to double bonds
having greater quantity of negative charge between two atomic nuclei
The greater force of attraction between the electrons and the nuclei
pull the atoms closer together resulting in a stronger bond
Bond energy measures the strength of a bond; it is the energy
needed to break one mole of a given bond in a gaseous molecule
Bond strength is one factor that influences the reactivity of a
compound
A pair of electrons in the bonds surrounding the central atom
will repel other electron pairs. This repulsion forces the pairs
of electrons apart until the repulsive forces are minimised.

o The shape and bond angles of a covalently bonded molecule depend

on the number of electron pairs and whether those pairs are lone or
bonded.
o Lone pair of electrons have a more concentrated electron charge cloud
than
bond
pairs so
they
are
wider
and
slightly
closer
to
the
nucleus
o Order
of

repulsion from greatest to least: lone pair-lone pair,lone pair-bonding

pair, bonding pair-bonding pair

o In the formation of a covalent bond, the atomic orbitals, each having a

single unpaired electron, overlap so a
combined orbital is formed containing two
electrons, forming a molecular orbital
o The greater the overlap, the stronger
the bond
o Hybridisation- the process of mixing atomic orbitals
sp hybridisation one s orbital and one p orbital overlap
sp2 hybridisation - one s orbital and two p orbitals overlap
sp3 hybridisation one s orbital and three p orbitals overlap
o When hybridised orbitals overlap end-on the bond is a sigma() bond
o The electron density of each sigma bond is symmetrical about a line
joining the nuclei of the atoms forming the bond
o Bonds formed by sideways overlap of p orbitals are called pi() bonds
o A pi bond is not symmetrical about the axes joining the nuclei of atoms
forming the bond
o Often draw a single pi bond as two clouds of electrons
o Ethane
All the bonds in ethane are formed by linear overlap of atomic
orbitals
They are all bonds
All the areas of electron density repel each other equally so the
bond angles are 109.5
o Ethene
Each carbon atom in ethene uses three of its four outer
electrons to form sigma bonds
Two sigma bonds are formed with the hydrogen atoms and one
sigma bond is formed with the other carbon atom
Fourth electron from each carbon atom occupies a p orbital
which overlaps sideways with a similar p orbital on the other
carbon atom forming a pi bond
Ethane is a planar molecule to ensure
maximum overlap of the p orbitals that form
the pi bond
Electron clouds that make the pi bond lie
above and below the plane of the carbon
and hydrogen nuclei
Due to the position of the pi bond the bond
angle is 117 to minimise the repulsive
forces
Metallic Bonding
o The atoms are packed closely together in a regular
arrangement called a lattice surrounded by a sea
of delocalised electrons

o The metal atoms tend to lose electrons and become positive ions
o The valence electrons occupy new energy levels and are free to move
around the lattice
o Electrostatic forces of attraction between the positive ions and
negatively charged delocalised sea of electrons
o The strength of metallic bonding increases with:
Increasing positive charge on the ions in the metal lattice
Decreasing size of metal ions in the lattice
Increasing number of mobile electrons per atom
o Most metals have high melting points and high boiling points
Takes a lot of energy to weaken the strong attractive forces
between metal ions and the delocalised electrons
o Metals conduct electricity
When a voltage is applied to a piece of metal, an electric current
flows in it because the delocalised electrons are free to move
o Metals conduct heat
The conduction of heat is partly due to the movement of the
delocalised electrons and partly due to the vibrations passed on
from one metal ion to the next
Intermolecular forces weak forces between molecules
o van der Waals forces
o Permanent dipole-dipole forces
o Hydrogen bonding
Electronegativity the ability of a particular atom which is
covalently bonded to another atom, to attract the bond pair of
electrons toward itself
o Increases across a period from group 1 to group 17
o Increases up each group
o Fluorine is the most electronegative element
When a covalent bond is formed between two atoms having
different electronegativity values, the electron distribution is
asymmetric making the bond polar
As the difference in electronegativity values increases, the bond
becomes more polar
The degree of polarity is measured as a dipole moment and the
direction of dipole is shown using an arrow
Some molecules contain polar bonds but have no overall
polarity because the dipole moments cancel each other out
Bond polarity influences chemical reactivity
van der Waals forces
o the electron charge clouds in a non-polar molecule are constantly
moving
o Sometimes, more of the charge cloud is one side of the molecule than
on the other side so one end of the molecule has more negative charge
than the other end

o A temporary dipole is set up which can set up a dipole on

neighbouring molecules
o Van der Waals forces increase with increasing number of electrons in
the molecule and increasing the number of contact points between the
molecules
Permanent dipole-dipole forces
o Molecules with a permanent
dipole are called polar molecules
o A fine jet of polar molecules will be attracted towards an electrically
charged plastic rod or comb
o The molecules have both negatively and positively charged ends
o Forces between two molecules having permanent dipoles are
permanent dipole-dipole forces
o Stronger than van der Waals forces
Hydrogen Bonding
o Is the strongest type of intermolecular forces
o Need one molecule having a hydrogen atom covalently bonded to
fluorine, oxygen, or nitrogen and a second molecule having a fluorine,
oxygen, or nitrogen atom with an available lone pair of electrons
o For maximum bond strength the angle between the covalent bond to
the hydrogen atom and the hydrogen bond is 180
o The average number of hydrogen bonds formed per molecule depends
on:
the number of hydrogen atoms attached to F, O or N in the
molecule
the number of lone pairs present on the F, O or N

Properties of Water
o Water has a much higher enthalpy change of vaporisation and
boiling point than expected due to its extensive hydrogen
bonding
o Hydrogen bonding reduces the ability of water to slide over
each other so the viscosity of water is high
o Hydrogen bonds in water also exert a significant downward
force at the surface of the liquid so water has a high surface
tension
Ice is less dense than water
o There is a three-dimensional hydrogen-bonded network of
water molecules producing a rigid lattice in which each
oxygen atom is surrounded by a tetrahedron of hydrogen
atoms
o The long hydrogen bonds provide a more open arrangement
allowing the water molecules to be further way in a solid than
in a liquid
Read pg. 76 -77

States of Matter
o Solids have a fixed shape and volume. Solid particles are touching each
other, are in a regular arrangement, and vibrate about fixed positions
o Liquids have a fixed volume but take the shape of the container they
occupy. Liquid particles are close together but arranged fairly randomly
and have limited movement in all directions
o Gases have no fixed shape or volume. Gas particles are far apart, are
randomly arranged, can move freely in all directions
o Kinetic Theory of Gases:
The idea that molecule in gases are in constant movement
Gas molecules move rapidly and randomly
The distance between gas molecules is much greater than the
diameter of gas molecules so volume of gas is negligible
There are no forces of attraction or repulsion between the
molecules
All collisions between gas molecules are elastic
The temperature of the gas is related to the average kinetic
energy of the molecules
Only for gases in low pressures and high temperatures
o At high pressures and low temperatures, ideal gases cease to
exist
The gas molecules come closer together
The volume of the gas is not negligible compared with volume
of container
There are van-der-Waals forces between molecules
Attractive forces pull molecules toward each other and away
from walls of container
Pressure and effective volume is smaller
o For ideal gases
Pressure is inversely proportional to volume
Pressure is directly proportional to temperature
pV=nRT; p=pressure in Pascals, V=volume in m3, n=number of
moles, R=molar gas constant, T=temperature in kelvin
o Melting:
When heating a solid the particles vibrate more vigorously
The forces of attraction between the particles weaken
The solid changes to a liquid when the temperature is
sufficiently high
o Freezing
Particles lose kinetic energy so they do not move around so
readily
Experience increasing forces of attraction so stop sliding past
each other when temperature is sufficiently low so the liquid
solidifies

o The particles in a liquid are still close to each other but they have
enough kinetic energy to keep sliding past each other
o Sometimes the particles are arranged in a slightly orderly way but they
gain kinetic energy from neighbouring particles
o When we heat a liquid, called vaporisation(the change from the liquid
state to the gas state):
the energy transferred to the liquid makes the particles move
faster
the forces of attraction between particles weaken
the particles with most energy are the first to escape from the
forces holding them together in the liquid
the liquid evaporates at a temperature below the boiling point
at the boiling point, the forces are weakened to an extent that
all the particles are completely free
o When we cool a vapour, called condensation(the change from the gas
state to the liquid state):
The particles lose kinetic energy
So they experience increasing forces of attraction
o In a closed container, evaporation and condensation take place
together.
o When the rate of evaporation is equal to the rate of condensation a
position of dynamic equilibrium is reached. The concentration of water
molecules in the vapour remains constant
o Vapour Pressure pressure exerted by a vapour in equilibrium with
its liquid
Increases with temperature
o The temperature at which the vapour pressure is equal to the
atmospheric pressure is the boiling point
o Read pg 88 to 94

Enthalpy Changes

Exothermic Reactions chemical

reactions which release energy to the
surroundings
o The temperature of the mixture
increases
Endothermic Reactions chemical
reactions which absorb energy from the
surroundings
The surroundings include:
o The solvent
o The air around the test tube
o The test tube itself
o Anything dipping into the test tube
Enthalpy changes the energy exchange between a chemical reaction
and its surroundings
o H=Hproducts-Hreactants
o For exothermic reactions the enthalpy change is negative
o For endothermic reactions the enthalpy change is positive
Standard Conditions
o A pressure of 105 Pascals
o A temperature of 298 K
o Each substance involved in its normal physical state
Standard enthalpy change of reaction Hr the energy change when
amounts of reactants in their standard states shown in the equation react
to give products under standard conditions
Standard enthalpy change of formation Hf the energy change
when one mole of a compound is formed from its elements in their
standard states under standard conditions
Standard enthalpy change of combustion Hc the energy change
when one mole of a substance in its standard state burns under excess
oxygen under standard conditions
Standard enthalpy change of neutralisation Hn the energy
change when one mole of water is formed by the reaction of an acid with
an alkali under standard conditions
Standard enthalpy change of solution Hsol when one mole of
solute is dissolved in a solvent to form an infinitely dilute solution under
standard conditions
Standard enthalpy change of atomisation Hat the enthalpy
change when 1 mole of gaseous atoms is formed from its element under
standard conditions
Standard enthalpy change of hydration H - the enthalpy change
when 1 mole of a hydrated salt is formed from 1 mole of the anhydrous
salt under standard conditions
Hesss law the total enthalpy change in a chemical reaction is
independent of the route by which the chemical reaction takes place as
long as the initial and final conditions are the same
Bond breaking is endothermic and bond forming is exothermic

The amount of energy needed to break a specific covalent bond is called

the bond dissociation energy or bond energy. They are always
positive.
Average bond energies are often used because the strength of a bond
between two particular types of atom is slightly different in different
compounds

Redox Reactions

Oxidation is gain of oxygen, loss of electrons and loss of hydrogen

and increase in oxidation number
Reduction is loss of oxygen, gain of electrons, and gain of
hydrogen and decrease in oxidation number
Redox reactions where oxidation and reduction take place
together in a reaction
Oxidation rules
1. The oxidation number of any uncombined element is zero.
2. Group 1 ions are always 1+
3. Group 2 ions are always 2+
4. Fluorine is always 15. Hydrogen is 1+ except in metal hydrides
6. Oxygen is 2- except in peroxides where it is -1 and F2O where
it is +2
7. The oxidation number of an element in a monoatomic ion is
always the same as the charge
8. The sum of the oxidation numbers in a compound is zero.
9. The sum of oxidation numbers in an ion is equal to the charge
on the ion
10.
In either a compound or an ion the more electronegative
element is given the negative oxidation number

Equilibrium

Reversible reaction a reaction in which the products can

react to re-form the original reactants
Concepts of equilibrium:
o It is dynamic
That the molecules or ions of reactants and
products are continuously reacting
Reactants are becoming products and products
are becoming reactants
o The rate of forward reaction=the rate of backward
reaction

o The concentrations of reactants and products remain

the same

o It requires a closed system

Where none of the reactants and products
escapes from the reaction mixture
Position of equilibrium refers to the relative amounts of
products and reactants present in an equilibrium mixture
Le Chateliers Principle if one or more factors that affect
an equilibrium is changed, the position of equilibrium shifts in
the direction that reduces the change
o If change concentration of reactants:
The system is no longer in equilibrium
The position of equilibrium shifts to the right to
reduce the effect of the increase in concentration
of reactant
More products are formed until equilibrium is
reached
o If change concentration of products:
The system is no longer in equilibrium
The position of equilibrium shifts to the left to
reduce the effect of the increase in concentration
of products
More reactants are formed until equilibrium is
reached
o If increase pressure

The molecules are closer together

The position of equilibrium shifts to the side with
fewer gas molecules to minimise the increase

o If increase pressure
The molecules are closer together
The position of equilibrium shifts to the side with
fewer gas molecules to minimise the increase
o If decrease pressure
The molecules are further apart
The position of equilibrium shifts to the side with
more gas molecules to minimise the decrease
o NOTE: If there are equal number of moles on
either side of reaction then the position of
equilibrium is not affected by change in pressure
o NOTE: In a reaction involving gases and solids, it
is only the molecules of gases that count when
determining how pressure affects the position of
equilibrium
o If increase temperature:
The energy of the surroundings increases
The reaction will go in the direction that opposes
the change in energy
So reaction will go in the direction that absorbs
energy which is the endothermic reaction
o If decrease temperature:
The energy of the surroundings decreases
The reaction will go in the direction that opposes
the change in energy
So reaction will go in the direction that releases
energy which is the exothermic reaction
o If add catalyst
No effect in position of equilibrium when it is
reached
Increase the rate of forward reaction and
backward reaction equally
If mA+nB->pC+qD then Kc=[C]p[D]q/[A]m[B]n
o Only involve gases and liquids
o Do not involve solids because its concentration remains
constant
o Units of Kc depends on equation
o If all other conditions remain constant, the value of Kc
does not change when the concentration of reactants or
products is altered

o If all other conditions remain constant, the value of Kc

does not change when pressure is altered
o For forward reactions which are endothermic, the value
of Kc increases when temperature increases
o For forward reactions which are exothermic, the value of
Kc decreases when temperature increases
At constant temperature, each gas in the mixture contributes
to the total pressure in proportion to the number of moles
present
Partial Pressure the pressure exerted by any one gas
The total pressure of a gas equals the sum of the partial
pressures of the individual gas Ptotal=PA+PB+PC
Kp=PA(product)/PB(reactant)
Equilibria is involved in the production of ammonia (Haber
Process) and sulfuric acid(Contact Process)
A Bronsted-Lowry acid is a proton donor
A Bronsted-Lowry base is a proton acceptor
Amphoteric substances that can act as either acids or
bases
Conjugate Pair if a reactant is linked to a product by the
transfer of a proton
Strong Acids/Bases acids/bases that dissociate almost
completely in solution
Weak Acids/Bases- acids/bases that dissociate almost
completely in solution

Rates of Reaction

Rate of reaction = (change in amount of reactants or

products)/time
Collision theory in order to
react with each other particles
must collide in the correct
orientation and with sufficient
energy
Activation energy the
minimum energy that colliding
particles must possess for a
successful collision to take place
A reaction will speed up if the
frequency of collisions increases
and the proportion of particles
with energy greater than the
activiation energy increases.
Catalyst a substance that
increases the rate of reaction by
providing an alternate pathway
with a lower activation energy and remains chemically
unchanged at the end of the reaction
The higher the concentration of the reactants, the greater the
number of particles of solute dissolved in a given volume of
solvent, so more frequent successful collisions between
reacting particles so a higher rate of reaction
The higher the pressure in a gas, the more the number of gas
molecules in a
given volume so
more frequent
collisions in a
given time so a
higher rate of
reaction
Boltzmann
distribution
the distribution of
energies at a
given
temperature
Distribution always goes through the origin
Curve approaches x-axis but does not touch it

 Peak represents most probable energy

Area under
curve=total
number of
particles

The effect of temperature

If temperature is increased, the average kinetic energy of
particles is increased
More frequent collisions will take place
The proportion of successful collisions will increase because
proportion of particles exceeding the activation energy
increases
The effect of catalysis
By providing a lower activation energy, a greater proportion
of molecules have sufficient energy to react
Rate at which effective collisions occur and so rate of
catalysed reaction is greatly increased

Enzymes biological catalysts

o Large protein molecules which enable the biochemical
reactions to take place very quickly at relatively low
temperatures
o Happen in solution and are homogenous catalysts
o More efficient that inorganic catalysts
o Very specific
o Dont produce byproducts
o Work under mild conditions at 37 degrees Celsius and
pH 7
o Substrate the specific substance which fits onto
surface of the enzyme called the active site and is
converted to product

Periodicity
For period 3:

Periodic patterns of atomic radii

o The atomic radii decrease across a period
o As you go across a period, the number of protons increase so
does the nuclear charge
o The shielding effect remains constant
o So the greater attractive force exerted by the increasing
positive nuclear charge on the valence electrons pulls them
closer to the nucleus
Periodic patterns of ionic radii
o The cations radii are smaller than its atoms radii but they
decrease across the period
Lost their outer shell of electrons and less shielding
added to increasing nuclear charge across the period
leads up to a greater attractive force pulling the valence
shell closer to the nucleus
o The anions radii are greater than their atoms radii but they
decrease across the period
Gain one or more electrons into the third principal
quantum shell increasing the repulsion between its
electrons whereas the nuclear charge remains constant
When the nuclear charge increases the anions radii
decrease
Periodic patterns of melting points and electrical conductivity
o The electrical conductivity and melting points increases across
the metals from sodium to aluminium
For the metals as the charge on the ion increases the
more electrons are donated to the sea of delocalised
electrons so more electrons available to drift through
the structure so conductivity increases
The metallic bonding is also stronger as the electrostatic
forces of attraction between its ions and the delocalised
electrons are stronger so more energy required to
overcome these forces of attraction so the melting
points increase
o Then drops dramatically to silicon and falls even further to the
non-metallic insulators
Have no delocalised electrons so no available charge
carriers
o Silicon has the highest melting point because every silicon
atom is bonded to its neighbouring atom by strong covalent
bonds

o S8>P4>Cl2 in terms of melting point but still lower than metals

because molecules are held by weak van der Waals forces
even though intramolecular forces are strong covalent bonds
o Argon gas exists as single atoms with very weak van der
Waals forces

Periodic patterns of first ionisation energies

o A general increase due to increasing nuclear charge and the
shielding and distance from nucleus to valence electrons
being relatively constant
o Aluminium has a dip because its valence electron is in the 3p
orbital which is further from the nucleus so nuclear charge not
properly experience by the valence electrons
o Sulfur has a dip due to spin pair repulsion
Reactions with chlorine
Element
Sodium

Magnesiu
m
Aluminiu
m
Silicon
Phosphor
us

Sulfur

Chlorine
Argon

Reaction
burns with orangeyellow flame to
give white products
Burns with bright
white flame to give
white products
Powder burns to
give white product
Burns if heated
strongly
Burns with yellow
flame to give
clouds of white
smoke
Burns with blue
flame to give
colourless blue gas
No reaction
No reaction

Products
Sodium oxide
and peroxide
Magnesium
oxide

Equation
4Na+O2=2Na2O
2Na+ O2=Na2O
2Mg+
O2=2MgO

Aluminium
oxide
Silicon dioxide

4Al+3
O2=2Al2O3
Si+ O2=SiO2

Phosphorus(III)o
xide
Phosphorus(IV)
oxide in excess
oxygen
Sulfur dioxide

P4+3O2=P4O6
P4+5O2=P4O10

S+O2=SO2

Reactions with chlorine

Element
Sodium
Magnesium
Aluminium

Reaction
Burns with a bright
orange flame
Burns with a bright
white flame
Burns with a yellow

Product
Sodium chloride

Equation
2Na+Cl2=4NaCl

Magnesium
chloride
Aluminium

Mg+Cl2= MgCl2
2Al+3Cl2=Al2Cl3

Silicon

Phosphorus

Sulfur

Chlorine
Argon

flame giving a pale

yellow product
Reacts when chlorine
gas passed over to form
a colourless liquid
Burns with yellow flame

Reacts when chlorine

gas passed over to form
an orange liquid
No reaction
No reaction

chloride
Silicon
tetrachloride

Si+2Cl2=SiCl4

Phosphorus(III)chl
oride
Phosphorus(V)chlo
ride
Disulfur chloride

P4+6Cl2=4PCl3
P4+10Cl2=4PCl5

2S+Cl2=S2Cl2

Group 2 Elements

Called as the alkaline earth metals

The metallic radii increase down the group as the outer two electrons occupy a
new principal quantum shell from the further the nucleus
Form 2+ ions as they lose their two valence electrons so act a reducing agents
Ionisation energies decreases down the group:
o The shielding effect increases down the group
o The distance between nucleus and valence electrons increase down the
group
o Both these factors outweigh the increasing nuclear charge down the group
o The group 2 metals get more reactive going down the group
Electronegativity decreases down the group
o As the size of the atom increases any bonding pair of electrons is further
from the nucleus which means it is less strongly held
o Increase the ionic character down the group

Element
Beryllium
Magnesium

Calcium

Difficult to ignite, flame

tinged with red
Difficult to ignite, flame
tinged with red
Difficult to ignite, flame
tinged with green

Strontium
Barium

Reactions with oxygen

Reluctant to burn, white
flame
Burns easily with a bright
white flame

Reaction with water

No reaction
Reacts vigorously with
steam, but very slowly with
water
Reacts moderately with
water
Reacts rapidly with water
Reacts vigorously with
water

General equation for reaction with oxygen: 2X+O2=2XO

Strontium ad barium forms a peroxide as well: Ba(Sr)+O2=Ba(Sr)O2
General equation for reaction with water: X+2H2O=X(OH)2+H2
o Magnesium forms only oxide with steam
o Solutions become more alkaline down the group due to solubility of
hydroxides increasing down the group so the pH increases down the group
o

Solubility of sulfates decreases down the group

Beryllium oxide is amphoteric but all other oxides are sparingly soluble producing
solutions with increasing base strength = XO+H2O = X(OH)2
Carbonates of magnesium,calcium,strontium,barium are all insoluble in water
o All react in dilute acids forming a salt,water, and carbon dioxide
With sulfuric acid: form a sulfate, water,and carbon dioxide
With hydrochloric acid: form a chloride, water, and carbon dioxide
With nitric acid: form a nitrate(soluble in water), water, and carbon
dioxide
Carbonates break down to form the metal oxide and carbon dioxide gas
Nitrates break down to form the metal oxide, nitrogen dioxide, and oxygen
Down the group, the nitrates and carbonates become more thermally stable and
need a higher temperature to decompose
Many of the compounds of Group 2 elements have important uses.
o Limestone, which contains mainly calcium carbonate, is used as a building
material and is used to make cement, which is a component in the
mixtures that make concrete and mortar.
o Slaked lime (calcium hydroxide) is used to neutralise acids in acidic soil.

Group 17

Known as the halogens

Atoms all have seven valence electrons
Are diatomic molecules at room temperature.
Have single covalent bonds between the two atoms
Fluorine is a pale yellow gas
Chlorine is a yellow-green gas
Bromine is a red-brown liquid
Iodine is a black solid but purple vapour
Melting and boiling points of halogens increase down the group
The boiling point values are relatively low so they have simple
molecular structures and have only weak van der Waals forces
between the two atoms
o These forces increase as the number of electrons increase
with increasing atomic number
o The greater the number of electrons, the greater the
opportunities for instantaneous dipoles to arise within
molecules and for induced dipoles to be produced on
neighbouring molecules
o So the
larger the molecules, the stronger the van der
Walls forces, so volatility of halogens decreases down the
group
Halogens need to get 1 electron to have a noble gas configuration
o Form ions with 1- charge
o Halogens are oxidising agents
o Halogens get less reactive going down group 2 due to
electronegativity decreasing down group 2

Fluorine has the smallest atomic radius so its outer shell

experiences most of the attractive force from the
nucleus and the least shielding from inner electrons so it
has the strongest pull on the electrons so has the
highest electronegativity
As you go down the group, the atomic radius increases
so the attractive force spreads out and the outer shell
experiences less and less of it and shielding increases so
the pull on electron decreases so electronegativity
decreases
A more reactive halogen can displace a less reactive halogen from a
halide solution of the less reactive halogen
Reactions with hydrogen

Eleme
nt
Flourin
e
Chlori
ne
Bromi
ne
Iodine

Equation

Reaction

H2+F2=2HF

Reacts explosively even in cool dark conditons

H2+Cl2=2HCl
H2+Br2=2HBr
H2+I2=2HI

Reacts explosively in sunlight

Reacts slowly on heating
Forms an equilibrium mixture on heating

The hydrogen halides get less thermally stable down the group
o Bond energies decrease down the group making it easier to
break the hydrogen-halide bond
o The larger the atom, the longer the bond length, the weaker
the bond is and the less energy it requires to break it
Halide Ion

Chloride
Bromide

Color of silver
halide
precipitate
when silver
nitrate is
added
White
Cream

Effect on
precipitate
when adding
dilute
ammonia

Effect on
precipitate
when adding
concentrate
d ammonia

Dissolves
Dissolve
Doesnt
Dissolve
dissolve
Iodide
Pale Yellow
Doesnt
Doesnt
dissolve
dissolve
Chloride, Bromide, Iodide ions will react with concentrated sulfuric
acid
o All reactions must be done in a fume cupboard
Prepare HCl by dropping conc. Sulfuric acid slowly onto NaCl crystals
o NaCl(s) + H2SO4 (l) NaHSO4 (s) + HCl(g)

o White fumes of HCl can be seen

o Cannot use this to produce HBr and HI because the conc
H2SO4 will oxidize these halides
If add conc H2SO4 to NaBr, NaBr(s) + H2SO4(l) ->
NaHSO4(s) + HBr(g), then HBr is oxidized further to :
2HBr(g) + H2SO4(l)Br2(g)+ SO2(g) + 2H2O(l)
a reddish brown gas is seen which is bromine
If add conc H2SO4 to NaI:
NaI(s) + H2SO4 (l) NaHSO4 (s) + HI(g)
followed by oxidation of HI(g):
2HI(g) + H2SO4(l) I2(g) + SO2(g) +
2H2O(l)
and:
6HI(g) + H2SO4(l) 3I2(g) + S(s) (yellow
solid) + 4H2O(l)
and:
8HI(g) + H SO (l) 4I (g) + H2S(g) (rotten
eggs) + 4H2O(l)
Easier to oxidise the hydrogen halides going down the group
Disproportionation the simultaneous reduction and oxidation of
the same species in a chemical reaction
o Chlorine in hot alkali(70C)
3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O
Cl2 + 6OH- Cl- + ClO3- + 3H2O
Chlorine is oxidised from 0 to +5 and reduced from 0 to
-1
o Chlorine in cold alkali (15C)
Cl2 + 2NaOH NaCl + NaClO + H2O
Cl2 + 2OH- Cl- + ClO- + H2O
Chlorine is oxidised from 0 to +1 and reduced from 0 to
-1
Uses of chlorine
o Chlorination of water
Will kill bacteria and make the water safer to drink
Undergoes disproportionation in water: Cl2 + H2O
HCl + HClO
HClO is chloric acid which decomposes slowly in
solution and produces reactive oxygen atoms that can
kill bacteria in water
o Bleach
made from an equal mixture of sodium chloride and
sodium chlorate(I)
bleaches colours and stains because oxygen atoms from
the chlorate(I) ions oxidise dye and coloured molecules

 also kill bacteria when toilets are cleaned

o Other uses of halogens
Found in many organic compounds such as PVC
Halogenated hydrocarbons are used as solvents,
refrigerants, and in aerosol

Nitrogen and Sulfur

Nitrogen
o A diatomic molecular gas in group 15 of the Periodic Table and
makes up of 78% of the atmosphere
o Unreactive gas that dilutes the effects of the reactive gas,
oxygen
Nitrogen gas form a triple bond to obtain a noble gas
configuration
The triple bond is very strong and require 100 kJ mol-1 of
energy to break
So nitrogen gas reacts under extreme conditions
such as in lightning storms where nitric acid rain
is formed
Lightning provides the activation energy for
reaction
N2 + O2 2NO
2NO + O2 2NO2
2NO2 + H2O + O 2HNO3 nitric acid falls as
rain IMPORTANT FACTOR OF NITROGEN CYCLE
Plants get nitrogen in a soluble form as nitrate
ions
Ammonia
o An alkaline gas
o Formed in a large scale in the Haber process
N2 + 3H2 2NH3
o Can form a co-ordinate bond with a proton from an acid to
form ammonium
An acid-base reaction where
ammonia acts as a base
o Uses of ammonium compounds
Fertilisers to replace nitrogen in
the soil
Ammonium chloride,
ammonium nitrate, ammonium phosphate,
ammonium sulfate
Ammonium chloride + salt salt + water + ammonia
2NH4Cl + Ca(OH)2 CaCl2 + 2H2O + 2NH3
Turns damp red litmus blue
TEST FOR AMMONIUM IONS
Uses of Ammonium Compounds and Ammonia
o Major nitrogen-based fertiliser is ammonium nitrate
manufactured from ammonia and nitric acid NH3 + HNO3
NH4NO3

Ammonium nitrate is heated to evaporate the water and melt

the solid which is then sprayed into a tower with air blown
into it which solidifies the ammonium nitrate into pellets
Nitric acid made from ammonia
Has other uses:
o Make explosives (TNT)
o Manufacture of detergents, paints, pigments, dyes, and
nylon

Environmental problems caused by nitrogen compounds

o Eutrophication
Nitrates can be washed, or leached out of the soil by rain into
groundwater which can find their way into rivers and lakes
Nitrates promote growth of water plants such as algae
A bloom of algae can spread across surface and block sunlight for
other plant life
When plants and algae die, bacteria feed on them using up the
dissolved oxygen and multiply
Without the dissolved oxygen, fish cant take in oxygen through
their gills, killing them and affecting the whole ecosystem
o Blue Baby Syndrome
Caused by nitrates in our drinking water
o Nitrogen oxides in the atmosphere
In car engines, fuel is compressed and ignited by a spark
In these conditions of high pressure and high temperature, nitrogen
and oxygen form nitrogen oxides
Nitrogen oxides are pollutants which cause acid rain and
photochemical smog
Also catalyse the oxidation of sulfur dioxide to sulfur trioxide which
dissolve in rainwater to form acid rain
NO2 + SO2 NO + SO3
NO + O NO2 regeneration of NO2
Cars fitted with catalytic converters to help reduce the pollutants
o On the platinum-coated honeycombed surface, nitrogen oxides
are reduced to nitrogen and oxygen 2NO2 N2 + 2O2
o Oxygen used to oxidise carbon monoxide to carbon dioxide
2CO + O2 2CO2
Sulfur and its oxides
o Sulfur dioxide is formed when we burn fossil fuels especially coal.
o Crude oil, coal, and natural gas has sulfur impurities which oxidize to sulfur
dioxide when burnt
o Sulfur dioxide also released from volcanic activity
o Sulfur dioxide oxidises to sulfur trioxide dissolves in rain water to form
sulfuric acid which is acid rain
SO3 + H2O H2SO4
Effect of acid rain:
Remove the waxy layer from leaves of plants which increase
rate of transpiration which causes plants to wilt
Leaches nutrients from the soil and make plants susceptible
to diseases and pests
Decrease pH of water killing marine life
Damages limestone and marble statues and buildings
o Sulfuric acid
Formed from the Contact Process

Raw materials are water, sulfur, and air

Sulfuric acid used to manufacture fertilisers, detergents, paints,
pigments, dyes, and synthetic fibres
Also used to make plastics, car batteries, tanning leather, cleaning
metal surfaces

Introduction to Organic Molecules

Hydrocarbons compounds containing only carbon and hydrogen

atoms
Represent organic molecules in a variety of different types of
formula
o Empirical Formula the simplest whole number ratio of the
different types of atoms present in the molecule
gives the least detail
calculated from experimental data
o Molecular Formula shows us the actual number of each
type of atom in a molecule
o Structural Formula o Displayed Formula
o Skeletal Formula
Functional Groups
General Formula
Sigma Bonds
o Single covalent bonds with four other atoms, a carbon atom
can gain a noble gas configuration
The four bonding pairs repel each other to form a
tetrahedral shape with angles of 109.5
o Pair of electrons in the bond found in a region of space
between the nuclei of the two atoms sharing the electrons
o Electrostatic force of attraction between the electrons and the
nuclei hold the bonds together
Pi Bonds
o Carbon can also form double bonds such as in alkenes
Made up of a sigma bond and a pi bond
o Carbon atoms will form 3 sigma bonds sp2 hybridisation
leaving a spare electron in the 2p orbital
o When the two p orbitals overlap, they form a pi bond which lie
above and below the plane of the molecule which maximise
overlap of p orbitals
o The three pair of electrons are all in the plane of the molecule
and repel each other to give bond angles of 120
Structural Isomerism isomers with the same molecular formula
but different structural formula

o Position Isomerism the position of the functional group varies in

each isomer

NOTE: Free rotation about C-C single bonds

o Functional Group Isomerism -there are different functional
groups present so have different chemical properties
o Chain Isomerism differ in the structure of their carbon
skeleton

Stereoisomerism
o Cis-Trans Isomerism
Only involve compounds with double bonds because
there is no free rotation about C=C double bond
Have different arrangements of atoms in space so they
are different compounds with different physical
properties and some different chemical properties
o Optical Isomer
Only for molecules whose carbon atom is bonded to 4
different atoms or groups of atoms. The carbon atom is
known as the chiral centre and is represented using an
asterisk
Are mirror images of each other, non-superimposable,
and differ in their effect on polarised light rotate the
plane of polarised light equally but in different directions
Homolytic Fission
o Both the atoms at each of the bond leave with one electron
from the pair of the covalent bond
o Species produced are known as free radicals have one
unpaired electron and are very reactive
o Initiation input of energy to break a covalent bond resulting
in two free radicals
o Propagation radicals attacking reactant molecules forming
more free radicals
o Termination two free radicals reacting together will form a
molecule ending the mechanism
Heterolytic Fission
o Uneven breaking of a covalent bond
o The more electronegative atom takes both the electrons in the
covalent bond
o A carbocation is formed
Three types primary, secondary, tertiary
Tertiary > secondary > primary in terms of stability
Alkyl groups tend to push electrons from themselves
positive inductive effect

The more the alkyl groups attached to the

carbocation the less the charge density is on the
carbon atom with the three covalent bonds
Organic intermediates are more stable when the
charge density is spread over several atoms
Electrophile is an acceptor of a pair of electrons
Nucleophile is a donator of a pair of electrons
Both resulting in a formation of a new covalent bond

Types of Organic Reactions

o Addition involve the formation of a single product from two
reactant molecules
o Substitution involve the replacement of one atom or group
of atoms
o Hydrolysis breakdown of a molecule by water
o Oxidation loss of electrons from a species, gain of oxygen,
and loss of hydrogen
o Reduction gain of electrons from a species, loss of oxygen,
and gain of hydrogen

Hydrocarbons

Alkanes
o Majority of compounds found in the mixture of hydrocarbons
in crude oil
o Saturated hydrocarbons that display sp3 hybridisation so have
maximum number of hydrogen atoms
o General formula: CnH2n+2
o Alkanes retrieved by fractional distillation of crude oil which
separates the wide range of different hydrocarbons into
fractions
The lower the relative molecular mass of the
hydrocarbons, the more volatile they are
They have lower boiling points and are collected near
the top of the fractionating column
o Generally unreactive due to:
the small difference in electronegativity between carbon
and hydrogen
they are nonpolar so not attacked by nucleophiles or
electrophiles
o Combustion of Alkanes:
To generate electricity in power stations
To hear our homes and cook food
To provide energy in industrial processes
To provide power for transportation
In plenty of oxygen, undergoes complete combustion:
Alkane + oxygen carbon dioxide + water
o Carbon dioxide absorbs infared radiation as
the Earth cools down at night so keeps the
Earth at the rifht temperature to support life
o Increased levels of carbon dioxide have
resulted in enhanced global warming
o Traps more heat so average temperature of
Earth rises, resulting in polar ice caps
melting, sea levels rising, resulting in
flooding
In limited supply of oxygen, undergoes incomplete
combustion:
Alkane + oxygen carbon monoxide +
water
Carbon monoxide is an odourless, toxic gas that
can bind on to haemoglobin and prevent efficient
transport of oxygen to the body, which can kill.
Victims will feel dizzy, lose consciousness, if not
removed will die

Can release nitrogen oxides which contributes to

acid rain
Ca also release unburnt hydrocarbons or volatile
organic compounds which are carciogenic

o Substitution reactions of alkanes

Will undergo free radical substitution reactions with
halogens in sunlight
Hydrogen atom in a molecule will be replaced by a
halogen atom
Initiation
Breaking of Cl-Cl bond by UV light from the sun
Homolytic fission to form two chlorine free radicals
Propagation
Free radicals are very reactive which will attack
the normally unreactive alkanes
Get a mixture of substitution products
The more the halogen gas to start with, the
greater the proportions of the substitution
products
Termination
Two free radicals react together to form a single
product and no radicals
Alkenes
o Formed from the cracking of large hydrocarbon molecules to
form smaller, more useful hydrocarbon molecules
o Unsaturated hydrocarbons with sp2 hybridisation
o So have a double bond with bond angles of 120C
o General formula: CnH2n
o Addition reactions:
One of the two bonds in the carbon-carbon double bond
is broken and a new single bond is formed from each of
the two carbon atoms
Addition of hydrogen
At a temperature of 140C hydrogen and alkene
passed over finely divided nickel catalyst to form
an alkane
Addition of steam
In the presence of concentrated phosphoric acid
as the catalyst at 330C and 6MPa alkene
becomes alcohol
Addition of hydrogen halides

When bubbled through a concentrated solution of

a hydrogen halide at room temperature to form a
halogenoalkane
Addition of halogens
If bubble an alkene through a solution of chlorine
or bromine at room temperature the chlorine or
bromine decolourises
TEST FOR ALKENES
o Addition of hydrogen halides and halogens are known as
electrophilic addition
There is an area of high
electron density around the
C=C double bond so alkenes
open to attack by electrophiles
Halogenoalkanes are polar
molecule due to the significant
difference between hydrogen and bromine
Hydrogen has a partial positive charge so it acts as an
electrophile accepting a pair of electrons from the C=C
double bond
As non-polar bromine molecules come near an ethane
molecule, the high electron density around the C=C
bond repels the pair of electrons in the Br-Br bond away
from the nearer Br atom making it partially positive
Both of them are the same mechanism
The bonds break heterolytically
The negative ion attacks the carbocation
intermediate
The positive ion attacks the partially negative
carbon atom
o Markownikoffs Rule when two products are formed the
major product is the one that has the halogen atom bonded to
the carbon with the least number of hydrogen atoms or the
most stable carbocation
Oxidation of the alkenes
o Cold, dilute acidified manganate(VII) solution
The pale purple solution turns colourless
Alkene converted into a diol
o Hot, concentrated manganate(VII) solution
The C=C bond is completely broken
Actual products depend on what is bonded to the carbon
atoms involved in the C=C bond
If hydrogens bonded to C atom, oxidised to carbon
dioxide

If a hydrogen and an alkyl bonded to a C atom

oxidized to aldehyde. If not distilled, further
oxidize to carboxylic acid
If alkyls only bonded to C atom, oxidize to ketone
Addition polymerisation
o Monomer a small reactive molecule that reacts to make
long-chain molecules called polymers
o Polymer a long-chain molecule made up of many repeating
units
o Need monomers which are unsaturated
o Involves the breaking of the pi bond in the C=C bond then the
monomers link together
o The polymer is the only product of the reaction
The disposal of poly(alkene) plastic waste is difficult, as much of it is
chemically inert and non-biodegradable. When burnt, waste plastics
may produce toxic products, such as hydrogen chloride from PVC
(poly(chloroethene)).

Halogenoalkanes

Alkanes that have one or more hydrogen atoms replaced by halogen

atoms
Substitution reactions with aqueous alkali
o A nucleophilic substitution
o Halogen atom replaced by OH-hydroxyl group
The hydroxyl group donates a pair of electrons to the
carbon atom
o Halogenoalkane + sodium hydroxide(aq) alcohol +
sodium halide
Hydrolysis of a halogenoalkane
o Carried out under reflux so no evaporation of the volatile
compounds in the reaction flask
o Halogenoalkane + water alcohol + hydrogen halide
o Investigate the rate of hydrolysis using aqueous silver nitrate
solution
Hydrolysis with water occurs more slowly than with OH(aq) because the negatively charged hydroxide ion is a
more effective nucleophile than a neutral water
molecule
Fluoroalkanes are the least reactive and the iodoalkanes are
the most reactive
o The substitution reactions involve the breaking of the carbonhydrogen bond
o The C-I bond energy is the weakest so it is broken most easily
Substitution with cyanide ions

o The nucleophile is the cyanide ions

o A solution of ethanolic potassium cyanide is heated under
reflux with the halogenoalkane
o Halogenoalkane + ethanolic cyanide ions nitrile +
halide ion
o An extra carbon atom is added to the original halogenoalkane
chain
Substitution with ethanolic ammonia
o If heated with an excess of ethanolic ammonia under pressure,
an amine is formed
o

Nucleophile is the ammonia molecule

o Halogenoalkane + ammonia amine + hydrogen
halide
o If ammonia is not in excess, get a mixture of amine products
Primary amine will act as a nucleophile and attack
halogenoalkane molecules forming secondary amines
and so on
Mechanism of nucleophilic substitution in halogenoalkanes
o Carbon-halogen bond is polarised due to a significant
difference in electronegativity
o SN2 mechanism for primary halogenoalkanes
rate of reaction which is determined by the slow step in
the reaction (rate-determining step) involves two
reacting species
o SN1 mechanism for tertiary halogenoalkanes
After the breaking of the carbon-halogen bond
(heterolytic fission), a tertiary carbocation is formed
which is attacked immediately by the nucleophile
Rate of reaction only depends on one reagent

Elimination Reaction

Involve the loss of a small molecule

Here hydrogen halides are lost

Halogenoalkane + ethanolic NaOH alkene + water +

sodium halide

Here use ethanolic sodium hydroxide

Ethanolic OH- ion acts as a base accepting a
proton from a halogenoalkane to form water
C-Halogen bond breaks heterolytically forming a
halide ion
The fluoroalkanes and fluorohalogenoalkanes have many uses,
including anaesthetics, solvents, refrigerants and aerosol
propellants.
Chlorofluoroalkanes have been responsible for damaging the Earths
ozone layer, but alternative inert compounds, such as fluoroalkanes,
are now replacing the use of CFCs.

Alcohols, esters, and carboxylic acids

Contain hydroxyl group OH group

General Formula: CnH2n+1

Alcohols have higher boiling points than expected when compared

with organic molecules with similar relative molecular masses due
to the hydrogen bonding between alcohol molecules
Combustion
o Complete combustion - Alcohol + oxygen carbon
dioxide + water
o Ethanol burns with a clean blue flame
o Biofuels ethanol used as a fuel
Conserve worlds supply of fossil fuels
Sugar cane absorbs carbon dioxide as it grows
Do not increase the levels of carbon dioxide
Substitution to form a halogenoalkane
o Carbon-hydroxyl bond is polarised so open to nucleophilic
attack
o Alcohol + hydrogen halide + halogenoalkane + water
o Alcohol heated under reflux with the reactants to make the
halogenoalkane which is then distilled off and collected as oily
droplets under water
o Preparing hydrogen chloride
Dry HCl can be made in situ
NaCl + H2SO4 NaHSO4 + HCl
o Using SOCl2
C2H5OH + SOCl2 C2H5Cl + HCl + SO2
HCl and SO2 are gases and escape from the mixture
leaving the halogenoalkane so need to distil it off
o Using phosphorus(V) chloride
Alcohol + PCl5 halogenoalkane + HCl + POCl3
must heat
Release of steamy fumes of HCl used a test for the
hydroxyl group
o Phosphorus (III) chloride can be used but no heating is
required
o For bromoalkanes and iodoalkanes can make the
phosphorus(III) halide in situ using red phosphorus and
bromine or iodine
Reaction with sodium metal
o Breaking of O-H bond
o Alcohol + sodium sodium alkoxide + hydrogen
o When excess ethanol is evaporated off a white crystalline solid
is left
o The longer the hydrocarbon chain, the less vigorous the
reaction
Esterification
o Breaking of O-H bond
o Carboxylic acid + alcohol ester + water
o Carboxylic acid and alcohol are heated under reflux with a
strong acid catalyst

o Reaction is reversible
Hydrolysis of esters
o Heating under reflux with an acid or base
o Refluxing with an acid simply reverses the preparation of the
ester and is a reversible reaction ester + acid
carboxylic acid + alcohol
o Refluxing with a base is not a reversible reaction and ester is
broken down by excess alkali. ester + alkali alcohol +
sodium salt of the carboxylic acid
Dehydration
o Water is removed
o Alcohol alkene + water
o Alkene gases are collected over water
o Alcohol vapour is passed over a hot catalyst of aluminium
oxide powder
Oxidation
o Can be oxidised by heated gently with potassium
dichromate(VI) acidified with dilute sulfuric acid
o If alcohol is oxidized the orange solution will turn green
o No reaction with tertiary alcohols
o Secondary alcohols will oxidize to ketones
o Primary alcohols oxidize to aldehyde and can be oxidized to
form ethanoic acid by refluxing with excess acidified
potassium dichromate(VI)
Carboxyllic acids
o When a nitrile is refluxed with dilute HCl, acid hydrolysis
occurs and the CN group is converted to -COOH group
o Nitrile + HCl + 2H2O carboxylic acid + ammonium
chloride
o Are weak acids small molecules dissociate to release protons
and ions
o React with alkalis to form a salt and water, reactive metals to
form a salt and hydrogen gas, carbonates to form a salt,
water, and carbon dioxide gas
o Carboxylic acids can be reduced to their corresponding
primary alcohol by using the reducing agent LiAlH4 in dry
ether at room temperature

Carbonyl Compounds

Aldehydes formed from the oxidation of primary alcohols

o Heat alcohol gently with acidified dichromate solution which is
added a drop at a time
o Aldehyde has to be distilled off otherwise further heating with
acidified dichromate will oxidise aldehyde to carboxylic acid
Ketones formed from the oxidation of secondary alcohols
o Heat alcohol gently with acidified dichromate solution
o Ketone cant be oxidised so no need to distil it off
Aldehyde reduced to primary alcohol and ketone reduced to
secondary alcohol
o Either by warming aldehyde or ketone with an aqueous
alkaline solution of NaBH4 or adding LiAlH4 in dry ether at
room temperature
Nucleophilic addition with HCN
o C=O bond is polarised due to significant
difference in electronegativity so C atom is
partially positive so can be attacked by
nucelophiles
o The HCN is generated in situ by the reaction of sodium
cyanide and dilute sulfuric acid
o Addition of HCN takes place across the C=O bond
o Increases the length of the hydrocarbon chain by one carbon
atom
o Nitrile group can be easily hydrolysed to a carboxylic acid by
refluxing with dilute hydrochloric acid
-CN + H+ + H2O -COOH + NH4+
o Nitrile group can be reduced to an amine by using sodium and
ethanol
-CN + 4[H] -CH2NH2
Testing for carbonyl group
o Add 2-4 DNPH to a solution, a deep-orange precipitate is
formed
o Precipitate can be purified by recrystallization and its melting
point found experimentally so can identify compound
o A condensation reaction as water is lost
Distinguishing between aldehydes and ketones
o Testing with Tollensreagent
Aqueous solution of silver nitrate in excess ammonia
solution
Silver ions act as an oxidising agent when warmed with
aldehyde
Oxidise aldehyde to form a carboxylate ion
Silver ions reduced to silver ions to form a silver mirror
Positive test for aldehydes not for ketone

o Testing with Fehlings solution (Positive for aldehydes not

for ketones)
An alkaline solution containing copper(I) ions
When warmed with an aldehyde, the Cu2+ ions act an
oxidising agent
Aldehyde is oxidised to a carboxylate ion while the Cu2+
ions are reduced to Cu+ ions
Clear blue solution turns an opaque red/orange colour
o Reactions to form tri-iodomethane
Forms as a yellow precipitate with methyl ketones
compounds containing the CH3CO-group even ethanol
Reagent used is an alkaline solution of iodine which is
warmed with the substance being tested
Reaction involves two steps:
The carbonyl group is halogenated the three
hydrogen atoms in CH3 are replaced by 3 iodine
atoms
The intermediate is hydrolysed to form the yellow
precipitate of tri-iodomethane CHI3 which have a
melting point of 119C
RCOCH3 RCOCI3RCOO-Na+ + CHI3
Can also be used to identify the presence of the
CH3CH(OH)-group
The CH3CH(OH)- group is firstly oxidised by the
alkaline iodine solution forming a methyl ketone
which then reacts via the two steps to give the
yellow precipitate
Two organic products formed here the triiodomethane yellow precipitate and the sodium
salt of the carboxylic acid
Infra-red spectroscopy helps to identify organic compounds by their
absorption of energy in the infra-red range of wavelengths,
matching their spectrum to a database of known infra-red spectra.